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    • 专利摘要:
    COMPOSITION, POLYURETHANE POLYETHER, POLYURETHANE FOAM, METHOD FOR PREPARING A POLYURETHANE POLYETHER AND METHOD FOR PREPARING A POLYURETHANE FOAM The present invention describes cyclic amines useful for catalysts for polyurethane foam forming compositions, as well as alcohols and alcohols. polyether polyols of amines formed from cyclic amines. The cyclic amines of the invention provide distinct benefits for reaction compositions, methods, and polyurethane foams based on their desirable catalytic and physical properties.
    公开号:BR112014015972B1
    申请号:R112014015972-6
    申请日:2012-12-28
    公开日:2020-12-29
    发明作者:Stephen W. King；Esther Quintanilla；Jean-Paul Massy；David H. Bank；Erin B. Vogel；Francois Rene Morgan Graf；Adrian J. Birch
    申请人:Dow Global Technologies Llc；
    IPC主号:
    专利说明:

    Field of invention
    [001] The present invention relates to cyclic amines, amine alkoxylates derived from cyclic amines, polyether polyethers of amines derived from cyclic amines, and polyurethane foams prepared from cyclic amines, amine alkoxylates, or polyether ethers of amines . Historic
    [002] Typically, polyurethane foams are produced by the reaction of polyols with isocyanates in the presence of water acting as a blowing agent. The reaction that leads to the polyurethane foaming reaction generally consists of the urethane reaction (gelation) and the urea reaction (expansion), which is associated with the production of carbon dioxide (CO2). Catalysts as well as other auxiliary agents, such as crosslinkers, chain extenders, surfactants, stabilizers, and antioxidants, are often included in the composition with the polyol and isocyanate components. Catalysts can play a key role in ensuring desirable foam properties by controlling and balancing gelling and expansion reactions during foam production. Catalysts can also have an effect on the moldability and the rate of cure of the foam.
    [003] Tertiary amines and organometallic salts have been used in the art as catalysts for polyurethane foams. However, commonly used tertiary amine catalysts give rise to several problems, particularly in applications of flexible, semi-rigid and rigid foams. Foams freshly prepared using these catalysts often have the typical odor of amines and give rise to fogging due to the emission of volatile products.
    [004] The presence, or formation, of tertiary amine catalyst vapors in polyurethane products is harmful to vinyl films or polycarbonate sheets exposed to them. Specifically, the tertiary amine catalysts present in polyurethane foams have been linked to the formation of stains on vinyl films and to the degradation of polycarbonate sheets. These problems of staining in PVC and decomposition of polycarbonate are especially common in environments where there are high temperatures for long periods of time, such as in car interiors.
    [005] The inventors of the present patent application understand that there are many difficulties in the production of desirable polyurethane foam products for the consumer and in industrial applications and that the preparation and identification of desirable amine catalysts for polyurethane foams is still an area. challenge. For example, although it is stated that some catalysts (for example, see US Patent No. 4,517,313) reduce odor and stain formation compared to the use of standard triethylenediamine catalysts, they unfortunately provide weaker catalytic activity, and do not achieve conventional catalyst standards. It is a challenge to change the chemical structure of the amine catalyst without adversely affecting its catalytic activity. In some cases, it is necessary to use catalysts at high levels in the polyurethane formulation to compensate for their lack of mobility or catalytic activity during the reactions.
    [006] Another problem concerns the stability of compositions, including foaming components. Pre-reacted components in a composition can exhibit a tendency to pre-gel and have poor storage stability. Another problem is that some catalysts that promote rapid gelation lead to foam processing and foam properties problems. For example, tear strength and elongation at tear can be adversely affected due to a high level of crosslinking. In addition, some catalysts, when subjected to high temperatures commonly found in car interiors, migrate inside a foam.
    [007] The present patent application provides compounds, compositions, and methods for forming polyurethane foams based on the use of cyclic amines, amine alkoxylates derived from cyclic amines, or polyether polyols of amines derived from cyclic amines. Summary of the invention
    [008] The present invention provides compositions, for amine alkoxylates, polyether polyol amines, and polyurethane foams including or derived from cyclic amines. The invention also provides methods for preparing amine alkoxylates, polyether polyether amines, and polyurethane foams using cyclic amines.
    [009] The compositions, amine alkoxylates, polyether polyol amines, and polyurethane foams are prepared using cyclic amines of Formula I:
    or Formula II

    [010] In Formulas I and II, R1-R7 and R1’-R7’s are selected independently from the group consisting of hydrogen and hydrocarbyl groups; x and x 'are independently 0 (a covalent bond) or an integer in the range 1-10, and if x or x' is greater than 1, then R1 and R1’s will be the same or different; and Z, Z ', and Z ”are selected independently from the group consisting of hydrogen, -CH2CH2OH, -CH2CH (CH3) OH, -CH (CH3) CH2OH, -CH2CH (CH2CH3) OH, or -CH (CH2CH3) CH2OH. Exemplary compounds of Formula I or II have x and x 'as 0 (a covalent bond) or 1; have R1-R7 and R1'-R7 'as hydrogen; and have Z, Z ', and Z ”as hydrogen, -CH2CH2OH, -CH2CH (CH3) OH, CH (CH3) CH2OH, -CH2CH (CH2CH3) OH, -CH (CH2CH3) CH2OH, or mixtures thereof. Chemical species in the compounds of Formula I and II include: the cyclic amines bis (2-piperazin-1-yl-ethyl) amine (“BPEA”), (3- (piperazin-1-yl) propyl) amine, bis (4-piperazin-1-yl) butyl) amine, bis (5-piperazin-1-yl) pentyl) amine, bis (6-piperazin-1-yl) hexyl) amine, bis (1- (piperazin-1 -yl) propan-2-yl) amine, bis (2- (piperazin-1-yl) propyl) amine, 2- (4- (2- (piperazin-1-yl) ethyl) piperazin-1-yl) ethanamine , 3- (4- (3- (piperazin-1-yl) propyl) piperazin-1-yl) propan-1-amine, 4- (4- (4- (piperazin-1-yl) butyl) piperazin-1 - yl) butan-1-amine, 5- (4- (5- (piperazin-1-yl) pentyl) piperazin-1-yl) pentan-1-amine, 6- (4- (6- (piperazin-1 -yl) hexyl) piperazin-1-yl) hexan-1-amine, 1- (4- (1- (piperazin-1-yl) propan-2-yl) piperazin-1-yl) propan-2-amine, and 2- (4- (2- (piperazin-1-yl) propyl) piperazin-1-yl) propan-1-amine; and amines alkoxylates 2,2 '- (4,4' - ((((2-hydroxyethyl) azanediyl) bis (ethane-2,1-diyl)) bis (piperazine-4,1-diyl)) diethanol, 1 , 1 '- (4,4' - ((((2-hydroxypropyl) azanediyl) bis (ethane-2,1-diyl)) bis (piperazine-4,1-diyl)) bis (propan-2-ol), and 1.1 '- (4.4' - ((((2-hydroxybutyl) azanediyl) bis (ethane-2,1-diyl)) bis (piperazine-4,1-diyl)) bis (butan-2-ol ).
