STAR-SHAPED MACROMOLECULES FOR DOMESTIC AND PERSONAL CARE

专利摘要:
star-shaped macromolecules for home and personal care. it is a polymer composition comprising star-shaped macromolecules. each star-shaped macromolecule has a nucleus and five or more arms, in which the number of arms within a star-shaped molecule varies throughout the composition of star-shaped molecules. the arms on a star are covalently attached to the star's core; each arm comprising one or more (co) polymer segments; and at least one arm and / or at least one segment exhibits a different solubility than at least one other arm or another segment, respectively, in a reference liquid of interest.
公开号:BR112013010458B1
申请号:R112013010458-9
申请日:2011-10-26
公开日:2020-02-18
发明作者:Wojciech Jakubowski；Patrick McCarthy；Nicolay Tsarevsky；James Spanswick
申请人:Pilot Polymer Technologies, Inc.；
IPC主号:

专利说明:

STAR-SHAPED MACROMOLECULES FOR CARE
HOUSEHOLD AND PERSONNEL
CROSS REFERENCE TO RELATED ORDERS
This claim claims priority benefit from Order No. ² US 12 / 926,143, filed on October 27, 2010, which is still a part of a continuation of Order No. US 12 / 799,411, filed on April 23, 2010, in which it claims additional priority of Provisional Order No. ² US 61 / 214,397, filed on April 23, 2009. All previous related orders, in their entirety, are incorporated by reference in this document.
FIELD OF THE INVENTION
The present invention relates to multi-arm star-shaped macromolecules that are used as rheology modifiers, which include use in home care, personal care and cosmetic compositions.
BACKGROUND AND PREVIOUS TECHNIQUE
Most personal care products on the market contain many types of polymers that vary in structure, chemistry and source of raw material (synthetic or natural) that are combined to provide to provide products with many different desired functions. A class of polymer additives is targeted at altering or modifying the product's rheological properties which are very important for consumer appeal. Often, additives that provide sufficient viscosity are necessary, especially for those formulations where the viscosity without additives is close to that of the pure solvent (water). However, just increasing viscosity is not enough, and in reality, modifiers should be selected to provide certain desired rheological properties for the formulation that depend on its nature, the mode of delivery, type of flow and the aesthetic appeal of the final application. Typically, low molecular weight surfactants are used to modify rheological properties, but they must be used in large concentrations. Resulting in relatively high cost and an adverse impact on the environment (eg water pollution).
Thickeners used in body care and cosmetic preparations must meet strict requirements. Above all, they need to show high compatibility and also - if possible - biodegradability so that many substances need to be rejected from the start for use in cosmetics. In addition, they should be universally usable in bases that contain oil, alcoholic, emulsifiable and aqueous, be readily processable and lead to a rheology that enables the product to be applied easily so that the preparations can be removed and distributed under simple and clean conditions. .
Thickeners that are designed at the molecular level to provide the desired properties would be expected to be compatible with many other auxiliaries, more particularly with salts and surfactants. The thickener itself and the other auxiliaries should also lend themselves to prompt incorporation into the formulation. Thickened preparations are also expected to show stable rheology and unchanging chemical and physical quality even in the event of long-term storage and changes in pH and temperature. Finally, thickeners should be inexpensive to produce without causing significant environmental pollution.
In view of this complex requirement profile, it is clear why, even today, there is still a demand for new thickeners in the cosmetics field.
SUMMARY OF THE INVENTION
Consequently, in one aspect the invention provides a polymer composition comprising star-shaped macromolecules, each star-shaped macromolecule having a nucleus and five or more arms, wherein the number of arms within a star-shaped macromolecule varies over the composition of star molecules; and the arms on a star are covalently attached to the core of the star; each arm comprises one or more (co) polymer segments; and at least one arm and / or at least one segment exhibits a different solubility than at least one other arm or another segment, respectively, in a reference liquid of interest.
Use of the polymer composition in personal care products and home care products is also provided.
In one aspect of the invention, there is a process for forming a star-shaped heteromacromolecule (mikto star macromolecule) comprising:
i) creating a reaction mixture comprising a plurality of first polymeric segments that have a functional end group of ATRP and a plurality of second monomers, wherein at least a portion of the first polymeric segments is formed by polymerizing a plurality of first monomers, non-limiting examples of first monomers include hydrophobic monomers;
ii) forming a second polymeric segment extending from said first polymeric segment by activating the functional end group of ATRP in said first polymeric segment to initiate the polymerization of a portion of the second monomers, to form a plurality of block copolymeric arms ;
iii) during the polymerization of the second monomers, introducing a plurality of second monomer initiators that have an ATRP functional end group within the reaction mixture;
iv) activating the functional end group of ATRP in said second monomer initiator to initiate the polymerization of a second portion of the second monomer, to form a plurality of homopolymeric arms; and
v) reticulate at least a portion of the block copolymeric arms and at least a portion of the homopolymeric arms to form at least one star-shaped heteromacromolecule.
In one aspect of the invention, there is a star-shaped macromolecule that forms a gel when dissolved in water at a concentration of at least 0.2% by weight and is formed:
i) creating a reaction mixture comprising a plurality of first polymeric segments that have a functional end group of ATRP and a plurality of second monomers, in which at least a portion of the first polymeric segments is formed by polymerizing a plurality of first monomers;
ii) forming a second polymeric segment extending from said first polymeric segment activating the functional end group of ATRP in said first polymeric segment to initiate the polymerization of a portion of the second monomers, to form a plurality of arms block copolymers;
iii) during the polymerization of the second monomers, introducing a plurality of second monomer initiators that have an ATRP functional end group inside the reaction mixture;
iv) activating the ATRP functional end group in said second monomer initiator to initiate the polymerization of a second portion of the second monomer, to form a plurality of homopolymeric arms; and
v) cross-linking at least a portion of the block copolymeric arms and at least a portion of the homopolymeric arms;
in what • The) O gel has a dynamic viscosity of hair less 20,000 cP; and B) The macromolecule star shaped have a
molecular weight of 150,000 g / mol and 600,000 g / mol.
In one aspect of the invention, there is a star-shaped macromolecule polymer composition comprising one or more star-shaped macromolecules prepared by an effective and enhanced arm-controlled first radical polymerization method, wherein one or more macromolecules star-shaped are represented by Formula X:
Formula X [(PI) _q i ~ (P2) _q2 ] _t- Nucleus [(P3) _q3 ] _r where:
The core represents a cross-linked polymeric segment;
PI represents a hydrophobic homopolymeric segment equipped with repeating units of monomeric residues of polymerized hydrophobic monomers;
P2 represents a hydrophilic homopolymeric segment equipped with repeating units of monomeric residues of polymerized hydrophilic monomers;
P3 represents a hydrophilic homopolymeric segment equipped with repeating units of monomeric residues of polymerized hydrophilic monomers;
qi represents the number of units in repetition in PI and has a value between 1 and 50; q2 represents the number of units in repetition in P2 and has a value between 30 and 500; q3 represents the number of units in repetition in P3 and has a value between 30 and 500; r represents the number of homopolymeric arms fixed from f covalent orma to the Nucleus; t represents the number of arms copolymerics fixed in covalent form to the Nucleus it's the; is at what the reason
molar r to t is in the range between 20: 1 and 2: 1.
In one aspect of the invention, there is a star-shaped macromolecule that has a molecular weight between 150,000 g / mol and 600,000 g / mol that forms a clear homogeneous gel when dissolved in water at a concentration of at least 0.2% by weight where the gel has:
i) a dynamic viscosity of at least 20,000 cP;
ii) a salt-induced break value of at least 60%;
iii) a pH-induced break value of at least 80%;
iv) a viscosity value that decreases under shear of at least 10; and / or
v) an emulsion value of> 12 hours.
In one aspect of the invention, there is a clear homogeneous gel that comprises a star-shaped macromolecule that has a molecular weight between 150,000 g / mol and 600,000 g / mol, and comprises the following properties:
i) a dynamic viscosity of at least 20,000 cP;
ü) one value break induced per salt in fur minus 60% fiii) one value break induced per salt in fur minus 80% /iv) one value of viscosity that decreases under
shear of at least 10; and / or
v) an emulsion value of> 12 hours.
wherein the clear homogeneous gel is formed when the star-shaped macromolecule is dissolved in water in a concentration of at least 0.2% by weight.
In one aspect of the invention, there is an emulsion-free emulsion comprising:
an macromolecule in form of star soluble in water that has:i) molecular weight in at least 150,000 g / mol; and
ii) a dynamic viscosity of at least 20,000 cP at a concentration of 0.4% by weight.
In one aspect of the invention, there is an emulsion that comprises:
a water-soluble star-shaped macromolecule that has:
i) a molecular weight of at least 150,000 g / mol; and ii) a dynamic viscosity of at least 20,000 cP at a concentration of 0.4% by weight.
In one aspect of the invention, there is a thickening agent that forms a clear homogeneous gel when dissolved in water at a concentration of at least 0.2% by weight, where the gel has:
i) a dynamic viscosity of at least 20,000 cP;
ü) one value breakage induced by salt of fur minus 60%. iü) one value breakage induced by pH of fur minus 80% iv) one value of viscosity that decreases under
shear of at least 10; and / or
v) an emulsion value of more than 12 hours.
In one aspect of the invention, the star-shaped macromolecule, emulsifier, gel, emulsifier-free emulsion, emulsion and / or thickening agent, includes those formed by the one-pot process, ATRP, CRP, and / or combinations of one or more of these processes, can be used to provide a certain level of control over consistency and viscosity factors in many oil-based and aqueous systems that include, for example, solvent and water-based coating compositions, dyes, paints, defoaming agents, substances antifreeze, corrosion inhibitors, detergents, oil well drilling fluid rheology modifiers, additives to enhance oil flooding during improved oil recovery, dental impression materials, personal care and cosmetic applications including hair comb, sprinklers for hair, mousses, hair gels, hair conditioners, shampoos, bath preparations, cream s cosmetics, cosmetic gels, lotions, ointments, deodorants, powders, skin cleansers, skin conditioners, skin emollients, skin humidifiers, skin cleansing wipes, sunscreen, shaving preparations and fabric softeners.
In one aspect of the invention, there is a macromolecule, which comprises: a plurality of arms comprising at least two types of arms, in which a first type of arm extends beyond a second type of arm and said first type of arm has a hydrophobic segment at its distal end, in which at least a portion of the hydrophobic segment may extend beyond the length of the second arm type or the size of the segments or monomeric segment (which can be varied by the length of the monomeric residue, the degree of polymerization, and / or both) to which the hydrophobic segment is attached. Recognize that the length of an arm or segment and the limitation of extending beyond may be theoretical, meaning that while it is not measured empirically it is understood to extend beyond and / or have a longer length in relation to the length of the second type of arm if the degree of polymerization is higher for monomeric residues of the same type or of the same theoretical length.
In one aspect of the invention, there is a star-shaped macromolecule, comprising: a plurality of arms comprising at least two types of arms, in which the degree of polymerization of a first type of arm is greater than the degree of polymerization of a second type of arm and wherein said first type of arm has a hydrophobic distal end portion. In another aspect of the invention, this star-shaped macromolecule can be formed by first obtaining or forming the hydrophobic portion and then forming the remainder of the first type of arm from the end of the hydrophobic portion and the second type of arm in one one-pot synthesis in which the polymerization of the second portion of the first arm type is initiated before the initialization of the second arm type, but there is at least some point where the portions, for example, substantial portions, of the first arm type and of the second type of arm are being extended simultaneously polymerically.
In one aspect of invention, exist an macromolecule in soluble star shape in oil, what comprises: an plurality of arms many different what
it comprises at least two types of arms, in which a first type of arm extends beyond a second type of arm and said first type of arm has a hydrophilic segment at its distal end.
In one aspect of the invention, there is an oil-soluble star-shaped macromolecule, comprising: a plurality of arms comprising at least two types of arms, in which the degree of polymerization of a first type of arm is greater than the degree for polymerizing a second type of arm and wherein said first type of arm has a hydrophilic segment at its distal end.
In one aspect of the invention, there is a star-shaped macromolecule, comprising: a plurality of arms comprising at least two types of arms, in which the degree of polymerization of a first type of arm is greater than the degree of polymerization of a second type of arm, and wherein said first type of arm has a distal end portion that is hydrophobic and the proximal portion of the first type of arm and the second type of arm are the same, the only difference being between the first type of arm and the second type of arm is that the first type of arm has a hydrophobic portion at its distal end. In another aspect of the invention, this star-shaped macromolecule can be formed by first obtaining or forming the hydrophobic portion and then forming the remaining portion of the first type of arm from the end of the hydrophobic portion and the second type of arm simultaneously in a one-pot synthesis.
In one aspect of the invention, star-shaped macromolecules may have an HLM greater than 0.85, for example, greater than 0.87 or 0.9 or 0.93 or 0.95 or 0.97 or 0.98 .
In one aspect of the invention, star-shaped macromolecules can have a calculated HLM greater than 0.85, for example, greater than 0.87 or 0.9 or 0.93 or 0.95 or 0.97 or 0, 98 and a viscosity greater than 60,000 cP at a pH between 7 and 10.5 and a molecular weight between 200,000 g / mol and 550,000 g / mol and a viscosity value that decreases under shear of at least 10 and, optionally, a value of salt-induced breakdown of at least 60%.
BRIEF DESCRIPTION OF THE DRAWINGS
The features and advantages of the present invention can be better understood by reference to the attached Figures, in which:
Figure 1: Illustration of the structure of a star-shaped macromolecule with segmented homo-arm and two different types of star-shaped macromolecules with hetero-arm (mikto-arm).
Figure 2: GPC curve for the polystyrene macroinitiator formed in step 1 of the synthesis of an exemplary star-shaped macromolecule (PSt-bPAA).
Figure 3: GPC curve for the polystyrene macroinitiator formed in step 1 of the synthesis of an exemplary star-shaped macromolecule (PSt-bPAA) and GPC curve for block copolymer formed after LBA chain extension in step 2 of synthesis.
Figure 4: The GPC curves of the PSt-b-tBA block copolymer and the star-shaped macromolecule formed after the core formation reaction is step 3 of the formation of an exemplary star-shaped macromolecule (PSt-b -PAA).
Figure 5: Image showing the thickening properties of the star-shaped macromolecule (PSt-bPAA).
Figure 6: Viscosity of the aqueous solution of the star-shaped macromolecule (PSt-b-PAA) versus the shear rate.
Figure 7: Viscosity of the aqueous solution of the star-shaped macromolecule (PSt-b-PAA) versus concentration.
Figure 8: Viscosity of an aqueous solution and a water / windex solution (1/1 v / v) of star-shaped macromolecule (PSt-b-PAA) versus shear rate.
Figure 9: Viscosity of an aqueous solution and the Carbopol EDT 2020 water / windex solution (1/1 v / v) versus shear rate.
Figure 10: GPC curves for preparing the precursor for a PAA star. Solid line PtBA M _n = 18,900 PDI = 1.14; Dashed line (PtBA) _x star with M _n , _app 112.600 PDI = 1.36
Figure 11: Viscosity of the aqueous solution of star-shaped macromolecule (PSt-b-PAA) and star-shaped macromolecule (PAA) versus shear rate.
Figure 12: Images that demonstrate the emulsifying properties of star-shaped macromolecules (PStb-PAA).
Figure 13: Synthesis of star-shaped macromolecule [(PSt-b-PtBA) / (PtBA)] using the first arm method.
Figure 14: GPC curves for star-shaped macromolecule with Cig-PtBA arm, Cis-PtBA solid line with M _n = 19,200 PDI = 1,16; dashed line (Cig-PtBA) _x star shaped macromolecule M _n , _app = 95,600 PDI = 1.48.
Figure 15: GPC curves for macromolecule star-shaped arm with _two -PtBA C, solid line C ₂ -PtBA _Mn = 17,500 PDI = 1.22; dashed line (Ci ₂ -PtBA) _x M _n , _app
113,900 PDI = 1.53.
