POLYSILOXAN COMPOUNDS, PROCESS FOR THE PRODUCTION OF POLYSILOXAN COMPOUNDS, USE OF POLYSILOXAN POLYM

专利摘要:
polysiloxane compounds, process for the production of polysiloxane compounds, use of polysiloxane polymers and w / o emulsions the invention relates to polysiloxane compounds as w / o emulsifiers, in textile softeners, defoamers, foam stabilizers and agrochemicals, in particular as emulsifiers w / o for cosmetic uses.
公开号:BR112012012335B1
申请号:R112012012335-1
申请日:2010-11-24
公开日:2020-01-07
发明作者:Roland Wagner；Walter Simon；Martin Kropfgans；Sabine Nienstedt；Albert Schnering；Katharina Streicher；Karl-Heinz Sockel；Sebastian Maass
申请人:Momentive Performance Materials Gmbh；
IPC主号:

专利说明:

POLYSILOXAN COMPOUNDS, PROCESS FOR THE PRODUCTION OF
POLYSILOXAN COMPOUNDS, USE OF POLYSILOXAN POLYMERS, AND
A / O EMULSIONS [001] The invention relates to modified hydrophilic and lipophilic polysiloxanes which preferably comprise ester units and which are preferably suitable as emulsifiers, textile softeners, defoamers, foam stabilizers, demulsifiers and agrochemicals, in particular as emulsifiers W / O for cosmetic uses.
[002] Siloxane based on W / O emulsifiers comprising ethylene oxide units are used extensively in liquid aesthetic paste-like formulations such as, for example, creams and lotions (US 2005/0008592, US 2004/0009131). By using these emulsifiers it has become possible to emulsify large amounts of water in oil (high internal phase ratio emulsions). Such emulsions cause a pleasant smooth sensation on the skin.
[003] Furthermore, the use of such emulsifiers in solid formulations has been described (US 7199095, US 7083800).
[004] In this context it has been shown that oils differ immensely in relation to molecular weight and polarity, such as hydrocarbon, fatty acid esters and silicone oil can be emulsified to become stable over the long term. This is due to the chemical structure of such siloxane based on W / O emulsifiers, which are composed of a siloxane structural chain, hydrophilic polyethylene oxide units and long chain hydrophobic alkyl group. Hydrophilic polyether units intermediate the connection to the water phase, long chain alkyl groups
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2/92 link the oil phase and siloxane chain structure to stay at the phase limit (US 4698178; D. Schafer, Tenside
Surf. Det. 1990, 3.154; B. Griining, P. Hameyer, C. Weitemeyer,
Tenside Surf. Det. 1992, 2, 78).
[005] During the development of this approach it was suggested to create emulsifiers by cohidrosylation of siloxanes containing SiH with allyl polyethers and undecenoic esters of fatty acid alcohol (US 6388042) or undecenoic esters of fluoroalcoholic acid (US 6727340) respectively, which has good compatibility and degradable fatty acid units as compatible lubricating components.
[006] As an alternative, trials have been undertaken to convert polyethylene oxide siloxanes based by esterification with fatty acids or esterification with dicarboxylic acids respectively in combination with alkoxylated fatty acids, alkoxylated fatty alcohols, glycerinated fatty acids or neutralizing the function of carbon acid with fatty amines in W / O emulsifiers (US 5226923, US 5180843, US 5136063, US 6891051, US 5475125, US 5446184, US 5446183, US 5411729, US 5248783, US 5210133). A specific disadvantage of this product group is that the hydrophilic and hydrophobic groups cannot orient independently of each other.
[007] A general disadvantage of all these ethylene oxide units containing siloxane-based W / O emulsifiers is that the proportion of polyethylene oxide units contained therein in combination with sunlight are factors responsible for skin sensitization. It is still well known to use modified glycerin siloxanes as a spreading additive (US 2005/0261133). Siloxanes from
Petition 870190106535, of 10/21/2019, p. 6/112
3/92 modified polyglycerol have become known as a component in formulations for treating fibers (JP 2005082925). Branched modified polyglycerol siloxanes are discussed in US patents 2005/0084467 and JP 2005-089494. The modified siloxanes are further described in EP 2030605, EP 2243799, EP 1816154 and in the references cited herein.
[008] For the prevention of the skin sensitization problems discussed above, siloxane-based W / O emulsifiers have been presented, based on the cohidrosylation of siloxanes containing SiH with unsaturated oligoglycerines and long chains of alkenes (SOFW-Journal, 132,122006, 31).
[009] The etherification of polyglycerin units positioned on the siloxane chain with, for example, lauryl alcohol leads to emulsifiers, which must be used in solid W / O emulsions (US 2006/0013793). In addition, this solution is disadvantageous since the hydrophilic and hydrophobic groups cannot guide one independently of the other. Dibenhatos derived from allyl glycerol were added to a, ω-SIH siloxanes and resulted in waxes, which do not understand the emulsion characteristics (US 2003/0096919). This is also the case for those waxes, which are derived from the fatty acid esters of ally alcohol (US 2004/0071741).
[010] None of the above mentioned solutions describes a way of oxide-free siloxane-based ethylene emulsifiers that have rapidly degradable hydrophobic fatty acid ester units and at the same time comprise hydrophilic hydroxylated carboxylic acid ester units, where these hydrophobic acid units
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4/92 fatty acids can be introduced independently from hydrophilic hydroxylated carboxylic acid ester units. Thus, it is the aim of the invention to describe the synthesis of polyethylene W / O emulsifiers based on oxide-free siloxane which have rapidly degradable fatty acid units as a soluble component of the oil and at the same time comprise hydroxide units of the carboxylic acid ester as a hydrophilic component and where the addition of hydrophilic and hydrophobic components can proceed independently of each other. It is a further object of the invention to describe the use of polyethylene W / O emulsifiers based on oxide-free siloxane in cosmetic formulations.
[011] It was surprisingly found that the polysiloxane compositions of the formula:
[M _to DbTcQd] and (I) where
M = R3SÍO1 / 2,
D = R2SIO2 / 2,
T = RSI3 / 2,
Q = SiO4 / 2, with a = 1-10 b = 0-100 c = 0-1 d = 0-1 e = 1-10 where
R = is an organic group, with the requirement that R comprise at least one group, preferably
Petition 870190106535, of 10/21/2019, p. 8/112
5/92 two R ⁹ groups that are selected from:
R ¹ = -Z- (AE) y, where
Z = is a bivalent or trivalent C2 to C2o hydrocarbon residue, linear, cyclic or branched, saturated or unsaturated, which may comprise one or more k
groups selected from -O-, -NH-, and can be replaced by one or more OH groups,
A is a divalent residue that can be selected from the group consisting of:
and
H —C-C-OH
I h ₂ y = 1 or 2
E is selected from the group consisting of: E ² = -OC (O) -R ² , where R ² = is a straight, cyclic or branched chain hydrocarbon residue, saturated or unsaturated with up to 50 hydrocarbon atoms, which can comprise one or more selected groups of -O-, -NH-, -NR 3 -, -C (O) -, and is replaced by one or more OH groups, where R ³ = a linear, cyclic hydrocarbon residue , saturated or unsaturated with up to 6 hydrocarbon atoms, and
E ³ =
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6/92
OH ¹ 2
OC CC- E h ₂ hh ₂ where E ² is defined as above, ex = 1 - 4,
E ⁵ = -NR ⁴ R ⁵ , where
R ⁴ and R ⁵ are the same or different and are selected from the group comprising:
hydrogen and a saturated or unsaturated cyclic or branched straight chain hydrocarbon residue with up to 30 hydrocarbon atoms that can comprise one or more groups selected from -O-, NH-, -NR ³ where R ³ is as defined above, - C (O) - and can be replaced by one or more OH- and / or H2N groups, and
R ⁶ = -ZE ² where E ² is as defined above, and
R7 = -ZE ⁶ , where E ⁶ = -NH-C (O) -R ⁴ , where R ⁴ is as defined above, and R ⁹ - in addition to at least one of R ¹ R ⁶ and R ⁷ - can be R ⁶¹ = -ZE, where E ¹ is -OC (O) -R ²¹ , where R ²¹ = a straight, cyclic or branched, saturated or unsaturated hydrocarbon residue with up to 50 carbon atoms, which may comprise one or more more selected groups of -O-, -NH-, -NR ³ -, -C (O) -, where R ³ is as defined above, but does not have a hydroxy substituent, can solve the problems defined above, particularly of preparation of emulsifiers, which do not substantially comprise polyalkylene oxide groups, and are capable of emulsifying extremely high amounts of water over a wide spectrum of various water-insoluble phases with great stability.
[012] Consequently, the polysiloxane compounds according to the invention do not comprise
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7/92 substantially polyalkylene oxide units, such as, in particular, polyethylene oxide and / or polypropylene oxide units with more than 4 repetitive alkylene oxide units. The polysiloxane compounds according to the invention preferably do not comprise polyalkylene oxide units.
[013] In a preferred embodiment the polysiloxane compounds according to the invention comprise siloxy structural elements selected from the following formulas:
R ⁸
I θϊβΤψ 'θί / 2' ο where R ⁸ = Ci to C22-alkyl, fluoroalkyl or aryl, and R ⁹ = R ¹ , R ⁶ and / or R ⁷ , and optionally R ⁶¹ , f = 0-600, where the R ⁸ groups can be the same or different and are selected from Ci to C22-alkyl, fluoro-substituted Ci to C22-alkyl and aryl, eg = 0-700,
R ⁸ θϊ / 2 ^_ θϊ / Γ “^ 1/2
Jh where R ⁸ is defined as above, eh = 0-10,
Petition 870190106535, of 10/21/2019, p. 11/112
8/92
where R ⁹ is defined as above, ei = 0-10, “R ⁸ a '
R — yes ^ _ R ⁹ Ji where R ⁸ and R ⁹ are defined as above, and j = 0-30,
T ⁸
R ^e - Si — O ^ R ⁸
L ^R Jk where R ⁸ and R ⁹ are defined as above, ek = 0-30,
where 1 = 0-10, f + g + h + i + j + k + 1 = 12 to 1000.
[014] In a particularly preferred embodiment the polysiloxane compounds according to the invention comprise two or more residues R ⁹ = R ¹ , R ⁸ and / or R7 and optionally R ⁶¹ . Preferably, the R ⁹ residues are
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9/92 selected from residues R ¹ and R ⁶ .
[015] In another preferred embodiment of polysiloxane compounds according to the invention, residues R ⁹ = R ¹ , R ⁶ and / or R7, preferably residues R ¹ and / or R ⁶ , comprise one or more, preferably one ( 1), ester unit (-C (O) O).
[016] In other preferred modalities R ⁹ is selected according to the following rules: R ⁹ is R ¹ and / or R ⁶ , and optionally R ⁶¹ , or
- R ⁹ is R7, and optionally R ⁶¹ , or
- R ⁹ is R ¹ and / or R ⁶ and R 7, and optionally R ⁶¹ , the last embodiment according to which R ⁹ comprises a hydroxy carboxylic acid residue R ¹ and / or R ⁶ and an aminofunctional residue R ⁷ being particularly preferred.
[017] In another preferred embodiment the polysiloxane compounds according to the invention comprise two or more R9 residues, which differ in their hydrophilic / lipophilic characteristics, corresponding to the hydrophilic residues R91 and the lipophilic residues R92.
[018] In another preferred embodiment, the polysiloxane compounds according to the invention comprise
- the waste hydrophilic R ⁹¹ , the which are has one logP (25 ° C) < 0.5, and - the waste lipophilic R ⁹² , the which are has one logP (25 ° C)> 0.5, Where logP (25 ° C) corresponds to coefficient in distribution in compounds corresponding H- R ⁹¹ e H- R ⁹² ,
corresponding to compounds HR ¹ , HR ⁶ (and HR ⁶¹ according to the optionally present residue R ⁶¹ ) and H-R7 in a water-octanol mixture at 25 ° C. According to the invention the coefficients of
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10/92 distribution are determined for simplification purposes using logP calculation software commercially available from the ACD company (ACD Inc., 133 Richmond St. W., Suite 605, Toronto, ON, Canada M5H 2L3, for example, in “ Perspectives in Drug Discovery and Design, 19: 99-116, 2000), which are based on well-characterized logP contributions of single atom structure fragments and intramolecular interaction between different fragments. Alternatively, experimental determination in a water / n-octanol mixture (water: 50 ml, octanol: 50 ml, substance to be determined HR ⁹¹ and HR ⁹² : 1 ml) at 25 ° C is also possible.
[019]
In another preferred embodiment, the polysiloxane compounds according to the invention comprise structural elements selected from the following formulas:
where R
C1 to C22-alkyl, fluoroalkyl or aryl preferably methyl
R ⁹¹ is as defined above or below, and f1
300 preferably 2 to
200 more preferably 2 to 50 even more to 30 where R ⁸ =
--Οητ-Si — O
1/2 Τ '
R ^â2
C1 a
C22-alkyl, fluoroalkyl or aryl preferably methyl, and
R ⁹² is as defined above or below
Petition 870190106535, of 10/21/2019, p. 14/112
11/92 and
f2 = 1 - 300, preferably 2 to 200, more preferably 2 to 50, even more 4 to 40,
4 ^Γ R ⁸ '
I
L ^R Jg where the groups R ⁸ can be the same or different and are selected from C ¹ to C ²² -alkyl, fluoro-substituted C1 to C22-alkyl and aryl, preferably methyl, eg = 0 - 700, preferably 3 to 500 , more preferably 5 to 200, even more preferably 10 to 100, ”Í
--Si-O;
^ 1/2 where R8 is, as defined above, preferably methyl, and h = 0-10, preferably 0
Where
R ⁹¹ is as defined above or below, and i1
0-5, preferably 0
Petition 870190106535, of 10/21/2019, p. 1/15
12/92 methyl, and
R ⁹²
Ο-ιίο Sí 0-1 «
1/2 y
91/2 where
R ⁹² is
1/2 i2 as defined above or below, and
- 5, preferably 0 i2
where R ⁸ is, as defined above, preferably
R ⁹¹ is as defined above or below, and j1 = 0-15, preferably 0
where R ⁸ is, as defined above, preferably methyl, and R ⁹² is as defined above or below, and j2
-15 preferably 0
where R8 is, as defined above, preferably methyl, and preferably 1 to 6 more preferably 2
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13/92
L θΐ «J _t where 1 = 0 - 10, preferably 0, f1 + f2 + g + h + i1 + i2 + j1 + j2 + k + 1 = 12 to 1000, preferably to 400, more preferably 20 to 200, still more preferably 30 to 150.
[020] Preferably the molar ratio of hydrophilic residues R91 and lipophilic residues R92 in the polysiloxane compounds according to the invention correspond to from 5: 1 to 1:10, more preferably from 2: 1 to 1: 7, even more preferably from 1 : 1 to 1: 5.
[021] In a preferred embodiment the group R91 and the lipophilic residues R92 in the polysiloxane compounds according to according to the invention correspond to from 5: 1 to 1: 100, more preferably from 5: 1 to 1:50.
[022] Preferably the molar ratio of R91 as well as siloxy units comprising R92 to non-modified, only siloxy units comprising R8 is 5: 1 to 1:10, more preferably 2: 1 to 1: 7, even more preferably 1: 1 to 1: 5. Polysiloxane compounds in which the ratio of R91 to R92 is equal to 1 and less than 1, are preferably used as W / O emulsifiers, as foam stabilizers for polyurethane foams, demulsifiers in the oil and gas industry, or also as defoamers or in defoaming formulations for, for example, diesel fuels or as a coated additive for fluidity and leveling of coating compositions, such as
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14/92 additive for anti-blocking, resistance to de-characterization, as a lubricant or lubricant additive, as fabric softeners or in fabric softener compositions as a self-emulsifying alkylene oxide free softener or as a cutting-cut emulsifier textile treatment.
[023] If the ratio R91 to R92 is the same or greater than 1, the use of defoamers, compatibilisers for lipophilic phases, for example, O / W emulsions and particularly preferred is the use as demulsifiers in the oil and oil industry. gas for faster and better separation of crude oil and water, coagulant for rubber latex, as an anti-blocking additive, resistance to de-characterization, as a lubricant or lubricating additive, as fabric emollients or in the fabric emollient composition as the self-emulsifying alkylene oxide free emollient or as a cutting stable emulsifier in textile treatment formulations, as foam stabilizers for aqueous foam indetergents, dishwashing liquids
and in liquids in cleaning general purpose, the fat phases cosmetics such how creams, adit plastic items and thermoplastics or elastomeric for hydrophilization and The wettability enhanced of surfaces thermoplastic or elastomeric.[024]It is particularly preferred that the
Polysiloxane compounds according to the invention comprise siloxy units of the formulas:
Petition 870190106535, of 10/21/2019, p. 18/112
15/92
where R ⁸
C1 a
C22-alkyl, fluoroalkyl or aryl preferably methyl
R ⁹¹ is defined as above or below, and f1
300 preferably 2 to 200 more preferably 2 to 50 even more preferably 30
where R ⁸ =
C1 a
C22-alkyl, fluoroalkyl or aryl preferably methyl and R ⁹² is defined as above or below f2
300 preferably 2 to
200 more preferably 2 to 50 even more preferably 4 to 40
where R8
C1 to
C22-alkyl, fluoroalkyl or aryl preferably methyl g = 0-700 and
where groups
R ⁸ can be the same or different
Petition 870190106535, of 10/21/2019, p. 1/1912
16/92 can be selected from C1 to C22-alkyl, fluoro-substituted to C22-alkyl and aryl, preferably methyl and k = 2.
[025] Accordingly, the polysiloxane compounds according to the invention are preferably end-stop linear trimethylsilyl polysiloxane compounds.
[026] In other preferred embodiments of polysiloxane compounds according to the invention at least one, several or all of the following definitions are fulfilled in each case:
R selected from: C1 to C10-alkyl, which, if necessary, can be substituted with 1 to 13 fluorine atoms, and aryl, and R ⁹ is selected from R ¹ , R ⁶ and R ⁷ , and optionally R ⁶¹ also can be present as R ⁹
Z = a C2 to C10- bivalent or trivalent straight-chain, cyclic or branched, saturated or unsaturated hydrocarbon residue, which may comprise -Oe groups may be substituted by one or more OH groups
700, preferably the
200 preferably to 150, preferably to
150 preferably
150, preferably 30 to 100 f1
200, preferably 1
100 preferably to 50, preferably preferably
30, preferably 5 to 30 f2
200, preferably 1 to
100 preferably to 50, preferably preferably
30, preferably 5 to 30, preferably 0 i1 = 0 to 5 and preferably 0, i2 = 0 to 5 and preferably 0,
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17/92
I = 0 to 5 and preferably 0, f1 + f2 + g + h + i1 + i2 + j1 + j2 + k + l = 10 to 500,
preferably 10 to 200, preferably 10 to 150, preferably 20 to 150, preferably 30 to 150, preferably 30 to 100. [027] In others preferred modalities of
polysiloxane compounds according to the invention one, several or all of the following definitions are fulfilled in each case:
R is selected from: C1 to C6-alkyl, where, if necessary, they can be replaced by 1 to 13 fluorine, phenyl,
Z = a C2 to C6 bivalent or trivalent straight-chain, cyclic or branched, saturated or unsaturated residue, which may comprise one or more groups -O- and may be replaced by one or more groups OH, y = 1.
R2 = a linear, cyclic or branched, saturated or unsaturated hydrocarbon residue with up to 30 carbon atoms, which may comprise one or more groups selected from -O-, -NH-, -NR3-, -C (O) - and can be replaced by one or more OH groups, where R3 is defined as above.
[028] Still other preferred embodiments of polysiloxane compounds according to the invention are characterized by the fact that:
R in each case comprises at least one, preferably in each case several groups R91 and R92 (for example, groups R91 as well as R92 are present), where R91 is selected from the group, which comprises:
R11 = -Z- (A-E) y, where
And it is selected from the group, which comprises:
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18/92
E2 = -OC (O) -R22, where R22 = a linear, cyclic or branched, saturated or unsaturated hydrocarbon residue with up to 9 carbon atoms, which may comprise one or more groups selected from -O-, -NH -, -NR3 -, -C (O) -, and is replaced by one or more OH groups, where R3 = is a hydrocarbon residue with up to 6 carbon atoms, and
E3 =
where E2 is as previously defined (for example,
E2 = -O-C (O) -R22), and x = 1 -4, E5 = -NR41R51, where
R41 and R51 are the same or different and selected from the group comprising: a hydrogen and a straight, cyclic or branched, saturated or unsaturated hydrocarbon residue with up to 9 carbon atoms, which may comprise one or more groups selected from -O -, -NH-, -NR3 -, where R3, as defined above, can comprise -C (O) - and can be replaced by one or more OH and / or H2N groups, and
R6 = -Z-E2 where E2 is as previously defined for R11 (for example, E2 = -O- C (O) -R22),
R7 = -Z-E6, where E6 = -NH-C (O) -R22, where R22 is as previously defined, and R92 is selected from the group, which comprises:
R1 = -Z- (A-E) y, where
And it is selected from the group, which comprises:
E2 = -O-C (O) -R23,
Petition 870190106535, of 10/21/2019, p. 22/112
19/92 where R23 = a straight, cyclic or branched, saturated or unsaturated hydrocarbon residue with 10 to 50 carbon atoms, which may comprise one or more groups selected from -O-, -NH-, -NR3 -, -C (O) and can be substituted by one or more OH groups (this includes long-chain hydroxy fatty acid residues, such as ricinoleic acid - a less preferred embodiment), where R3 = a chain hydrocarbon residue linear, cyclic or branched, saturated or unsaturated with up to 6 carbon atoms, and
E3 = "OH"
I2 —O-C-C-CE
H ₂ H h ₂
--I X where E2 is as previously defined R92 (for example, 0-C (O) -R23), and x = 1 - 4,
E5 = -NR42R52, where
R42 and R52 are the same or different and are selected from the group comprising: a hydrogen and a linear, cyclic or branched, saturated or unsaturated hydrocarbon residue with 10 to 30 carbon atoms, which may comprise one or more selected groups of
-O-, -NH-, -NR3- where R3 is as defined above, C (O) -, and can be replaced by one or more OH- and / or H2N groups, and
R6 = -Z-E2 where E2 is as previously defined for R92
R7 = .Z-E6, where E6 = -NH-C (O) -R42, where R42 is like
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20/92 defined above.
[029] In other preferred embodiments of polysiloxane compounds according to the invention, at least one, several or all of the following definitions are fulfilled in each case:
R is selected from methyl, R91 and R92, where R91 and R92 are each as defined above,
Z = -CH2CH2CH2-O-CH2-, -CH2CH2CH2-,
z = 1 to 4, (where * indicates a connection in each case) -CH = CH2CH2, -CH = CH2CH2CH2-,
-CH2C = CHCH2 where the connection to the silicone is in position 2.
x = 1.
[030] In particular:
R8 = C1 to C6-alkyl, fluoroalkyl or phenyl,
Z = a C1 to C8 straight, cyclic or branched, saturated or unsaturated hydrocarbon residue, which may comprise one or more
I, more groups -O -, - NH-, -C (O) -, and can be replaced by
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21/92 one or more OH groups,
Especially preferred are R8 = methyl,
-Z- =
----- (CH ₂ ) ₃ - -o- c H ₂
Particularly in version R6 = -Z-E2, Z can also be selected from cyclic structures that are derived from cyclic epoxides, such as
[031] According to the invention, the polysiloxane compounds are preferably produced by the following processes, which are characterized by (a) a functional epoxy polysiloxane is reacted with one or more, preferably several carboxylic acids and, if necessary, subsequently with the primary or secondary amines,
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22/92 (b) a functional epoxy polysiloxane is reacted with one or more, preferably several carboxylic acids and the carboxylic acid anhydrides, where the carboxylic acid anhydrides, if necessary, are partially converted by the addition of monovalent or polyvalent alcohols, and, if necessary, also subsequently with the primary or secondary amines, (c) a functional SiH polysiloxane is reacted with (i) one or more mono-functional olefinic or acetylenic unsaturated ethers of glycerin or glycerin oligomers whose hydroxyl groups, if necessary, may be silylated and / or acetalised and / or quetalised and / or
esterified, and (ii) one or more esters of acids fatty with alcohols not saturated,(d) the polysiloxanes amino functional are esterified in acids carboxylic or reacted with
functional epoxy compounds.
More specifically the following synthetic paths are available:
(a) the saturated or unsaturated functional epoxy polysiloxane is reacted with a mixture, containing short chain carboxylic acids, preferably functionalized hydroxy, and long chain carboxylic acids, preferably hydroxy free, and optionally later with the primary or secondary amines ;
(b) the saturated or unsaturated functional epoxy polysiloxane is reacted with a mixture, containing short chain carboxylic acids, preferably functionalized hydroxy, and long chain carboxylic acids,
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23/92 preferably free of hydroxy, and optionally later with primary or secondary amines, where carboxylic acids are obtained by esterification or partial amidation of carboxylic acid anhydrides with alcohols or the corresponding amines;
(c) the saturated or unsaturated functional epoxy polysiloxane is reacted with long chain carboxylic acids, preferably free of hydroxy, and optionally later with the primary or secondary amines, where optionally the carboxylic acids can be obtained by esterification or partial amidation of carboxylic acid anhydrides with alcohols or the corresponding amines;
(d) a functionalized SiH polysiloxane is reacted with one or more of an acetylenically unsaturated monofunctional ether of glycerol or glycerol oligomers, optionally having silylated, acetified, quetalized or esterified OH groups, and one or more of an ester of fatty acids with alcohols olefinically or acetylenically unsaturated;
(e) a functionalized SiH polysiloxane is reacted with one or more of an olefinically unsaturated monofunctional ether of glycerol or glycerol oligomers, optionally having silylated, acetified, quetalized or esterified OH groups, and one or more of an fatty acid ester with alcohols acetylenically unsaturated;
(f) a functionalized SiH polysiloxane is reacted with one or more of a monofunctional unsaturated alkali or alkene and one or more of an olefinically or acetylenically unsaturated monofunctional epoxide and subsequently with a mixture containing carboxylic acids
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24/92 short chain, preferably functionalized hydroxy, and long chain carboxylic acids, preferably hydroxy free, and optionally later with primary or secondary amines, where optionally carboxylic acids can be obtained by esterification or partial amidation of anhydrides carboxylic acid with alcohols or the corresponding amines;
(g) a functionalized SiH polysiloxane is reacted with one or more of a monofunctional unsaturated alkali and one or more of an olefinically or acetylenically unsaturated monofunctional epoxide and subsequently with long chain carboxylic acids, preferably free of hydroxy, and optionally later with the primary or secondary amines, where optionally carboxylic acids can be obtained by esterification or partial amidation of carboxylic acid anhydrides with alcohols or the corresponding amines;
(h) a functionalized SiH polysiloxane is reacted with one or more of a monofunctional unsaturated alkali or alkene and one or more of an olefinically or acetylenically unsaturated monofunctional epoxide and one or more of an olefinically or acetylenically unsaturated fatty acid ester and subsequently with an mixture, containing short chain carboxylic acids, preferably functionalized hydroxy, and long chain carboxylic acids, preferably hydroxy free, and optionally later with primary or secondary amines, where optionally carboxylic acids can be obtained by partial esterification or amidation of carboxylic acid anhydrides with alcohols or the corresponding amines;
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25/92 (i) a functionalized SiH polysiloxane is reacted with one or more of an olefinically or acetylenically unsaturated monofunctional epoxide and one or more of an olefinically or acetylenically unsaturated fatty acid ester and subsequently with a mixture containing short-chain carboxylic acids , preferably functionalized hydroxy, and long-chain carboxylic acids, preferably hydroxy-free, and optionally later with primary or secondary amines, where optionally carboxylic acids can be obtained by esterification or partial amidation of carboxylic acid anhydrides with alcohols or the corresponding amines;
(j) a functionalized SiH polysiloxane is reacted with one or more of an unsaturated monofunctional alkali or alkene and one or more of an olefinically or acetylenically unsaturated monofunctional epoxide and one or more of an olefinically or acetylenically unsaturated fatty acid ester and subsequently with acids short-chain carboxylics, preferably functionalized hydroxy, and optionally later with primary or secondary amines, where optionally carboxylic acids can be obtained by esterification or partial amidation of carboxylic acid anhydrides with corresponding alcohols or amines;
(k) a functionalized SiH polysiloxane is reacted with one or more of an olefinically or acetylenically unsaturated monofunctional epoxide and one or more of an olefinically or acetylenically unsaturated fatty acid ester and subsequently with short chain carboxylic acids, preferably functionalized hydroxy, and optionally later with primary or secondary amines, where optionally carboxylic acids can be obtained by
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26/92 partial esterification or amidation of carboxylic acid anhydrides with alcohols or the corresponding amines;
(l) a functionalized SiH polysiloxane is reacted with one or more of a monofunctional unsaturated alkali or alkene and one or more of an olefinically or acetylenically unsaturated monofunctional epoxide and one or more of an olefinically or acetylenically unsaturated fatty acid ester and subsequently carboxylic acids long-chain, preferably hydroxy-free, and optionally later with primary or secondary amines, where optionally carboxylic acids can be obtained by partial esterification or amidation of carboxylic acid anhydrides with alcohols or the corresponding amines;
(m) a functionalized SiH polysiloxane is reacted with one or more of a monofunctional unsaturated alkali or alkene one or more of an olefinically unsaturated monofunctional epoxide and one or more of an acetylenically unsaturated fatty acid ester and subsequently with long chain carboxylic acids, preferably hydroxy free, and optionally later with primary or secondary amines, where optionally carboxylic acids can be obtained by partial esterification or amidation of carboxylic acid anhydrides with alcohols or the corresponding amines;
(n) a functionalized SiH polysiloxane is reacted with one or more of an acetylenically unsaturated monofunctional epoxide and one or more of an acetylenically or olefinically unsaturated fatty acid ester and subsequently long chain carboxylic acids, preferably free of hydroxy, and optionally later with primary or secondary amines, where optionally the
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27/92 carboxylic acids can be obtained by partial esterification or amidation of carboxylic acid anhydrides with alcohols or the corresponding amines;
(o) a functionalized SiH polysiloxane is reacted with one or more of an olefinically unsaturated monofunctional epoxide and one or more of an acetylenically unsaturated fatty acid ester and subsequently with long chain carboxylic acids, preferably free of hydroxy, and optionally later with primary or secondary amines, where optionally carboxylic acids can be obtained by partial esterification or amidation of carboxylic acid anhydrides with alcohols or the corresponding amines;
(p) an aminofunctional polysiloxane is reacted with esters of short-chain and / or long-chain carboxylic acids, lactones, carboxylic acid halides or silyl esters of carboxylic acid;
(q) an aminofunctional polysiloxane is reacted with lower and / or long-chain alkyl or aryl-substituted carbonates;
(r) an aminofunctional polysiloxane is reacted with epoxides substituted by short and / or long chain alkyl.
[032] The starting point for the synthesis consists particularly of the functional SiH polysiloxanes, where hydrogen is formally substituted by substituents corresponding to R9.
[033] Since these SiH-functional polysiloxanes are not commercially available, they can be produced by known processes, for example, by equilibration (Silicone, Chemie und Technologie, Vulkan-Verlag Essen 1989, p. 82-84).
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28/92 [034] It is in accordance with the invention to use several different SiH-functional polysiloxanes.
[035] In one embodiment, epoxy groups are first introduced from SiHfunctional polysiloxanes, preferably by hydrosilylation reaction with olefinically or acetylenically unsaturated epoxy compounds.
[036] Thus, preferred functional epoxy precursor structures are formed.
' ₀ -
[037] Alternatively, appropriate aminosiloxanes can be produced through known catalyzed alkaline equilibration reactions, which, for example, comprise:
-CH2CH2CH2NH2
-CH2CH2CH2NHCH3
-CH2CH2CH2NHCH2CH2NH2 substituents on D-siloxane units (Silicone,
Chemie und Technologie, Vulkan Verlag Essen 1989, p.28-30). These reactive functionalized siloxane intermediate stages can be converted to a further stage in the polysiloxane compounds according to the invention, for example, by reaction with carboxylic acids under the formation of amines, with the functional epoxy compounds under the formation of amino alcohols or with hydroxylated alcohols, also under the formation of amino alcohols.
[038] To introduce hydrophilic elements
R91, the intermediate stages reactively functionalized
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29/92 mentioned above, for example, are reacted with
-hydroxyl groups comprising carboxylic acids or
-at least one carboxylic acid group and at least one hydroxyl group comprising
- esters or
- lactones.
[039] The esterification of epoxides with carboxylic acids, if necessary in the presence of catalysts such as, for example, tertiary amines, is known (E.Sung, W.Umbach, H. Baumann, Fette Seifen Anstrichmittel 73, 1971, p. 88).
[040] The formation of amide through the reaction of amines with esters and lactones is well known (Organikum, VEB Deutscher Verlag der Wissenschaften, 17th Edition, 1988, p. 408-412; DE OS 4318536 Example 22).
[041] The hydroxyl groups comprising carboxylic acids are monohydroxy and polyhydroxy carboxylic acids, for example, glycolic acid, lactic acid, Y-hydroxy butyric acid, 2,3-dihydroxy propionic acid, α, β-dihydroxy butyric acid, a, Y- dihydroxy butyric acid, gluconic acid, glucopyranosilarabinoic acid. The use of long-chain hydroxy carboxylic acids, for example, ricinoleic acid is possible, but less preferred.
[042] It is within the limits of the invention to use acids to carry out the reaction as an acid or also as an ester, particularly methylester or lactone, for example, Y-butyrolactone, gluconic acid lactone and glucopyranosilarabinoic acid lactone.
[043] The use of long-chain lactone, for
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For example, 5-dodecanolide is possible, but less preferred.
[044] The use of acids with more than one function of carboxylic acid, for example, mucic acid or its epimer glucaric acid is possible, but less preferred. Using difunctional carboxylic acids a specific increase in molecular weight can be achieved through partial cross-linking.
[045] Alternatively, at least one group and carboxylic acid esters comprising at least one hydroxyl group can be used for the introduction of the hydrophilic residue R91. A preferred embodiment includes monoesters of dicarboxylic acids. Examples of dicarboxylic acids are oxalic acid, succinic acid, maleic acid, fumaric acid, phthalic acid, terephthalic acid. It is within the limits of the invention to convert carboxylic acids in the form of their anhydrides.
[046] The alcohols used for esterification are at least dihydroxy-functional alcohols with a chain length of C3 atoms. Examples of alcohols are 1,2-propane diol, 1,3-propane diol, glycerol, pentaerythrol and sorbitol.
[047] The R91 group can also be synthesized through a hydrosilylation reaction of a polyhydric monoether, where the rest of the hydroxy groups are blocked by a protecting group, such as a ketal group or a trimethylsilyl group. Preferred precursors are monoalylether, for example, of glycerol or polyglycerols.
[048] It is within the limits of the invention to convert alcohols, in the form of their epoxides, for example, propylene oxide, with acids.
[049] The use of tri- and carboxylic acids
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Higher functional 31/92 is possible, but less preferred. An example is trimellitic acid, which can be converted to a non-carboxylic acid ester structure starting particularly from trimellitic acid anhydride chloride.
[050] Another example is pyromelitic dianhydride acid, which preferably forms a dicarboxylic diester acid structure. As already discussed, an increase in molecular weight through partial cross-linking can be achieved using difunctional carboxylic acids.
[051] To introduce hydrophilic elements
R91 of the reactively functionalized intermediate stages mentioned above, particularly the functionalized epoxy intermediate stages, can be partially reacted with, for example,
- hydroxyl groups comprising primary or secondary amines or
- at least one primary or secondary amino group and at least one hydroxyl group comprising amino amides.
[052] Hydroxyl groups containing primary or secondary amines are, for example, ethanol amine, diethanol amine, 1-amino- (2-hydroxy) propane, 1-amino- (3 hydroxy) propane, 1-amino-2,3- dihydroxy propane, glucamine, N-methyl-glucamine.
[053] Amino amides are preferably reaction products of primary-secondary amines with lactones, particularly hydroxylated lactones. Examples of preferred primary-secondary amines are H2NCH2CH2NHCH2CH2NH2 and H2NCH2CH2CH2NHCH2CH2CH2NH2. Examples of preferred lactones are Y-butyrolactone, δ-gluconolactone,
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32/92 lactone of glucopyranosilarabinoeic acid. The production of such an amino amide complex is defined in DE 4318536, Examples 11 to
18.
[054] To introduce the lipophilic element R92, the above reactively functionalized intermediate stages are preferably reacted with
- carboxylic acid or
- at least one carboxylic acid group comprising esters.
[055] In the context of the invention, fatty acids are understood to be monocarboxylic functional carboxylic acids. Examples of suitable fatty acids are acetic acids, caprylic acid, 2-ethylcaproic acid, lauric acid, tetraláuric acid, hexaluric acid, octaláuric acid, unláuric acid, oleic acid, linoleic acid, linolenic acid.