    [011] The compounds of Formulas I and II provide significant advantages in the areas of cyclic amines, and amine alkoxylates prepared from said cyclic amines, for use in the preparation of polyurethane foams. These compounds represented by BPEA have desirable physical and catalytic properties for the production of polyurethane foams.
    [012] Compounds of Formulas I and II have one or more of the following properties: (a) liquid at room temperature, (b) a low profile of volatile organic compound (VOC) (boiling point greater than 250 ° C measured at a pressure atmospheric standard), (c) desirable viscosity, (d) good color, (e) no undesirable odor, and (f) desirable catalytic activity. The use of these compounds can provide distinct benefits for foaming compositions, methods for preparing foams, and polyurethane foams per se.
    [013] The liquid and viscosity properties of the cyclic amine of Formula I or II can guarantee better mixing in the foaming compositions, and lend easier handling when compared to more volatile amines or amines that are in solid form. For example, due to both the exothermic nature of the foaming reactions and the high reaction temperatures, many known amine catalysts that are volatile cause an odor release that may be undesirable. In addition, viscosity allows for better molecular mobility which can lead to a more complete distribution of the compound with improved foaming reactions that ultimately provides a foam with improved properties. In addition, the molecular structure of cyclic amines and amine alkoxylates is sterically favorable, facilitating access to reagents to promote desired reactions.
    [014] As another benefit, the cyclic amines and alkoxylates of Formula I or II cyclic amines have good color and no undesirable odor. These desirable properties can extend to products produced from cyclic amine or cyclic amine alkoxylate, such as polyether amine polyethers, and polyurethane foams. For example, polyurethane foams with a good color can be colorless or substantially colorless, and can be used to make articles resistant to stain formation, etc., and which have greater value for the consumer. Polyurethane foam that has no unpleasant odor is also of greater value to the consumer.
    [015] Cyclic amines and amine alkoxylates of Formula I or II also provide good catalytic activity. For example, studies associated with the present invention have shown that the inclusion of a cyclic amine of Formula I or II provided very good catalytic activity catalyzing the expansion reaction during the generation of polyurethane foam.
    [016] In one aspect, the invention provides a composition comprising a reaction product derived from reagents comprising (a) a cyclic amine of Formula I or II and (b) a polyol generating monomer; or a reaction composition having reagents comprising (a) a cyclic amine of Formula I or II and (b) a polyol generating monomer. The groups R1-R7, R1'-R7 ', Z, Z', and Z "are as described herein. Exemplary polyol generating monomers include epoxides, such as ethylene oxide, propylene oxide, or butylene oxide. Halogenated alcohols can also be used as polyol-generating monomers. The reaction product of (a) and (b) can be described as an amine polyether polyol.
    [017] In a related aspect, the invention provides a method for preparing a polyether polyol mine comprising a step of reacting a cyclic amine of Formula I or II as described herein with a polyol generating monomer.
    [018] In another aspect, the invention provides an amine polyether polyol of Formula III
    or Formula IV

    [019] In Formula III or IV, R1-R7, R10, R1'-R7 ', R10' and R10 ”are selected independently from the group consisting of hydrogen and hydrocarbyl groups; x and x 'are independently 0 (a covalent bond) or an integer in the range 1-10, and if x or x' is greater than 1, then R1 and R1’s will be the same or different; R8, R8 ', R8 ”, R9, R9' and R9” are independently selected from hydrogen, -CH2CH2-, -CH2CH (CH3) -, -CH (CH3) CH2-, -CH2CH (CH2CH3) -, and - CH (CH2CH3) CH2-, ey, y ', ey "are independently 0 or an integer in the range d 1 to 250, as long as the sum of y, y', ey" is greater than or equal to 1.
    [020] The polyether polyol amine can be used in a composition as a reagent, catalyst, or as both. If the amine polyether polyol has reagent properties and catalytic properties, the amine functionality of the amine polyether polyol can promote reaction catalysis, and the hydroxyl functionalities can react in a bonding process, such as in crosslinking where the amine polyether polyol reacts. with a polyisocyanate and is incorporated in a polymeric network.
    [021] In another aspect, the invention provides a polyurethane foam derived from a composition comprising, or the composition per se comprising: (a) a cyclic amine of Formula I or II, (b) a polyol, and (c) a polyisocyanate . The groups R1-R7, R1'-R7 ', Z, Z', and Z "are as described herein.