Figure 16:
is a graph that compares the viscosity of Advantomer and Carbopol thickener variant.
Figure 17:
ETD 2020 in% by weight of agent is a graph that compares the viscosity of Advantomer and Carbopol ETD 2020 at varying shear rates.
Figure
18: is a graph that compares the viscosity of Advantomer and
Carbopol
ETD 2020 by weight of NaCl
Figure
19: it is one that compares the viscosity of Advantomer and Carbopol ETD 2020 in pH variant.
Figure 20: is a graph that compares the viscosity of Advantomer and Carbopol ETD 2020 in% by weight of H ₂ O ₂ variant.
Figure 21: is a graph that compares the viscosity of Advantomer and Carbopol ETD 2020 at varying temperatures.
Figure 22: is a graph comparing the viscosity% by weight of Advantomer NaCl and Carbopol ETD 2 02 0 in variant.
Figure 23: GPC curves for the reaction product resulting from step 2 of Example 9.
Figure 24: GPC curves for the reaction product resulting from step 3 of Example 9.
DETAILED DESCRIPTION OF THE INVENTION
The term solubility or soluble is understood to mean that when a component is mixed in a solvent and tested, in STP in a 1 cm cuvette, it has a light transmittance value, at a wavelength in one or around a minimum UV / Vis wavelength for the mixture of at least 40%, for example, at least 50%, 70%, 85%, or at least 95%.
The term clear as used to describe a homogeneous gel or homogeneous solution is understood to mean that when the gel or solution is tested, in STP in a 1 cm cuvette, it has a light transmittance value, at a wavelength at or around a minimum UV / Vis wavelength for the gel or solution of at least 40%, for example, at least 50%, 70%, 85%, or at least 95%.
The term water-soluble monomer is understood to mean a monomer that has at least about 10% by weight of water solubility in STP. For example, a water-soluble monomer can have at least 15% by weight, 20% by weight, 25% by weight, or at least 30% by weight water solubility in STP.
The term water-insoluble monomer is understood to mean a monomer that has less water solubility than a water-soluble monomer, for example, less than about 5% by weight, such as less than 1% by weight or 0.5% by weight solubility in water in STP.
The term macromolecule in the form of a star soluble in water is understood to mean a macromolecule in the form of a star that is soluble in water, the pH is adjusted, if necessary, to a pH not greater than 8 with sodium hydroxide, in a concentration of at at least 5 g / 1, for example, between 8 g / 1 to 100 g / 1, such as at least 10 g / 1, 12 g / 1, 15 g / 1, or at least 20 g / 1. For example, a water-soluble star-shaped macromolecule that has an aqueous solubility of at least 10 g / 1 may include introducing at least 10 g of the star-shaped macromolecule in approximately 1 l of water, neutralizing the mixture if necessary, adjusting the pH of the resulting mixture to about pH 8 (for example, with the addition of base, such as sodium hydroxide), and stirring vigorously at a temperature of not more than 100 ° C for no more than about 60 minutes, to achieve the dissolution of the star-shaped macromolecule and testing the solubility in STP.
The term oil-soluble star-shaped macromolecule is understood to mean a star-shaped macromolecule that is soluble in mineral oil in a concentration of at least 5 g / 1, for example, between 8 g / 1 to 100 g / 1, such as at least 10 g / 1, 12 g / 1, 15 g / 1, or at least 20 g / 1 mineral oil. For example, an oil-soluble star-shaped macromolecule that has an oil solubility of at least 10 g / 1 may include introducing at least 10 g of the star-shaped macromolecule into approximately 1 1 of mineral oil and shaking vigorously at a temperature no higher than 100 ° C for no more than about 60 minutes, to achieve the dissolution of the star-shaped macromolecule and testing the solubility in STP.
The term hydrophilic is understood to mean, in relation to a material, such as a polymeric arm or a polymeric segment of a polymeric arm, that the material is water-soluble and comprises hydrophilic segments that have an HLB equal to or greater than 8, for example, an HLB equal to 16 to 20, or equal to or greater than 18, 19, or 19.5. In certain embodiments, the hydrophilic segment may comprise at least 75 mol% of water-soluble monomer residues, for example, between 80 mol% to 100 mol% or at least 85 mol%, 90 mol%, 95 mol%, or at least 97 mol% of water-soluble monomer residues.
The term hydrophobic is understood to mean, in relation to a material, such as a polymeric arm or a polymeric segment of a polymeric arm, that the material is insoluble in water and comprises hydrophobic segments that have an HLB less than 8, for example , an HLB less than 7. In certain embodiments, the hydrophobic segment may comprise at least 75 mol% of water-insoluble monomer residues, for example, between 80 mol% to 100 mol% or at least 85 mol% , 90 mol%, 95 mol%, or at least 97 mol% of water-insoluble monomer residues.
The term monomer residue or monomeric residue is understood to mean the residue resulting from the polymerization of the corresponding monomer. For example, a polymer derived from the polymerization of an acrylic acid monomer (or derivatives thereof, such as derivatives protected against acrylic acid which includes, without limitation, methyl or t-butyl acrylic acid), will provide polymeric segments, identified as PAA, which comprises repeat units of monomeric acrylic acid residues, that is, -CH (CO2H) CH2-. For example, a polymer derived from the polymerization of styrene monomers will provide polymeric segments, identified as PS, that comprise repeating units of styrene monomeric residues, that is, -CH (0 & Η ₅ ) CH ₂ -. For example, a polymer derived from the polymerization of monomeric divinylbenzene monomers will provide polymeric segments that comprise repeating units of monomeric divinylbenzene residues, i.e., CH ₂ CH (C ₆ H ₅ ) chch ₂ -.
The term emulsifier is understood to mean a component that comprises an appreciable weight percentage of an amphiphilic compound that has a molecular weight of less than 5,000 MW. Emulsifiers are generally linear organic compounds that contain both hydrophobic moieties (tails) and hydrophilic moieties (heads), that is, they are amphiphilic. Examples of emulsifiers include, without limitation: alkyl benzenesulfonates, alkanesulfonates, olefin sulfonates, alkylethersulfonates, glycerol ether sulfonates, alpha-ester methyl sulfonates, sulfograxic acids, alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, hydroxy ether mixed sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono- and dialkylsulfosuccinates, mono- and dialkylsulfosuccinamates, sulfotriglycerides, ether carboxylic acids and salts thereof, fatty acid isotyanates, fatty acid sarcosinates, fatty acid sarcosinates, fatty acid, acyl lactylates, acyl tartrates, acyl glutamate, acyl aspartates, alkyl oligoglucoside sulfates, protein fatty acid condensates (particularly wheat-based vegetable products) and alkyl (ether) phosphates, alkylbetaines, alkylamidobetains, aminopropionates, aminoglycinates, imidazoliniumbetaines and sulfobetaines.
The term emulsifier-free is understood to mean a composition or mixture in which the formulation is substantially lacking in any emulsifiers, for example, less than 0.1% by weight of emulsifier, relative to the total composition, or less than 0, 05% by weight of emulsifier, in relation to the total composition, or less than 0.01% by weight of emulsifier, in relation to the total composition, or a formulation in which there is no emulsifier.
The term STP is understood to mean standard conditions for temperature and pressure for measurements
experimental, in that temperature default is an temperature of 25 ° C and the standard pressure is an pressure of 1 atm. Structure polymer composition Macromolecules in shape in star with
multiple arms are shown schematically in Figure 1
In one embodiment, the arms in a star-shaped macromolecule are provided with two or more segments of (co) polymer selected to modify the rheology of the reference liquid of interest. The star-shaped macromolecule structure is represented by the following formula [F- (Ml) _p i- (M2) _p2 ] _n ~ C where
i. [F- (Ml) _p ] - (M2) _p2 ] represents an arm with a segmented (co) polymer chain in which each (co) polymer segment, ii. (Ml) _p i- and (M2) _p2 - are compositionally distinct adjacent (co) polymer segments in which each segment is endowed with one or more monomers with a block, gradient, random or homo (polymer) structure and in that pl and p2 represent the degree of polymerization of each segment of copolymer, iii. F- represents an optionally functional mixture or group of functional groups present at the end of the arm chain, iv. (Ml) pi is not soluble or not completely soluble in the reference liquid of interest,
v. (M2) _p2 is soluble or generally soluble in the reference liquid of interest, vi. and C represents the reticulated nucleus of the star-shaped macromolecule that is endowed with
reticulator (Mx) crosslinker (Mx) and monomer (My), reticulator (Mx) and (M2), or a mixture from (Mx), (My) and (M2), andsaw: l. n represents the number average of arms
covalently attached to the star-shaped macromolecule nucleus.
In another embodiment, the star-shaped macromolecule structure can be represented by the following formula, [F- (Ml) _pl - (M2) _p2 ] _n -C- [(M3) p3 ~ F] _m where
i. [F- (Ml) _pl - (M2) _P 2] represents an arm consisting of a segmented (co) polymer chain, ii. (Ml) _pl - and (M2) _P 2- are compositionally distinct adjacent (co) polymer segments in which each segment consists of one or more monomers with a block, gradient, random or homo (polymer) structure and in that pl and p2 represent the degree of polymerization of each segment of copolymer, iii. F- represents an optionally functional group or a mixture of functional groups present at the chain end of the arm, iv. (Ml) _p i is not soluble or not completely soluble in the reference liquid of interest,
v. (M2) _P 2 is soluble or mostly soluble in the liquid of ref interest, saw . and C represents the reticulated core of macromolecule in star shape that consists of reticulator (Mx) crosslinker (Mx) and monomer (My), crosslinker (Mx) and (M2), or a mixture from (Mx), (My) and (M2), andvii n represents the number average of arms
fixed covalently to the star-shaped macromolecule nucleus.
viii. (M3) _P 3 is a (co) polymer segment that consists of one or more monomers with a block, gradient, random or homo (polymer) structure with a degree of polymerization p3 and ix. m is the number of (M3) _p3 (co) polymer arms covalently attached to the core
X. (M3) _P 3 is soluble or mostly soluble in the liquid of reference of interest and xi. M2 and M3 can be made up of the same (co) monomers or different (co) monomers. In an additional modality, the composition of
polymer comprises star-shaped macromolecules in which the structure of a star can be represented by the following formula, [F- (Ml) pi] _S -C- [(M3) _p3 -F] _m where
i. [F- (Ml) _p i- (M2) _p2 ] represents an arm
consisting of a segmented (co) polymer chain
ii. (Ml) _p i- is a (co) polymer segment in which
each segment consists of one or more monomers with
structure of (co) block polymer, gradient, random or
homo with a degree of polymerization pl, iii. F- optionally represents a group
functional or mixture of functional groups present in the
chain end of the arm
iv. (Ml) pi is not soluble or not completely
soluble in the reference liquid of interest
v. C represents the reticulated nucleus of
macromolecule in the shape of a star that consists of
reticulator (Mx), crosslinker (Mx) and monomer (My), reticulator (Mx) and (M2), or a mixture of (Mx), (My) and
(M2), and
saw . (M3) _P 3 is a (co) polymer segment that is constituted of one or more monomers with structure of (co) polymer block, gradient, random or homo with a
degree of polymerization p3 and vii. (M3) p3 is soluble or mostly soluble in the reference liquid of interest and
viii. m is the number of (M3) _P 3 arms in (co) polymer fixed in covalently to the core , θix. s is O average number of (Ml) pi arms in (co) polymer fixed in covalently to the core
In one embodiment, the polymer composition, the number of arms on any particular star varies across the population of star-shaped macromolecules in each composition, due to the synthetic process used for the synthesis of the composition. This process is called the arm method first and is described in detail below in this document. Due to the variation in the number of arms in star-shaped macromolecules, the number of arms n, m and s are called an average number of arms.
Star-shaped macromolecules with a single peak on the GPC curve with a polydispersity index (PDI) above 1.0 and below 2.5 are preferred.
As used herein, the term reference liquid of interest means the liquid to which the polymer composition will be added. Suitable examples of reference liquids include, but are not limited to, water, oil or a mixture thereof or water with additives that include, but are not limited to, surfactants, oils, fats and waxes, emulsifiers, silicone compounds, UV protectors, antioxidants, various water-soluble substances, biogenic agents, deodorants, odor absorbers, antiperspirants and germ and enzyme inhibitors. Such agents are disclosed in U.S. Patent Nos. 6,663,855 and U.S. 7,318,929 which are incorporated herein by reference to provide definitions for those terms.
Arms of a star may have the same composition or may be different (for example a star-shaped macromolecule with formula (1) vs. (2) or (3), these stars are shown in Figure 1). The difference can be in the composition or in the molecular weight or both (for example, different units of monomer M1, M2, M3 and / or different degrees of polymerization p1, p2, p3).
The term (co) polymer is defined as a polymer derived from two (or more) monomeric species (monomer units)
More preferred specific monomer units such as a Ml, M2, M3 and My building block include those selected from protected and unprotected acrylic acid, methacrylic acid, ethacrylic acid, methyl acrylate, ethyl acrylate, .alpha.butyl acrylate , isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, octyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, 2-ethylhexyl, decyl methacrylate, methyl ethacrylate, ethyl ethacrylate, n-butyl ethacrylate, isobutyl ethacrylate, t-butyl ethacrylate, 2-ethylhexyl ethacrylate, 2,3-dihydroxy acrylate ethacrylate , 2,3-dihydroxypropyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxypropyl methacrylate, glyceryl monoacrylate, glyceryl monoethacrylate, glycidyl methacrylate, glycidyl acrylate, acrylamide acid, methacrylamide, ethacrylamide, N-methyl acrylamide, N, N-dimethyl acrylamide, N, N-dimethyl methacrylamide, N-ethyl acrylamide, N-isopropyl acrylamide, N-butyl acrylamide, N-acrylic acrylamide butyl, N-acrylamide, N-di-n-butyl,
N, N-diethylacrylamide, N-octyl acrylamide,
N-octadecyl, N, N-diethylacrylamide, N-phenyl acrylamide, N-methyl methacrylamide, N-ethyl methacrylamide, N-dodecyl methacrylamide, N, N10 dimethylaminoethyl acrylamide, N-dimethylamine, N-dimethylamine; N, N-dimethylaminoethyl methacrylamide, N, N-dimethylaminoethyl methacrylamide, N, N-dimethylaminoethyl acrylate, N methacrylate, quaternized, methacrylated, N-dimethylaminoethylate, methacrylate, methacrylate, N of 2-hydroxyethyl, 2-hydroxyethyl methacrylate, 2-hydroxyethyl ethacrylate, glyceryl ethacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-methoxyethyl ethacrylate, 220 ethoxyethyl methacrylate, 2-methoxyethyl ethoxyethylate maleic acid, maleic anhydride and its ester media, fumaric acid, itaconic acid, itaconic anhydride and its ester media, crotonic acid, angelic acid, diallyldimethyl ammonium chloride, imidazole vinyl vinyl pyrrolidone, methyl vinyl ether, methyl vinyl ketone, maleimide, vinyl pyridine, vinyl pyridine-Noxide, vinyl furan, styrene sulfonic acid and its salts, ally alcohol, ally citrate, ally tartrate, vinyl acetate, alcohol vinyl, 30 vinyl caprolactam, vinyl acetamide, vinyl formamide and mixtures thereof.
Even more preferred monomer units as a construction part of Ml, M2, M3 and My are those selected from methyl acrylate, methyl methacrylate, methyl ethacrylate, ethyl acrylate, ethyl methacrylate, ethyl ethacrylate, n acrylate -butyl, n-butyl methacrylate, n-butyl ethacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl ethacrylate, N-octyl acrylamide, 2-methoxy ethyl acrylate, 2-hydroxyl acrylate N, Ndimethylaminoethyl, N methacrylate, N-dimethylaminoethyl, acrylic acid, methacrylic acid, Nt-butylacrylamide, Nsec-butylacrylamide, N, N-dimethylacrylamide, 2-hydroxyethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl acrylate -hydroxyethyl, benzyl acrylate, 4-butoxycarbonylphenyl acrylate, butyl acrylate, 4-cyanobutyl acrylate, cyclohexyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, heptyl acrylate, isobutyl acrylate, 3-methoxybutyl, 3-methoxypropyl acrylate, methyl acrylate, N-butyl acrylamide, N, N-dibutyl acrylamide, ethyl acrylate, methoxyethyl acrylate, hydroxyethyl acrylate, diethylene glycol acrylate, styrene (optionally substituted with one or more branched or linear alkyl groups (C.sub.1 to C.sub.12), alpha-methylstyrene, t-butylstyrene, p-methylstyrene, and mixtures thereof.