[056] For the introduction of lipophilic residues R92 preferably monocarboxylic functional carboxylic acids with> C10 atoms are used, as these have a particularly strong ability to bond solubility in the oil phase.
[057] For the introduction of hydrophilic residues R91 preferably mono or polycarboxylic functional carboxylic acids with <C10 atoms or hydroxy functional carboxylic acids are used.
[058] Carboxylic acids used as precursors for R92 or R91 can be introduced through a reaction with an epoxide group attached to a siloxy group or over a hydrosilylation reaction with esters comprising carbon double or triple bonds and groups
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33/92
SiH. It is preferred to use allyl esters of monocarboxylic carboxylic acids. It is within the scope of the invention to use acids to carry out the reaction as an acid or also as an ester, particularly methyl ester, for example, methyl ester of oleic acid.
[059] The use of acids with more than one function of carboxylic acid, for example lauric diacid or succinic acid dodecenyl and their anhydrides respectively, is possible, but less preferred. The use of difunctional carboxylic acids can specifically achieve an increase in molecular weight through partial cross-linking.
[060] Alternatively, at least one carboxylic group comprising ester can be used for the introduction of residue R9.
[061] They are monoesters of dicarboxylic acids in a preferred embodiment. Examples of dicarboxylic acids are oxalic acid, succinic acid, maleic acid, fumaric acid, phthalic acid, terephthalic acid. It is within the scope of the invention to convert carboxylic acids in the form of their anhydrides. The alcohols used for esterification are preferably monohydroxy functional alcohols. Examples of alcohols are ethyl alcohol, 2-propanol, 2-ethylhexanol, dodecanol, undecenol, isotridecanol, hexadecanol, oleyl alcohol, octadecanol, mono and oligopropoxylates of the functional monohydroxy alcohols, HOCH2CH2 (CF2) 5CF3 and HO (CH2) 6 ) 3.
[062] It is within the scope of the invention to convert alcohols in the form of their epoxides, for example, dodecene oxide, such as diacids.
[063] The use of tri and carboxylic acids
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34/92 higher functional is possible, but less preferred. An example is trimellitic acid, which, starting with trimellitic acid anhydride chloride, can be converted into a monocarboxylic diester structure. Another example is pyromelitic acid dianhydride, which preferably forms a dicarboxylic diester acid structure. As already discussed, a specific increase in molecular weight can be achieved by using difunctional carboxylic acids through partial cross-linking.
[064] It is within the scope of the invention to react the respective intermediate epoxy or amino polysiloxane functional stages with one or more hydrophilic components and / or one or more lipophilic components for the introduction of the R9 groups.
[065] It is preferred in one embodiment of the invention to react the respective intermediate stages of the respective epoxy or amino functional siloxane with a mixture of the hydrophilic and lipophilic acid components. In a further preferred embodiment of the invention, the respective intermediate stages of the respective epoxy or amino functional siloxane are first reacted with the hydrophilic acid components and then the lipophilic acid components are added to the reaction preparation. The reverse order, which consists of the first reaction with the lipophilic acid component and then the addition of the hydrophilic acid component, is also possible.
[066] The application of the concepts mentioned above in relation to
- various components of hydrophilic and / or lipophilic acids
- multiple strings in addition
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35/92 leads the chemically composed component parts differently which ultimately enter the finished product.
[067] The molar ratio of the epoxide amine respectively: the component amounts of the acid component is 1: 1 to 1: 2, preferably 1: 1 to 1: 1.5, especially 1: 1 to 1: 1.1 .
[068] In order to regulate the characteristics of the polysiloxane copolymers according to the invention as W / O emulsifiers, the ratios of the individual structural elements are significant. These can, within the scope of the invention, be adapted to the chemical structure of the oil to be emulsified and to the desired proportion of the water phase: oil phase.
[069] An increase in the proportion of conventional unmodified siloxane units tends to result, for example, in better compatibility with siloxane-based oil phases.
[070] An increase in the proportion of hydrophilic units tends to result, for example, in better compatibility with the water phase.
[071] An increase in the proportion of lipophilic units tends to result, for example, in a better compatibility with oil phases based on hydrocarbon.
[072] It is within the scope of the invention to carry out the reactions for the production of the polysiloxane compounds according to the invention without solvents or in the presence of solvents. Suitable solvents are, for example, esters or mixtures comprising ester, such as ethyl acetate, butyl acetate, methoxypropyl acetate,
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36/92 aromatic ester substances, such as, for example, dicyclopentadiene acetic acid esters, ether or mixtures comprising ether, such as dibutyl ether, aromatic ether substances, such as, for example, methyl dicyclopentadiene ether, alcohols, such as ethyl alcohol, e-propanol, propylene glycol and glycerol. The optional choice of a solvent and its required amount is among other things dependent on the structure of the component acid and the intended purpose of the application. Thus, it may be advantageous to carry out the synthesis in a solvent now, which is, for example, a component of the final W / O formulation.
[073] The reactions are preferably carried out on a temperature scale between room temperature and 180 ° C, preferably room temperature and 150 ° C, more preferably 50 ° C and 150 ° C.
[074] The reaction times are determined by the complete reaction of the epoxy and amino groups. These can be easily observed using appropriate methods (IR, NMR, Titration).
PREFERRED MODALITIES [075] Changing the ratios R ⁹¹ to R ^{92 it} is possible to change the solubility characteristics considerably. If the ratio R ⁹¹ : R ⁹² is the same or greater than 1 in particular effects such as reduced dynamic friction and antistatic characteristics on hydrophobic surfaces can be achieved.
[076] This characteristic of the more hydrophilic compounds, compared to pure polydimethylsiloxanes, an improved solubility in polar solvents, such as alcohols, other hydrocarbons comprising oxygen,
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37/92 sulfur and nitrogen.
[077] A further preferred embodiment of the invention relates to the use of the modified hydrophilic / lipophilic polysiloxane compounds according to the invention for the production of viscosity regulators, antistatic agents, components for the silicone rubbers that can be attached to elastomers, by peroxides or by hydrosylation (platinum catalyst) and by the connection in this case to the modification of the surface characteristics, modification of the mixture of the diffusion of gas, liquids, etc., modify the expansion characteristics of the silicone elastomers, for example, compared to water, respectively.
[078] In particular, use as an additive for the hydrophilization of polydimethylsiloxane elastomer surfaces generally, or as a viscosity regulator in silicone rubbers comprising unbound silicic acid is preferred. Here, silicone rubbers mean that in particular the modeling or sealing of low-viscosity masses is known as Room-Temperature Vulcanization - “Room- Temperature-Vulcanizatiorí '(RTV) component 1 or 2 rubbers. For these 1C or 2 rubbers -V RTV adjustment of the high or low flow limit depending on the use is desired. The organomodified polydimethylsiloxane according to the invention is applied in the amounts of 0.5 to 15% by weight relative to the silicone rubbers during the production of the rubber composition or on the surface of the elastomer.
[079] They can also be applied to the surface as lubricants by dipping, pouring or spreading and can be partially removed again by rubbing or
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38/92 rinsing after use or configuration.
[080] A further preferred embodiment of the invention relates to the use of the modified hydrophilic / lipophilic polysiloxane compounds according to the invention for the production of altering agents for thermoplastic plastic materials such as polyolefins, polyamide, polyurethanes, poly (meth) acrylates and polycarbonates. This includes, in particular, the use or production of modified low temperature impact resistance agents.
[081] For this the polysiloxane compounds can be used directly as modifying agents or, meanwhile, be prepared beforehand by producing the main mixture, composition or batch in an appropriate form.
[082] An additional use of the copolymers according to the invention includes coatings, such as anti-caking, non-viscous coatings, coatings and compatible fabric materials.
[083] Other uses include anti-fog coatings or precursors for the production of these for the headlight glass (internal surface), the plates for residential buildings, cars or medical equipment as well as additives for cleaning agents, detergents or preservatives, such as an additive for toilet articles, as a coating agent for wood, paper and cardboard, as a mold release agent, as a biocompatible material for medical uses such as contact lenses, as a coating agent for textile fibers or textile fabrics, as a coating agent for natural materials such as, for example, leather and furs
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39/92 or the wool.
[084] The hydrophilic / lipophilic modified polysiloxanes can also serve as cosmetic articles, toilet articles, paint additives, detergent additives, foaming formulations and in textile processing.
[085] In a preferred use the hydrophilic / lipophilic modified polysiloxanes with R ⁹¹ : R ⁹² <1 is applied for the defoaming of diesel oil and diesel fuels respectively, where the concentration of silicone in diesel oil is less than 5 ppm, more preferably less than 2 ppm.
[086] A further preferred use is the application of the hydrophilic / lipophilic modified polysiloxanes with R ⁹¹ : R ⁹² <1 as a foam stabilizer in cold or warm hardening hard polyurethane or flexible foam, preferably in the amount of 0.5 to 5 wt%, more preferably 1 to 3 wt% per polyol component applied with the additional blowing agents whose boiling points are between -60 and 50 ° C, such as, in particular, cyclopentane, iso-pentane, and / or iso-butane. The ratio of (g + f2): f1 is preferably 1 to 15: 1, more preferably 2 to 9: 1. The index f2 of the lipophilic units is 0 to 60, more preferably 1 to 10. The sum of the units g + f2 + f1 of the siloxy is 15 to 200, more preferably, 30 to 150 measured as the average degree of polymerization Pn based on the number of the medium medium Mn of a chromatic determination of the molar weight of the gel (GPC). Linear polyorganosiloxanes with siloxy units, which are indicated with g, f 1, f2 and k, are preferably used. In
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40/92 another preferred use of modified hydrophilic / lipophilic polysiloxanes with R ⁹¹ : R ⁹² <1 is the defoaming of diesel oils or hydrocarbon fuels respectively, where the concentration of silicone in the diesel oil is less than 5 ppm, more preferably less than 2 ppm.
[087] These uses include the production of softening agents for textile fibers for the treatment of textile fibers before, during and after washing of agents for the modification of natural and synthetic fibers, such as hair, cotton fibers and synthetic fibers, such as polyester fibers and polyamide fibers, as well as blended fabrics, coating agents for textile materials, as well as formulations comprising detergents, such as detergents or cleaning agents.
[088] The preferred amounts in this case are 0.1 to 5% by weight, 0.3 to 3% by weight, corresponding to the mass of the fiber.
[089] The preferred field of application for the polysiloxanes according to the invention is use as an emulsifier for the production of water-in-oil emulsions.
[090] In another preferred embodiment of the invention the hydrophilic / lipophilic polyorganosiloxanes modified with R ⁹¹ : R ⁹² <1 of the invention are used as an adjuvant in pesticides, agriculture, horticulture, peat, ornamental and forestry or emulsifiers in compositions used there. The preferred siloxanes for this use are linear polyorganosiloxanes with siloxies with M and D units, which are indicated as g, f1, f2, jek, where j + k = 2 eg, f 1, f2 = 1-100 on average. Preferably each of the groups R ⁹¹ and R ⁹² are present
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41/92 and the molar ratio of siloxy units comprising R ⁹¹ hydrophilic to R ⁹² lipophilic groups is <1. These siloxane compounds preferably showing a low value of HLB <8 improve the dispersibility of the active materials and stabilize the emulsions when diluted with more water. Various applications of pesticides require the addition of an adjuvant to the spray mixture to provide wettability and spread to leaf surfaces. Usually this adjuvant is a surfactant, which can perform a variety of functions, such as increasing spray drip retention on leaf surfaces that are difficult to wet, increasing spreading to improve spray coverage, or to provide herbicide penetration into the cuticle of the plant. These adjuvants are supplied either as an additive in a side reservoir or used as a component in pesticidal formulations.
[091] Typical uses for insecticides include agricultural, horticultural, peat, ornamental, residential and gardening, veterinary and forestry applications.
[092] The pesticidal compositions of the present invention also include at least one insecticide, where the compounds of the present invention are present in an amount sufficient to deliver between 0.005% and 2% at the final concentration of use, as a concentrate or diluted in a mixture the reservoir. Optionally, the pesticidal composition can include excipients, co-surfactants, solvents, foam control agents, deposit aids, traction retardants, biologicals, micronutrients, fertilizers and the like. The term insecticide means any compound used to destroy pests, for example,
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42/92 rodenticides, insecticides, miticides, fungicides, and herbicides. Illustrative examples of insecticides that can be used include, but are not limited to, growth regulators, photosynthesis inhibitors, pigment inhibitors, mitotic inhibitor, lipid biosynthesis inhibitors, cell wall inhibitors, and cell membrane cleaver. The amount of insecticide used in the compositions of the invention varies with the type of insecticide used. More specific examples of insecticide compounds that can be used with the compounds or compositions of the invention are, but are not limited to, herbicides and growth regulators, such as: phenoxy acetic acids, phenoxy propionic acids, phenoxy butyric acids, acids benzoic, triazines and striazines, substituted urea, uracil, bentazone, demedipam, methazole, fenmedipham, pyridate, amitrol, clomazone, fiuridone, norflurazone, dinitroanilines, isopropalin, orizalin, pendimethaline, sulfamethyl, dylamine, prodiamine, triamine, triamine -methyl, phenoxaprop-ethyl, fluazifop-pbutil, haloxifop-methyl, quizalofop, setoxidim, diclobenil, isoxabene, and bipyridyl compounds.
[093] Fungicidal compositions that can be used with the compounds of the present invention include, but are not limited to, aldimorf, tridemorf, dodemorf, dimetomorf; flusilazole, azaconazole, cyproconazole, epoxiconazole, furconazole, propiconazole, tebuconazole and the like; imazalil, thiophanate, benomyl carbenda2 im, clorothialonil, dichloran, trifloxystrobin, fluoxystrobin, dimoxystrobin, azoxystrobin, furcaranil, prochloraz, flusulfamide, famoxadone, captan, maneb, mancozeb, dodicina, dodina, and metala.
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43/92 [094] The insecticidal, larvicidal, miticidal and ovicidal compounds that can be used with the composition of the present invention, but are not limited to: Bacillus Thuringiensis, spinosad, abamectin, doramectin, lepimectin, pyrethrins, carbaryl, primicarb, aldicarb, methomyl, amitraz, boric acid, chlordimeform, novaluron, bistriflurone, triflumuron, diflubenzuron, imidacloprid, diazinon, aphosphate, endosulfan, kelevan, dimetoate, azinfos-ethyl, azinfos-methyl, izoxation, chlorpyrine, chlorpyrine, chlorpyrine , cypermethrin and the like.
[095] The insecticide can be a liquid or a solid. If it is a solid, it is preferable since it is soluble in a solvent, or in the compounds of the present invention, before application, and the compounds of the invention can act as a solvent, or surfactant for such solubility or additional surfactants can perform this function.
Agricultural Excipients:
[096] Standard buffers, preservatives, carriers and other excipients known in the art can also include the compounds of the invention.
[097] Solvents can also be included in compositions comprising the compounds of the present invention. These solvents are in a liquid state at room temperature (25 ° C). Examples include water, alcohols, aromatic solvents, oils (i.e., mineral, vegetable oil, silicone oil, and so on), lower alkyl esters of vegetable oils, fatty acids, ketones, glycols, polyethylene glycols, diols, paraffinic, and so on. The particular solvents would be 2,2,4 - trimethyl, 1,3-pentanediol and alkoxylated versions (especially
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44/92 ethoxylated) of these as illustrated in the US patent
5,674,832 incorporated herein by reference, or N-methylpyrrolidone.
Co-surfactants:
[098] In addition, co-surfactants, which have short-chain hydrophobes that do not interfere with super-spreading as described in US patents US 5,558,806; US 5,104,647; and US 6,221,811 is included here by reference.
[099] Useful co-surfactants here include nonionic, cationic, anionic, amphoteric, zwitterionic, polymeric surfactants, or any mixture thereof. Surfactants are typically hydrocarbon-based, silicone-based or fluorocarbon-based.
[0100] Useful surfactants include alkoxylates, especially ethoxylates, containing block copolymers that include copolymers of ethylene oxide, propylene oxide, butylene oxide, and mixtures thereof; alkylarylalkoxylates, especially ethoxylates or propoxylates and their derivatives that include alkyl phenol ethoxylate; arylarylalkoxylates, especially ethoxylates or propoxylates and their derivatives; amine alkoxylates, especially amine ethoxylates; fatty acid alkoxylates; fatty alcohol alkoxylates; alkyl sulfonates; alkyl benzene and naphthalene alkyl sulfonates; sulfated fatty alcohols, amines or acid starches; acid esters of sodium isethionate; esters of sodium sulfosuccinate; sulfated or sulfonated esters of fatty acid; petroleum sulfonates; N-acyl sarcosinates; alkyl polyglycosides; alkyl ethoxylated amines; and so on.