    [022] In a related aspect, the invention provides a polyurethane foam derived from a composition comprising, or a composition per se comprising: (a) an amine polyether polyol of Formula III or IV, (b) optionally a polyol, and ( c) a polyisocyanate. The groups R1-R10, R1'-R10 ', and R8 "-R10" of Formula III or IV are as described herein.
    [023] In a related aspect, the invention provides a method for preparing a polyurethane foam comprising a step of reacting a polyol and a polyisocyanate in the presence of a cyclic amine or amine alkoxylate of Formula I or II; or a step of reacting a Formula III or IV amine polyether polyol with a polyisocyanate, optionally in the presence of a polyol.
    [024] Polyurethane foams, including those that are flexible or rigid, formed using Formula I or II cyclic amine or amine alkoxylate or Formula III or IV polyether polyol can be used in a variety of applications. Such applications include use in household and commercial furniture and bedding; in commercial and private vehicles, such as seats and interior panels; refrigerators and freezers; building materials, such as residential or commercial buildings; clothing, costumes, and shoes; packaging materials; as well as electronics and industrial machinery, among others. Brief summary of figures
    [025] Figure 1 is a graph showing the increase in height of polyurethane foam compositions over time;
    [026] Figure 2 is a graph showing the increase in height of polyurethane foam compositions over time; and
    [027] Figure 3 is a graph showing the increase in height of polyurethane foam compositions over time. Detailed description of the invention
    [028] Detailed reference will now be made to representative embodiments of the invention. Although the invention will be described together with the listed embodiments, it will be understood that they are not intended to limit the invention to those embodiments. On the contrary, the invention is intended to cover all alternatives, modifications, and equivalent that may be included within the scope of the present invention defined by the claims.
    [029] Those skilled in the art will recognize many methods and materials similar or equivalent to those described herein, which can be used in the practice of the present invention and which are within the limits of their scope. In no way is the invention limited to the methods, materials and compositions described herein.
    [030] Unless defined differently, technical and scientific terms used here have the same meaning commonly understood by those skilled in the technique to which this invention belongs. While any methods, devices, and materials similar or equivalent to those described herein can be used in the practice or testing of the invention, the preferred methods, devices and materials will now be described.
    [031] In some respects, the polyurethane foams of the invention can be prepared using cyclic amines or amine alkoxylates of Formula I:
    or Formula II

    [032] In Formula I or II, R1-R7 and R1’-R7’s are selected independently from the group consisting of hydrogen and hydrocarbyl groups; x and x 'are independently 0 (a covalent bond) or an integer in the range 1-10, and if x or x' is greater than 1, then R1 and R1’s will be the same or different; and Z, Z ', and Z ”are selected independently from the group consisting of hydrogen, -CH2CH2OH, -CH2CH (CH3) OH, -CH (CH3) CH2OH, -CH2CH (CH2CH3) OH, or -CH (CH2CH3) CH2OH.
    [033] The hydrocarbyl groups mentioned herein are substituted or unsubstituted, linear, branched or cyclic hydrocarbyl groups, such as alkyl, aryl, aralkyl, or the like; a monovalent portion including one or more heteroatoms; polyether chains comprising one or more oxyalkylene repeating units such as -R11O-, in which R11 is often alkylene of 2 to 4 carbon atoms; other oligomeric or polymeric chains of at least 2 repeat units. Any of R1-R7 and R1'-R7 'can be selected independently from the group consisting of hydrocarbyl groups, such as those described herein. In more specific embodiments, R1-R7 and R1'-R7 'are H, or a normal, branched or cyclic hydrocarbyl group such as alkyl of 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms. In even more specific incorporations all of R1-R7 and R1’-R7 'are H.
    [034] In the practice of this invention, the values of x and x 'are 0 or an integer in the range 1 to 10, such as in the range 2 to 5, or in the range 2 to 3, and most preferably 0 or 1 .
    [035] Exemplary compounds of Formula I or II have x and x 'as 0 (a covalent bond); have R1-R7 and R1'-R7 'as hydrogen; and have Z, Z ', and Z ”as hydrogen, -CH2CH2OH, -CH2CH (CH3) OH, -CH (CH3) CH2OH, -CH2CH (CH2CH3) OH, or -CH (CH2CH3) CH2OH.
    [036] Examples of cyclic amines of Formula I include bis (2-piperazin-1-yl-ethyl) amine (“BPEA”), (3- (piperazin-1-yl) propyl) amine, bis (4-piperazin- 1-yl) butyl) amine, bis (5-piperazin-1-yl) pentyl) amine, bis (6-piperazin-1-yl) hexyl) amine, bis (1- (piperazin-1-yl) propan-2 -yl) amine, bis (2- (piperazin-1-yl) propyl) amine, 2- (4- (2- (piperazin-1-yl) ethyl) piperazin-1-yl) ethanamine, 3- (4- (3- (piperazin-1-yl) propyl) piperazin-1-yl) propan-1-amine, 4- (4- (4- (piperazin-1-yl) butyl) piperazin-1-yl) butan-1 -amine, 5- (4- (5- (piperazin-1-yl) pentyl) piperazin-1-yl) pentan-1-amine, 6- (4- (6- (piperazin-1-yl) hexyl) piperazin -1-yl) hexan-1-amine, 1- (4- (1- (piperazin-1-yl) propan-2-yl) piperazin-1-yl) propan-2-amine, and 2- (4- (2- (piperazin-1-yl) propyl) piperazin-1-yl) propan-1-amine.