Monomer units in the arms can be connected to C-C covalent bonds. This is believed to make them difficult to degrade so that the star-shaped macromolecule can function as an effective thickening agent in an aggressive environment (very high / low pH or in the presence of strong oxidizing agents).
When C represents the cross-linked nucleus of the macromolecule in the form of a star, it can consist of crosslinker (Mx), crosslinker (Mx) and
monomer (My), crosslinker (Mx) and (M2), or a mixture of (Mx), (My) and (M2). Suitable crosslinkers (Mx) encompass all
compounds that have the ability, under the conditions of polymerization, to cause cross-linking. These include, but are not limited to, di-, tri- and tetrafunctional (meth) acrylates, di-, tri- and tetrafunctional styrenes and other multi- or polyfunctional crosslinkers.
Some examples of crosslinking agents may include, but are not limited to, 1,2-divinylbenzene, 1,3divinylbenzene and 1,4-divinylbenzene, 1,2-ethanediol di (meth) acrylate, 1, (meth) acrylate, 3-propanediol, 1,4butanediol di (meth) acrylate, 1,5hexanediol di (meth) acrylate, divinylbenzene, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylethylene glycol di (meth) acrylate, di (meth) triethylene glycol acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and polybutylene glycol di (meth) acrylate, and glyceryl di (meth) acrylate, tri (meth) acrylate trimethylolpropane acrylate, pentaerythritol tetra (meth) acrylate, allyl methacrylate, allyl acrylate.
The terms 'mostly soluble', 'not completely soluble', and 'non-soluble' are used to describe the extent to which a composition is capable of being dissolved in a reference liquid of interest.
The term 'mostly soluble' is used to describe a composition that has the ability to dissolve completely with the exception of a slight cloudiness in the reference liquid of interest. The term 'not completely soluble' is used to describe a composition that is dispersed with a cloudiness in the reference liquid of interest. The term 'non-soluble' is used to describe a composition that is not dispersed and remains as a solid in the reference liquid of interest. A list of solvents and nonsolvents for polymers can be found in Polymer Handbook, 4th Edition edited by Brandrup J .; Immergut, Edmund H .; Grulke, Eric A .; Abe, Akihiro; Bloch, Daniel R., John Wiley & Sons: 2005.
Multiple arm star shaped macromolecules are the preferred topology for a modality of the present invention since they adopt a globular shape in which the internal segment, (M2) _p2 of each arm covalently fixed to the nucleus, can extend in chain in a selected solvent to achieve a highly swollen stable structure. The dispersing medium can be water, oil or a mixture thereof. The degree of polymerization p2 of the segment (M2) must be higher than that of pl of the segment (Ml) to achieve a stable, highly soluble structure. A star-shaped macromolecule with p2> (3 x pl) is more preferred.
In one embodiment, a star-shaped macromolecule described with formula (2) and shown in Figure 1B, which comprises a fraction of segmented (co) polymer [F (M1) _pi - (M2) _P 2] arms, the average number of arms, n, must be greater than two per star, preferably greater than three, and may comprise a mole fraction between 0.5 and 100% of the arms in the average star-shaped macromolecule. The ratio between nor is most preferably between 100 and 0.1.
In one embodiment, in a star-shaped macromolecule described with formula (3) and shown in Figure 1C that comprises a fraction of arms [F- (Ml) _p i], the average number of arms, o, must be greater than two per star, preferably greater than three, and may comprise a fraction of mole between 0.5 and 100% of the arms in the average star-shaped macromolecule. The oem ratio is most preferably between 100 and 0.1.
One embodiment of the present invention can be exemplified through a star-shaped macromolecule with multiple arms in which the average number of arms in the star-shaped macromolecule is between 5 and 500, preferably between 10 and 250.
In one embodiment, the star-shaped macromolecule has a core that contains additional functionality and / or expanded free volume. 'Expanded free volume' of the core is defined as the core with the lowest crosslink density. The free volume in the core is generated when, during the crosslinking process, the crosslinker Mx with the monomer M2 or My is used. If M2 or My are monomers with functional groups, those groups will be incorporated into the nucleus.
In one embodiment, the star-shaped macromolecule can store and release small molecules at a controlled rate. 'Small molecules' are fragrances, UV absorbers, vitamins, minerals, dyes, pigments, solvents, surfactants, metal ions, salts, oils or drugs. These small molecules can be stored within the star-shaped macromolecule nucleus and then released. Each small molecule has some affinity to the nucleus, it is soluble in the nuclear environment. Higher affinity of the small molecule to the nucleus will result in the lower rate of release of the star-shaped macromolecule. Affinity can be increased or decreased through non-covalent forces that include interactions of metal chelation, coordination, hydrophobic, electrostatic and H bonding.
In one embodiment, the star-shaped macromolecule exhibits viscosity behavior that decreases under shear. 'Viscosity that decreases under shear' is defined as an effect in which viscosity decreases the increasing rate of shear stress. The extent of the viscosity behavior that decreases under shear is characterized by the use of a Brookfield type viscometer in which viscosities are measured at different shear rates.
In one embodiment, the star-shaped macromolecule comprises a functional group that exhibits electrostatic, metal chelating, hydrophobic, coordination and / or H bonding forces. It represents an optionally functional group or a mixture of functional groups present in the chain end of the arm. Functional groups (F) encompass all compounds that have the ability to interact through non-covalent forces that include metal, coordination, hydrophobic, electrostatic and H bonding chelation.
Some examples of F-end groups that have the H-binding capacity include, but are not limited to, base-modified adenine, thymine, guanine, cytosine or derivatives thereof, peptides, etc. Some examples of groups of extremities that have the capacity for electrostatic interactions include, but are not limited to, carboxylate, phosphate, sulfonate, secondary, tertiary and quaternary amines. Some examples of end groups that have the capacity for hydrophobic interactions include, but are not limited to, aliphatic groups C1 to C30, benzyl aliphatic and benzyl groups, saturated and unsaturated hydrophobes. Some examples of end groups that have the ability to coordinate interactions include, but are not limited to, metal ions and / or metal ion binders. Some examples of end groups that have the capacity for metal chelation interactions include diethylenetriamino-N, N, N ', N', N''pentaacetic acid (DTA) derivatives, ethylenedinitrilotetraacetic acid (EDTA) or nitrilotriacetic acid (NTA ).
In one embodiment, the star-shaped macromolecule comprises a functional group F that is designed to interact with small molecule surfactant micelles. 'Interact with' is defined as any intermolecular force between two molecules. These intermolecular forces include electrostatic, hydrogen bonding, hydrophobic, steric, dipole-dipole, pi-pi, or other intermolecular forces.
Surfactants represent a class of molecules with a hydrophobic tail and a hydrophilic head. Some examples of surfactants include, but are not limited to, linear alkyl benzene sulfonate (LAS) salts, alkyl ether sulfate salts (AEOS), alkyl polyglycosides (APG), alcohol ethoxylates, fatty acid glycoamides, betaines, alpha-olefin sulfonate salts , polysorbates, PEGs, alkylphenol ethoxylates, esterquates, imidazolium salts, quaternary ammonium salts of diamide, etc.
In one embodiment, the arms of the star-shaped macromolecule comprise a segment of (co) polymer that exhibits a higher, or higher, critical solution temperature (UCST or HCST) by which the star-shaped macromolecule is soluble in a liquid at higher temperatures, that is, above 44 ° C, then at a lower use temperature in which the outer cover polymer segments become insoluble and aggregate to form a shear-sensitive gel or in another embodiment of the invention, the outer cover star macromolecule arms comprise a (co) polymer segment that exhibits a lower critical solution temperature (LCST), for example 5 ° C, whereby the macromolecule in star shape is soluble in a liquid at a lower temperature then at the temperature of use the outer shell polymer segments become insoluble and aggregate to form a sensitive gel shear. In the case of a LOST, a copolymer segment with a LOST below 10 ° C, preferably below 5 ° C, is expected to be optimal. A non-limiting example would be a copolymerization of BuMA and DMAEMA and the preparation of copolymers with projected LCST. A copolymer with 10% BuMA has an LCST close to 0 ° C and an individual would use less BuMA or a less hydrophobic monomer such as MMA to increase the LCST to ~ 5 ° C. In fact, the Tg of the star segment can be selected to allow the star to dissolve in aqueous media at room temperature.
In one embodiment, a star-shaped macromolecule additionally comprises a cosmetic and personal care product and / or formulation. Cosmetic and personal care products include, but are not limited to, a shampoo, conditioner, hair lotion, tonic, hair spray, hair mousse, hair gel, hair dyes, moisturizers, suntan lotion, color cosmetic, body lotion, cream hand, baby skin care product, face cream, lipstick, mask, blush, eye liner, baby shampoo, baby moisturizer, baby lotion, shower gel, soap, shaving product, deodorant, cream bath, liquid soap, wax, cream, solid, gel, lubricant, jelly, balm, toothpaste, whitening gel, disposable towel, disposable handkerchief or ointment.
In one embodiment, a star-shaped macromolecule additionally comprises a household care product and / or formulation. Home care products include, but are not limited to, a surface cleaner, window cleaner, laundry detergent, toilet cleaner, fabric cleaner, fabric softener, dish detergent, cleaning bar, stain bar, cleaners spray, sprayable formulations, lubricants, disposable towel or disposable tissue.
The polymer chains that comprise the arms are preferably provided with a higher molecular weight
that or equal to 500 what can reach 2,000,000. Those numbers correspond the pl, p2, p3 in the range of 5 to 20,000, preferably at banner of 8 to 2,000.On a example, at macromolecules in the form of
stars comprising arms of segmented copolymers are intended for use in aqueous media. The stars comprise a cross-linked core, and arms made of water-soluble copolymer (M2) _p2 and a hydrophobic (co) polymer (Ml) _pl . Therefore, in a non-limiting example, the stars comprise a cross-linked core, and arms that comprise a water-soluble (co) polymer (for example poly (acrylic acid), poly (2-hydroxyethyl acrylate), poly (N-isopropylacrylamide) , poly (ethylene glycol) methacrylate, quaternized poly (dimethylaminoethyl methacrylate, etc.) and a hydrophobic (co) polymer (e.g., substituted polystyrene or polystyrene, poly (alkyl (meth) acrylate), etc.) or a hydrocarbon-based segment. Suitable hydrocarbon-based segments can comprise low molecular weight α-olefin. Low molecular weight α-olefins are commercially available and higher molecular weight species can be prepared by telomerizing mixtures of ethylene propylene or ethylene. [Kaneyoshi, H .; Inoue, Y .; Matyjaszewski, K. Macromolecules 2005, 38, 5425 to 5435.]
In one embodiment, polymer compositions can be added in solution to provide a certain level of control over the consistency and viscosity factors in many oil-based or aqueous systems where control over rheology is an issue. Applications include; coating compositions based on solvent and water, paints, paints, antifoaming agents, antifreeze substances, corrosion inhibitors, detergents, oil well drilling fluid rheology modifiers, additives to enhance water flooding during enhanced oil recovery, dental impression materials, personal care and cosmetic applications including hair styler, hair conditioners, shampoos, bath preparations, cosmetic creams, gels, lotions, ointments, deodorants, powders, skin cleansers, skin conditioners, skin moisturizers, skin wipes, sunscreens, shaving preparations, and fabric softeners, with the rheology modifier providing high gel resistance features, high viscosity features that decrease under shear, versatile low viscosity soluble concentrations in shapes, and interactions synergistic with additional agents s to adjust their rheology profile to optimize properties such as sedimentation, flow and leveling, warping, splashing, etc.
A non-limiting field of applications that can exemplify the usefulness of the revealed star-shaped macromolecules is that of personal care and cosmetic compositions such as hair styling spray, mousses, gels and shampoos, often containing resins, gums and adhesive polymers to provide a variety of benefits, for example, film forming ability, thickening, sensory properties and capillary fit and conformation. Polymers designed for rheological control, such as thickening agents, in such compositions generally focus on graft or linear copolymers that contain multiple monomers in a random or alternating block configuration.
Suitable hydrophobic monomers that can be used to form an arm or arm segment, such as polymeric arm segments, of a star-shaped macromolecule may include, but are not limited to, methyl acrylate, ethyl acrylate, acrylate n-butyl, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, octyl acrylate; methyl methacrylate; ethyl methacrylate; n-butyl methacrylate; isobutyl methacrylate; t-butyl methacrylate; 2-ethylhexyl methacrylate; decyl methacrylate; methyl ethacrylate; ethyl ethacrylate; n-butyl ethacrylate; isobutyl ethacrylate; t-butyl ethacrylate; 2-ethylhexyl ethacrylate; decyl ethacrylate; 2,3-dihydroxypropyl acrylate; 2,3-dihydroxypropyl methacrylate; 2-hydroxypropyl acrylate; hydroxypropyl methacrylate; glycidyl methacrylate; glycidyl acrylate, acrylamides, styrene; styrene optionally substituted with one or more C 1-12 straight or branched chain alkyl groups; or alkylacrylate. For example, the hydrophobic monomer can comprise styrene; alpha-methylstyrene; t-butylstyrene; p-methylstyrene; methyl methacrylate; or t37 butyl acrylate. For example, the hydrophobic monomer can comprise styrene. In certain embodiments, the hydrophobic monomer may comprise a protected functional group.