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45/92 [0101] Specific examples include acetylenic alkyl diols (SURFONYL® from Air Products), pyrrilodone-based surfactants (eg SURFADON®-LP 100 - ISP), 2-ethyl hexyl sulfate, isodecyl ethoxylates (eg example, RHODASURF® DA 530 -Rhodia), ethylene diamine alkoxylates (TETRONICS® - BASF), and ethylene oxide / propylene oxide copolymers (PLURONICS® - BASF) and Gemini surfactants (Rhodia).
[0102] Preferred surfactants include ethylene oxide / propylene oxide (EO / PO) copolymers; amine ethoxylates; alkyl polyglycosides; ethoxylates, oxo-tridecyl alcohol, and so on.
Use in coatings and paints:
[0103] In a more preferred embodiment of the invention the hydrophilic / lipophilic modified polyorganosiloxanes of this invention are used in coating compositions. Generally, coating formulations can include the compounds of the present invention as a wet or surfactant agent for emulsification, component compatibility, leveling, increased flow, de-aeration and the reduction of surface defects. In addition, the compounds of the invention can provide improvements in the cured or dry film, such as improved abrasion resistance, anti-blocking, and hydrophilic and hydrophobic properties. Coating formulations can exist as solvent borne coatings, water borne coatings and powder coatings.
[0104] The coating components can be used as: Architectural coatings; OEM product coatings such as coatings
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46/92 automotive and spiral coatings; special purpose coatings such as industrial maintenance coatings and marine coatings; Typical resins include polyester polymers, alkyds, acrylics, epoxies, and polyurethanes.
[0105] A more preferred use is the application of modified hydrophilic / lipophilic polysiloxanes with predominantly hydrophilic characteristics R ⁹¹ : R ⁹² > 1 as an additive for hydrophilisation, improved wettability and antistatic finish of the thermoplastic polymer and elastomeric surfaces. The preferred amounts in this case are 0.2 to 15% by weight, 0.5 to 10% by weight relative to the thermoplastic or elastomeric composition. Another preferred application of modified hydrophilic / lipophilic polysiloxanes is the use in heat-sensitized coagulation of rubber latex for the manufacture, for example, of gloves, condoms, balloons and other latex-based articles, where the solubility in the latex emulsion decreases when heated to> 35 ° C; it prevents premature clotting at room temperature.
[0106] Another preferred application is the use as demulsifiers in the oil and gas industry for better and faster separation of crude oil and water, as an anti-blocking additive, anti-embedding to prevent water droplets on surfaces, resistance to de-characterization, as a lubricant or lubricating additive, as fabric softeners or in fabric softener composition as a self-emulsifying alkylene oxide-free softener or as a stable cutting emulsifier in textile treatment formulations, as foam stabilizers for aqueous foams in detergents, liquids for washing dishes and
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47/92 in cleaning products for general purposes, such as additives for hydrophilization of plastic and thermoplastic or elastomeric surfaces and the improved wettability of thermoplastic or elastomeric surfaces.
Production of water-in-oil emulsions (W / O emulsions):
[0107] The preferred ester units according to the invention comprising polysiloxanes can in this case be used here alone as well as in combination of various structures and, even more so, in combination with other emulsifiers. Emulsifiers W / O generally comprise a less external polar phase, which is referred to here as an oil phase, an internal polar phase, which is here called an aqueous phase and an emulsifier or emulsifiers. Various raw materials can be introduced into the polar phase, respectively non-polar.
Water phase [0108] In this regard, the aqueous phase of the described W / O emulsions may comprise water, alcohols and polyols such as, for example, glycerin and its ester, ethylene glycol, diethylene glycol and its ester, propylene glycol, dipropiplenoglycol, butylene glycol and its ester, ethanol, isopropanol and sorbitol as well as combinations of these. In addition, soluble substances, such as, for example, salts, active substances, preservatives, inorganic and organic dyes, oxidants and pH regulators can be introduced into the aqueous phase.
Emulsifiers [0109] The following emulsifiers can be used together with the polysiloxane compounds according to the invention in combinations of these respectively. The
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48/92 emulsifiers which comprise the polyalkylene oxide groups can also be used in the process, where they can be applied in small amounts using the polysiloxane compounds according to the invention, or they can be completely dispensed with. Anionic emulsifiers such as metal soaps are fatty acid salts of polyvalent metals, such as, for example, stearates, myristates, laureates or magnesium, zinc and aluminum oleate.
[0110] Amphoteric emulsifiers are phospholipids and proteins such as lecithin and lactoproteins.
[0111] Nonionic emulsifiers such as fatty alcohols, absorption or ointment bases based on different raw materials such as petroleum gel, paraffin, mineral oil, beeswax, lanolin, cholesterol and alcohols with a high molecular weight and the esters of these, lecithin and eucerite, (the alcohol purified from wool wax) are produced, alcohol from wool wax and its fractions (in particular, cholesterol), partial esters of multivalent alcohols with more fatty acids sterols as well as oleate, ricinolates and lanolates of sorbitan, pentaerythrit, glycerin and polyglycerin.
- Silicone emulsifiers such as PEG-x / PPG-y dimethicone (x = 0 - 100, y = 0 - 100, where x + y> 1)> alkyl PEG-x / PPG-y dimethicone (alkyl = alkyl residues or linear and branched aryl with 2-50 carbon atoms, x = 0 - 100, y = 0 -100, x + y 2: 1), poly-glyceryl-x disyloxane dimethicone (x = 2 - 10), polyglyceryl- x polydimethylsiloxy-ethyl dimethicone (x = 2 - 10) and alkyl polyglyceryl-x polydimethylsiloxyethyl dimethicone; alkyl = alkyl residues
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49/92 respectively linear and branched aryl with 2-50 carbon atoms, x = 2 -10).
[0112] Particularly suitable emulsifiers, which can be used alone or together in any combination with the polysiloxanes according to the invention, are glyceryl oleate, glyceryl isostearate, sorbitan trioleate, sorbitan sesquioleate, sorbitan sesquiisostearate, sorbitan oleate sorbitan, sorbitan isostearate, methyl glucose dioleate, methyl glucose sesquistearate, dicocoil pentaerythrityl distearyl citrate, pentaerythrityl tetralaurate, polyglyceryl-2, polyglyceryl-3, polyglyceryl-3-sesquiisostearate , polyglyceryl oleate4, PEG-4 oleate, PEG-6 dioleate, PEG-5 soy sterol, Peg-7 hydrogenated castor oil, olet-2, olet-3, isosteraride2, isostearyl diglyceryl succinate, trioleyl phosphate, calcium stearoyl lactylate, laurylmethylone copolyol and cetyl dimethicone copolyol.
Oil phase [0113] In this consideration the oil phase may comprise an oil or, in the meantime, combinations of two or more oils and also other oil-compatible cosmetic raw materials. The oils that are used in cosmetics differ in their polarity. These may, according to the literature (Cosmetology - Theory and Practice; Volume 3, page 31, table 10,2; Editors: K. Schrader, A. Domsch; Verlag für chemische Industrie, 2005), are described by their tension of surface (also defined as the polarity index). A particular feature of polysiloxane compounds of
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50/92 according to the invention is that, in this respect, they are able to stabilize emulsions with a wide range of oil polarities. In this regard, the preferred oil polarities represented by the polarity index are on a scale between 4 and 55 mN / m, with the scale between 13 and 39 mN / m being particularly preferred. In this regard, it is self-evident that the values of the polarities of the oil are in the preferred scale or in the most preferred scale and can be achieved by mixing or mixing two or more components. The following materials are named as possible components for the oil phase, as an example, but not limited, where the materials can be introduced alone or in combinations of different components. Triglycerides are, for example, avocado oil, peanut oil, hydrogenated peanut oil, oat oil, mink oil, olive oil, castor oil, hydrogenated castor oil, cocoa butter oil, soybean oil , sunflower oil, sesame oil, peach kernel oil, wheat germ oil, macadamia oil and oenothera biennis oil.
[0114] Silicones such as linear and cyclic volatile polydimethyl siloxane (hexamethyl disiloxane, ethyl-, propyl butyl-disiloxane, diethyl-, dipropyl- and dibutyl disiloxane, octamethyl disyloxane, octamethyl trisiloxane, pentamethylmethylsilane , various propyl- and dipropyltrisiloxanes, various butyl trisiloxanes, various pentyl trisiloxanes, various hexyl trisiloxanes, cyclotetrasiloxanes, cyclopentasiloxanes, cyclohexyloxanes, cycloheptasiloxanes and other further variations), dimethicone (viscosity 3-100 kPa.sa 25 ° C as well as mixtures of viscosities of 25 ° C as well as mixtures of viscosities of 25 ° C as well as mixtures of viscosities it's from
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51/92 different solutions of dimethicones in silicones and volatile hydrocarbons), modified phenyl silicones (phenyltrimethicones and phenyldimethicones with different viscosities as well as mixtures thereof), modified alkyl and aryl silicones (caprylmethylones, stearyl-, cetyl, cetearyl-, C26- C28-alkyl C30-C45-alkyl methicones and dimethicones, phenylpropyl dimethylsiloxysilicate), modified silicone polyether (INCI: PEG-x / PPG-y dimethicones), the functional amino silicones (amo-dimethicones), modified fluoroalkyl silicones, silicone resins (trimethylsiloxides, trimethylsiloxy polymethylsilsesquioxanes, diisostearyl trimethylolpropane siloxysilicates and trifluoropropyl / trimethylsiloxysilicates), silicone acrylates (dimethicone PEG-8 Polyacrylates) and silicone elastomers and silicone crosspolymers (cross-polymer dimethylene / dimethyl vinyl ether, cross-methyl dimethyl ether, polyethylene dimethyl 30, dimethicone, cetearyl crosspolymer dimethicone, dimethicone / PEG-10/15 crosspolymer, PEG-15 / lauryl dimethicone crosspolymer, PEG-10 / lauryl dimethicone crosspolymer, dimethicone / polyglycerin-3 crosspolymer, lauryl dimethicone / polyglycerin-3 crosspolymer and dimethylethyl vinyl chloride).
[0115] Hydrocarbons such as paraffin oils with various viscosities, petroleum gel, paraffin (hard and soft), microcrystalline waxes, ozocerites, ceresin, squalenes, squalanes and volatile, linear and / or branched hydrocarbons with 5 to 20 carbon atoms.
[0116] Fatty alcohols as consistency regulators such as, for example, lauryl-, myristyl-cetyl
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52/92, oleyl- and stearyl alcohol, and mono- and diglycerides of fatty acids. Natural waxes and fats and those based on natural products such as Japanese wax, lanolin, cocoa butter, cetyl palmitate, beeswax (natural and synthetic), carnauba wax, candelilla wax and jojoba oil. Fatty acid esters of monoalcohols such as isopropyl myristates, isopropyl palmitate, isopropyl stearates, oleyl oleate, decyl oleate and cetearyl ethylhexanoates.
Stabilizers [0117] A particularly important group of the substance for use in the external phase consists of the so-called stabilizers, which can be very important for the production of stable emulsions. These substances are usually incorporated in the oil phase and form gel-like structures. Particularly suitable for this purpose are fatty alcohols such as, for example, lauryl, myristyl, cetyl, oleyl and stearyl alcohol, hydrocarbon and polymer gels such as, for example, petroleum jelly, polyethylene, paraffin wax (a microcrystalline wax), wax esters such as, for example, cetyl palmitate, beeswax and substitutes, carnauba wax and candelilla wax, lanolin, multivalent fatty acid metal soaps such as, for example, zinc and magnesium ricinoleate as well as alkaline lanoates, calcium and magnesium soaps and multivalent metal stearate, bentonite and modified bentonite soaps, EO-PO blocking copolymers such as, for example, PEG22 / dodecylglycol copolymer, PEG- copolymer 40 / dodecylglycol, and the types of poloxameters from BASF, silicone waxes such as
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53/92 comostearyl, cetyl, cetearyl, C26-C28-alkyl, C30-C45alkyl methicone and dimethicone and silicone elastomers and silicone crosspolymers such as, for example, dimethicone / vinyl dimethicone crosspolymer, C30C45-alkyl cetearyl dimethicone crosspolymer, cross-polymer cetearyl dimethicone, cetearyl dimethicone, dimethicone crosspolymer, cetearyl dimethicone crosspolymer, dimethicone crosspolymer / PEG-10/15, PEG-15 / lauryl dimethicone crosspolymer, PEG-10 / lauryl dimethicone crosspolymer, dimethicone / polyglycerin-3 polypolymerine-crosspolymer, crosspolymer-3, crosspolymer 3 and dimethicone / vinyltrimethyl siloxysilicate crosspolymer.
[0118] Consistency agents [0119] Consistency agents are monovalent, primary alcohols with a carbon chain length of more than 4 carbon atoms such as lauryl, myristyl, cetyl, stearyl, oleyl and cetyl alcohol as well as mixtures thereof, mono and diglycerides of fatty acids, natural waxes and those with natural bases, such as Japanese wax (Wax japonica), lanolin, cocoa butter, cetyl palmitate, beeswax (white, bleached and synthetic), carnauba wax, wax of candelilla and jojoba oil, fatty acid esters of monovalent alcohols such as isopropyl myristates, isopropyl palmitates, isopropyl stearates, oleyl oleates, decyl oleates and cetearyl ethylhexanoates, silicone waxes such as stearyl, cetyl-, cetearyl-, cetearyl-, -alkyl, C30-C45-alkyl methicones and dimethicone and silicone elastomers and silicone crosspolymers such as, for example, dimethicone / vinyl dimethicone crosspolymer, C30-C45-alkyl ce polymer loomyl dimethicone, cetearyl dimethicone crosspolymer, dimethicone crosspolymer, cetearyl dimethicone crosspolymer,
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54/92 dimethicone / PEG-10/15 crosspolymer, PEG-15 / lauryl dimethicone crosspolymer, PEG-10 / lauryl dimethicone crosspolymer, dimethicone / polyglycerin-3 crosspolymer, lauryl dimethicone / polyglycerin-3 crosspolymer and dimethicone / vinyltrimethyl cross-polymer.
Active substances or active ingredients for skin care products [0120] The active ingredients suitable for the production of W / O emulsions with the polysiloxane compounds according to the invention are propolis or propolis wax, which is used because of its antimicrobial and antioxidant effect of the flavonoids included in this, royal jelly, which is suitable as a consolidation additive because of its high content of vitamins, amino acids, sugars, enzymes and biopeptin, collagen to stabilize the moisture of the corneal layer , collagen hydrolyzate to improve skin and mucous membrane tolerance, elastin hydrolyzate (hydrolyzed elastin) alone or in combination with soluble collagen to improve skin elasticity through hydration, phytosterols (unsaponized avocado oil, oil of unsaponified soybeans) for a positive effect on the connective tissue of the skin, vitamins such as vitamin A (retinol, retinyl acetate, retinyl palmitate and retinyl propionate) for the treatment and prevention of dry, rough, cornified skin and aging and atrophy of the transpiring glands, beta-carotene which in the form of provitamin A exhibits the same effects than vitamin A, vitamin E (tocopherol, tocopherol acetate and tocopherol nicotinate) because of their antioxidant effect, improving the surface structure of the skin, increasing the properties of
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55/92 corneal moisture retention, anti-inflammatory effect, accelerating epithelialization of superficial wounds, increase in skin enzyme activity and boosting skin blood circulation, pyridoxine or pyridoxine HCI (vitamin B6) for the treatment of pellagra particularly in combination with fatty acids, niacin or niacin essential starches for the treatment of pellagra and skin changes caused by deficiency symptoms, biotin (vitamin H) for the treatment of hair loss and anti-seborrheic vitamin panthenol or dpantenol and calcium panthenate for improving and increasing the moisture retention properties of the skin, for inhibiting inflammation and irritation, for stimulating epithelialization (accelerated healing of wounds), and for improving the conditioning of damaged hair , vitamin C (ascorbic acid, sodium ascorbate and ascorbyl palmitate) because of its antioxidant effect and for reducing the formation of nitrosamine, essential fatty acids such as vitamin F (linoleic acid (e) linolenic acid (e) archidonic acid), vitamin-F-glycerol ester (glyceryl linolenic acid (e) glyceryl linolenic acid (e) glyceryl archidonic acid ) and Vitamin-F-ethyl ester (ethyl linolenic acid (e) ethyl linolenic acid (e) ethyl archidonic acid) for the treatment of deficiency symptoms caused by a deficiency of linoleic acid such as dryness, scaly skin itching, ceramide to increase moisture in the corneal layer, anti-inflammatory substances such as bisabolol, chamomile extracts, panthenol, glycyrrhizinic acid, hazelnut extract and certain peptides, keratin hardening substances that react with proteins in the upper layers of the skin and so they seal it to some extent,
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56/92 as formaldehyde or also aluminum potassium sulphate, aluminum hydroxide, aluminum lactate, aluminum chlorohydride sodium acetate and the aluminum circonium tetrachlorohydrate-glycine complex that obstruct capillaries and also sweat glands , antimicrobial substances, hyperemic substances that stimulate blood circulation such as essential oils such as mountain pine oil, lavender, rosemary, juniper, horse chestnut extract, birch leaf extract, extract cornflower, ethyl acetate, nettle extract, camphor, menthol, nicotinic acid and derivatives, peppermint oil, eucalyptus oil and turpentine oil, liposome to increase skin penetration, glycolipids such as glyco -glycerol lipids, glycosfingolipids (neutral glycosfingolipids, sulfates and gangliosides) and cerebrosides, lipoproteins and zinc oxide for action the anti-inflammatory.
Micropigments [0121] Micropigments are also called UV blockers. They are characterized by the fact that they are insoluble in oil and in the aqueous phases of the emulsion and offer UV protection that reflect and disperse UV light regardless of their size. In this regard, attention should also be paid to the fact that as the particle size decreases, the whitening effect of pigment residues on the skin is reduced. Mainly magnesium oxide, calcium carbonate, magnesium carbonate, bentonite, titanium dioxide and zinc oxide are used. Titanium dioxide and zinc oxide are used more often, with the use of zinc oxide being favored because of their effect