    [037] Cyclic amines of Formulas I and II where Z, Z ', and Z "are hydrogen, can be prepared according to the processes of provisional US serial application No. 61 / 581,323 entitled" Formation of Higher Molecular Weight Cyclic Polyamine Compounds From Cyclic Polyamine Compounds ”, filed on December 29, 2011 (King). US 61 / 581,323 describes processes of transamination of a cyclic amine of lower molecular weight having at least two amine groups separated from each other by a spacing of two primary carbons (C2 spacing) in the cyclic ring to produce a cyclic amine of greater molecular weight Formula I or II. In particular, compounds of Formula I or II where Z, Z ', and Z ”are hydrogen can be prepared using cyclic amines of lower molecular weight such as 2- (piperazin-1-yl) ethanamine (AEP), 3- (piperazin -1-yl) propan-1-amine, 4- (piperazin-1-yl) butan-1-amine, 5- (piperazin-1-yl) pentan-1-amine, 6- (piperazin-1-yl) hexan-1-amine, 1- (piperazin-1-yl) propan-2-amine, or 2- (piperazin-1-yl) propan-1-amine.
    [038] As described in U.S. 61 / 581,323, compounds of Formula I or II where Z, Z ', and Z "are hydrogen can be prepared using a hydrogenation / dehydrogenation catalyst that can catalyze the transamination reaction. In preferred embodiments in which a heterogeneous catalyst incorporates nickel and rhenium, a useful support is one of alumina / silica. Such catalysts and methods for preparing such heterogeneous catalysts on such supports are further described in U.S. Patent No. 6,534,441. Such catalysts are also described further in published US patent applications No. 2010-0137642-A1 (King et al.), 2010-0087682-A1 (King et al.), 2010-0087683-A1 (Cook et al.) , 2010-0087684-A1 (Do et al.), And 2010-0087681-A1 (Petraitis et al.).
    [039] As described in US 61 / 581,323, the lower molecular weight cyclic amine to be transaminated can be contacted with the catalyst at any appropriate temperature and pressure that promote the production of the higher molecular weight cyclic amine of Formulas I and II . Preferred temperatures are in the range of 100 ° C to 200 ° C, more preferably 120 ° C to 180 ° C. Typically, the pressure is in the range of 100 psi to 1500 psi, preferably 200 psi to 1200 psi, more preferably 300 psi to 1000 psi. Pressures in the range of 300 psi to 800 psi are most preferred.
    [040] In other respects, the compound of Formula I or II is an amine alkoxylate. For amine alkoxylates of Formula I or II, Z, Z ', and Z ”are selected independently from -CH2CH2-, -CH2CH (CH3) -, -CH (CH3) CH2-, -CH2CH (CH2CH3) -, or - CH (CH2CH3) CH2-. In some respects, amine alkoxylates are derived from a halogenated alcohol with the generic structure X-CH2CH2-OH, X-CH2CH (CH3) -OH, X-CH (CH3) CH2-OH, X-CH2CH (CH2CH3) - OH , or X-CH (CH2CH3) CH2-OH where X is Cl, Br, or I.
    [041] An amine alkoxylate of Formula I or II, in which Z, Z ', and / or Z ”is -CH2CH2-, -CH2CH (CH3) -, -CH (CH3) CH2-, -CH2CH (CH2CH3) -, or -CH (CH2CH3) CH2- can be formed by reacting a compound of Formula I or II, in which Z, Z ', and / or Z ”is H (for example, BPEA) with ethylene oxide, propylene oxide , butylene oxide or a mixture thereof under alkoxylation conditions known to those skilled in the art.
    [042] Specific examples of Formula I amine alkoxylates include 2.2 '- (4.4' - (((2-hydroxyethyl) azanediyl) bis (ethane-2,1-diyl)) bis (piperazine-4, 1-diyl)) diethanol, 1,1 '- (4,4' - ((((2-hydroxypropyl) azanediyl) bis (ethane-2,1-diyl)) bis (piperazine4,1-diyl)) bis (propan -2-ol), and 1,1 '- (4,4' - ((((2-hydroxybutyl) azanediyl) bis (ethane-2,1-diyl)) bis (piperazine4,1-diyl)) bis (butan -2-ol).
    [043] Specific examples of Formula II amine alkoxylates include 2.2 '- ((2- (4- (2- (4- (2-hydroxyethyl) piperazin-1-yl) ethyl) azanediyl) diethanol, 1, 1 '- ((2- (4- (2- (4- (2-hydroxypropyl) piperazin-1-yl) ethyl) azanediyl) bis (propan-2-ol), or 1,1' - ((2- (4- (2- (4- (2-hydroxybutyl) piperazin-1-yl) ethyl) (piperazin-1-diyl) ethyl) azanediyl) bis (butan-2-ol).
    [044] Prior to further modification, or use in a polyurethane foaming composition, compounds of Formula I or II may be separated (refined) by any method known in the art. Methods for purification or separation include conventional distillation technology using partition wall columns, membrane separation, melt crystallization, and reactive distillation.
    [045] Compounds of Formula I or II can be used in "pure" form, for example, a liquid, without any solvent. For example, bis (2- (piperazin-1-yl) ethyl) amine (BPEA) is a liquid at room temperature (~ 25 ° C), and has a boiling point of ~ 360 ° C. Alternatively, compounds of Formula I or II can be used together with a solvent, or combination of solvents. Desirably, the solvent does not react unduly with the cyclic amine product of Formula I or II. If the solvent is present, it can be transported from the synthesis of the cyclic amine product as referred to herein. Some examples of solvents that may be mixed with the cyclic amine include saturated hydrocarbons such as pentane, hexane, octane, nonane, decane, or the like; aromatic hydrocarbons such as toluene, benzene, xylene, ether, combinations thereof, and the like.
    [046] In other aspects of the invention, polyether polyols of amines are provided, which can be prepared using the cyclic amines or amine alkoxylates of Formula I or II as starting materials.