Suitable hydrophilic monomers that can be used to form an arm or arm segment, such as a polymeric arm segment of a star-shaped macromolecule, may include, but are not limited to, protected and unprotected acrylic acid, such as methacrylic acid, ethacrylic acid, methyl acrylate, ethyl acrylate, al-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, octyl acrylate; methyl methacrylate; ethyl methacrylate; n-butyl methacrylate; isobutyl methacrylate; tbutyl methacrylate; 2-ethylhexyl methacrylate; decyl methacrylate; methyl ethacrylate; ethyl ethacrylate; nbutyl ethacrylate; isobutyl ethacrylate; t-butyl ethacrylate; 2-ethylhexyl ethacrylate; decyl ethacrylate; 2,3-dihydroxypropyl acrylate; 2,3-dihydroxypropyl methacrylate; 2-hydroxyethyl acrylate; 2-hydroxypropyl acrylate; hydroxypropyl methacrylate; glyceryl monoacrylate; glyceryl monoethacrylate; glycidyl methacrylate; glycidyl acrylate; acrylamide; methacrylamide; ethacrylamide; N-methyl acrylamide; N acrylamide, Ndimethyl; N, N-dimethyl methacrylamide; Netyl acrylamide; N-isopropyl acrylamide; N-butyl acrylamide; N-t-butyl acrylamide; N, N-di-n-butyl acrylamide; N, N-diethylacrylamide; N-octyl acrylamide; N-octadecyl acrylamide; N, N-diethylacrylamide; N-phenyl acrylamide;
N-methyl methacrylamide; N-ethyl methacrylamide; N-dodecyl methacrylamide; N acrylamide, Ndimethylaminoethyl; N, N-dimethylaminoethyl acrylamide; N, N-dimethylaminoethyl methacrylamide; quaternized N, N-dimethylaminoethyl methacrylamide;
N, N-dimethylaminoethyl acrylate; N methacrylate, Ndimethylaminoethyl; quaternized N, N-dimethylaminoethyl acrylate; quaternized N, N-dimethylaminoethyl methacrylate; 2-hydroxyethyl acrylate; 2-hydroxyethyl methacrylate; 2-hydroxyethyl ethacrylate; glyceryl ethacrylate; 2-methoxyethyl acrylate; 2methoxyethyl methacrylate; 2-methoxyethyl ethacrylate; 2ethoxyethyl acrylate; 2-ethoxyethyl methacrylate; 2ethoxyethyl ethacrylate; maleic acid; maleic anhydride and its ester means; fumaric acid; itaconic acid; itaconic anhydride and its ester means; crotonic acid; angelic acid; diallyldimethyl ammonium chloride; vinyl pyrrolidone imidazole vinyl; methyl vinyl ether; methyl vinyl ketone; maleimide; vinyl pyridine; vinyl pyridine-Noxide; furan vinyl; styrene sulfonic acid and its salts; allyl alcohol; allyl citrate; allyl tartrate; vinyl acetate; vinyl alcohol; vinyl caprolactam; vinyl acetamide; or vinyl formamide. For example, the hydrophilic monomer can comprise protected and unprotected acrylic acid, such as methacrylic acid, ethacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-acrylate. -ethylhexyl, decyl acrylate, octyl acrylate; methyl acrylate; methyl methacrylate; methyl ethacrylate; ethyl acrylate;
ethyl methacrylate; ethyl ethacrylate; nbutyl acrylate; n-butyl methacrylate; n-butyl ethacrylate; 2-ethylhexyl acrylate; 2-ethylhexyl methacrylate; 2-ethylhexyl ethacrylate; N-octyl acrylamide; 2-methoxyethyl acrylate; 2-hydroxyethyl acrylate; N, N-dimethylaminoethyl acrylate; N methacrylate, Ndimethylaminoethyl; acrylic acid; methacrylic acid; N-tbutylacrylamide; N-sec-butylacrylamide; N, Ndimethylacrylamide; N, N-dibutylacrylamide; N, Ndihydroxyethylacrylamide; 2-hydroxyethyl acrylate; 2-hydroxyethyl methacrylate; benzyl acrylate; 4-butoxycarbonylphenyl acrylate; butyl acrylate; 4-cyanobutyl acrylate; cyclohexyl acrylate; dodecyl acrylate; 2-ethylhexyl acrylate; heptyl acrylate; isobutyl acrylate; 3-methoxybutyl acrylate; 3-methoxypropyl acrylate; methyl acrylate; N-butyl acrylamide; N, N-dibutyl acrylamide; ethyl acrylate; methoxyethyl acrylate; hydroxyethyl acrylate; or diethylene glycolethyl acrylate. For example, the hydrophilic monomer may comprise protected and unprotected acrylic acid, such as methacrylic acid, ethacrylic acid, methyl acrylate, ethyl acrylate, abutyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate , decyl acrylate, octyl acrylate; 2-hydroxyethyl acrylate; N-isopropylacrylamide; ethylene glycol methacrylate; (polyethylene glycol) methacrylate; or quaternized dimethylaminoethyl methacrylate. For example, the hydrophilic monomer may comprise acrylic acid, methacrylic acid, 2-hydroxyethyl acrylate, acrylamide, vinyl pyrrolidone, vinyl pyridine, styrene sulfonic acid, PEG-methacrylate, ethyl 2 (dimethylamino) methacrylate, 2- ( trimethylamino) ethyl, 2-acrylamide-2-methylpropane sulfonic acid. For example, the hydrophilic monomer can comprise acrylic acid.
Suitable monomers that can be used to form a core of a star-shaped macromolecule may include, but are not limited to, a multifunctional monomer, for example, a hexafunctional monomer, a pentafunctional monomer, a tetrafunctional monomer, a trifunctional monomer, or a bifunctional monomer. For example, a crosslinker can be a hydrophobic monomer or a hydrophilic monomer, such as a hydrophobic multifunctional monomer or a hydrophilic multifunctional monomer, for example, a hydrophobic bifunctional monomer or a hydrophilic bifunctional monomer. For example, the crosslinker can be a hydrophobic crosslinker, which includes, but is not limited to, 1,2-divinylbenzene; 1,3divinylbenzene; 1,4-divinylbenzene; 1,2ethanediol di (meth) acrylate; 1,3-propanediol di (meth) acrylate; 1,4butanediol di (meth) acrylate; 1.5hexanediol di (meth) acrylate; divinylbenzene; ethylene glycol di (meth) acrylate; di (ethylene glycol) diacrylate (DEGlyDA); propylene glycol di (meth) acrylate; butylene glycol di (meth) acrylate; triethylene glycol di (meth) acrylate; polyethylene glycol di (meth) acrylate; polypropylene glycol di (meth) acrylate; polybutylene glycol di (meth) acrylate; alii (met) acrylate; glycerol di (meth) acrylate; trimethylolpropane tri (meth) acrylate; pentaerythritol (meth) acrylate; allyl methacrylate; or allyl acrylate. For example, the crosslinker can be di (ethylene glycol) diacrylate (DEGlyDA) or divinylbenzene. For example, the crosslinker can be divinylbenzene.
Suitable star-shaped macromolecules may include, but are not limited to, a star-shaped heteromacromolecule, a water-soluble star-shaped macromolecule, a gel-forming star-shaped macromolecule, thickening-star macromolecules / emulsifier or combinations thereof. In certain embodiments, star-shaped macromolecules may have a molecular weight greater than 100,000 g / mol, for example, between 100,000 g / mol and 2,000,000 g / mol, such as between 125,000 g / mol and 1,750,000 g / mol; between 150,000 g / mol and 1,750,000 g / mol; between 200,000 g / mol and 1,500,000 g / mol; between 225,000 g / mol and 1,250,000 g / mol; between 125,000 g / mol and 1,000,000 g / mol; between 125,000 g / mol and 900,000 g / mol; between 125,000 g / mol and 800,000 g / mol; between 125,000 g / mol and 700,000 g / mol; between 150,000 g / mol and 650,000 g / mol; between 200,000 g / mol and 600,000 g / mol; between 225,000 g / mol and 650,000 g / mol; between 250,000 g / mol and 550,000 g / mol; between 350,000 g / mol and 500,000 g / mol; between 300,000 g / mol and 500,000 g / mol; or between 350,000 g / mol and 750,000 g / mol.
Suitable star-shaped macromolecules may have a Polydispersity Index (PDI) of less than 2.5, for example, a PDI of less than 2.0, such as less than 1.7. For example, a star-shaped macromolecule can have a PDI of between 1.0 to 2.5, such as between 1.0 and 2.3; between 1.0 and 2.0; between 1.0 and 1.9; between 1.0 and 1.8; between 1.0 and 1.7; between 1.0 and 1.6; between 1.0 and 1.5; between 1.0 and 1.4; between 1.0 and 1.3; between 1.0 and 1.2; between 1.0 and
1.1; between 1.05 and 1.75; between 1.1 and 1.7; between 1.15 and 1.65; or between 1.15 and 1.55.
Suitable star-shaped macromolecules can comprise arms that are of the same type of a different type and are homopolymeric, copolymeric, comprise multiple block segments, random segments, gradient segments or no particular segment. In certain embodiments, the star-shaped macromolecule may comprise, for example, one or more types of arm, such as two or more, three or more, four or more, five or more types of arm. Suitable arm types may include, but are not limited to, homopolymeric arms, copolymeric arms, such as random copolymeric arms or block copolymeric arms, or combinations thereof. For example, a star-shaped macromolecule can comprise homopolymeric arms and copolymeric arms, such as block copolymeric arms. Suitable arm types may also include, but are not limited to, hydrophilic arms, hydrophobic arms, or amphiphilic arms. In certain embodiments, a star-shaped macromolecule arm may comprise hydrophilic polymeric segments that comprise hydrophilic monomeric residues, hydrophobic polymeric segments that comprise hydrophobic monomeric residues, amphiphilic polymeric segments that comprise amphiphilic monomeric residues, or combinations thereof. For example, in certain embodiments, a star-shaped macromolecule may comprise homopolymeric arms and copolymeric arms, such as hydrophilic homopolymeric arms and copolymeric arms that comprise hydrophilic polymeric segments and hydrophobic polymeric segments.
Suitable star-shaped macromolecules may also comprise arms that are covalently attached to the core of the star-shaped macromolecule. In certain embodiments, the arms of a star-shaped macromolecule can be covalently connected to the core of the star-shaped macromolecule via crosslinking, such as crosslinking with a crosslinker, for example, a hydrophobic bifunctional crosslinker or a hydrophilic bifunctional crosslinker . For example, arms of a star-shaped macromolecule, such as homopolymeric arms and block copolymeric arms of a star-shaped heteromacromolecule, can be covalently linked together to form a nucleus by crosslinking one end of the arms with a crosslinker, such as with a hydrophobic bifunctional crosslinker or a hydrophilic bifunctional crosslinker.
Suitable star-shaped macromolecules may further comprise arms of varying degree of polymerization and / or length. In certain embodiments, for example, a star-shaped macromolecule may comprise homopolymeric arms and copolymeric block arms, where the homopolymeric arms of a shorter length and / or a lower degree of polymerization in relation to the copolymeric block arms. In certain embodiments, for example, a star-shaped macromolecule may comprise homopolymeric arms and block copolymeric arms, wherein the block copolymeric arms of a longer length and / or a greater degree of polymerization in relation to the homopolymeric arms. In certain embodiments, a star-shaped macromolecule can comprise hydrophilic homopolymeric arms and block copolymeric arms, which comprise hydrophobic polymeric segments distal to the star core and hydrophilic polymeric segments that are proximal to the star core, where a distal portion of the segments hydrophilic polymeric copolymeric arms extends beyond a distal portion of the hydrophilic homopolymeric arms. For example, a star-shaped macromolecule may comprise hydrophilic homopolymeric arms that comprise polymerized hydrophilic monomeric residues and block copolymeric arms that comprise hydrophobic polymeric segments distal to the star core and hydrophilic polymeric segments that are proximal to the star core, where the distal hydrophobic polymeric segments extend beyond the most distal portion, in relation to the nucleus, of the hydrophilic homopolymeric arms, and / or in which a distal portion of the proximal hydrophilic polymeric segments of the copolymeric arms extend beyond the most distal portion, in relation to the nucleus , of the hydrophilic homopolymeric arms. In certain embodiments, a star-shaped macromolecule may comprise hydrophilic homopolymeric arms and block copolymeric arms, which comprise hydrophobic polymeric segments distal to the star core and hydrophilic polymeric segments that are proximal to the star core, in which the degree of polymerization of the hydrophilic polymeric segments of the copolymeric arms is greater than, for example, 20% greater than, such as between 30% to 300% greater than, between 40% to 250%, between 50% to 200%, or between 75% to 250% greater than, the degree of polymerization of the hydrophilic homopolymeric arms, so that a distal portion of the hydrophilic polymeric segments of the copolymeric arms extends beyond a distal portion of the hydrophilic homopolymeric arms.
In certain embodiments, a star-shaped macromolecule may comprise hydrophilic homopolymeric arms that comprise polymerized hydrophilic monomeric residues and block copolymeric arms that comprise hydrophobic polymeric segments distal to the star core and hydrophilic polymeric segments proximal to the star core, where the residues polymerized hydrophilic monomers of the homopolymeric arm and the hydrophilic polymeric segments of the copolymeric arm can be derived from the same hydrophilic monomers, and can have the same or different degree of polymerization, for example, a degree of polymerization between 50 to 500 monomeric residues, such as, among 50 to 400 monomeric residues; between 50 to 300 monomeric residues; between 50 to 200 monomeric residues; between 100 to 250 monomeric residues; between 125 to 175 monomeric residues; or between 150 to 300 monomeric residues. For example, a star-shaped macromolecule can comprise hydrophilic homopolymeric arms that comprise polymerized hydrophilic monomeric residues and block copolymeric arms that comprise hydrophobic polymeric segments distal to the star core and hydrophilic polymeric segments proximal to the core of the star.
6 star, in which the polymerized hydrophilic monomeric residues of the homopolymeric arm and the hydrophilic polymeric segments of the copolymeric arm can be derived from the same hydrophilic monomers, and can have the same degree of polymerization, and in which the hydrophilic polymeric segments of the copolymeric arm can have a degree of polymerization from 1 to 60 monomeric residues, such as from 1 to 50 monomeric residues; between 1 to 45 monomeric residues; between 5 to 40 monomeric residues; between 8 to 35 monomeric residues; between 10 to 30 monomeric residues; between 12 to 25 monomeric residues; between 14 to 20 monomeric residues; between 15 to 30 monomeric residues; or between 5 to 20 monomeric residues.
Suitable star-shaped macromolecules can have a wide range of total number of arms, for example, a star-shaped macromolecule can comprise more than 15 arms. For example, a suitable star-shaped macromolecule can comprise between 15 and 100 arms, such as between 15 and 90 arms; between 15 and 80 arms; between 15 and 70 arms; between 15 and 60 arms; between 15 and 50 arms; between 20 and 50 arms; between 25 and 45 arms; between 25 and 35 arms; between 30 and 45 arms; or between 30 and 50 arms.
Suitable star-shaped macromolecules can have more than one type of arm, such as two or more different types of arms, where a molar ratio of the different types of arms can be between 20: 1 and 1: 1. For example, a star-shaped macromolecule comprising two different types of arms, such as a homopolymeric arm, for example, a hydrophilic homopolymeric arm, and a copolymeric arm, for example, a copolymeric arm comprising hydrophilic polymeric segments and hydrophobic polymeric segments , can have a molar ratio of the two different types of arms between 20: 1 to 2: 1, as between 15: 1 to 2: 1; between 10: 1 to 2: 1; between 9: 1 to 2: 1; between 8: 1 to 2: 1; between 7: 1 to 2: 1; between 6: 1 to 2: 1; between 5: 1 to 2: 1; between 4: 1 to 2: 1; between 3: 1 to 2: 1; between 2: 1 to 1: 1; between 8: 1 to 3: 1; between 7: 1 to 2: 1; or between 5: 1 to 3: 1.
Suitable star-shaped macromolecules may include, but are not limited to, comprising arms that have a molecular weight of more than 10,000 g / mol. For example, a star-shaped macromolecule can comprise arms that have a molecular weight between 10,000 g / mol and 200,000 g / mol, such as between 10,000 g / mol and 175,000 g / mol; between 10,000 g / mol and 150,000 g / mol; between 10,000 g / mol and 125,000 g / mol; between 10,000 g / mol and 100,000 g / mol; between 10,000 g / mol and 90,000 g / mol; between 10,000 g / mol and 80,000 g / mol; between 10,000 g / mol and 70,000 g / mol; between 60,000 g / mol and 50,000 g / mol; between 10,000 g / mol and 40,000 g / mol; between 10,000 g / mol and 30,000 g / mol; between 10,000 g / mol and 20,000 g / mol; between 20,000 g / mol and 175,000 g / mol; between 20,000 g / mol and 100,000 g / mol; between 20,000 g / mol and 75,000 g / mol; between 20,000 g / mol and 50,000 g / mol; between 15,000 g / mol and 45,000 g / mol; or between 15,000 g / mol and 30,000 g / mol.
Suitable arms of a star-shaped macromolecule may include, but are not limited to, arms that have an HLB value of at least 17 (where HLB is calculated using the formula presented in the test procedures). For example, suitable arms of a star-shaped macromolecule may have an HLB value of more than 17.25, such as more than 18.5; at least 19; between 17.5 to 20; between 17.5 to 19.5; between 18 to 20; between 18.5 to 20; between 19 to 20; between 19.5 to 20; between 18 to 19.5; between 18.5 to 19.75; between 18.2 to 19.2; or between 18.75 to 19.5.
Suitable hydrophobic polymeric segments of a star-shaped macromolecule copolymeric arm may include, but are not limited to, hydrophobic polymeric segments that have an HLB value of less than 8. For example, suitable hydrophobic polymeric segments may have a value HLB of less than 7, as less than 6; less than 5; less than 4; less than 3; less than 2; or about 1.