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57/92 additional anti-inflammatory. These latter organic compounds are also used as micropigments. An example of this is bis-ethylhexyloxyphenyl triazine (Tinosorb S, Ciba). When using micropigments it is important that they are easily dispersed in the incorporated phase in order to ensure an ideal skin coverage, which then results in more effective UV protection. For this, the aforementioned pigments are also used as surface treatment materials or as pre-dispersions. For the production of dispersions all substances, which have already been mentioned above, while the components for the oil phase or the aqueous phase can be used. The surface treatment also results from these substances. In addition, for surface treatment dimethicone, simethicone and silicones and their cyclic emulsions, hexamethyldisiloxane, hexamethyldisiloxane, alkyl- and aryl-functionalized silicones with alkyl or aryl residues comprising 2 to 50 carbon atoms , methyl-, alkyl- or aryl-functionalized alkyl or halogen silanes with alkyl- or aryl residues comprising 2 to 50 carbon atoms or polyether-modified silicones are often used. Micropigments can be introduced alone or in combinations. A combination with the following UV filters to improve UV protection is also possible.
UV filters [0122] UV filters are substances that selectively absorb UVA and / or UVB radiation. Depending on the requirement profile, UV filters can be combined together and / or with micropigments. List of suitable UV filters can be found at International
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Cosmetic Ingredient Dictionary and Handbook Eleventh Edition
2006, Volume 3, page 2881 and “Cosmetology - Theory and
Practice Volume 3, pages 161 - 168; Editors: K. Schrader, A.
Domsch; Verlag fur Chemische Industrie, 2005.
Tanning agents of the skin [0123] In this respect, examples of the substances that tan the skin to be named are dihydroxyacetone, DHA and nut extract.
Skin whitening agents [0124] Skin whitening agents are used to treat age spots or freckles. The active substances that can be used in producing cosmetic compositions with the aid of the polysiloxane compounds according to the invention are hydroquinone, ascorbic acid, various peroxides, 5-hydroxy-2- (hydroxymethyl) - 4H-pyran-4-one, 4hydroxyphenyl- PD-glucopyranosides and plant extracts. Other substances can be found in the “International Cosmetic Ingredient Dictionary and Handbook Eleventh Edition 2006, Volume 3, page 2814.
Dyes and dyes pigments [0125] A list of appropriate dyes and pigments can be found in “International Cosmetic Ingredient Dictionary and Handbook, Eleventh Edition 2006, Volume 3, pages 2670 - 2677 and“ Cosmetology - Theory and Practice Volume 3, pages 222 - 223; Editors: K. Schrader, A. Domsch; Verlag fur Chemische Industrie, 2005.
Other fillers [0126] This is understood to include particles and solids that influence light reflection and increase the diffuse proportion of light in this regard.
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59/92 reflected. Thus, a soft focus effect is achieved in a way that allows the skin to appear smoother and less wrinkled. Suitable additives are polymethyl silsesquioxanes, bornitride, nylon (Nylon-12), polyethylene (plastic powder), polyethylene / PTFE, dimethicone / vinyl dimethicone (e) lauroyl lysine crosspolymer, dimethicone / vinyl dimethicone (e) aluminum crosspolymer / dimethicone crosspolymer / dimethicone vinyl (e) titanium dioxide, dimethicone / vinyl dimethicone crosspolymer, dimethicone / vinyl dimethicone crosspolymer (e) silicone, polymethyl methacrylate, silicone and silicone silylate. These substances are also suitable for the absorption of sebum, which reduces the shine of the skin.
Insect repellent agents [0127] Suitable ingredients are, among other things, ethyl butylacetylaminopropionate, diethyl toluamide and the insect repellent IR3535 from Merck.
Deodorants and antiperspirants [0128] The ingredients suitable for the production of antiperspirants with the polysiloxane compounds of the invention are fragrances, fragrance oils, triclosan, chlorhexidine, sodium carbonate and hydrogen, clathrates such as zinc ricinolate and others, ion exchangers , triethylcitrate, o-acyl serine, acyl actylate, aluminum hydroxychloride, aluminum sodium hydroxyl chloride, aluminum hydroxychloride with propylene glycol and zirconium salts such as, for example, the zB tetrachlorohhydrex of aluminum and GLY zirconium and aluminum trichlorohydride and GLY GLY zirconium. Other active antiperspirant substances are mentioned in “Cosmetology - Theory and Practice Volume 2, pages 268 - 269; Editors: K. Schrader, A. Domsch; Verlag fur
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Chemische Industrie, 2005. A special form of antiperspirants are clear gels. These can be produced with the polysiloxane compounds according to the invention by matching the refractive indices of the water and oil phases.
Ingredients for hair products [0129] The polysiloxane compounds according to the invention are also suitable for the production of W / O emulsions for hair care. In particular leave-in conditioners such as hair conditioners, hair gels, styling gels, hair forming agents, hair bleaching agents and hair coloring substances should be mentioned here. The ingredients used in these compositions can be found in Cosmetology - Theory and Practice Volume 2; Editors: K. Schrader, A. Domsch; Verlag fur Chemische Industrie, 2005.
Additives [0130] Additives as ingredients for cosmetic formulations are defined in: A. Domsch, Die kosmetischen Praparate, Verlag fur chem. Industrie, 4. Auflage, 1992; and in: Kosmetikjahrbuch 1995, Verlag fur Chemische Industrie, 1995.
[0131] The following suitable additives are exemplary, however, non-limiting, as ingredients for formulations: inorganic and organic acids, bases and buffers, salts, alcohols such as, for example, ethanol, isopropanol, ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, ether glycol and glycerin, thickeners, stabilizers for emulsions such as, for example, xanthan gum, emollients, preservatives, foam stabilizers, anti
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61/92 foaming agents, pearls and opacifiers such as, for example, distearatoglycol and titanium dioxide, collagen hydrolyzate, keratin hydrolyzate, silk hydrolyzate, anti-dandruff agents such as, for example, zinc piritio, salicylic acid, selenium disulfide, sulfur and tar preparations, polymer emulsifiers, vitamins, dyes, UV filters, bentonites, perfume oils, fragrances, styling polymers, moisturizers, plant extracts and still natural natural and identical raw materials.
[0132] The preferred use of the substances according to the invention is the use of the production of cosmetic compositions for the treatment of substances comprising keratin, such as human skin or human hair. In this regard, the specific cosmetic formulations for the use of the polysiloxane compounds according to the invention are creams and lotions for the care of the face and body, creams and lotions for protection against UV radiation, self-tanners, skin illuminators and products for the treatment of hyperpigmentation such as age spots and freckles (skin whiteners), makeup removers, pigmented products like rims, eyeliner, lipsticks and liquid makeup (liquid foundation), deodorants and antiperspirants like, for example, roll-ons, conditioners and emulsions “leave in for hair such as, for example, deep hair conditioners and cures and gels, hair styling products such as hair gels, styling mousses and hair creams and waxes, hair bleaching agents, hair styling agents hair formation, hair curling agents, hair coloring substances. The substances according to the invention are suitable for the
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62/92 use as W / O emulsions and can of course also be used in multiple emulsions.
[0133]
A typical W / O emulsion according to the invention is produced so that the oil phase is supplied and the emulsifier or emulsifiers are added to the oil phase. Subsequently, the water phase is added by stirring. This process can, depending on the composition of the phases, be carried out in cold temperature as well as in hot temperature. Subsequently, it is possible to proceed with a homogenization step in order to possibly increase stability. With this procedure all the oil-compatible substances mentioned above are dissolved or dispersed in the oil phase, while the hydrophilic substances are incorporated in the water or polar phase.
[0134]
In this regard, a general W / O emulsion according to the invention has the following composition in weight%:
0.1 - 20% polysiloxanes according to the invention
10-60% oil phase
0-10% additives
- 89.9% water phase [0135]
The following compositions have been found to be particularly advantageous for the use of polysiloxane compounds according to the invention in cosmetic formulations:
[0136]
A typical composition for a W / O cream according to the invention, which, however, does not limit the invention, comprises the following components in% by weight:
0.2-10% polysiloxane compounds according to the invention
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- 5% co-emulsifiers
- 55% oil or combination of oils
-10% stabilizers
-10% consistency agents
0-20% active substances or active ingredients for skin care products
0-10% other fillers
0 -10% adjuvants up to 100 % completed with Water.[0137] A composition specific W / O cream, the which, however, does not limit the invention, understands the
following components in% of weight:
0.5-6% polysiloxane compounds according to the invention
- 3% co-emulsifiers
- 40% oil or combination of oils
- 5% stabilizers
- 5% consistency agents
0-20% active substances or active ingredients for skin care products
0-10% other fillers
-10% adjuvants up to 100% supplemented with water.
[0138] A typical composition of a W / O lotion according to the invention, which, however, does not limit the composition of the invention, comprises the following components in weight%:
0.2-10% polysiloxane compounds according to the invention
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- 5% co-emulsifiers
- 50% oil or combination of oils
0-10% stabilizers
-10% consistency agents
- 20% active substances or active ingredients for skin care products
0-10% other fillers
-10% adjuvants up to 100% supplemented with water.
[0139] A specific composition of a W / O lotion, which, however, does not limit the invention, comprises the following components in weight%:
0.5 - 6% polysiloxane compounds according to the invention
- 3% co-emulsifiers
- 40% oil or combination of oils
- 5% stabilizers
- 5% consistency agents
- 20% active substances or active ingredients for skin care products
0-10% other fillers
0-10% adjuvants up to 100% supplemented with water.
[0140] A typical composition of sunscreen W / O according to the invention, which, however, does not limit the invention, comprises the following components in weight%:
0.2-10% polysiloxane compounds according to the invention
- 5% co-emulsifiers
10-50% oil or combination of oils
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0-10% stabilizers
-10% consistency agents
0-20% micropigments
0-20% UV filters
- 20% active substances or active ingredients for skin care products
0-10% other fillers
-10% adjuvants up to 100% supplemented with water.
[0141] A specific composition of sunscreen W / O, which, however, does not limit the invention, comprises the following components in% by weight
0.5 - 6% polysiloxane compounds according to the invention
0 - 3 O% co-emulsifiers 1040 % oil or combination of oils 0 - 5 O% stabilizers 0 - 5 O% consistency agents
- 20% micropigments
- 20% UV filters
- 20% active substances or active ingredients for skin care products
0-10% other fillers
-10% adjuvants up to 100% supplemented with water.
[0142] A typical composition of a W / O sunscreen lotion, which, however, does not limit the invention, comprises the following components in weight%:
0.2-10% polysiloxane compounds according to the invention
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- 5% co-emulsifiers
- 45% oil or combination of oils
-10% stabilizers
- 1 0% consistency agents
- 20% micropigments
- 20% UV filters
- 20% active substances or active ingredients for skin care products
- 1 0% other fillers
-10% adjuvants up to 100% supplemented with water.
[0143] A specific composition of a W / O sunscreen lotion, which, however, does not limit the invention, comprises the following components in weight%:
0.5 - 6% polysiloxane compounds according to the invention
0 - 3 O% co-emulsifiers 1540 % oil or combination of oils 0 - 5 O% stabilizers 0 - 5 O% consistency agents
- 20% microparticles
- 20% UV filters
- 20% active substances or active ingredients for skin care products
0-10% other fillers
-10% adjuvants up to 100% supplemented with water.
[0144] A typical self-tanning composition
W / O, which, however, does not limit the invention, comprises the following components in% by weight:
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0.2-10% polysiloxane compounds according to the invention
- 5% co-emulsifiers
- 50% oil or combination of oils
0-10% stabilizers
- 1 0% consistency agents
0.5 -15% skin tanning agents
- 10% active substances or active ingredients for skin care products
- 1 0% other fillers
-10% adjuvants up to 100% supplemented with water.
[0145] A specific composition of a W / O self-tanner, which, however, does not limit the invention, comprises the following components in% by weight:
0.5 - 6% polysiloxane compounds according to the invention
- 3% co-emulsifiers
- 40% oil or combination of oils
- 5% stabilizers
- 5% consistency agents
-15% skin tanning agents
- 10% active substances or active ingredients for skin care products
0-10% other fillers
-10% adjuvants up to 100% supplemented with water.
[0146] A typical composition of a W / O skin illuminator, which, however, does not limit the invention, comprises the following components in weight%:
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0.2-10% polysiloxane compounds according to the invention
- 5% co-emulsifiers
- 50% oil or combination of oils
- 1 0% stabilizers
-10% consistency agents
0.5 -15% skin lightening agents
- 1 0% active substances or active ingredients for skin care products
- 1 0% other fillers
-10% adjuvants up to 100% supplemented with water.
[0147] A specific composition of a W / O skin illuminator, which, however, does not limit the invention, comprises the following components in weight%:
0.5 - 6% polysiloxane compounds according to the invention
- 3% co-emulsifiers
- 40% oil or combination of oils
- 5% stabilizers
- 5% consistency agents
-15% skin lightening agents
- 10% active substances or active ingredients for skin care products
0-10% other fillers
0-10% adjuvants up to 100% supplemented with water.
[0148] A typical makeup composition for liquid skin W / O, which, however, does not limit the invention, comprises the following components in weight%:
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0.2-10% polysiloxane compounds according to the invention
- 5% co-emulsifiers
- 50% oil or combination of oils
0-10% stabilizers
- 10% consistency agents
- 20% UV filters
- 20% dyes and dyeing pigments
- 10% active substances or active ingredients for skin care products
0-10% other fillers
- 10% adjuvants up to 100% supplemented with water.
[0149] A specific composition of a makeup for liquid skin W / O, which, however, does not limit the invention, comprises the following components in weight%:
0.5 - 6% polysiloxane compounds according to the invention
- 3% co-emulsifiers
- 40% oil or combination of oils
- 5% stabilizers
- 5% consistency agents
- 1 5% dyes and dye pigments
- 20% UV filters
- 10% active substances or active ingredients for skin care products
0-10% other fillers
0-10% adjuvants up to 100% supplemented with water.
[0150] A typical W / O mask composition, a
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70/92 which, however, does not limit the invention, comprises the following components in weight%:
0.2-10% polysiloxane compounds according to the invention
- 5% co-emulsifiers
- 50% oil or combination of oils
- 20% stabilizers
- 20% consistency agents
- 20% dyes and dyeing pigments
- 1 0% other fillers
-10% adjuvants up to 100% supplemented with water.
[0151] A specific W / O mask composition, which, however, does not limit the invention, comprises the following components in% by weight:
0.5 - 6% polysiloxane compounds according to the invention
- 3% co-emulsifiers
- 40% oil or combination of oils
- 20% stabilizers
2- 20% consistency agents
4-15% dyes and dyeing pigments
- 10% active substances or active ingredients for skin care products
0-10% other fillers
-10% adjuvants up to 100% supplemented with water.
[0152] A typical W / O antiperspirant composition, which, however, does not limit the invention, comprises the following components in% by weight:
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0.2-10% polysiloxane compounds according to the invention
- 5% co-emulsifiers
- 50% oil or combination of oils
- 20% stabilizers
- 20% consistency agents
- 60% anti-perspirant (active substance)
-10% adjuvants up to 100% supplemented with water.
[0153] A specific composition of antiperspirant W / O, which, however, does not limit the invention, comprises the following components in% by weight:
0.5 - 6% polysiloxane compounds according to the invention
- 3% co-emulsifiers
- 40% oil or combination of oils
- 20% stabilizers
- 20% consistency agents
- 50% antiperspirant (active substance)
- 10% active substances or active ingredients for skin care products
-10% adjuvants up to 100% supplemented with water.
[0154] A typical composition for hair treatment according to the invention, which, however, does not limit the invention, for conditioner (soften and improve the potential of combining moisture and dryness), to stylize hair, to soften, curling, lightening or coloring the hair comprises the following components in% of weight:
0.2-10% polysiloxane compounds according to
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- 5% co-emulsifiers
- 50% oil or combination of oils
- 20% stabilizers
- 20% consistency agents
0.1 - 20% ingredients for hair products
-10% adjuvants up to 100% supplemented with water.
Examples [0155] The following examples are intended to explain the invention in greater detail, without, however, limiting it.
Example 1 [0156] Production of a copolymer comprising lactic acid ester units - lauric acid ester and stearic acid ester.
[0157] 1.33 g (14.76 mmol) DL- lactic acid, 5.49 g (27.41 mmol) lauric acid, 3.00 g (10.3 mmol) stearic acid,
0.4 g triethyl amine and 20.18 g (52.5 mmol epoxy groups) of a siloxane of structure
[0158] 1 methoxypropylacetate is dissolved in 70 g and heated for 12 hours at 120 ° C.
After
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73/92 after the reaction, all volatile components in a vacuum are removed at 71 ° C / 20mbar with 2 hours. The solid contents are 96.4% (15min / 160 ° C).
[0159] A brown and clear polymer of structure
with
O
O
is obtained.
[0160] The molar ratio of hydrophilic residues according to R ⁹¹ based on lactic acid ester units to lipophilic residues according to R ⁹² based on lauric acid and stearic acid ester units is here approximately 7: (13 +5) = approximately 1: 2.6. The molar ratio of the hydrophilic or lipophilic modified siloxide units, which comprises residues R ⁹¹ as well as R ⁹² , to unmodified siloxy units, which comprises only residues R8, is here approximately 25/70 = approximately 1: 2.8.