    [047] The polyether polyols of amines are according to Formula III:
    or according to Formula IV:

    [048] In Formulas III and IV, R1-R7, R10, R1'-R7 ', R10' and R10 ”are selected independently from the group consisting of hydrogen and hydrocarbyl groups; x and x 'are independently 0 (a covalent bond) or an integer in the range 1-10, and if x or x' is greater than 1, then R1 and R1’s will be the same or different; and R8, R8 ', R8 ”, R9, R9' and R9” are independently selected from hydrogen, - CH2CH2-, -CH2CH (CH3) -, -CH (CH3) CH2-, - CH2CH (CH2CH3) -, or - CH (CH2CH3) CH2-, ey, y ', ey ”are independently 0 or an integer in the range d 1 to 250, as long as the sum of y, y', ey” is greater than or equal to 1.
    [049] Compounds of Formula III or IV can be prepared by polymerizing polyol-generating monomers in the presence of a compound of Formula I or II, in which Z, Z ', and / or Z ”is - CH2CH2OH, -CH2CH (CH3) OH , -CH (CH3) CH2OH, -CH2CH (CH2CH3) OH, or -CH (CH2CH3) CH2OH.
    [050] Exemplary polyol generating monomers include ethylene oxide, propylene oxide, or butylene oxide which can generate a polyether polyol chain (for example, - R8O (R9O) R10) extending from one or more nitrogen in the ring piperazinyl. Compounds of Formula I or II can be used to initiate the polymerization reaction; optionally, the polymerization can be carried out in the presence of other initiators or catalysts, such as a strong base such as potassium hydroxide or a double metal cyanide catalyst such as zinc hexacyanocobaltate / t-butanol complex. Other polyol generating monomers include halogenated alcohols, such as chlorinated alcohols exemplified by ClCH2CH2OH, ClCH2CH (CH3) OH, ClCH (CH3) CH2OH, ClCH2CH (CH2CH3) OH, and ClCH (CH2CH3) CH2OH.
    [051] The preparation of polyether polyol, such as by polymerization of propylene oxide, is well known in the art and has been re-examined by Villa (Ind. Eng. Chem. Res. 2007, 46, 5815-5823). The length of the polyether polyol chain can be controlled by one or more factors, such as the ratio (molar%) of the compounds of Formula I or II to the polyol generating monomers, the type and amount of catalyst used, and the conditions reaction time, including time and temperature. For polymerization, exemplary ranges of a compound of Formula I or II for the polyol generating monomer (mol: mol) are ranges from about 1: 3 to about 1: 1500, from about 1:30 to about 1 : 600, or more specifically from about 1:75 to about 1: 300.
    [052] In exemplary embodiments, in Formula III or IV, y, y ', y and y "are independently 0 or whole numbers in the range 1 to about 250, or from about 10 to about 100, or more specifically about from 25 to about 75, provided that the sum of y, y ', y and y is greater than or equal to 1. Polyether polyols of Formula III or IV amines can also be described in terms of the hydroxyl index. In exemplary embodiments, compounds of Formula III or IV have a hydroxyl index in the range of about 401.6 mg / g to about 24 mg / g, or more specifically from about 250 mg / g to 50 mg / g.
    [053] Polyether polyols of Formula III or IV amines can also be described in terms of the molecular weight of the entire compound or portions of the compound, such as one or more polyol arms extending from the piperazinyl rings. Polyether polyethers of Formula III or IV amines have a molecular weight in the range of about 296 Da to about 8000 Da, from about 420 Da to about 7000 Da, from about 750 Da to about 6000 Da, or about 1000 Da to about 5000 Da. The one or more polyol arms extending from the piperazinyl rings can have a combined molecular weight in the range of about 45 Da to about 7750 Da, from about 300 Da to about 6500 Da, or more specifically about 500 Da to about 5500 Da.
    [054] Optionally, compounds of Formula III or IV can be described in terms of their physical properties. For example, polyether polyols of Formula III or IV amines can be in a liquid (pure) form. For preparing polyurethane foam, in some modes of practice, the amine polyether polyol of Formula III or IV is in liquid form or has a molecular weight in the range of about 1000 Da to about 5000 Da, or both.
    [055] Optionally, compounds of Formula III or IV can be described in terms of their solubility properties. For example, in some cases, polyether polyols of Formula III or IV amines are soluble in a polar protic solvent (for example, water, methanol, ethanol, isopropanol, etc.) or in a polar aprotic solvent (for example, tetrahydrofuran (THF ), dimethyl sulfoxide (DMSO), acetonitrile, etc.).
    [056] Other aspects of the invention include compositions for making polyurethane foams, methods for making polyurethane foams, and polyurethane foams manufactured using cyclic amine, amine alkoxylate, or polyether polyol amine of the invention.
    [057] In some modes of practice, cyclic amines of Formula I or II can be used in a composition to provide catalytic activity during the foaming reaction. Included in the composition together with (a) the cyclic amine or alkoxylated amine: (b) a polyol, and (c) a polyisocyanate.
    [058] In other modes of practice, polyether polyols of Formula III or IV amines can be used in a composition to provide not only catalytic activity but also a source of reagent during the foaming reaction. The polyether polyol amine can be used as the only polyol material in the composition, or it can be used together with one or more other polyols. Therefore, the composition includes (a) the polyether polyols of amines: (b) optionally, another polyol, and (c) a polyisocyanate.
    [059] Cyclic amines of Formula I or II can be used in a composition at a desired concentration to provide catalytic activity during the foaming reaction. Exemplary concentrations of the cyclic amine of Formula I or II are in the range of about 0.05% by weight to about 1.5% by weight, from 0.1% by weight to about 1% by weight, or from 0 , 2% by weight to about 0.8% by weight.