Suitable arms of a star-shaped macromolecule may include, but are not limited to, arms that have a polydispersity index (PDI) value of less than 2.5. For example, suitable arms of the star-shaped macromolecule may have a PDI value of less than 2.25, such as less than 2.0; less than 1.7; between 1.0 to 2.5, as between 1.0 and 2.3; between 1.0 and 2.0; between 1.0 and 1.9; between 1.0 and 1.8; between 1.0 and 1.7; between 1.0 and 1.6; between 1.0 and 1.5; between 1.0 and 1.4; between 1.0 and 1.3; between 1.0 and 1.2; between 1.0 and 1.1; between 1.05 and 1.75; between 1.1 and 1.7; between 1.15 and 1.65; or between 1.15 and 1.55.
Suitable nuclei of a star-shaped macromolecule can be formed by or derived from, but are not limited to, crosslinking a plurality of arms and a crosslinker. For example, a core may be formed by, or derivatives of, crosslinking a plurality of homopolymeric arms and a plurality of copolymeric arms with a crosslinker, such as a multifunctional monomer crosslinker, for example, the hydrophobic bifunctional monomer crosslinker. In certain embodiments, the core may be formed or derived from crosslinking, a plurality of hydrophilic homopolymeric arms and a plurality of copolymeric arms, comprising hydrophilic polymeric block segments and hydrophobic polymeric block segments, with a crosslinker, such as a monomer crosslinker hydrophobic bifunctional, for example, divinylbenzene, in which the molar ratio of the homopolymeric arms to the copolymeric arms can be between 20: 1 to 2: 1.
Suitable star-shaped macromolecules may include, but are not limited to, comprising a core that has a molecular weight of more than 3,000 g / mol. For example, a star-shaped macromolecule can comprise a core that has a molecular weight between 3,000 g / mol and 50,000 g / mol, such as between 3,000 g / mol and 45,000 g / mol; between 3,000 g / mol and 40,000 g / mol; between 3,000 g / mol and 30,000 g / mol; between 3,000 g / mol and 20,000 g / mol; between 3,000 g / mol and 15,000 g / mol; between 5,000 g / mol and 40,000 g / mol; between 6,000 g / mol and 30,000 g / mol; between 7,000 g / mol and 25,000 g / mol; between 8,000 g / mol and 20,000 g / mol; between 5,000 g / mol and 15,000 g / mol; between 7,000 g / mol and 12,000 g / mol; between 5,000 g / mol and 9,000 g / mol; between 8,000 g / mol and 10,000 g / mol; or between 9,000 g / mol and 15,000 g / mol.
Suitable star-shaped macromolecules can be used to form the clear homogeneous gel when dissolved in water at a concentration of at least 5.05 by weight at a pH of about 7.5 in STP. For example, a star-shaped macromolecule can form a clear homogeneous gel when dissolved in water at a concentration of between 0.05% by weight and 3% by weight, as between
0.1% by weight to 2.5% by weight; between 0.1% by weight to 2% by weight; between 0.2% by weight to 2.0% by weight; between 0.2% by weight to 1.5% by weight; between 0.2% by weight to 1.0% by weight; in between
0.2% by weight to 2.5% by weight; between 0.3% by weight to 2.5% by weight; between 0.4% by weight to 2.0% by weight; between 0.5% by weight 10 to 2.0% by weight; between 0.6% by weight to 2.0% by weight; in between
0.7% by weight to 1.5% by weight; between 0.8% by weight to 1.2% by weight; between 0.9% by weight to 1.1% by weight; between 0.5% by weight to 2.5% by weight; between 0.75% by weight to 1.5% by weight; or between 0.8% by weight to 1.6% by weight.
Suitable star-shaped macromolecules, in accordance with the pH Efficiency Range Test Procedure described below in this document, can be used to form a clear homogeneous gel, in which the star-shaped macromolecule at a concentration of
0.4% by weight may have a viscosity of at least
20,000 cP, at a pH between about 4 to about 12, for example, at a pH between about 5 to about 11.5 as at a pH between about 5 to about 11; between about 5 to about 10.5; between about 5 to about 10; between about 5 to about 9.5; between about 5 to about 9; between about 5 to about 8.5; between about 5 to about 8;
between about 6 to about 11; between about 5.5 to about 10; between about 6 to about 9; between about 6.5 to about 8.5; between about 7 to about 8; between about
7.5 to about 8.5; or between about 6.5 to about 7.5.
In certain embodiments, for example, suitable star-shaped macromolecules, in accordance with the pH Efficiency Range Test Procedure described below in this document, can be used to form a clear homogeneous gel, in which the macromolecule in the form of star at a concentration of 0.4% by weight can have a viscosity of at least 20,000 cP at a pH between about 5.5 to about 11. For example, at a pH between about 5.5 to about of 11, it can have a viscosity of at least 30,000 cP, such as at least 40,000 cP; between 20,000 cP to 250,000 cP; between 20,000 cP to 250,000 cP; between 20,000 cP to 225,000 cP; between 20,000 cP to 200,000 cP; between 20,000 cP to 175,000 cP; between 20,000 cP to 150,000 cP; between 20,000 cP to 125,000 cP; between 30,000 cP to 250,000 cP; between 30,000 cP to 200,000 cP; between 40,000 cP to 175,000 cP; or between 40,000 cP to 150,000 cP. For example, a gel at a pH between about 6 to about 11 may have a viscosity of at least 20,000 cP, such as at least 30,000 cP; at least 40,000 cP; between 20,000 cP to 250,000 cP; between 20,000 cP to 250,000 cP; between 20,000 cP to 225,000 cP; between 20,000 cP to 200,000 cP; between 20,000cP to 175,000cP; between 20,000 cP to 150,000 cP; between 20,000cP to 125,000cP; between 30,000 cP to 250,000 cP; between 30,000cP to 200,000 cP; between 40,000 cP to 175,000 cP; or between 40,000 cP to 150,000 cP. For example, at a pH between about 7 to about 10.5 it can have a viscosity of at least 60,000 cP, such as at least 70,000 cP; between 60,000 cP to 250,000 cP; between 60,000 cP to 225,000 cP; between 60,000 cP to 200,000 cP; between 60,000 cP to 175,000 cP; between 60,000 cP to 150,000 cP; between 60,000 cP to 125,000 cP; between 60,000 cP to 115,000 cP; between 60,000 cP to 105,000 cP; or between 60,000 cP to 100,000 cP. For example, at a pH between about 7.5 to about 9.0 it can have a viscosity of at least 95,000 cP, such as at least 100,000 cP; between 95,000 cP to 250,000 cP; between 95,000 cP to 225,000 cP; between 95,000 cP to 200,000 cP; between 95,000 cP to 175,000 cP; between 95,000 cP to 150,000 cP; between 95,000 cP to 125,000 cP; between 95,000 cP to 115,000 cP; or between 95,000 cP to 105,000 cP.
Suitable star-shaped macromolecules, in accordance with the Dynamic Viscosity and Viscosity Test Procedure which decreases under shear described below in this document, can be used to form a clear homogeneous gel, in which the star-shaped macromolecule in a concentration 0.4%, by weight, can have a viscosity of less than 5,000 cP at a shear rate of 4 sec ^-1 , as well as a viscosity of less than 4,000 cP. For example, the star-shaped macromolecule at a concentration of 0.4% by weight may have a viscosity of less than 5,000 cP at a shear rate of 6 sec ¹ , with a viscosity of less than 4,000 cP or less than 3,000 cP. For example, a gel may have a viscosity of less than 15,000 cP at a shear rate of 0.7 sec ^-1 , as a viscosity of less than 14,000 cP or less than 13,000 cP. Suitable gels can include, but are not limited to, gels that have a viscosity value that decreases under shear of at least 5, as a viscosity value that decreases under shear of at least 6, or between 5 to 15, such as between 5 to 15; between 7 to 12; between 8 to
10; or between
13.
Suitable star-shaped macromolecules, in accordance with the Dynamic Viscosity and Viscosity Test Procedure that decreases under shear described below in this document, include those that have a viscosity value that decreases under shear of at least 15, as a value of viscosity that decreases under shear between 15 to 100, as between 15 to 90; between 20 to 80; between 25 to 70; between 25 to 50; or between 30 to 40.
Suitable star-shaped macromolecules, in accordance with the Salt Induced Break Test Procedure described below in this document, include those that have a salt-induced break value of at least 50%, such as a salt-induced break value between 65% to 100%, as between 75% to 100%; between 80% to 95%; in between
75% to 90%; between 50% at 85%; in between 70% 95%; or between 60% to 100%. Macromolecules in form in star appropriate, in compliance with Procedure in test Range in
PH efficiency described below in this document, includes those that have a pH-induced break value of at least 15%, such as a pH-induced break value of between 15% to 100%, such as between 25% to 100%; between 30% to 95%; between 40% to 90%; between 50% to 85%; between 70% to 95%; between 80% to 97%; between 90% to 99%; between 95% to 100%; or between 60% to 100%.
Suitable star-shaped macromolecules, in accordance with the Dynamic Viscosity and Viscosity Test Procedure that decreases under shear described below in this document, include those that have a dynamic viscosity value of more than 20,000
cP in 1 rpm, and in a concentration of 0, 2%, in Weight, how one value in ' viscosity dynamics of more of what 24. 000 cP; bad _s of what 28,000 cP; or more than what 30. . 000 cP in an concentration 0.2% in Weight.
Suitable emulsions may include, but are not limited to, emulsions that are free of emulsifiers and in which the emulsion is thickened by a star-shaped macromolecule. For example, the star-shaped macromolecule that can be included in the emulsifier-free emulsion 10 can be a water-soluble star-shaped macromolecule, wherein the water-soluble star-shaped macromolecule emulsifies the emulsifier-free emulsion.
Suitable star-shaped macromolecules include star-shaped macromolecules that have an emulsion value of more than 60 minutes, for example, more than 3 hours, such as more than 6 hours; more than 10 hours; more than 20 hours; more than 40 hours; or more than 100 hours.
Suitable star-shaped macromolecules according to Formula X may include star-shaped macromolecules in which P1, P2, and / or P3 comprise hydrophobic monomers, hydrophilic monomers, amphiphilic monomers, or combinations thereof. For example, PI comprises hydrophobic monomers, P2 comprises hydrophilic monomers, and P3 comprises hydrophilic monomers. For example, star-shaped macromolecules, according to Formula X, may include star-shaped macromolecules where ql can have a value between 1 to 100, for example, between 1 to 60, such as between 1 to 45; between 5 to 40;
between 8 to 35; between 10 to 30; between 12 to 25; between 14 to 20;
between 15 to 30; or between 5 to 20; and q2 and / or q3 has a value between 50 to 500, for example, between 50 to 400, such as between 50 to 300; between 50 to 200; between 100 to 250; between 125 to 175; or between 150 to 300. For example, star-shaped macromolecules, according to Formula X, can include star-shaped macromolecules where r or t, or the sum
from r and t, can to be more of that 15like between 15 « 2 100 in between 15 and 90; in between 15 and 80; in between 15 and 70; in between 15 and 60 in between 15 and 50; in between 20 and 50; in between 25 and 45; in between 25 and 35 in between 30 and 45; or between 30 and50. Per ex example
star-shaped macromolecules, according to Formula X, can include star-shaped macromolecules in which the rat molar ratio is in the range between 20: 1 to 2: 1, as well as between 15: 1 to 2: 1 ; between 10: 1 to 2: 1; between 9: 1 to 2: 1; between 8: 1 to 2: 1; between 7: 1 to 2: 1; between 6: 1 to 2: 1; between 5: 1 to 2: 1; between 4: 1 to 2: 1; between 3: 1 to 2: 1; between 2: 1 to 1: 1; between 8: 1 to 3: 1; between 7: 1 to 2: 1; or between 5: 1 to 3: 1. For example, star-shaped macromolecules, according to Formula X, can include star-shaped macromolecules in which the core can be derived from crosslinker monomers, such as hydrophobic crosslinker monomers. For example, star-shaped macromolecules, according to Formula X, can include star-shaped macromolecules in which the core may comprise monomeric crosslinker residues, such as hydrophobic crosslinker monomeric residues. For example, star-shaped macromolecules, according to Formula X, may include star-shaped macromolecules in which the [(Pl) _q j. (P2) _q 21t arm can be homopolymer or copolymeric, such as block copolymer.
6
Suitable star-shaped macromolecules may include, but are not limited to, star-shaped macromolecules formed by crosslinking the arms with a crosslinker, such as crosslinking homopolymeric arms and block copolymeric arms with a hydrophobic crosslinker. For example, the homopolymeric arms and copolymeric arms of a star-shaped macromolecule can be covalently attached to the core by crosslinking with a crosslinker. For example, a prepared star-shaped macromolecule nucleus can be
made by reticulation one end of one arm homopolymeric with an far end in one arm copolymeric, how an far end in one arm
hydrophilic homopolymer with a hydrophilic end of a copolymeric arm. For example, the core of prepared star-shaped macromolecules can be formed by crosslinking an end of the functional end group of ATRP from a homopolymeric arm with an end of functional end group of ATRP of a copolymeric arm.
Suitable primers that can be used to form the star-shaped macromolecules disclosed herein may include, but are not limited to, nitroxide initiators, such as stable nitroxide initiators, for example, 2,2,6,6-Tetramethylpiperidine- 1oxy, sometimes called TIME; transition metal complexes, such cobalt containing complexes; ATRP initiators, which comprise halides, such as, bromide, chloride, or iodide, and transition metal sources, such as copper, iron, ruthenium transition metal sources; iodide with RCTP catalysts, such as germanium or tin catalysts; RAFT initiators, such as dithioesters, dithiocarbamates, or xanthates; ITP catalysts, which comprise iodides; tellurium compounds (e.g., TERP); stibin compounds (for example, SBRP); or bismuth compounds (e.g., BIRP). For example, in certain embodiments, a primer may further comprise a monomeric residue, a polymeric segment comprising monomeric residues, or a small molecule. For example, in certain embodiments, a primer can comprise an ATRP primer, where the ATRP primer serves as a functional end group. For example, in certain embodiments, a primer may comprise an ATRP functional end group, which comprises an ATRP primer, such as halides and transition metal sources.
Suitable materials comprising the star-shaped macromolecules disclosed in this document include, but are not limited to, lotions, such as cosmetic lotions, personal care lotions, body lotions, free of emulsifying body lotions; serums, such as anti-aging serums; sunscreens, such as sunscreens SPF 30, sunscreens SPF 35, sunscreens SPF 40, sunscreens SPF 50; creams, such as facial creams, cosmetic creams; hair products, such as shampoos, hair styling products, hair sprays, mousses, hair gels, hair conditioners, bath preparations; gels, such as cosmetic gels or personal care gels; products for application to the skin, such as ointments, deodorants, personal care powders, skin cleansers, skin conditioners, skin emollients, skin moisturizers, skin cleansers, shaving preparations; softeners; dental impression materials; or variations thereof.
Suitable materials comprising an emulsifier-free emulsion, in which the emulsion is thickened by a star-shaped macromolecule disclosed in this document, may include, but are not limited to, lotions, such as cosmetic lotions, personal care lotions, lotions bodily, free of emulsifying body lotions; serums, such as anti-aging serums; sunscreens, such as sunscreens SPF 30, sunscreens SPF 35, sunscreens SPF 40, sunscreens SPF 50; creams, such as facial creams, cosmetic creams; hair products, such as shampoos, hair styling products, hair sprays, mousses, hair gels, hair conditioners, bath preparations; gels, such as cosmetic gels or personal care gels; products for application to the skin, such as ointments, deodorants, personal care powders, skin cleansers, skin conditioners, skin emollients, skin moisturizers, skin cleansers, shaving preparations; softeners; dental impression materials; or variations thereof.
In one embodiment, examples of suitable lotion formulations include body lotion formulations, which comprise an emulsifier-free emulsion, wherein the emulsion is thickened by a star-shaped macromolecule disclosed herein, which may include, but are not limited to a, formulations comprising one or more of the following: Deionized water; Dxssodrco EDTA;
1,3-Butylene glycol; Glycerin; Allantoin; Urea; 99% TEA; Edible oils (N.F.); Karite butter; Wickenol 171; Squalane; Crodamol CAP; Crodamol STS; Crodacol C; Tween 20; Lipo GMS 470; PEG 100 stearate; Cetyl Palmitate; Crodamol PTIS; Crodafos CES; DC 1401; Evening primrose oil; Vitamin E acetate; D-Panthenol; Distinctive HA2; Diocide; or derivatives or combinations thereof.
