Polyurethane elastomer catalyst and application thereof in preparation of polyurethane elastomer

Abstract

The invention belongs to the technical field of high polymer material preparation, and relates to a polyurethane elastomer catalyst and application thereof in preparation of a polyurethane elastomer. The polyurethane elastomer catalyst provided by the invention is a double-component mixture of the iodine elementary substance and the nitrogen / phosphorus-containing organic base, and the two components have a synergistic effect, so that the polymerization reaction speed is increased when the polymerization of isocyanate and polyol is catalyzed; the polyurethane elastomer material catalytically synthesized by adopting the polyurethane elastomer catalyst disclosed by the invention has excellent physical properties, good elasticity, relatively good flexibility and relatively good low-temperature resistance.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer material preparation, and relates to a polyurethane elastomer catalyst and application thereof in the preparation of polyurethane elastomer. Background Art

[0002] Polyurethane elastomers (PU elastomers for short) are a class of polymer materials with excellent elasticity and wear resistance, mainly composed of polyurethane segments and flexible segments. Polyurethane elastomers are widely used in automotive parts, footwear, sports equipment, seals, gaskets, flooring materials and industrial tires. They are also used to manufacture products with excellent elasticity and mechanical properties, such as elastomer coatings, sealants and flexible pipes. Polyurethane elastomers are widely used in various industrial and consumer products due to their good elasticity, wear resistance and chemical resistance.

[0003] Polyurethane elastomers are made through polyurethane reactions, usually including the reaction products of polyisocyanates (such as MDI or TDI) and polyols (such as polyether alcohols or polyester alcohols), which are obtained by catalytic reactions at a certain temperature. A commonly used type of catalyst in the synthesis of polyurethane elastomers is metal organic compounds. The earliest such organometallic catalysts were organic compounds containing lead and mercury. However, because lead and mercury are heavy metals, they are harmful to the human body and will cause serious environmental pollution, and have been listed as products prohibited from use.

[0004] The great importance of catalysts in the preparation of polyurethane elastomers is well recognized. Organotin compounds mainly fill this catalytic role, and they participate in the polymerization reaction as Lewis acids with remarkable catalytic activity. However, the removal of catalysts from polyurethane elastomers is usually very difficult and cost-prohibitive, which is a significant disadvantage in most applications. For example, residual metal catalysts have adverse reactions with dielectric materials, toxicity, and harmful side reactions. It is worth noting that these disadvantages are usually overlooked in many studies, but should be seriously considered when designing polyurethane elastomers, especially for biomedical use. Therefore, people have been working hard to develop tin-free catalysts for the synthesis of polyurethane elastomers to avoid these adverse effects.

[0005] Organocatalysis has become a valuable tool in polymer synthesis, with its use demonstrated in ring-opening, anionic, zwitterionic, and group transfer polymerizations. Despite this, the application of organocatalysis to other polymerization reactions, such as step-growth polymerizations, remains underexplored relative to traditional metal-based polymerizations. Recently, the use of organic bases such as guanidines, amidines, N-heterocyclic carbonyls, and organic “strong or superstrong” Lewis bases to catalyze the synthesis of metal-free polyurethane elastomers has been shown to be competitive with the commercially widely used dibutyltin dilaurate and dibutyltin diacetate catalysts. Summary of the invention

[0006] The technical problem to be solved by the present invention is that the tin-free organic metal catalyst in the prior art not only has low catalytic activity but also has poor performance of the polyurethane elastomer material catalyzed and synthesized, and provides a polyurethane elastomer catalyst and its application in the preparation of polyurethane elastomer, specifically providing a polyurethane elastomer that is beneficial to the environment and avoids organic tin-based catalysts, and its preparation method and application.

[0007] Invention idea: In the preparation of polyurethane elastomers in this application, iodine element and nitrogen-containing organic base / phosphorus-containing organic base are used to react to form a complex. There are two σ holes at both ends of the iodine molecule, one hole is combined with the nitrogen-containing organic base / phosphorus-containing organic base, and the other end is combined with the oxygen of isocyanate. Compared with organic metal catalysts, the catalytic activity is improved and the performance of the catalytically synthesized polyurethane elastomer material is improved.