    [060] Exemplary polyols that can be used to produce polyurethane materials with the cyclic amines or amine alkoxylates of Formula I or II, or optionally with the polyether polyols of Formula III or IV amines, include those that are well known in the art . These include polyols described herein, commercially obtainable polyols, and polyols described in the literature. General classes of polyols that can be used in the polyurethane foaming composition include polyether polyethers, polyester polyols, polyhydroxy-terminated acetal resins, hydroxyl-terminated amines, and polyamines (see, for example, US patent 4,394,491) . Other classes of polyols include polyols based on poly (alkylene carbonate) and polyols based on polyphosphate. Some copolymer polyols, some of which can be prepared by grafting methodologies, include styrene / acrylonitrile copolymer polyols (SAN), polyisocyanate polyaddition polyols (PIPA), and Harnstoff polydispersion copolymer polyols (PHD). Copolymer polyols can include polymeric segments other than the polyol portion to introduce desirable properties into the copolymer polyol, such as hardness. Exemplary polyols are also described in the Polyurethane Handbook (G. Oertel, Hanser Publishers). The polyurethane foaming composition may optionally include mixtures of one or more different types of polyols, such as mixtures of two different polyols selected from polyol homopolymers and polyol copolymers.
    [061] Exemplary polyols are included in the polyurethane foaming composition: alkylene oxide-based polyols prepared from polyol-generating monomers such as ethylene oxide, propylene oxide, butylene oxide, or combinations thereof. Alkylene oxide-based polyols can be prepared from monomeric initiators with active hydrogen atoms, such as those having two or more hydroxyl or amine groups. In some polyol preparations, the monomeric initiators to prepare these polyols have 2 to 8, or more specifically, 2 to 6 active hydrogen atoms. Exemplary monomeric initiators include organic dicarboxylic acids, such as succinic acid, adipic acid, phthalic acid and terephthalic acid and polyhydric alcohols, in particular dihydric to octahydric alcohols or dialkylene glycols, for example, ethanediol, 1,2- and 1,3-propanediol , diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, glycerol, trimethylolpropane, pentaerythritol, sorbitol and sucrose or mixtures thereof. These monomeric initiators can be incorporated into the product polyol. Other initiators include linear and cyclic compounds containing an amine functionality such as N-methyl-diethanolamine and triethanolamine.
    [062] The amount of particular polyol, mixture of polyols, and polyol used in the polyurethane foaming composition can be chosen based on factors such as desired properties of polyurethane foam and / or particular end use of the foam product. Polyol properties such as molecular weight or hydroxyl index can be chosen to provide foam characteristics selected from: low density, high density foam, conventional, high resilience, hot molding, cold, flexible, and rigid molding, and combinations desired results. For many applications or foam properties, the hydroxyl index of the polyol is in the range of about 15 to about 800.
    [063] Compositions for the production of flexible polyurethane foams typically include a polyether polyol and / or a polyester polyol. Generally, the polyol has an average functionality ranging from 2 to 5, preferably 2 to 4, and an average hydroxyl index ranging from 20 to 100 mg KOH / g, preferably 20 to 70 mg KOH / g (see, for example, US 7361695).
    [064] For molded foam, the hydroxyl index of the polyol-base can be in the range of about 20 to about 60 with ethylene oxide (EO) capping, and for foam board material can be in the range of about from 25 to about 75 (see, for example, US 7361695).
    [065] Polyurethane foam forming compositions also include a polyisocyanate such as a polyisocyanate selected from aliphatic, cycloaliphatic, arylaliphatic, and aromatic polyisocyanates. For the production of flexible foam, aromatic polyisocyanates are preferred.
    [066] Aromatic polyisocyanates include the 4,4'-, 2,4’- and 2,2’- isomers of diphenyl methane diisocyanate (MDI), mixtures thereof; mixtures of monomeric and polymeric MDI, toluene 2,4- and 2,6-diisocyanate (TDI), mixtures thereof; TDI’s modified with biuret, TDI / MDI mixtures; polymerized isocyanates, m- and p-phenylene diisocyanate, chlorophenylene 2,4-diisocyanate, diphenylene 4,41-diisocyanate, 4,4'-diisocyanate-3,3'-dimethyl-diphenyl, 4,4'-diisocyanate of 3-methyl-diphenyl-methane, diphenyl ether diisocyanate, 2,4,6-triisocyanate-toluene, and 2,4,4'-diphenyl ether triisocyanate (see, for example, US patent No. 7,361,695) .
    [067] Examples of aliphatic polyisocyanates include ethylene diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, cyclohexane 1,4-diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, saturated analogs of aromatic isocyanates mentioned above and mixtures thereof.
    [068] Isocyanate-terminated prepolymers are prepared by reacting an excess of polyisocyanate with polyols, including amine polyols or imines / enamines thereof, or polyamines (see, for example, US 7361695).
    [069] In some ways of preparing polyurethane foams, water is used as a blowing agent. Exemplary amounts of water are in the range of about 0.5 to about 10 parts by weight, or more specifically in the range of about 1 to about 6 parts by weight based on 100 parts by weight of the polyol. Generally, low density foams can be prepared using larger amounts of water, such as near the upper ends of these bands, while high density foams can be prepared using smaller amounts of water, such as near the lower ends of these bands. Carboxylic acids or salts can also be used as blowing agents.
    [070] Carbon dioxide can be used, either as a gas or as a liquid, as an auxiliary blowing agent in addition to water. During foaming, atmospheric pressure can be adjusted, foaming can be used, or a combination of both, as described in U.S. Patent No. 5,194,453 to vary foam density and comfort.
    [071] The composition may include components other than Formula III or IV polyisocyanate and polyether polyol, or in addition to Formula I or II cyclic amine catalyst, and polyol. These other components include, but are not limited to, surfactants, preservatives, flame retardants, colorants, antioxidants, reinforcing agents, stabilizers, and fillers.