In one embodiment, examples of suitable lotion formulations include emulsifier-free personal care lotion formulations, which comprise an emulsifier-free emulsion, wherein the emulsion is thickened by a star-shaped macromolecule disclosed in this document, and may be include, but are not limited to, formulations that comprise one or more of the following: Deionized water; Disodium EDTA; 1,3-Butylene glycol; Glycerin; Allantoin; Urea; 99% TEA; Edible oils (N.F.); Wickenol 171; Myritol 318; Squalane; Crodamol PTIS; Isododecane; Evening primrose oil; Vitamin E acetate; D-Panthenol; Distinctive HA2; Diocide; or derivatives or combinations thereof.
In one embodiment, examples of suitable formulations include serum formulations, such as anti-aging serum formulations, which comprise an emulsifier-free emulsion, in which the emulsion is thickened by a star-shaped macromolecule disclosed in this document, and may be include, but are not limited to, formulations that comprise one or more of the following: Deionized water; Disodium EDTA; Glycerin; 1,3Butylene glycol; Caffeine; Allantoin; 99% triethanolamine; Crodamol STS; Myritol 318; Wickenol 171; Tween 20; Crodafos
CES; BVOSC; Vitamin E acetate; Vitamin A Palmitate; Vitamin D3; Gransil IDS; D-Panthenol; DC Upregulex; DC Skin Bright MG; Japanese Green Tea Actiphyte G; Grape Seed Actiphyte G; DC Hydroglide; Diocide; or derivatives or combinations thereof.
In one embodiment, suitable formulations include sunscreen formulations that comprise an emulsifier-free emulsion, in which the emulsion is thickened by a star-shaped macromolecule disclosed in this document, which may include, but is not limited to, formulations that comprise one or more of the following: Deionized water; Disodium EDTA; Glycerin; 99% triethanolamine; Homomethyl salicylate; Ethylhexyl salicylate; Avobenzone; Benzophenone 3; Myritol 318; Lexfeel 7; Octocylene; Cetyl alcohol; PEG-15 Cocamine; Lipo GMS 470; Crodafos CS-20; Vitamin E acetate; Aloe Vera Leaf Juice; Diocide; or derivatives or combinations thereof.
In one embodiment, examples of suitable formulations include facial cream formulations, which comprise an emulsifier-free emulsion, in which the emulsion is thickened by a star-shaped macromolecule disclosed herein, which may include, but is not limited to , formulations comprising one or more of the following: Deionized water; Disodium EDTA; 1.3 Butylene glycol; Glycerin; Caffeine; Allantoin; 99% triethanolamine; Myritol 318; Octyl palmitate; Wickenol 171; Crodafos CES; Cetyl alcohol; Pationic SSL; Cetyl Palmitate; Vitamin E acetate; BVOSC; Lexfeel 7; Lipo GMS 47 0; Vitamin A / D3 in Corn oil; DC 1401; Japanese Green Tea Actiphyte G; Grape Seed Actiphyte G; DC Hydroglide; Diocide; or derivatives or combinations thereof.
Synthesis of the Rheology Modifier
Although any conventional method can be used for the synthesis of the multi-arm star macromolecules of the invention, free radical polymerization is preferred and live / controlled radical polymerization (CRP) is the most preferred process.
CRP has emerged over the past decade as one of the most robust and powerful techniques for polymer synthesis, as it combines some of the desirable attributes of conventional free radical polymerization (for example, the ability to polymerize a wide range of monomers, tolerance of various functionalities in monomer and solvent, compatibility with simple industrially viable reaction conditions) with the advantages of live ionic polymerization techniques (for example, preparation of low polydispersity index polymer (PDI = M _w / M _n ) and (co ) block polymers and homopolymers functionalized at the chain end). The basic concept behind the various CRP procedures is the reversible activation of dormant species to form the propagation radical. A dynamic and fast balance between dormant and active species minimizes the likelihood of bimolecular radical termination reactions and provides an equal opportunity for propagation to all polymer (or dormant) chains.
CRP procedures can be classified into three main groups based on the reversible activation mechanism: (a) Stable Free Radical Polymerization (SFRP, Scheme la), (b) Polymer Transfer Polymerization
Degenerative Chair (DT, Scheme 1b), and (c) Atomic Transfer Radical Polymerization (ATRP, Scheme 1c).
(a) stable free radical polymerization (SFRP)
(b) degenerative chain transfer (DT) polymerization
(c) atom transfer radical polymerization (ATRP) 'CuÇO-X / L -— P _r * - CuniAXz. ·' L k ,. l / 'Scheme 1. Three main groups of controlled radical polymerization based on the reversible activation mechanism: (a) Stable Free Radical Polymerization (SFRP), (b) Transfer Transfer Polymerization
Degenerative Chair (DT), and (c) Atomic Transfer Radical Polymerization (ATRP).
As shown in Scheme 1, several terminating agents, X, are used for the different CRP procedures and they are summarized in Scheme 2. They include stable nitroxides (Scheme 2a), transition metal complexes (Scheme 2b), halides with transition metal catalysts (Scheme 2c), iodine with catalysts (Scheme 2d), sulfur compounds (Scheme 2e), iodine (Scheme 2e) 2f), and organometallic compounds (Scheme 2g).
• a: Nitroxides (NMP) A “/ ^1! UPO; etc. Transition metal complexes Χ- <Γ) and <c. ít; Halides with transition metals (ATRP) .X = “Mr. Cl j tCu. r 'íd; iodine with i'RCTP 'X «-t * Ge catalysts. Sn. etc. (e) Dithioester, dithiocarbamate and xanthate (RAFT) X = -sc = s 2 i Z = Ph, CHj, ti Et ;. ΟΈ t. etc. i íf; sludge (ITP) tg ·; Tellurium, stibin and bismuth compounds (TERP, SBRP and BIRP) X »- = R s = ~ i SbsrBí. R '= CH ₅ , ete.} Scheme 2. Examples of terminating agent X. Star-shaped polymers are materials in
nano scale with a globe shape. As illustrated in
Figure 1, stars formed by the first procedure
arm, discussed in detail below, may have a reticulated core and may optionally have multiple segmented arms of similar composition. Stars can be projected as stars with homo-arms or stars with hetero-arms. Figure IA represents a star with
homobraço with block copolymer arms. Stars with
heterobrape have arms with different composition or different molecular weight; Figure IB and 1C. Both stars with homo-arms and stars with hetero-arms can optionally have a high density of peripheral functionality.
invention The synthesis of star-shaped polymers can be performed using
live polymerization through one of three strategies: 1) first nucleus that is carried out by growing arms of a multifunctional initiator; 2) in a coupling that involves fixing preformed arms to a multifunctional core and 3) first arm method which involves the crosslinking of preformed linear arm precursors with the use of a divinyl compound.
Although all the polymerization procedures controlled above are suitable for the preparation of a modality of the revealed self-assembling star-shaped macromolecules, other modalities are also exemplified, for example, the preparation of the stars of multiple self-assembling arms with narrow MWD, in contrast to the prior art with the use of ATRP. The reason for using the Controlled Radical Polymerization (CRP) process known as ATRP; disclosed in U.S. Patent Nos. 5,763,546; 5,807,937; 5,789,487; 5,945,491; 6,111,022; 6,121,371; 6,124,411: 6,162,882: and U.S. Patent Applications 09 / 034,187; 09 / 018,554; 09 / 359,359; 09 / 359,591; 09 / 369,157; 09 / 126,768 and 09/534827, and discussed in numerous publications listed elsewhere with Matyjaszewski as co-author, which are incorporated in this application, is that convenient procedures have been described for the preparation of polymers that exhibit control over the molecular weight of polymer, distribution molecular weight, composition, architecture, functionalities and the preparation of molecular composites and tied polymeric structures that comprise radically (co) polymerizable monomers, and the preparation of controllable macromolecular structures under mild reaction conditions.
One aspect of the present invention relates to the preparation and use of multi-arm star-shaped macromolecules by a first arm approach, discussed by Gao, H .; Matyjaszewski, K. JACS; 2007, 129, 11,828. The document and references cited therein are hereby incorporated by way of reference to describe the fundamentals of the synthetic procedure. The supplementary information available in the cited reference provides a procedure for calculating the number of arms in the formed star-shaped macromolecule.
Biphasic systems such as a miniemulsion or an ab initio emulsion system are also expected to be suitable for this procedure, since miniemulsion systems have been shown to function as dispersed volume reactors [Min, K .; Gao, H .; Matyjaszewski, K. Journal of the American Chemical Society 2005, 127, 3,825 to 3,830] with the added advantage of minimizing core-core coupling reactions based on compartmentalization considerations.
In one embodiment, star-shaped macromolecules are prepared with the composition and molecular weight of each predetermined segment for realization as rheology modifiers in aqueous-based solutions. The first segmented linear (co) polymer chains formed are strands extended with a crosslinker that forms a crosslinked core.
In another embodiment, a simple industrially scalable process for preparing star-shaped macromolecules is provided in which the arms comprise segments selected to induce self-assembly and in which the self-assembling star-shaped macromolecules are suitable for use as control agents. of rheology in water-based and solvent-based coatings, adhesives, cosmetics and personal care compositions.
The invention is not limited to the specific compositions, components or process steps disclosed in this document, however, they may vary.
It should also be understood that the terminology 10 used in this document is only for the purpose of describing the particular modalities and is not intended to be limited.
The procedure for preparing star-shaped macromolecules can be exemplified by (co) polymerization of linear macromolecules, which include macroinitiators (MI) and macromonomers (MMs), with a multi-vinyl crosslinker, with a divinyl crosslinker it is used in the examples revealed in this document, to form a core of the star. The formation of the star core can also be formed through a copolymerization reaction in which a monovinyl monomer is added to expand the free volume of the core to allow the incorporation of additional arms in the congested core to form the environment or provide free volume 25 enough inside the star core to encapsulate small functional molecules. A molecule that acts as an initiator and a monomer, an enemy, can also be used in the preparation of the star-shaped macromolecule nucleus. When added to the reaction, it works to form a three-arm branch at the nucleus of the molecule and then acts in a similar way
to the monomer added to increase the volume free at the inside the core star. THE fraction core volume from the star can to be controlled per appropriate selection of the molecule in
crosslinker or for conducting a copolymerization between the crosslinker and a vinyl monomer or an enemy. The core composition can be selected to provide an environment for encapsulating small molecules, such as fragrances, and to control the rate of diffusion of the fragrance of the self-assembling thickening agent after deposition in a part of the human body.
The core of the star-shaped polymers may contain additional functionality. These additional functionalities can be of direct use in certain applications or they can be used to tie or encapsulate additional functional materials such as fragrances, stimulus-sensitive molecules or bio-responsive molecules to the star core through chemical or physical interactions.
Star-shaped macromolecules can be prepared in diluted solution when reaction and crosslinker conditions are chosen to prevent or reduce star-star coupling reactions.
The synthesis of multi-arm star polymers in which the periphery of the star polymers contains additional functionality is possible. This functionality can be introduced by using a primer that comprises the desired functionality in the residue of the low molecular weight initiator remaining at the α chain end of each arm.
One embodiment of the present invention can be exemplified by the preparation of a multi-arm star-shaped macromolecule in which the number of arms in the star-shaped macromolecule is between 5 and 500, preferably between 10 and 250, with segments selected to induce self-assembly when the star-shaped macromolecule is dispersed in a liquid in which the self-assembling star-shaped macromolecules are suitable for use as thickening agents or rheology modifiers in cosmetics and personal care compositions at low concentrations of the solid in the thickened solution, preferably less than 5% by weight and optimally less than 1% by weight. The dispersion medium may comprise water-based or oil-based systems.
The structure of a new exemplary thickening agent or rheology modifier of a modality is a segmented star macromolecule with multiple arms in which the nucleus is prepared by controlled radical polymerization using a first arm method. Scheme 3 provides a simple four-step procedure that can be employed for the preparation of an initial non-limiting example case, the procedure is a macroinitiator method of first atom transfer radical polymerization arm. In this approach, the precursor of the arm (s) comprises a linear copolymer chain with a single terminal activatable group, as will be understood by one skilled in the art, having this disclosure as a guide, the precursor of the active arm will have a functionality of terminal ω which under the conditions of the polymerization procedure can reversibly generate a radical. Scheme 3 illustrates the concept for the sequential polymerization of styrene and tBA. These monomers are purely exemplary monomers and should not limit the applicability of the procedure in any way as other monomers of similar phyllity may be employed. In Scheme 3, the polystyrene segment can be considered the outer cover of the star and the final poly (acrylic acid) segments, the internal water-soluble cover and the segment formed by the chain that extends the linear copolymer macroinitiators by the reaction with the divinylbenzene crosslinker, the star core.
Star Star
PSt-b-PtBA PSt-b-PAA
Step 1 Step 2 Step 3 Step 4
Scheme 3. Multistage synthesis of PSt-b-PAA block copolymer stars
Similar structures can also be prepared using the macromonomer method or a combination of the macromonomer and macroinitiator method in a controlled polymerization process or even through free radical copolymerization conducted in macromonomers, as known to those skilled in the art. [Gao, H .; Matyjaszewski, K. Chem .-- Eur. J.2009, 15, 6107 to 6111.]
Both the macromonomer and macroinitiator procedures allow the incorporation of polymer segments prepared by different CRP procedures [WO 98/01480] into the final star-shaped macromolecule. The polymer segments can comprise segments that are biodegradable or are formed from monomers prepared from biological sources.
As noted above, the first formed ATRP macroinitiator can be prepared by conducting a sequential (co) polymerization of hydrophobic and hydrophilic monomers or precursors thereof or can be prepared by other polymerization procedures that provide a functional terminal group or atom which can be converted into an ATRP initiator with a bifunctional molecule in which one functionality comprises an atom or transferable group and the other functionality, an atom or group which can react with the functionality first present in the (co) polymer prepared by a not ATRP. [WO 98/01480]
In aqueous solutions, the composition and molecular weight of the external cover of hydrophobes or agents that participate in molecular recognition can be selected to induce self-assembly in aggregates and act as physical crosslinkers. Above a certain concentration, corresponding to the formation of a reversible three-dimensional network, the solutions will behave like physical gels thereby modifying the solution's rheology.
In one embodiment, the polymer compositions of the invention have a significantly lower critical concentration for network formation (gel) compared to networks formed with block copolymers, grafts and stars with a specific low number of linked arms due to:
multiple arm structure (many
junctions transients possible in between parts hydrophobic stars ) • Weight molecular much high in each star (5 thousand to 5 million or greater) allows an swelling reason
high molecules in solution • molecular organization on large scales (> lpm)
Although the examples above and below describe the preparation and use of block copolymers as arms with a well-defined transition from one segment to the adjacent segment, a segmented copolymer with a gradient in composition can also be used. The presence of a gradient can be created by adding a second monomer before consuming the first monomer and will affect the volume fraction of the monomer units present in the transition from one domain to the other. This would affect the shear responsiveness of the formed star-shaped macromolecule.
Narrow polydispersed star-shaped macromolecules comprising arms with block copolymer segments can be formed with as little as 5 arms by selecting the appropriate reagent concentration, crosslinker and reaction temperature.
Ί2.
Star-shaped macromolecules can be prepared in a miniemulsion or reverse miniemulsion polymerization system. The first block copolymers formed are used as reactive surfactants for 5-star synthesis by reaction with a crosslinker selected in the miniemulsion.
Example 1: Synthesis, purification and properties of star thickener
The initial examples of a star thickening agent with the structure shown below in Figure 1 as structure A are star-shaped macromolecules with PSt-b-PAA arms or PSt-b-P (HEA) arms.
Example 1: Preparation of a Star-shaped Macromolecule (PSt-b-PAA) _x .