[0008] In order to solve the above technical problems, the technical solution adopted by the present invention is as follows:

[0009] The invention discloses a polyurethane elastomer catalyst, wherein the polyurethane elastomer catalyst is a composition of iodine and an organic base;

[0010] Wherein, the organic base is any one or a combination of the compound represented by the following formula I-1, the compound represented by the following formula I-2, the compound represented by the following formula I-3, the compound represented by the following formula II-1, the compound represented by the following formula II-2 and the compound represented by the following formula II-3;

[0011]

[0012] in,

[0013] R 1 , R 2 , R 3 Independently selected from hydroxy, substituted or unsubstituted C1-C4 alkyl, substituted or unsubstituted C1-C4 alkoxy, or substituted or unsubstituted phenyl;

[0014] R is selected from hydroxy, amino, carboxyl, or substituted or unsubstituted C1-C4 alkyl.

[0015] In some embodiments, preferably, R is selected from hydroxy, amino, carboxyl, ethyl, isopropyl, tert-butyl or sec-butyl.

[0016] In some embodiments, R 1 , R 2 , R 3 Independently selected from substituted or unsubstituted C1-C4 alkyl, wherein the C1-C4 alkyl is ethyl, propyl, tert-butyl or sec-butyl.

[0017] In some embodiments, preferably, R 1 , R 2 , R 3 Independently selected from hydroxy, substituted or unsubstituted C1-C2 alkyl, substituted or unsubstituted C1-C2 alkoxy, or substituted or unsubstituted phenyl.

[0018] In some embodiments, further preferably, R 1 , R 2 , R 3 Independently selected from hydroxy, ethyl, ethoxy or phenyl.

[0019] In some embodiments, the polyurethane elastomer catalyst is a composition of iodine and an organic base, and the molar ratio of the iodine and the organic base is (0.5-5.0):1.0.

[0020] In some embodiments, preferably, the polyurethane elastomer catalyst is a composition of iodine and an organic base, and the molar ratio of the iodine and the organic base is (0.5-2.0):1.0.

[0021] In some embodiments, further preferably, the polyurethane elastomer catalyst is a composition of elemental iodine and an organic base, and the molar ratio of the elemental iodine to the organic base is 1.0:1.0.

[0022] The use of the above-mentioned polyurethane elastomer catalyst in the preparation of polyurethane elastomer is also within the protection scope of the present invention.

[0023] Furthermore, the present invention discloses a polyurethane elastomer, which is prepared using polyol, diisocyanate, the above-mentioned polyurethane elastomer catalyst, and a chain extender as raw materials;

[0024] Wherein, the weight parts of each raw material are as follows:

[0025] Polyol, 10-100 parts;

[0026] Diisocyanate, 1 to 10 parts;

[0027] Polyurethane elastomer catalyst, 0.1-1.0 part;

[0028] Chain extender, 0.1 to 1.0 parts.

[0029] In some embodiments, the polyol is any one of polyether polyol and polyester polyol or a combination of two thereof; and / or, the polyester polyol is polycarbonate diol; and / or, the acid value of the polyol is less than 1.0 mgKOH / g; and / or, the hydroxyl value of the polyol is 26-62 mg KOH / g; and / or, the diisocyanate is any one of 4,4-diphenylmethane diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, 4,4-dicyclohexylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, meta-xylylene diisocyanate and 1,5-naphthalene diisocyanate or a combination thereof; and / or, the chain extender is any one of 1,4-butanediol, polyether diamine, polyester diamine, 1,4-butanediamine and 1,6-hexanediamine or a combination thereof.

[0030] In some embodiments, preferably, the polyol is a polyester polyol.

[0031] In some embodiments, preferably, the number average molecular weight of the polycarbonate diol is 400-5000 g / mol, for example, it can be 500 g / mol, 1000 g / mol, 1500 g / mol, 2000 g / mol, 2500 g / mol, 3000 g / mol, 3500 g / mol, 4000 g / mol, 4500 g / mol, etc., and more preferably 2000-3500 g / mol.

[0032] In some embodiments, the acid value of the polyol is less than 1.0 mg KOH / g, for example, it may be 0.2 mg KOH / g, 0.4 mg KOH / g, 0.6 mg KOH / g, 0.8 mg KOH / g, etc.

[0033] In some embodiments, the hydroxyl value of the polyol is 26-62 mg KOH / g, for example, 30 mg KOH / g, 35 mg KOH / g, 40 mg KOH / g, 45 mg KOH / g, 50 mg KOH / g, 55 mg KOH / g, 60 mg KOH / g, etc.