    [072] In the preparation of polyurethane foam, it is generally preferred to use an amount of a surfactant to stabilize the foaming reaction mixture until it has cured. In some embodiments, the composition includes a liquid or solid organic silicone surfactant. Other surfactants include polyethylene glycol ethers of long chain alcohols, tertiary amine or alkanolamine salts of alkyl acid sulfate esters, alkyl sulfonic esters and alkyl aryl sulfonic acids. Surfactants can be used in sufficient quantities to stabilize the foaming reaction mixture against collapse and the formation of a desired cell structure. Exemplary amounts of surfactant are in the range of about 0.2 to about 3 parts of the surfactant per 100 parts by weight of total polyol. Mixtures of surfactants can be used.
    [073] In some formulations, the composition may include an organometallic catalyst to promote the reaction of the polyol with the polyisocyanate. Exemplary organometallic catalysts include organic mercury, lead, iron III and tin catalysts. Exemplary tin catalysts include stannous chloride, tin salts of carboxylic acids such as dibutyl tin dilaurate, as well as other organometallic compounds such as are disclosed in U.S. Patent No. 2,846,408. A catalyst for the trimerization of polyisocyanates, resulting in a polyisocyanurate, such as an alkali metal alkoxide, can also be used optionally in the foaming compositions. Exemplary amounts of organometallic catalysts range from about 0.001 to about 1 percent in the composition.
    [074] Other components that can optionally be added to the foaming composition include crosslinking agents (crosslinkers) and chain extenders. Exemplary crosslinking agents and chain extenders include low molecular weight polyhydric alcohols such as ethylene glycol, diethylene glycol, 1,4-butanediol, and glycerin; low molecular weight amine polyols such as diethanolamine and triethanolamine; diamines such as ethylenediamine and xylene-diamine, and methylene-bis (o-chloroaniline). The use of such cross-linking agents or chain extenders is known in the art as disclosed in U.S. Patent Nos. 4,863,979 and 4,963,399 and EP 549,120.
    [075] Foams produced using compounds of the invention can be used in applications known in the industry. For example, flexible foams find use in applications such as vehicle parts, such as seats, armrests, dashboards or instrument panels, light shields, door linings, and noise insulation parts. Exemplary placement of foams includes locations such as under the carpet or in other parts of the car interior or in the engine compartment. The foam of the invention can also be used in many household applications such as shoe soles, fabric upholstery, instruments, furniture and bedding.
    [076] Processes for producing polyurethane foam products are well known in the art. In general, the polyurethane-forming reaction mixing components can be mixed in any convenient manner, for example, using any mixing equipment described in the prior art such as in Polyurethane Handbook, by G. Oertel, Hanser Publisher.
    [077] Polyurethane products can be produced continuously or discontinuously, by injection, casting, spraying, casting, calendering, etc. Foams can be prepared under free-lift or molded conditions, at atmospheric pressure, at reduced or increased air pressure, with or without release agents, mold coating, or with any inserts or films placed in the mold. Flexible molded foams can be mono or double hard.
    [078] Optionally, polyurethane foams can be described by one or more foam properties, including, but not limited to, density, indentation force deflection (IFD), permanent compression deformation, tensile strength, elongation ( elongation), and tear resistance.
    [079] Density is weight per unit volume (weight / volume) and typically expressed as pound / foot3 (pcf) or g / L. Exemplary densities are in the range of about 20 g / L to about 80 g / L, or more specifically in the range of about 25 g / L to about 32 g / L.
    [080] Compression force deflection (CFD), as measured by the ISO 3386/1 standard, is a standard test designed to measure compression stress / strain (load divided by specimen surface area by a given percentage of compression) foam characteristic. CFD is also a measure of consistency (firmness) and is expressed in pounds per square inch (psi) at a given percentage of deflection. Exemplary densities are in the range of about 20 g / L to about 80 g / L, or more specifically in the range of about 25 g / L to about 32 g / L.
    [081] Percentage permanent compression strain (CS), as measured by the ISO 1856 standard, is a measure of the permanent deformation of a foam after it has been compressed between two metal plates for a controlled time and temperature condition. Standard conditions are 22 hours at 70 ° C (158 ° F). Exemplary values of permanent compression strain are in the range of about 1 to about 20, or more specifically in the range of about 5 to about 7.
    [082] Tensile strength is a measure of the amount of force required to break an area of foam when it is disassembled, and is usually expressed in pounds per square inch (psi). Foam compositions can be prepared to provide foams with a desired tensile strength, or with a tensile strength within the limits of a desired range.
    [083] Elongation, as measured by the ISO 1798 standard, is a measure of the extent to which the foam can be stretched before it breaks and is expressed as a percentage of its original length. Elongation is measured at the same time as the tensile strength is determined; therefore, the sample size is the same. Exemplary elongation values are in the range of about 50 to about 200, or more specifically in the range of about 110 to about 130.