The simple four-step procedure was developed for the preparation of a star-shaped macromolecule based on poly (acrylic acid) is described in Scheme 3. 1 kg of the star-shaped macromolecule with PSt-b-PtBA arms was prepared as Follow.
STEP 1: Synthesis of a polystyrene macroinitiator using ICAR ATRP. The reaction conditions are St / DEBMM / CuBr ₂ / TPMA / AIBN = 50/1 / 0.002 / 0.003 / 0.05 by mass at T = 60 ° C, t = 10.2 hours. The reaction was performed at ~ 30% conversion resulting in the molecular weight of the hydrophobic polystyrene segment = 1,600 which is equivalent to an average degree of polymerization (SD) of 16.
The GPC trace obtained for the macroinitiator is shown in Figure 2.
STEP 2: Synthesis of macroinitiator of segmented block copolymer of polystyrene-b-poly (tbutyl acrylate). The reaction conditions for the synthesis of the PSt-b-PtBA macroinitiator arm are: tBA / PSt / CuBr ₂ / TPMA / Sn (EH) ₂ = 200/1 / 0.01 / 0.06 / 0.008 in anisole (0 , 5 equivalent volume versus tBA), T = 55 ° C, t = 18.0 hours. A higher molecular weight precursor in the water-soluble segment was targeted to allow the significant degree of swelling of the inner cover of the final functional star-shaped macromolecule. The final molecular weight of the poly (t-butyl acrylate) segment in the block copolymer was -15,400 which is equivalent to a DP = 120. The GPC curves of the polystyrene macroinitiator and the formed block copolymer macroinitiator are shown in Figure 3 and clearly indicate that a clean chain extension has occurred.
STEP 3: Synthesis of the star-shaped macromolecule (PSt-b-PtBA) x.
A multi-arm star-shaped macromolecule was prepared by conducting an additional chain extension reaction with the block copolymer macroinitiator formed in step 2. The reaction was conducted with a 1:12 molar ratio of block copolymer to divinylbenzene in anisole. The reaction conditions are: DVB / PSt-b-PtBA / CuBr ₂ / TPMA / Sn (EH) ₂
12/1 / 0.02 / 0.06 / 0.1 in anisole (38 equivalent volume versus DVB), T = 80 ° C, t = 21.0 hours). The GPC curves and results of the star formation reaction are provided in Figure 4. It can be seen that a multi-arm star-shaped macromolecule with a reticulated nucleus has been formed. The molecular weight of the star's GPC was 102,700 with a PDI of 1.29, which would indicate an average of six arms, but this is an underestimation of the actual number of arms since the star-shaped molecule is a compact molecule. In fact, in this situation, the number of arms in the star-shaped molecule is close to 30.
The number of arms can be modified by conducting the core formation reaction with a ratio other than the crosslinking agent to arm precursor or by carrying out the reaction with a different concentration of reagents.
STEP 4: Deprotection of the star-shaped macromolecule (PSt-b-PtBA) x for star-shaped block copolymer (PSt-b-PAA) x to provide water-soluble poly (acrylic acid) segments in the shaped macromolecule of multiple arms star. The PSt-b-PtBA arms of the star-shaped macromolecule were transformed into PSt-b-PAA arms using a new procedure. The polymer was dissolved in methylene chloride and trifluoroacetic acid to unprotect the tBu groups, the reaction was carried out at room temperature for 60.0 hours. Then, the polymer was decanted and washed 3 times with acetonitrile. The polymer was then solubilized in THE and precipitated in acetonitrile. The star-shaped macromolecule was dried in a vacuum oven for 3 days at 50 ° C. The amount of polymer obtained after purification was 550 g, which would correspond to the complete conversion of PtBA to PAA.
Example 2: Properties of the star-shaped macromolecule (PSt-b-ΡΆΑ) as a thickening agent
The thickening properties of the final star-shaped macromolecule were investigated in aqueous solution. 100 mg of the star-shaped macromolecule (PSt-bPAA) were dissolved in 0.5 ml of THF and transferred to 10 ml of water. The solution was then neutralized with 2 ml of basic water (with NaOH). After a few minutes of shaking, a gel was formed, see the image in Figure 5.
The rheological properties of the multi-arm star constructed with a longer hydrophilic (acrylic acid (PAA) inner core segment and a short hydrophobic polystyrene (PSt) peripheral segment were investigated. The viscosities of aqueous solutions containing different concentrations of the macromolecule star-shaped versus shear rate were measured; using a Brookfield LVDV-E, Spindle No. 31 (or No. 34, No. 25) at T = 25 ° C and the results are shown in Figure 6 It is evident that even at very low concentrations of the star-shaped macromolecule in water (<0.6% by weight) the apparent viscosity of the sample is very high (in the range of 50,000 to 100,000 centipoise (cP)).
In comparison, the main thickeners on the market for personal care products (for example, the natural non-ionic vegetable-derived thickener Crothix Liquid with CRODA or the synthetic acrylate-based copolymer DOW CORNING RM 2051) are used at level 2 to 5% by weight and only increase the viscosity of a water-based solution to 5,000 to 20,000 cP.
Figure 7 shows the viscosity of the aqueous solution of a star-shaped macromolecule (PSt-b-PAA) versus concentration. The measurement was conducted in a Brookfield LVDV-E with spindle no. 31 (or no. 34, no. 25) at a temperature = 25 ° C and rate = 1 RPM. It can be seen that for this particular star-shaped macromolecule 0.3% by weight of star-shaped macromolecule in water is a minimum amount for gel formation and that higher concentrations significantly increase the viscosity of the resulting solution.
Tests indicated that the thickening agent provided formulations that exhibited a lack of stickiness, a very pleasant feeling on the skin.
Example 3: Properties of the star-shaped macromolecule (PSt-b-PAA) as a thickening agent in adverse environments
The thickening properties of the final star-shaped macromolecule were investigated in aqueous solution in the presence of an oxidizing agent and at a high pH. Figure 8 shows the viscosity of an aqueous solution of the star-shaped macromolecule (PSt-b-PAA) and the viscosity of the water / windex solution (1/1 v / v) of the star-shaped macromolecule (PSt-b -PAA) and Figure 9 shows the results obtained with Carbopol EDT 2020 in the same medium. The pH of the aqueous solution was 6 to 7 while for the water / Windex solution pH = 9 to 10. (The viscosity measurement was carried out using a Brookfield LVDVE, Spindle n ° 31 (or n ° 34, n ° 25), T = 25 ° C.) It can be seen that the viscosity of the water / windex solution is greater than that of the water solution. The performance of the star-shaped macromolecule (PSt-b-PAA) as a thickening agent is not diminished in this adverse environment presented by the windex / water solution with a pH = 9 to 10 resulting from the presence of a high amount of D-ammonia. In comparison, the thickening properties of the main thickener on the market, Carbopol EDT 2020, were decreased under similar conditions and Figure 9 shows that the viscosity of the water / windex solution is less than that of the pure aqueous solution.
The unsatisfactory performance of the
Carbopol versus star-shaped macromolecule (PSt-bPAA) as a thickening agent in the water / Windex solution is a consequence of the high amount of ester bonds in its structure that can interact with ionic species present in such an adverse environment or can be even degraded. On the other hand, the star-shaped macromolecule (PSt-b-PAA) has only C-C bonds, which make this thickening agent stable in the water / Windex solution and the total thickening performance is not diminished.
Example 4: Properties of the star-shaped macromolecule (PSt-b-PAA) versus the star-shaped macromolecule (ΡΆΆ) as a thickening agent
A star-shaped macromolecule (PAA) was synthesized in order to compare its properties to those determined for the star-shaped macromolecule (PStb-PAA). The synthesis of the star (PAA) was performed in a similar way as for the synthesis of the star-shaped macromolecule (PSt-b-PAA), but starting with pure PtBA arms.
The final star (PAA) had similar molecular weight, number of arms and molecular weight distribution similar to the star-shaped macromolecule (PSt-b-PAA), Figure 10. The only difference between the two star-shaped macromolecules is the external cover comprising PSt with degree of polymerization 16 in the star-shaped macromolecule (PSt-b-PAA) while this star-shaped macromolecule has pure PAA homopolymeric arms. Figure 11 shows the viscosity of the aqueous solutions of the star-shaped (PAA) and star (PSt-bPAA) macromolecules. The measurement was carried out using a Brookfield LVDV-E fitted with a No. 31 spindle at a temperature = 25 ° C and pH = 7. It can be seen that the viscosity of the star-shaped macromolecule with an external hydrophobic covering it has very strong thickening properties, where the pure star (PAA) has a low thickening effect on water.
Therefore, it can be concluded that in order to thicken the water-based medium, the multi-arm star macromolecules proposed must have a block structure, with a hydrophilic inner cover and a hydrophobic outer cover. Without intending to be limited by a proposed mechanism, it is believed that these results in the aqueous environment can be explained by the self-assembly of hydrophobic segments in aggregates, hydrophobes act as junctions between aggregates and above a certain concentration, a three-dimensional reversible physical network it is formed with a behavior similar to conventional gels.
Example 5: star-shaped macromolecule (PSt-b-PAA) as a thickening and emulsifying agent
Due to its well-defined structure, the multi-arm star-shaped macromolecule (PStb-PAA) can act not only as a thickening agent, but also as an effective emulsifying agent. Figure 12 presents images that demonstrate the emulsifying properties of the star-shaped macromolecule (PSt-bPAA). The first photograph shows the mixture of water with 2% by volume of pure lemon oil. After vigorous mixing, the water and oil quickly separated into two phases. The second photo shows water with 2% by volume of lemon oil and 0.6% by weight of thickening agent. After vigorous mixing, phase separation did not occur and the thickening properties did not increase. The solutions were shaken for 1 minute and photographs were taken hours after mixing.
Its hydrophobic core (as well as the hydrophobic outer cover) can act as a storage location for small organic molecules (for example, vitamins, fragrances, sun protection agents, etc.). This provides the possibility for the delivery of functional organic molecules, for example, fragrance for slow release or UV absorption molecules in sunscreens to any part of the body in a pleasant-feeling emulsion.
In order to provide an equivalent response for the non-polar medium, the phyllicity of the inner and outer coverings would have to be reversed.
Example 6: Star-shaped macromolecules with heteroblock
A multi-arm star-shaped macromolecule was synthesized. The procedures for forming the PSt-b-PtBA and PtBA arms were similar to that described in Example 1. Then, two different arms were cross-linked together to form a star-shaped macromolecule. The reaction conditions for the core formation crosslinking reaction: DVB / [PSt-bPtBA / PtBA] / CuBr2 / TPMA / Sn (EH) 2 = 17/1 / 0.02 / 0.06 / 0.2 in anisole (38 equivalent volume versus DVB), (1667 ppm Cu) T = 95 ° C, t = 53.0 hours, PSt-b-PtBA / PtBA = 1/4. Then, PtBA was transformed into PAA by deprotection with acid as described in Step 4 in Example 1.
Figure 13 shows the GPC curves of the arms and the star-shaped macromolecule with heteroblast formed before and after purification by precipitation. Scheme 13B shows a representation of such a star-shaped macromolecule with hetero-arm.
The synthesis of stars with smaller amounts of the external PSt block was successfully performed. Two stars were synthesized, one with 50% and one with 20% pure PSt-b-PAA arms and 50% and 80% pure PAA arms (WJ-08006-234 and WJ-06-235) by the procedures detailed above. Studies show that these star-shaped macromolecules can be dispersed directly in hot water. The thickening properties of these two new stars were as good as the first exemplary star with 100% PSt-b-PAA arms.
Stars with different external hydrophobic coverings can be prepared. An example that provides an external cover that exhibits a Tg below the usage temperature is a star prepared with an external PnBA cover.
Another approach that can reduce the cost of preparing an external hydrophobic coating is the conversion of commercially available oc-olefins into an ATRP initiator by reaction with a haloalkyl (meth) acrylate.
Example 7: Stars with different hydrophobic segments
A parameter that can significantly change the viscosity of the thickening agent as well as its interaction with surfactant in shampoo formulations is the type of hydrophobic unit terminated at the peripheral end of a fraction of the star-shaped macromolecule arms. Two additional stars were synthesized to compare with the star-shaped macromolecule (PSt _{] fi} 84
PAA ₁₂₀ ) x (before deprotection: M _n , _app = 102,700 g / mol, PDI = 1.29).
These stars include:
A) Ci ₈ -PAA ₁₄₆ ) x: M _n , _app = 95,600 g / mol, PDI = 1,48, ⁵ B) Ci2-PAA ₁₃₄ ) _x : M _n , _app = 113,900 g / mol, PDI = 1, 53,
Each star was prepared in three stages:
i) preparation of PtBA arm, ii) cross-linking arms in star-shaped macromolecule, ¹⁰ üi) deprotection of tBu groups. All stars had a relatively low PDI with a low amount of unreacted arms (<15% by weight).
A new PtBA macroinitiator was prepared from a primer containing a linear C _x8 15 alkyl chain for the preparation of the star (C ₁₈ -PAA ₁₄₆ ) _x . The synthesis of this Ci ₈ -PtBA-Br arm precursor was performed with the use of tBA ARGET ATRP with the use of functionalized C ₄₈ alkyl chain EBiB. The conditions and properties of the synthesized polymer are shown in Table 1.
This macroinitiator was then cross-linked with the use of DVB in a star-shaped macromolecule. After the deprotection of the tBu groups by stirring the reaction for 3 days in the presence of TFA resulting in the transformation into PAA units, the star was precipitated from CH ₂ C1 ₂ . The viscosity of the resulting star (C _i8 -PAA) x and of the star (Ci2-PAA) x can be compared to (PSt-b-PAA) x in water and shampoo formulations.
Example 8: Stars with an internal P (ΗΕΆ) cover
P-shaped macromolecules (HEA) that comprise water-soluble, non-ionizable hydrophilic segments selected to make the star-shaped macromolecules compatible with solutions that additionally comprise dissolved / dispersed salts that are additionally stable over a wide pH range.
The arm precursor PSt-b-PHEA was prepared using ICAR ATRP. The conditions for polymerization and characterization of the resulting polymer are shown in Table 2. The polymerization was well controlled and the well-defined block copolymer was prepared with relatively low (PDI = 1.26 and 1.20). This is the first example of a successful ICAR ATRP for acrylate-type monomer. The arm precursor PSt-b-PHEA was purified by precipitation in ethyl ether and vacuum dried over two days at 50 ° C.
Different cross-linking agents were investigated, including DVB and in the 08-006-159 di (ethylene glycol) diacrylate (DEGliDA) run and in the 08-006-161 DEGliDA run with a small amount of the HEA monomer. The reaction was not completely controlled when the conversion of the added divinyl crosslinker was triggered to a high conversion as a consequence of the star-star coupling reactions resulting in gel formation. However, at a lower conversion of the crosslinker and under more diluted conditions, star-shaped macromolecules were formed.
Example 9: Preparation of a Star-shaped Macromolecule with Heteroblast (PSt ₁₅ -b-PAA ₂₉₀ / PAA ₁₅₀ ) ^ ₃₀ (referred to herein as Advantomer) A simple four-step procedure was developed for the preparation of a macromolecule in form of star with heterobraço based on poly (acrylic acid) is described in Scheme 4. 1 kg of the star-shaped macromolecule with heteroblock with PSt-b-PtBA arms (4/1 molar ratio of arms) was prepared as follows.