[0034] In some embodiments, further preferably, the hydroxyl value of the polyol is 26-40 mg KOH / g.

[0035] In some embodiments, preferably, the diisocyanate is 4,4-diphenylmethane diisocyanate.

[0036] In some embodiments, preferably, the chain extender is 1,4-butanediol.

[0037] In some embodiments, the polyurethane elastomer catalyst is a composition of iodine and an organic base; wherein the organic base is any one or a combination of the compound shown in Formula I-1, the compound shown in Formula I-2, the compound shown in Formula I-3, the compound shown in Formula II-1, the compound shown in Formula II-2 and the compound shown in Formula II-3;

[0038]

[0039] in,

[0040] R 1 , R 2 , R 3 Independently selected from hydroxy, substituted or unsubstituted C1-C4 alkyl, substituted or unsubstituted C1-C4 alkoxy, or substituted or unsubstituted phenyl;

[0041] R is selected from hydroxy, amino, carboxyl, or substituted or unsubstituted C1-C4 alkyl.

[0042] In some embodiments, preferably, R 1 , R 2 , R 3 Independently selected from hydroxy, substituted or unsubstituted C1-C2 alkyl, substituted or unsubstituted C1-C2 alkoxy, or substituted or unsubstituted phenyl.

[0043] In some embodiments, further preferably, R 1 , R 2 , R 3 Independently selected from hydroxy, ethyl, ethoxy or phenyl.

[0044] In some embodiments, the polyurethane elastomer catalyst is a composition of iodine and an organic base, and the molar ratio of the iodine and the organic base is (0.5-5.0):1.0.

[0045] In some embodiments, preferably, the polyurethane elastomer catalyst is a composition of iodine and an organic base, and the molar ratio of the iodine and the organic base is (0.5-2.0):1.0.

[0046] In some embodiments, further preferably, the polyurethane elastomer catalyst is a composition of elemental iodine and an organic base, and the molar ratio of the elemental iodine to the organic base is 1.0:1.0.

[0047] In some embodiments, the raw material of the polyurethane elastomer further includes a solvent; and / or, the raw material of the polyurethane elastomer further includes a solvent, and the solvent is any one or a combination of several of ethyl acetate, acetone, cyclohexanone, dioxane, tetrahydrofuran, benzene, toluene, xylene, dichloromethane, chloroform, tetrachloromethane, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide and acetonitrile;

[0048] And / or, when the raw materials of the polyurethane elastomer also include a solvent, the polyurethane elastomer is prepared from polyol, diisocyanate, the above-mentioned polyurethane elastomer catalyst, chain extender and solvent as raw materials;

[0049] Wherein, the weight parts of each raw material are as follows:

[0050] Polyol, 10-100 parts;

[0051] Diisocyanate, 1 to 10 parts;

[0052] Polyurethane elastomer catalyst, 0.1-1.0 part;

[0053] Chain extender, 0.1-1.0 part;

[0054] Solvent, 0.1 to 5.0 parts.

[0055] In some embodiments, the polyol is any one of polyether polyol and polyester polyol or a combination of two thereof; and / or, the polyester polyol is polycarbonate diol; and / or, the acid value of the polyol is less than 1.0 mgKOH / g; and / or, the hydroxyl value of the polyol is 26-62 mg KOH / g; and / or, the diisocyanate is any one of 4,4-diphenylmethane diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, 4,4-dicyclohexylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, meta-xylylene diisocyanate and 1,5-naphthalene diisocyanate or a combination thereof; and / or, the chain extender is any one of 1,4-butanediol, polyether diamine, polyester diamine, 1,4-butanediamine and 1,6-hexanediamine or a combination thereof.

[0056] In some embodiments, preferably, the polyol is a polyester polyol.

[0057] In some embodiments, preferably, the number average molecular weight of the polycarbonate diol is 400-5000 g / mol, for example, it can be 500 g / mol, 1000 g / mol, 1500 g / mol, 2000 g / mol, 2500 g / mol, 3000 g / mol, 3500 g / mol, 4000 g / mol, 4500 g / mol, etc., and more preferably 2000-3500 g / mol.

[0058] In some embodiments, the acid value of the polyol is less than 1.0 mg KOH / g, for example, it may be 0.2 mg KOH / g, 0.4 mg KOH / g, 0.6 mg KOH / g, 0.8 mg KOH / g, etc.