Example 2 [0161] Production of a copolymer comprising glycolic acid ester units - and acid ester
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74/92 stearic.
0.98 g (12.87 mmol) glycolic acid, 11.57 g (40.66 mmol) stearic acid
0.5 g triethyl amine and 17.45 g (53.5 mmol of epoxy groups) of a siloxane of structure
[0162]
They are dissolved in 70 g of 1-methoxy-2propanol and heated for 12 hours at
120 ° C. After the reaction is complete, all volatile components in the vacuum are removed
71 ° C / 20mbar with 5 hours. Solid contents represent 93.8 (15min / 160 ° C).
[0163]
A light brown, wax-like polymer
is obtained.
molar ratio of residues
A hydrophilic according to R ⁹¹ based on glycolic acid ester units for lipophilic residues according to
R ⁹² based on
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75/92 units of stearic acid here is approximately 6:19 = approximately 1: 3.2.
[0164] The molar ratio of the hydrophilic or lipophilic modified siloxide units to the unmodified siloxide units is here approximately 25/51 = approximately 1: 2.0.
Example 3 [0165] Production of a copolymer comprising units of the glycerol ester of succinic acid and ester of stearic acid
11.3 g (122 mmol) glycerol, 12.3 g (122 mmol) succinic acid anhydride and 0.24 g triethyl amine are dissolved in 23.6 g 1-methoxypropyl acetate and heated to room temperature for 3 hours at 90 ° C. The complete opening of the anhydride ring under the formation of the semester was established by NMR mass spectroscopy.
4.72 g (12.3 mmol of acidic groups) of the succinic acid semester solution, 16.56 g (51.2 mmol of epoxy groups) of a siloxane of structure
11.08 g (38.9 mmol) of stearic acid and 0.54 g triethyl amine are dissolved in 67.64 g methoxypropyl acetate and heated for 12 hours at 120 ° C.
[0166] After the reaction is complete, all volatile components in a vacuum are removed at 71 ° C / 20mbar with
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76/92 hours. Solid contents represent 86.7% (15 min / 160 ° C).
[0167] A light brown polymer, like wax structure
is obtained. The molar ratio of hydrophilic residues corresponding to R ⁹¹ based on succinic acid ester units to lipophilic residues R ⁹² based on stearic ester units is approximately 6: 19 = approximately 1: 3.2. The molar ratio of the hydrophilic or lipophilic modified siloxide units to the unmodified siloxide units is here approximately 25/51 = approximately 1: 2.0.
Example 4 [0168] Production of a copolymer comprising lactic acid ester units, lauric acid ester, stearic acid ester and N-methyl glucamine units
0.6 g (7mmol) DL- lactic acid, 3.0 g (15 mmol) lauric acid, 0.85 g (3 mmol) stearic acid, 0.1 g triethyl amine and 8.23 g (25 mmol of groups epoxy) of a siloxane structure
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they are dissolved in 29.8 g of propylene glycol monomethyl ether and heated for 26 hours at 120 ° C.
[0169] At this time point a conversion of 95.8% epoxy groups was found.
[0170] Subsequently, 0.49 g (2.5 mmol) of Nmethylglucamine is added and the reaction is continued for 10 hours at 120 ° C.
[0171] A 100% epoxide conversion is found.
[0172] After the reaction is complete, all volatile components in a vacuum are removed at 70 ° C / 20 mbar with hours.
[0173] A light brown polymer of approximate structure
with
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is obtained.
The molar ratio of the hydrophilic residues corresponding to R ⁹¹ based on the lactic acid ester units and N-methyl glucamine units to the lipophilic residues R ⁹² based on the lauric acid ester units and N-methyl glucamine units is here approximately 8:17 approximately 1: 2.1. The molar ratio of respectively hydrophilic modified lipophilic siloxide units to the unmodified siloxide units is here approximately 25/52 = approximately 1: 2.1.
Example 5
Production of W / O emulsions [0174] W / O emulsions of the following compositions are produced, where in each case a solution of glycerin and NaCl in water was added slowly to an oil premix and the W / O emulsifier according to the invention.
Emulsion W / O Example-No, 5.1 5.2 5.3 5.4
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Mineral oil (g) 2, 5 D5 (g)2.5 Isopropyl myristate (g) 2.5Castor oil (g) 2.5 Ex Emulsifier,1(g) 0.11 0.11 0.11 0.11 Water (g) 7, 1 7.1 7.1 7.1 Glycerin (g) 0, 2 0.2 0.2 0.2 NaCl (g) 0.1 0.1 0.1 0.1 Appearance of W / O emulsion creamy, highlyviscous, light oil tank creamy, highly viscous creamy, low viscosity Highly viscous, lightweight water tank
W / O Emulsion 5, 5 5, 6 5.7 5, 8 Mineral oil (g) 2, 5 D5 (g)2.5 Isopropyl myristate ⁽ g) 2.5Castor oil (g) 2.5 Ex Emulsifier,2(g) 0.11 0.11 0.11 0.11 Water (g) 7, 1 7.1 7.1 7.1 Glycerin (g) 0, 2 0.2 0.2 0.2 NaCl (g) 0.1 0.1 0.1 0.1 Appearance of emulsion w / o creamy, highly viscous highly viscous creamy, low viscosity Highly viscous, lightweight water tank
D5 = decameticiclopentasiloxane
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W / O Emulsion 5, 9 5.10 5.11 5.12 Mineral oil (g) 2.5 D5 (g)2, 5 Isopropyl myristate (g) 2.5Castor oil (g) 2.5 Emulsifier Ex, 3 (g) 0.11 0.11 0.11 0.11 Water (g) 7, 1 7.1 7.1 7.1 Glycerin (g) 0, 2 0.2 0.2 0.2 NaCl (g) 0, 1 0.1 0.1 0.1 Emulsion appearancew / o creamy, highly viscous creamy, very highly viscous creamy, low viscosity, light oil deposit highly viscous, lightweight water tank
W / O Emulsion 5.13 5.14 5.15 5.16 Mineral oil (g) 2.5 D5 (g)2, 5 Isopropyl myristate (g) 2.5Castor oil (g) 2.5 Emulsifier Ex, 4 (g) 0.11 0.11 0.11 0.11 Water (g) 7.1 7, 1 7.1 7.1 Glycerin (g) 0.2 0, 2 0.2 0.2 NaCl (g) 0.1 0, 1 0.1 0.1 Emulsion appearance creamy, creamy, creamy, highly w / o highly much low slimy,slimy highly viscosity deposit of slimylight water
[0175] The data from formulations 5.1 to 5.16 indicate that the emulsifiers according to the invention comprise a wide spectrum in relation to the oil phase
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81/92 tolerable for emulsification. Non-polar oils (mineral oils), semi-polar oils (isopropyl myristate, D5 (decamethylcyclopentasiloxane)) and strong polar oils (castor oil) can be used.
Example 6 (starting material)
Production of allyl ester of stearic acid
569 g (2 mol) of stearic acid are supplied under N2 and heated to 80 ° C.
262 g (2.2 mol) SOCI2 are added dropwise and the mixture is heated for 2 hours at 95 ° C. Subsequently, all volatiles up to 95 ° C / 20 mbar are distilled.
[0176] For 30 minutes 139.2 g (2.4 mol) of allyl alcohol are added dropwise at 80 ° C and the mixture is stirred for an additional hour at this temperature.
[0177] The crude product is washed with 500 ml of a 20% NaHC03 solution followed by 3 times 500 ml of deionized water and then air dried. Yield 584 g of stearic acid ally:
O
[0178] Using this starting material a lipophilic residue corresponding to R ^{92 can} be introduced into the SiH-functional starting polysiloxanes through hydrosylation.
Example 7 (starting material)
Production of a ester of lauric acid and propylated allyl alcohol
600 g (3 mol) lauric acid are supplied under N2 and heated to 60 ° C.
392.7 g (3.3 mol) SOCI2 are added in
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82/92 drip for 30 minutes and the mixture is heated for 2 hours at 70 ° C. Subsequently, all volatiles up to 70 ° C / 20 mbar are distilled.
650 g of lauric acid chloride are obtained.
[0179] In a separate bottle 471 g (3.12 mol) of an ally propoxylated alcohol of structure
are supplied under N2 and heated to 80 ° C. During 1 hour 650 g of lauric acid chloride are added in a drip and the mixture stirred for another 2 hours. All components boiling to 150 ° C / 20 mbar are distilled.
[0180] Yield of 934 g of an ester of structure:
[0181] Using this starting material a lipophilic residue corresponding to R ⁹² can be introduced into SiH-functional starting polysiloxanes via hydrosilylation.
Example 8
Production of a copolymer comprising oleic acid ester units and N-methyl glucamine units
14.12g (50mmol) of oleic acid, 0.5g triethyl amine and 31.58g (50mmol of epoxy groups) of a siloxane structure
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they are dissolved in 70g of 1-methoxy-2-propanol and heated for 12 hours at 120 ° C. Conversion is 90.9% determined by 1H-NMR.
[0182]
Subsequently
0.98 g (5 mmol) of Nmethylglucamine is added and the reaction is continued for 8 hours at 120 ° C. After the reaction is complete, the volatile components in a vacuum are removed at 70 ° C / 20 mbar for 2 hours.
[0183]
Conversion is 100% determined by 1 H-NMR.
[0184]
A light brown oily polymer of approximate structure
with
is obtained, where R ⁹¹ : R ⁹² is 2: 23.
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Example 9
Production of W / O emulsions [0185] W / O emulsions of the following compositions are produced, where in each case a titration solution (II) consisting of water, glycerin and NaCl was added slowly to a premix (I) of the oil and the W / O emulsifier, for example, the polysiloxane according to the invention. This titration solution was prepared by mixing 355 g of water with 10 g of glycerin and 5 g of NaCl.
W / O Emulsion 9.1 9, 2 9, 3 9.4 9.5 D5 (g) 25 25Mineral oil (g)25 Isopropyl myristate (g) 2525 EmulsifierExample 8 (g) 1.1 1.1 1.1 1.1 1.1 Titration Solution(g) 70 70 70 120 120 Stability ofEmulsion 14 days RT * 4 5 5 5 5 Viscosity ofEmulsion 14 daysRT ** 4 5 2 5 5 Sensitivity ofskin***45 5 Scattering ****55 5
Emulsion Stability 14 days RT (room temperature) *: Scale from 1 to 5 with 1 = complete separation in oil and water and 5 = completely homogeneous.
Emulsion Viscosity 14 days RT **: Scale 1 a with 1 = low viscosity close to water and 5 = stable under
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Skin sensitivity ***: Scale from 1 to 5 with 1 = strongly adhesive to 5 = soft, soft.
Scattering ****: Scale from 1 to 5 with 1 = rubber type, high resistance to 5 = easily spread without resistance.
[0186] The data indicates that when using the emulsifiers according to the invention, large amounts of water can be removed by the emulsion formulations. Specifically, an increase in the water content leads to an increase in viscosity and thus also the stability of the formulation is improved. This applies to systems based on type D5 siloxane as well as the system based on isopropyl myristate oil. Skin sensitivity and spreadability are very good.
Example 10
Production of a copolymer comprising stearic acid ester units and N-methyl glucamine units
85.7 g (300mmol) of stearic acid, 1.25 g of triethyl amine and 164.9 g (300 mmol of epoxy groups) of a siloxane of structure
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86/92 [0187] They are dissolved in 107 g of propylene glycol monomethyl ether and heated for 10 hours at 120 ° C. Using these reaction conditions, a 97.1% conversion of epoxy groups is found by 'H-NMR control. Subsequently, 5.84 g (30 mmol) of N-methylglucamine are added and the reaction is continued for 4 hours at 120 ° C. The conversion of the epoxy group is 100%. After the reaction is complete, the volatile components in a vacuum are removed at 70 ° C / 20 mbar for 2 hours. A pale grayish yellow polymer of medium structure
with
It is obtained, where R ⁹¹ : R ⁹² is 0.7: 24.3.
Example 11
Production of a copolymer comprising stearic acid ester units, oleic acid ester and diethyl amine units
21.62 g (76 mmol) of stearic acid, 6.78 g (24 mmol) of oleic acid, 0.5 gd and triethyl amine and 53.67 g (100 mmol of epoxy groups) of a siloxane of structure
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[0188] They are dissolved in 35 g of propylene glycol monomethyl ether and heated for 10 hours at 120 ° C. Subsequently, 0.73g (10 mmol) of diethyl amine is added and the reaction is continued for 4 hours at 120 ° C. The conversion of the epoxy group is 100%. After the reaction is complete, the volatile components in a vacuum are removed at 70 ° C / 20 mbar for 2 hours.
[0189] A pale yellow polymer of medium structure
with
are obtained, where R ⁹¹ : R ⁹² is 1: 24.
Example 12
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Production of a copolymer comprising two different ester units, for example, stearic acid ester units and lactic acid units and
N-methyl glucamine
a) 22 g (68.9 mmol) of propargyl ester of oleic acid and 10.5 g (91.8 mmol) of allylglycidylether are heated in the atmosphere of N2 at 80 ° C. 2g (9.18 mmol SiH) of a SiH oil of structure M-D55-D ^H 25-M and subsequently 0.1 g of 1% Pt containing the solution of HbPtCle in ethanol was added by dripping. The temperature rose to 140 ° C and for an additional 0.5 hour 23g (105.6 mmol SiH) of a SiH oil of structure M-D55-D ^H 25-M was added by dropping. The reaction is continued for 2 hours at 140 ° C. Subsequently, volatile components up to 150 ° C / 20mbar were removed. A yellowish and cloudy viscous oil is obtained.
b) 2.82 g (10 mmol) of oleic acid, 0.9 g (10 mmol) of lactic acid, 0.46 g of triethyl amine and 23.37 g (2 mmol) of epoxy units and acid ester units oleic acid comprising the siloxane according to step a) are dissolved in 63 g of monomethyl ether propylene glycol and heated for 10 hours at 120 ° C. Subsequently, 0.98 g (5 mmol) of Nmethylglucamine is added and the reaction is continued for 4 hours at 120 ° C. The conversion of the epoxy group is 100%.
[0190] After the reaction is complete, the volatile components are removed under vacuum at 70 ° C / 20 mbar for 2 hours. A pale brown polymer is obtained is obtained, which shows 1 H-NMR signals from propenylester groups attached to the silicone atoms, reaction products from propyloxy groups epoxy groups attached to the silicone atoms with lactic acid, oleic acid and with N-methylglucamine.
Example 13
Production of a copolymer comprising two
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89/92 different units, for example, oleic ester units and N-methyl glucamine units
a) 15 g (47 mmol) of propargyl ester of oleic acid and 3.5 g (31 mmol) of propargyl glycidyl ether are dissolved under N2 in 70 ml of toluene and subsequently 0.1 g of 1% Pt containing the H2PtCI6 solution in ethanol is added via drip. The mixture is heated to 140 ° C. During 0.5 hours a mixture, consisting of 17.23 g (75 mmol SiH) of a SiH oil of structure M-D55-D ^H 25-M and 30 g of toluene is added by dripping and the temperature is maintained by 4 hours.
[0191] Subsequently, volatile components up to 150 ° C / 20mbar are removed. A yellowish brown liquid is obtained.
101.41 g (5 mmol) of oleic acid, 0.2 g of triethyl amine and 7 g (0.566 mmol) of epoxy units and ester units of oleic acid comprising the siloxane according to step a) are dissolved in 30g of propylene glycol monomethyl ether and heated for 10 hours at 120 ° C. Subsequently, 0.14 g (0.7 mmol) of N-methylglucamine is added and the reaction is continued for 4 hours at 120 ° C. The conversion of the epoxy group is 100%. After the reaction is complete, the volatile components are removed under vacuum at 70 ° C / 20 mbar for 2 hours. A dark brown pasty polymer is obtained, which shows' H-NMR signals from propenylester groups attached to the silicone atoms, reaction products of the epoxy group linked by the propenyloxy groups to the silicone atoms with N-methylglucamine.
Example 14
Production of a copolymer comprising oleic acid ester units, lactic acid and N-methyl glucamine
0.45 g (5 mmol) of lactic acid, 0.2 g of triethyl
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90/92 amine and 7 g (0.566 mmol) of epoxy units and oleic acid ester units comprising siloxanes obtained according to example 13 a) are dissolved in 30 g of propylene glycol monomethyl ether and heated for 10 hours at 120 ° C. Subsequently, 0.98 g (5 mmol) of N-methylglucamine is added and the reaction is continued for 4 hours at 120 ° C. The conversion of the epoxy group is 100%. After the reaction is complete, the volatile components are removed under vacuum at 70 ° C / 20 mbar for 2 hours. A brown pasty polymer is obtained, which shows ¹ H-NMR signals of propenylester groups attached to the silicone atoms, reaction products of the epoxy group linked by a propenyloxy group to the silicone atoms with lactic acid and with N-methylglucamine.
Example 15
Production of a copolymer comprising octadecyl units, oleic ester, lactic acid ester and N-methyl glucamine
a) 22.7 g (90 mmol) of octadecene and 8.9 g (78 mmol) of allyl glycidyl ether are dissolved under N2 in 60 g of 2propanol. The mixture is heated under reflux and 6.3 g (16.8 mmol) of a SiH oil of an M-D90-D ^H 25-M structure and subsequently 0.2 g of 1% Pt containing the solution of H2PtCI6 in ethanol were added via drip. For an additional 0.25 hours 50 g (133.2 mmol SiH) of the SiH oil of MD90-D ^H 25-M structure were added by dripping and the temperature is maintained for 4 hours. Subsequently, volatile components up to 150 ° C / 20mbar are removed. A swollen and pale brown polymer is obtained.
b) 2.85 g (10 mmol) of stearic acid, 0.9 g (10 mmol) of lactic acid and 0.5 g of triethyl amine and 26.54 g (2
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91/92 mmol) of octadecyl units and epoxy units containing siloxane obtained in step a) were dissolved in 71 g of propylene glycol monomethyl ether and heated for 10 hours at
120 ° C.
Subsequently, 0.39 g (2 mmol) of N-methylglucamine is added and sanding is continued for 4 hours at 120 ° C. The conversion of the epoxy group is 100%. The product shows ¹ HNMR signals of C18-alkyl groups attached to the silicone atoms, products of the reaction of the epoxy group linked by a propyloxy group to the silicone atoms with lactic acid, stearic acid and N-methylglucamine.
Example 16
Production of W / O emulsions
W / O emulsions of the following compositions are produced, where in each case a mixture (II) consisting of 100 g of water, 1.4 g of NaCl and 2.8 g of glycerin, were added to a premix (I) oil and the W / O emulsifier, the polysiloxane according to the invention under stirring.
Emulsion W / O Example-No, 16.1 16.2 16.3 16.4 D5 (g) 2525Mineral oil (g)2525 Mixture (g)Water / NaCl / Glycerin 102 84 124 102 Emulsifier Ex, 10 (g) 1.1 1.1 Emulsifier Ex, 11 (g) 1.1 1.1
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Appearance of W / O emulsion creamy, highly viscous creamy, highly viscous creamy, highly viscous creamy, highly viscous Emulsion W / O ExampleNo, 16.5 16.6 16.7 16, 8 16, 9 16.10 D5 (g) 252525Mineral oil(g)252525 Mixture(g) Water / NaCl / Glycerin 94 103 70 70 70 87 Emulsifier n Ex, 12 (g) 1, 1 1.1 Emulsifying Ex,I3 (g) 1.1 1.1 Emulsifier n Ex, 14 (g) 1.1 1.1 Appearance of W / O emulsion creamy, highly viscous creamy, highly viscous creamhealth, low viscosity and creamy, low viscosity creamy, low viscosity creamy,low viscosity
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权利要求:
Claims (19)
[1]
1. POLYSILOXAN COMPOUNDS, characterized by being of general formula (I):
[M _to DbTcQd] and (I) where;
= R3SÍO1 / 2 = R2SiO2 / 2 = RSiO3 / 2 = SiO4 / 2 with a = 1-10
b = 0-1000 c = 0-1 d = 0-1
e = 1-10 where
R = is an organic group, with the requirement that R comprise at least one group R9, which is selected from:
R ¹ = -Z- (AE) y, where
Z = a C2 to C20- residue of bivalent or trivalent straight-chain, cyclic or branched, saturated or unsaturated hydrocarbon, which can comprise one or more groups selected from -O-, -NH-, and can be replaced by one or more OH groups,
A is a bivalent residue, which is selected from the group comprising:

I OH
H ₂
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[2]
2/14 and
Η —C-C-OH
I h ₂ y = 1 or 2
And it is selected from the group that comprises:
E ² = -OC (O) -R ² , where R = is a straight, cyclic or branched, saturated or unsaturated hydrocarbon residue with up to 50 carbon atoms, which may comprise one or more groups selected from - O-, -NH-, -NR ³ -, -C (O) - and is replaced by one or more OH groups, where R ³ = a linear, cyclic or branched, saturated or unsaturated hydrocarbon residue with up to 6 carbon atoms, and
E ³ =
OH —occc h ₂ hh

—2 c where E ² is as defined above, ex = 1 - 4,
E ⁵ = -NR ⁴ R ⁵ , where
R ⁴ and R ⁵ are the same or different and are selected from the group comprising: hydrogen and a linear, cyclic or branched, saturated or unsaturated hydrocarbon residue with up to 30 carbon atoms, which may comprise one or more groups selected from -O-, NH-, -NR ³ -, where R ³ is as defined above, -C (O) -, and can be replaced by one or more OH- and / or H2N- groups,
R ⁶ = -ZE ² where E ² is as defined above, and
R7 = -ZE ⁶ , where E ⁶ = -NH-C (O) -R ⁴ , where R ⁴ is as defined above,
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[3]
3/14 and R ⁹ plus at least one of R ¹ , R ⁶ and R ⁷ is R ⁶¹ = ZE ¹ , where E ¹ is -OC (O) -R ²¹ , where R ²¹ = a chain hydrocarbon residue linear, cyclic or branched, saturated or unsaturated with up to 50 carbon atoms, which can comprise one or more groups selected from -O-, NH-, -NR ³ -, -C (O) -, where R ³ is as defined above, but has no hydroxy substitute.
2. COMPOUNDS, according to claim 1, characterized by comprising structural elements selected from the following formulas:

⁰ 1/2 ^{S 0}
R ⁸
R ⁹ where R8
C1
1/2 _lf to C22-alkyl fluoroalkyl or aryl, and
R ⁹ = R ¹
R ⁶ and / or R ⁷ , and in addition is R ⁶¹ f = 0-600,
[4]
4R ⁸ θϊ / 2 θϊ / 2 * ⁸ i where the R ⁸ groups can be the same or different and are selected from C1 to C22-alkyl, C1 to C22-fluorosubstituted alkyl and aryl, eg = 0-700,
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where R ⁸ is defined as above h = 0-10

where R ⁹ is defined as above
0-10

where R ⁸ and R ⁹ are defined as above, j = 0-30,
Γ tf Ί
3 ^!
R --- SÍ— _ * ⁸ 1 where R ⁸ and R ⁹ are defined as above, k = 0-30,
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[5]
5/14

where l
0-10 f + g + h + i + j + k + l = 12 to 1000.
3.
COMPOUNDS according to claim 2 characterized in that they comprise two or more different R9 residues.
4.
COMPOUNDS according to either of claims 2 or 3, characterized in that they comprise two or more different R ⁹ residues, which differ in their hydrophilic characteristics.
5.
COMPOUNDS according to any one of claims 2 to 4, characterized in that they comprise hydrophilic residues R ⁹¹ and lipophilic residues R ⁹² .
[6]
6.
COMPOUNDS according to any one of claims 2 to 5, characterized in that they comprise hydrophilic residues R ⁹¹ and lipophilic residues R ⁹² , where
- the hydrophilic residues R ⁹¹ have a log P (25 ° C) <0.5 and
- R ⁹² lipophilic residues have log P (25 ° C)> 0.5 determined based on the corresponding compounds
HR ⁹¹ and HR ⁹² corresponding to compounds HR ¹ , H - R ⁶ , HR ⁶¹ and
H-R7.
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6/14
[7]
7. COMPOUNDS claims 1 a according to any one of those characterized by comprising structural elements selected from the following

The _d —Si — O
R ⁹¹

C1 formulas:
where R ⁸ to C22-alkyl fluoroalkyl or aryl
R ⁹¹ is as defined in the claim
6 or in claim 10 f1 = 1 -300

where R ⁸ = C1 a
C22-alkyl fluoroalkyl or aryl
R ⁹² is as defined in the claim
6 or claim 10, and f2 = 1 - 300
4R ⁸ * ⁸ 1 where the R ⁸ groups can be the same or different and are selected from C1 to C22-alkyl, C1 to C22-fluorosubstituted alkyl and aryl, eg = 0 - 700,
Petition 870190106535, of 10/21/2019, p. 102/112
7/14

where R8 is, as defined above, and
0 -10
R ⁹¹ θι / 2 θι / 2 i1 where R ⁹¹ is as defined above and i1
0-5

where R ⁹² is as defined above, and i2 = 0 - 5,

where R8 = C1 to C22-alkyl, fluoroalkyl or aryl and
R ⁹¹ is as defined in claim 6 or claim 10, and j1 = 0-15,
Petition 870190106535, of 10/21/2019, p. 103/112
[8]
8/14

where R ⁸
R ⁹² is = C 1 to C 22 -alkyl fluoroalkyl or aryl as defined in claim
6 or in claim 10 j2 = 0 -15

where R ⁸ = C1 to C22-alkyl fluoroalkyl or aryl k = 0 - 30

where l = 0-10 f1 + f2 + g + h + i1 + i2 + j1 + j2 + k + 1 = 12 to 1000.
8. COMPOUNDS according to any one of claims 1 to 7, characterized by:
R is selected from: C1 to C10-alkyl, which, if necessary, can be replaced by
1 to 13 fluorine, aryl, and R ⁹ atoms are selected from R ¹ , R ⁶ and R ⁷ , and additionally R ⁶¹ may be present as R ⁹
Z = divalent or trivalent straight-chain, cyclic or branched, saturated or unsaturated C2 to C10 hydrocarbon residue that can comprise one or more groups -O- and can be replaced by one or more groups OH,
Petition 870190106535, of 10/21/2019, p. 104/112
[9]
9/14 g = 10 to 700, preferably 10 to 200, preferably 10 to 150, preferably 20 to 150, preferably 30 to 150, preferably 30 to 100, f1 = 1 to 200, preferably 1 to 100, preferably 1 to 50, preferably 1 to 30, preferably 3 to 30, preferably 5 to 30, f2 = 1 to 200, preferably 1 to 100, preferably 1 to 50, preferably 1 to 30, preferably 3 to 30, preferably 5 to 30,
h = 0 The 5 and preferably 0,i1 = 0 The 5 and preferably 0,i2 = 0 The 5 and preferably 0,l = 0 The 5 and preferably 0,f1 + f2 + g + h + i1 + i2 + j1 + j2 + k + l = 10 The 500
preferably 10 to 200, preferably 10 The 150, preferably 20 to 150, preferably 30 The 150, preferably 30 to 100. 9. COMPOUNDS, of according to any an of claims 1 to 8, characterized by: R is selected from : C1 to C6-alkyl, Where, if necessary, they can to be replaced by
1 to 13 fluorine, phenyl atoms,
Z = a C2 to C6 bivalent or trivalent straight-chain, cyclic or branched, saturated or unsaturated residue, which may comprise one or more groups -O- and may be replaced by one or more groups OH, y = 1,
R ² = a straight, cyclic or branched, saturated or unsaturated hydrocarbon residue with up to 30 carbon atoms, which may comprise one or more selected groups
Petition 870190106535, of 10/21/2019, p. 105/112
[10]
10/14 of -O-, -NH-, -NR ³ -, -C (O) - and can be substituted by one or more OH groups, where R ³ is defined as above.
10. COMPOUNDS according to any one of claims 1 to 9, characterized by:
R each comprises at least one of the groups R ⁹¹ and R ⁹² , where
R ⁹¹ is selected from the group, which comprises:
R ¹¹ = -Z- (AE) y, where
And it is selected from the group, which comprises:
E ² = -OC (O) -R ²² , where R ²² = a straight, cyclic or branched, saturated or unsaturated hydrocarbon residue with up to 9 carbon atoms, which may comprise one or more groups selected from -O- , -NH-, -NR ³ -, -C (O) -, and is replaced by one or more OH groups, where R ³ = is a linear, cyclic or branched, saturated or unsaturated hydrocarbon residue with up to 6 carbon atoms, and
E ³ = 'OH' —OCC-CE h ₂ hh ₂
--J x where E ² is as previously defined, ex = 1 -4,
E5 = -NR ⁴¹ R ⁵¹ , where
R ⁴¹ and R ⁵¹ are the same or different and selected from the group comprising: hydrogen and a straight, cyclic or branched, saturated or unsaturated hydrocarbon residue with up to 9 carbon atoms, which may comprise one or more groups selected from - O-, -NH-, -NR ³
Petition 870190106535, of 10/21/2019, p. 106/112
[11]
11/14 where R ³ , is as defined above, -C (O) - and can be replaced by one or more groups OH and / or H2N, and
R6 = -ZE ² where E ² is as previously defined (that is, E ² = -O- C (O) -R ²² ),
R7 = -ZE ⁶ , where E ⁶ = -NH-C (O) -R ⁴¹ , where R ⁴¹ is as previously defined, and
R ⁹² is selected from the group, which comprises:
R ¹ = -Z- (AE) y, where
And it is selected from the group, which comprises:
E ² = -OC (O) -R ²³ , where R ²³ = a linear, cyclic or branched, saturated or unsaturated hydrocarbon residue with 10 to 50 carbon atoms, which may comprise one or more groups selected from -O -, -NH-, -NR3 -, -C (O) -, where R ³ = a linear, cyclic or branched, saturated or unsaturated hydrocarbon residue with up to 6 carbon atoms, and
E ³ =
I 2 —O-C-C-C - E
H ₂ H h ₂
- - * x where E ² is as previously defined for R ^{92 and} x = 1 - 4,
E ⁵ = -NR ⁴² R ⁵² , where
R ⁴² and R ⁵² are the same or different and are selected from the group comprising: hydrogen and a linear, cyclic or branched, saturated or unsaturated hydrocarbon residue with 10 to 30 carbon atoms, which may comprise one or more selected groups of -O-, -NH-, -NR ³ Petition 870190106535, of 10/21/2019, p. 107/112
[12]
12/14 where R ³ is as defined above, -C (O) -, and can be replaced by one or more OH- and / or H2N groups, and
R6 = -ZE ² , where E ² is as previously defined for R ⁹² ,
R7 = -ZE ⁶ , where E ⁶ = -NH-C (O) -R ⁴² , where R ⁴² is as defined above.
11. COMPOUNDS, according to any of the
claims 1 to 10, characterized by R ⁹to be selected according at following conditions:R ⁹ is R ¹and / or R ⁶ , and, optionally, is_R 61 _,or R ⁹ is_R 7 _,and optionally, it is R ⁶¹ , orR ⁹ is R ¹and / or R ⁶ and R ⁷ , and is R ⁶¹ .12. PRODUCTION PROCESS IN COMPOUNDS
POLYSILOXANES, as defined in any one of claims 1 to 11, characterized in that (a) a functional epoxy polysiloxane is reacted with one or more, preferably several carboxylic acids and subsequently with the primary or secondary amines, if necessary, (b) a Functional epoxy polysiloxane is reacted with one or more, preferably several carboxylic acids and carboxylic acid anhydrides, where the carboxylic acid anhydrides are partially esterified by the addition of monovalent or polyvalent alcohols, if necessary, and subsequently also reacted with the primary or secondary, if necessary, (c) a functional SiH polysiloxane is reacted with (i) one or more olefinically unsaturated or acetylenically unsaturated glycerin ethers or
Petition 870190106535, of 10/21/2019, p. 108/112
[13]
13/14 of the glycerin oligomers, whose hydroxyl groups can be silylated and / or acetalised and / or quetalised and / or esterified, if necessary, and (ii) one or more esters of fatty acids with unsaturated alcohols, (d) the polysiloxanes functional amino acids are reacted with carboxylic acids or with functional epoxy compounds
13. PROCESS according to claim 12, characterized in that unsaturated alcohols are selected from mono and difunctional alcohols, such as alkenols and alkynols: CH2 = CHCH2OH, CH2 = CHCH2CH2OH, CH2 = CHCH2CH2CH2CH2OH, CH ^ CCH.OH, HC) CH2C ^ CCHOH, HOCH2CH = CHCH2OH, CH ^ CHCH., CH., CH., CH., O'H, hexynodiols: HOCH2CH2C = CCH2CH2OH and ethylene oxide-free poly (alkoxylates), preferably alkylene or alkoxy (poly) propoxylates.
[14]
14. PROCESS, according to claim 12, characterized in that the fatty acids are selected from the carboxylic acids which do not comprise the unsaturated hydrosilylated groups, such as, for example: acetic acid, caprionic acid, 2-ethyl caprionic acid, lauric acid, tetradecenoic acid, capriodecenoic acid, octadecenoic acid, oleic acid, linoleic acid, linolenic acid and elaidic acid.
15. USE OF POLYMERS POLYSILOXANaccording defined in any one of claims 1 to 11, featured for being like emulsifiers. 16. USE OF POLYMERS POLYSILOXANaccording defined in any one of claims 1 to 11, featured for being to the formulations production
Petition 870190106535, of 10/21/2019, p. 109/112
14/14 cosmetic.
[15]
17. USE, according to claim 16, characterized in that the cosmetic formulation is a sunscreen formulation.
[16]
18. USE OF POLYSILOXAN POLYMERS, as defined in any one of claims 1 to 11, characterized by being for the production of defoamer or defoamer compositions.
[17]
19. USE OF POLYSILOXAN POLYMERS as defined in any one of claims 1 to 11, characterized in that it is for the production of foam stabilizers for polyurethane foams.
[18]
20. USE OF POLYSILOXAN POLYMERS as defined in any one of claims 1 to 11, characterized in that it is for the production of agricultural compositions.
[19]
21. A / O EMULSIONS, characterized in that they comprise one or more polysiloxane polymers as defined in any one of claims 1 to 11.

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法律状态:
2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|

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2019-03-26| B06T| Formal requirements before examination|

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2019-07-23| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application according art. 36 industrial patent law|

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2019-11-12| B09A| Decision: intention to grant|

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2020-01-07| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 24/11/2010, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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