STEP 1
STEP 2

St
ICAR ATRP
ARGET ATRP
Ή _____ _k tBA
ARGET ATRP at a given conversion + EtBiB
PSt PSt-b-PfBA
PSt-b-PfBA and PíBA
STEP 3 STEP 4
DVB
Controlled crosslinking
hydrolysis
Star Star [(PSt-ò-PtBA) _x / (PtBA) _y ] -DVB [(PSt-d-PAA) _x / (PAA) _y ] -DVB
Scheme 4. Multistage synthesis of heteropolymer star copolymers [PSt-b-PAA / PAA]
STEP 1: Synthesis of a 5-polystyrene (PSt) Macroinitiator that has 15 DP
A polystyrene macroinitiator was formed using ICAR ATRP by introducing the following components into the reaction vessel at the following molar ratio: St / DEBMM / CuBr ₂ / TPMA / AIBN = 50/1 / 0.002 / 0.003 / 0.05 by weight at T = 60 ° C, t 0 - 10.2 hours. The reaction was performed at ~ 30% conversion. The resulting reaction product was purified to obtain PSt in powder form. A portion of the powdered PSt was dissolved in THF and passed through the GPC column. The GPC trace obtained for the macroinitiator is shown in Figure 2. The measured molecular weight of the hydrophobic polystyrene segment = 1,600 which is equivalent to an average degree of polymerization (DP) of about 15 to 16 and the PDI was measured to be 1.24.
niAPA 2: Onc-pot Synthesis of Macroinitiator of
Polystyrene-b-Poly (t-butyl acrylate) and Poly (t-butyl acrylate)
The following components were introduced into the reaction vessel at the following molar ratio: tBA / PSt (da etapal) / CuBr ₂ / TPMA / Sn (EH) ₂ = 200 / 0.2 / 0.01 / 0.06 / 0, 1, in anisole (0.5 equivalent volume versus tBA), T = 55 ° C. About 2.0 hours after the reaction was started, the tBA conversion reached about 6% and a portion of the PStb-PtBA was recovered and measured by GPC with the following results M _n - 19,800 g / mol; PDI = 1.16. It was determined that the following PSti ₅ -b-PtBA ₁₄₀ copolymer block was obtained. Then, the amount of molar ratio 0.8, relative to the components initially introduced, of ethyl 2bromoisobutyrate (EBiB) was injected into the polymerization mixture. The reaction was continued and stopped after about 19.8 hours. The reaction product was purified and the product was analyzed by GPC. Based on the measured GPC values, the final molecular weight of the product was determined to be the poly (t-butyl acrylate) segment in the block copolymer was -37,200 g / mol (PSti ₅ -b-PtBA ₂₉₀ ) and the molecular weight of poly (t-butyl acrylate) initiated from EBiB was 19,200 g / mol which is equivalent to a DP -150. The total molecular weight of the mixture of arms resulted in M _n = 20,800 g / mol and PDI = 1.27. The GPC curves of the polystyrene macroinitiator and the mixture of the formed block copolymer PSt ₁₅ -b-PtBA ₂₉₀ arms and poly (t-butyl acrylate) PtBA ₁₅₀ arms are shown in Figure 23. The sign of the block copolymer is overlapping the homopolymer signal, but this result clearly indicates that a clean chain extension of PSL has occurred
STEP 3: Synthesis of the star-shaped macromolecule with heteroblast (PSt-b-PtBA / PtBA) _κ30 .
A hetero-arm multi-star star macromolecule was prepared by conducting an additional chain extension reaction with the block copolymer and homopolymer macroinitiators formed in step 2. The reaction was conducted with a molin ratio of the macroinitiators to divinylbenzene of 1: 16 in anisole. The following components were introduced into the reaction vessel at the following molar ratio: DVB / [PSt-b-PtBA / PtBA] (from step 2) / CuBr ₂ / TPMA / Sn (EH) ₂ = 16/1 / 0.02 / 0.07 / 0.15 in anisole (38 equivalent volume versus DVB), T = 95 ° C, t - 20.6 hours. The reaction product was purified and the product was analyzed by GPC. The GPC curves and results of the star formation reaction are provided in Figure 24. It can be seen that a multi-arm star-shaped macromolecule with a reticulated nucleus has been formed. The apparent molecular weight of the star's GPC was 109,400 with a PDI of 1.52, which would indicate an average of six arms, but this is an underestimation of the actual number of arms since the star-shaped molecule is a compact molecule. In fact, in this situation, the number of arms in the star-shaped molecule is close to 30.
The number of arms can be modified by conducting the core formation reaction with a ratio other than the crosslinking agent to arm precursor or by carrying out the reaction with a different concentration of reagents.
STEP 4: Deprotection of (PSt-b-PtBA / PtBA) to (PSt-b-PAA / PAA)
The deprotection of the star-shaped macromolecule (PSt-b-PtBA / PtBA) ^ 30 to 0 star block copolymer (PSt-b-PAA / PAA) -. ₃₀ to provide water-soluble poly (acrylic acid) segments in the multi-arm star-shaped macromolecule with hetero-arm. The PSt-b-PtBA / PtBA arms of the star-shaped macromolecule with hetero-arm were transformed into PSt-b-PAA / PAA arms with the following procedure. The polymer was dissolved in methylene chloride and trifluoroacetic acid to unprotect the tBu groups, the reaction was carried out at room temperature for 60.0 hours. Then, the polymer was decanted and washed 3 times with acetonitrile. The polymer was then solubilized in THE and precipitated in acetonitrile. The star-shaped macromolecule was dried in a vacuum oven for 3 days at 50 ° C. The amount of polymer obtained after purification was 550g, which would correspond to the complete conversion of PtBA to PAA.
Test Results Table - comparison of the star-shaped macromolecule formed in Example 9 (Advantomer) against the commercially available thickening agent, Carbopol ETD 2020.
properties Advantomer Carbopol ETD 2020 (conform formed Example andat the9) Viscosity25,830 cP @ 48,000 cP @ 0.2% Dynamics (@Irpm) 0.2% in Weight by weight Value in smash 87.8% @ 0.7% 52, -4% ê ^- 0, 4 % in induced per salt by weightWeight Value in smash 99.3% @ 0.4% 12.6% @ 0.2 % in induced per pH by weightWeight Valuein 32.7 @ 0, 2% in 12.9 @ 0.2% in Weight
structural ipe weight
Strong gel; Yes Vimj
Emulsion value> 12 hours <5 minutes;
jHLM j> 0.96 U / A
Testing Procedures
Sample Preparation
The aqueous gel compositions were prepared in various concentrations (for example, 0.2% by weight, 0.25% by weight, 0.4% by weight, 0.6% by weight, 0.7% by weight and 1.0% by weight) heating and stirring, as needed (for example, mixing vigorously at a temperature of about 60 ° C) the sample material (for example, a macromolecular powder in the form of star or Carbopol ETD 2020) in water with pH adjusted as needed (for example, a pH of about 7.5 with the addition of sodium hydroxide) to obtain a homogeneous mixture.
Dynamic Viscosity and Test Procedure
Viscosity that decreases under shear
A portion of the sample preparation was introduced into a Brookfield LVDV-E digital viscometer, using a # 31 rod for mixing, in STP, over a wide range of rates (for example, 0.3 to 100 rpm) and the shear rate and viscosity were recorded. Viscosity measurements were taken in the following sequence without interrupting the instrument, 0.3, 0.5, 1, 2, 5, 10, 20, 30, 50 and 100 rpm. The dynamic viscosity was determined as the viscosity in centipoise (cP) at 0.3 rpm. A viscosity value that decreases under shear was determined by dividing the dynamic viscosity value at 0.3 rpm by the dynamic viscosity value at 20 rpm .____________________
Rate ofViscosity [cP] Shear RPM Advantomer Carbopol [s' ¹ ]0.2% in 0.2% by weight
Weight0. 102 0.3 67,100 85,000 0.17 0.5 46,980 65,600 0.34 1 25,830 48,000 0.68 2 13,880 23,300 1.7 5 6,580 15,800 3, 4 10 3,620 10,400 6, 8 20 2,050 6,600 10.2 30 1,480 4,800 17 50 1,000 3,300 34 100 690 2,250
Salt Induced Break Test Procedure
A portion of the sample preparation was introduced into a 20 ml glass scintillation vial. A measured portion of NaCl was added to the flask (for example, 0.05% by weight relative to the total weight of the sample in the flask. After adding the finished NaCl, the flask was closed and shaken for 10 min. Then, the viscosity of the The sample was measured according to the dynamic viscosity and the viscosity test procedure that decreases under shear, above, and the dynamic viscosity at 1 rpm was recorded.This procedure was repeated for different concentrations of NaCl. The results are shown in Figures 18 and 22. The breakage value induced by salt, in percentage, is determined by the following equation:
Initial Dynamic Viscosity (0% NaCl) Dynamic Viscosity (0.05% by weight of NaCl) / Initial Dynamic Viscosity (0% NaCl) x 100%.
PH Efficiency Range Test Procedure
A 0.4% by weight aqueous gel composition was prepared for the star-shaped macromolecule of example 9, at a starting pH of about 5, and a separate 0.2¾ by weight aqueous gel composition from the gel composition. Carbopol ETD 2020 aqueous solution, at a starting pH of about 3, was prepared by mixing and heating as needed (for example, mixing vigorously at a temperature of about 60 ° C). Then, the sample viscosity was measured according to the dynamic viscosity and the viscosity test procedure that decreases under shear, above, and the dynamic viscosity at 1 rpm was recorded. This procedure was repeated for different pH values, adjusted by adding sodium hydroxide. The results are shown in Figure 19. The pH-induced break value, in percent, is determined by the following equation:
Dynamic Viscosity (at 1 rpm) at a pH of 7.5 Dynamic Viscosity (at 1 rpm) at a pH of 5 / Dynamic Viscosity (at Irpm) at a pH of 7.5 x 100%.
Emulsion Test Procedure
A quantity of 340 ml of water was added to a 500 ml beaker and stirred vigorously with an overhead stirrer. 1.6 g of the material to be tested for an emulsifying effect was added and heated to 80 ° C. The solution was adjusted to pH with 400 mg of NaOH and stirring continued until a homogeneous gel was obtained. 60 ml of sunflower oil was added while vigorous stirring was continued with a shaker greater than 80 ° C for 10 min or until a homogeneous emulsion was obtained. The mixture was allowed to cool to room temperature. Once the system cools to room temperature, start a timer. The emulsion value is the time, in minutes, it takes for the system to form two visible layers (phase separation).
Strong Gel Test Procedure ml portion of the material sample preparation was introduced into a 20 ml glass scintillation vial. After the transfer was complete, the vial was placed on a surface and remained intact for about 20 minutes in STP. The vial was then gently inverted (placed upside down) and placed on the surface and a timer started. If after 5 minutes there is no visible flow, then the sample is said to be a strong gel.
Lipophilic-Hydrophilic Arm (HLB) / Calculation of
Segment
HLB = 20 * Mh / M where Mh is the molecular mass of the hydrophilic portion of the polymer arm or segment, and M is the molecular mass of the entire polymer arm or segment.
Calculation of Lipophilic-Hydrophilic Macromolecule • --------- M-M
0,3 ÃfJFKtíc / ío + Yj Λ / JF »
HLM = divided by ^M_1 where
MW _n is the molecular weight for the respective arm,
HLB _n is the HLB, as calculated from the HLB arm calculation, for the respective arm, and
MWnúcieo is the molecular weight for the nucleus, and
M is the total number of arms.
The revealed star-shaped macromolecules can be useful in a spectrum of applications that include, but are not limited to; personal care: which includes shampoos / conditioners, lotions, serums, creams, solids, jellies, cosmetics: which include mask, blush, lipstick, powders, perfumes and home care: which include window cleaners, home and work surfaces, toilet, laundry, and dishwasher and dishwasher applications.

权利要求:
Claims (15)
[1]
1. Star-shaped macromolecule represented by Formula X:
Formula X [(P1) q1- (P2) q2] t-Core - [(P3) q3] r characterized by the fact that:
Nucleus represents a cross-linked polymeric segment;
P1 represents a homopolymeric segment comprised of repeated units of monomeric residues of polymerized hydrophobic monomers;
P2 represents a homopolymeric segment comprised of repeated units of monomeric residues of polymerized hydrophilic monomers;
P3 represents a homopolymeric segment comprised of repeated units of monomeric residues of polymerized hydrophilic monomers;
q1 represents The amount in units repeated in P1 and has a value between 1 and 50; q2 represents The amount in units repeated in P2 and has a value between 30 and 500; q3 represents The amount in units repeated in P3
and has a value between 30 and 500;
r represents the number of homopolymeric arms covalently attached to the Nucleus;
t represents the number of copolymeric arms covalently attached to the Nucleus; and
Petition 870190118939, of 11/18/2019, p. 12/21
[2]
2/4 where the molar ratio of r to t is in the range between 20: 1 and 2: 1.
2. Star-shaped macromolecule according to claim 1, characterized by the fact that it has a molecular weight between 100,000 g / mol and 2,000,000 g / mol, as determined by GPC.
[3]
3. Star-shaped macromolecule, according to claim 1, characterized by the fact that the molar ratio of r to t is in the range between 8: 1 and 3: 1.
[4]
4. Star-shaped macromolecule according to claim 1, characterized by the fact that both q2 and q3 have a value greater than 100, and where q2 is greater than q3.
[5]
5. Star-shaped macromolecule according to claim 1, characterized by the fact that the arms represented by [(P1) q1- (P2) q2] have an HLB value greater than 18.
[6]
6. Star-shaped macromolecule according to claim 1, characterized by the fact that the homopolymeric segment P1 is a hydrophobic polymeric segment that has an HLB value less than 7.
[7]
7. Star-shaped macromolecule according to claim 1, characterized by the fact that the core comprises a hydrophobic cross-linked polymeric segment.
Petition 870190118939, of 11/18/2019, p. 13/21
3/4
[8]
8. Star-shaped macromolecule according to claim 1, characterized by the fact that the star-shaped macromolecule is a water-soluble star-shaped heteromacromolecule.
[9]
9. Star-shaped macromolecule according to any one of claims 1 to 8, characterized by the fact that it forms a clear and homogeneous gel when dissolved in water at a concentration of 0.2% by weight; wherein the gel has a dynamic viscosity of at least 20,000 cP, according to the dynamic viscosity and viscosity test procedure which decreases under shear.
[10]
10. Star-shaped macromolecule according to any one of claims 1 to 8, characterized by the fact that it forms a clear and homogeneous gel when dissolved in water at a concentration of 0.2% by weight; wherein the gel has a salt-induced break value between 60% and 100%, according to the salt-induced break test procedure.
[11]
11. Star-shaped macromolecule according to any one of claims 1 to 8, characterized by the fact that when dissolved in water at a concentration of 0.4% by weight, it has a viscosity value that decreases under shear of at least 5, according to the dynamic viscosity and viscosity test procedure which decreases under shear.
Petition 870190118939, of 11/18/2019, p. 14/21
4/4
[12]
12. Star-shaped macromolecule according to any of claims 1 to 8, characterized by the fact that it forms a clear and homogeneous gel when dissolved in water at a concentration of 0.2% by weight; wherein the gel has an emulsion value greater than 10 hours, according to the emulsion test procedure.
[13]
13. Star-shaped macromolecule according to any one of claims 1 to 8, characterized in that, when dissolved in water at a concentration of 0.4% by weight, it has a viscosity of at least 40,000 cP with pH between 5.5 and 11, according to the pH efficiency range test procedure.
[14]
14. Star-shaped macromolecule according to any one of claims 1 to 8, characterized by the fact that, when dissolved in water at a concentration of 0.4% by weight, it has a viscosity of less than 5,000 cP at a shear rate of 4 sec ^-1 , according to the dynamic viscosity and viscosity test procedure which decreases under shear.
[15]
15. Emulsion, characterized by the fact that it comprises the star-shaped macromolecule according to any one of claims 1 to 14, wherein the emulsion is optionally an emulsifier-free emulsion.

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法律状态:
2017-08-15| B15I| Others concerning applications: loss of priority|

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2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-01-29| B25D| Requested change of name of applicant approved|Owner name: PILOT POLYMER TECHNOLOGIES, INC. (US) |

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2019-08-20| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-02-04| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-02-18| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 26/10/2011, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US12/926,143|2010-10-27|

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US12/926,143|US8173750B2|2009-04-23|2010-10-27|Star macromolecules for personal and home care|

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PCT/US2011/057789|WO2012058255A2|2010-10-27|2011-10-26|Star macromolecules for personal and home care|

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