[0059] In some embodiments, the hydroxyl value of the polyol is 26-62 mg KOH / g, for example, 30 mg KOH / g, 35 mg KOH / g, 40 mg KOH / g, 45 mg KOH / g, 50 mg KOH / g, 55 mg KOH / g, 60 mg KOH / g, etc.

[0060] In some embodiments, further preferably, the hydroxyl value of the polyol is 26-40 mg KOH / g.

[0061] In some embodiments, preferably, the diisocyanate is 4,4-diphenylmethane diisocyanate.

[0062] In some embodiments, preferably, the chain extender is 1,4-butanediol.

[0063] In some embodiments, the polyurethane elastomer catalyst is a composition of iodine and an organic base; wherein the organic base is any one or a combination of the compound shown in Formula I-1, the compound shown in Formula I-2, the compound shown in Formula I-3, the compound shown in Formula II-1, the compound shown in Formula II-2 and the compound shown in Formula II-3;

[0064]

[0065] in,

[0066] R 1 , R 2 , R 3 Independently selected from hydroxy, substituted or unsubstituted C1-C4 alkyl, substituted or unsubstituted C1-C4 alkoxy, or substituted or unsubstituted phenyl;

[0067] R is selected from hydroxy, amino, carboxyl, or substituted or unsubstituted C1-C4 alkyl.

[0068] In some embodiments, preferably, R 1 , R 2 , R 3 Independently selected from hydroxy, substituted or unsubstituted C1-C2 alkyl, substituted or unsubstituted C1-C2 alkoxy, or substituted or unsubstituted phenyl.

[0069] In some embodiments, further preferably, R 1 , R 2 , R 3 Independently selected from hydroxy, ethyl, ethoxy or phenyl.

[0070] In some embodiments, the polyurethane elastomer catalyst is a composition of iodine and an organic base, and the molar ratio of the iodine and the organic base is (0.5-5.0):1.0.

[0071] In some embodiments, preferably, the polyurethane elastomer catalyst is a composition of iodine and an organic base, and the molar ratio of the iodine and the organic base is (0.5-2.0):1.0.

[0072] In some embodiments, further preferably, the polyurethane elastomer catalyst is a composition of elemental iodine and an organic base, and the molar ratio of the elemental iodine to the organic base is 1.0:1.0.

[0073] Furthermore, the present invention discloses a method for preparing the above-mentioned polyurethane elastomer, comprising the following steps:

[0074] The polyol, diisocyanate and the polyurethane elastomer catalyst in the above-mentioned weight proportions are mixed and stirred to carry out a prepolymerization reaction, and then a chain extender is added and stirred continuously to carry out a final polymerization reaction. After the reaction is completed, the polyurethane elastomer is obtained by removing bubbles and aging.

[0075] or,

[0076] The polyol, diisocyanate, the above-mentioned polyurethane elastomer catalyst and solvent in the above-mentioned parts by weight are mixed and stirred for prepolymerization reaction, and then a chain extender is added and stirred continuously for final polymerization reaction. After the reaction is completed, the polyurethane elastomer is obtained by degassing and ripening.

[0077] In some embodiments, the prepolymerization reaction has a reaction temperature of 25°C to 90°C; and / or, the prepolymerization reaction has a reaction time of 2h to 24h; and / or, the final polymerization reaction has a reaction temperature of 25°C to 90°C; and / or, the final polymerization reaction has a reaction time of 2h to 24h.

[0078] In some embodiments, preferably, the prepolymerization reaction has a reaction temperature of 55°C to 75°C, more preferably 65°C.

[0079] In some embodiments, preferably, the prepolymerization reaction has a reaction time of 2 h to 6 h, more preferably 4 h.

[0080] In some embodiments, preferably, the final polymerization reaction has a reaction temperature of 55°C to 75°C, more preferably 65°C.

[0081] In some embodiments, preferably, the final polymerization reaction has a reaction time of 2 h to 6 h, more preferably 4 h.

[0082] In some embodiments, preferably, the debubbling is performed using a high-speed centrifuge.

[0083] In some embodiments, preferably, the aging is carried out in a constant temperature drying oven at 35 to 80° C. for 4 to 24 hours.

[0084] In some embodiments, further preferably, the aging is carried out in a constant temperature drying oven at 55° C. for 10 hours.

[0085] The application of the above-mentioned polyurethane elastomer in biomedical materials and / or plastic packaging materials is also within the protection scope of the present invention.