    [084] Tear resistance (tear), as measured by the ASTM D 3574 standard, is a measure of the force required to continue a tear in the foam after a split has been initiated and is expressed in pounds per linear inch (pli). Exemplary tear strengths are in the range of about 50 to about 350, or more specifically in the range of about 195 to about 230. Table 1
    Polyol A: DNC 701.01 Polyol B: SPECFLEX NC632; Specialty capped polyol with high Mw, functionality and primary hydroxyl content. Catalyst A: BPEA. Catalyst B: DABCO 33LV; contains 33% triethylenediamine and 67% dipropylene glycol (Air Products). Catalyst C: NIAX A-1; contains 70 percent bis (2-dimethylamino ethyl) ether, diluted with 30 weight percent dipropylene glycol (Momentive). DEOA: diethanolamine. Surfactant: Silicone surfactant TEGOSTAB B8736 LF2 (Evonik). VORANATE T-80: TDI 80/20 (Dow) Examples 7-9 Preparation of polyurethane foam
    [085] Foams from Examples 7-9 were prepared according to the method described in Examples 2-6 using reagents in quantities according to Table 2. Various foam properties shown in Table 3 were tested. Table 2
    Polyol C: SPECFLEX NC700; copolymer polyol formed by polymerization at the styrene and acrylonitrile site. Polyol B: SPECFLEX NC632; Specialty capped polyol with high Mw, functionality and primary hydroxyl content. Catalyst A: BPEA. Catalyst B: DABCO 33LV; contains 33% triethylenediamine and 67% dipropylene glycol (Air Products). Catalyst C: NIAX A-1; contains 70 percent bis (2-dimethylamino ethyl) ether, diluted with 30 weight percent dipropylene glycol (Momentive). DEOA: diethanolamine. Surfactant: Silicone surfactant TEGOSTAB B8736 LF2 (Evonik). VORANATE T-80: TDI 80/20 (Dow) Table 3
    权利要求:
    Claims (11)
    [0001]
    1. Composition, characterized by the fact that it comprises a reaction product derived from reagents comprising, or a reaction composition having reagents comprising: (a) a cyclic amine or amine alkoxylate of Formula I:
    [0002]
    2. Polyether polyol of amine, characterized by the fact that it is Formula III:
    [0003]
    3. Polyurethane foam, characterized in that it is derived from a composition comprising, or a composition having components comprising: (a) a cyclic amine or amine alkoxylate of Formula I:
    [0004]
    4. Method for preparing an amine polyether polyol, characterized in that it comprises a step of reacting a cyclic amine or amine alkoxylate of Formula I or II as defined by claim 1 with a polyol generator monomer.
    [0005]
    5. Method for preparing a polyurethane foam, characterized in that it comprises a step of reacting a polyol and a polyisocyanate in the presence of a cyclic amine or amine alkoxylate of Formula I or II as defined by claim 1; or a step of reacting an amine polyether polyol of Formula III or IV as defined by claim 3 with a polyisocyanate.
    [0006]
    6. Composition, as defined in claim 1 or method, as defined in claim 4, characterized in that the polyol-generating monomer is selected from the group consisting of halogenated epoxides or alcohols, or from the group consisting of ethylene oxide, propylene oxide , and butylene oxide.
    [0007]
    7. Composition, as defined in claim 1, polyether polyol of amine, as defined in claim 2, or foam, as defined in claim 3, characterized in that in Formula I, II, III, or IV, x and x 'are 0 (covalent bond).
    [0008]
    8. Composition, as defined in claim 1, or foam, as defined in claim 3, characterized in that in Formula I or II, R, R1-R7, and R1'-R7 'are hydrogen; or the polyether polyol of amine, as defined in claim 2, or the foam, as defined in claim 3, characterized in that in Formula III or IV, R, R1-R7, R10, R1'-R7 ', and R10' be hydrogen.
    [0009]
    9. Composition as defined in claim 1, or foam as defined in claim 3, characterized in that the cyclic amine of Formula I is bis (2-piperazin-1-yl-ethyl) amine; the cyclic amine of Formula II is 2- (4- (2-piperazin-1-yl) ethyl) piperazin-1-yl) ethanamine; the Formula I amine alkoxylate is 2.2 '- (4.4' - (((2-hydroxyethyl) azanediyl) bis (ethane-2,1-diyl)) bis (piperazine-4,1-diyl)) diethanol, 1,1 '- (4,4' - (((2-hydroxypropyl) azanediyl) bis (ethane-2,1-diyl)) bis (piperazine-4,1-diyl)) bis (propan-2- ol), or 1,1 '- (4,4' - (((2-hydroxybutyl) azanediyl) bis (ethane-2,1-diyl)) bis (piperazine-4,1-diyl)) bis (butan- 2-ol); or the Formula II amine alkoxylate is 2.2 '- ((2- (4- (2- (4- (2-hydroxyethyl) piperazin-1-yl) ethyl) azanediyl) diethanol, 1,1' - ( (2- (4- (2- (4- (2-hydroxypropyl) piperazin-1-yl) ethyl) azanediyl) bis (propan-2-ol), or 1,1 '- ((2- (4- ( 2- (4- (2-hydroxybutyl) piperazin-1-yl) ethyl) (piperazin-1-diyl) ethyl) azanediyl) bis (butan-2-ol).
    [0010]
    10. Polyether polyol of amine, as defined in claim 2, or foam as defined in claim 3, characterized in that in Formula III or IV, y, y ', y and y are independently whole numbers in the range 1 to 250, 10 to 100, or 25 to 75; compounds of Formula III or IV have a hydroxyl index in the range of 401.6 mg / g to 24 mg / g, or 250 mg / g to 50 mg / g; or compounds of Formula III or IV have a molecular weight in the range of 296 Da to 8000 Da, 420 Da to 7000 Da, 750 Da to 6000 Da, or 1000 Da to 5000 Da.
    [0011]
    11. Polyurethane foam according to claim 3, characterized in that it is derived from reagents further comprising (d) an amine catalyst that is different from (a) cyclic amine or Formula I or II amine alkoxylate or ( a) amine polyether polyol of Formula III or IV.
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    法律状态:
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-10-29| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2020-10-13| B09A| Decision: intention to grant|
    2020-12-29| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 28/12/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201161581323P| true| 2011-12-29|2011-12-29|
    US61/581,323|2011-12-29|
    US201261717901P| true| 2012-10-24|2012-10-24|
    US61/717,901|2012-10-24|
    PCT/US2012/072032|WO2013102053A1|2011-12-29|2012-12-28|Amine polyether polyols and polyurethane foam compositions made from cyclic amine compounds|
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