[0086] Beneficial effects:

[0087] (1) The polyurethane elastomer catalyst provided by the present invention is a two-component mixture of iodine and nitrogen-containing / phosphorus-containing organic base. The organic base and iodine are easily available in industry as raw materials. The raw materials are cheap and easily available and have no by-products. The iodonium salt is generated in situ by a simple mixing method and forms a charge transfer complex with the isocyanate oxygen atom.

[0088] (2) The polyurethane elastomer catalyst provided by the present invention is a two-component mixture of iodine and nitrogen-containing / phosphorus-containing organic base. The two components act synergistically to increase the polymerization reaction rate when catalyzing the polymerization of isocyanate and polyol. The polyurethane elastomer material synthesized by using the polyurethane elastomer catalyst of the present application has excellent physical properties, good elasticity, good flexibility and low temperature resistance.

[0089] (3) The present invention aims to provide a two-component catalyst for preparing polyurethane elastomers to improve the crosslinking efficiency, mechanical properties and durability of polyurethane elastomers. The polyurethane elastomer catalyst is a two-component catalyst of iodine and a Lewis base (nitrogen-containing, phosphorus-containing). When used to prepare polyurethane elastomers, the synergistic effect of the two components of iodine and nitrogen-containing / phosphorus-containing Lewis base increases the polymerization reaction rate when catalyzing the polymerization of isocyanate and polyol, and the obtained polyurethane elastomer material has excellent physical properties, does not contain heavy metal elements at all, is an environmentally friendly catalyst, and solves the technical problem of ensuring environmental safety and catalytic efficiency of polyurethane elastomer catalysts at the same time.

[0090] (4) The mixture of iodine and nitrogen / phosphorus-containing organic base in the present invention is an efficient two-component catalyst for polyurethane elastomer, which is stable to air and water, does not contain metal, and has mild reaction conditions. It can catalyze the synthesis of polyurethane elastomer from polyol and isocyanate. The polyurethane elastomer catalyst provided by the present invention is not sensitive to the environment, which greatly enhances the process feasibility of the reaction.

[0091] (5) The iodine and nitrogen / phosphorus organic bases selected by the present invention are both raw materials with relatively mature industrial synthesis technology, which are cheap and easy to obtain, and have no by-products. The composition composed of iodine and nitrogen / phosphorus organic bases is used as a catalyst that is inexpensive and easy to prepare, which can reduce the cost in industrial production.

[0092] (6) The present invention uses the aforementioned two-component mixture of iodine and nitrogen-containing / phosphorus-containing organic base as a polyurethane elastomer catalyst to efficiently synthesize polyurethane elastomer. Compared with the polyurethane elastomer synthesized using a tin-containing catalyst, the polyurethane elastomer obtained by the method of the present invention has no metal residue and has broad application prospects. It has great commercial application potential in the fields of biomedicine and microelectronics.

[0093] (7) Experimental results show that the polyurethane elastomer catalyst provided by the present invention has high catalytic activity. Under certain reaction conditions, the polymerization reaction of isocyanate and polycarbonate diol is completed faster. Moreover, while ensuring the catalytic activity, the polyurethane elastomer prepared therefrom has excellent physical properties and better tensile strength.

[0094] (8) The experimental results show that the polyurethane elastomer adhesive prepared by the polyurethane elastomer catalyst provided by the present invention has excellent physical properties: the compressive strength, elastic modulus and shear strength are all maintained at a high level, the shrinkage rate is small, the elongation at break is high, and it has excellent bonding effect on porous materials such as foam plastics, wood, and leather. BRIEF DESCRIPTION OF THE DRAWINGS

[0095] The present invention will be further described in detail below in conjunction with the accompanying drawings and specific embodiments, and the above and / or other advantages of the present invention will become more clear.

[0096] Figure 1 This is the hydrogen nuclear magnetic resonance spectrum (400 MHz, DMSO-d6) of the polyurethane elastomer obtained in Example 1 of the present invention.

[0097] Figure 2 This is the carbon nuclear magnetic resonance spectrum (101 MHz, DMSO-d6) of the polyurethane elastomer obtained in Example 1 of the present invention.

[0098] Figure 3 The polyurethane elastomer 3D printed dumbbell-shaped spline obtained in Example 1 of the present invention. DETAILED DESCRIPTION

[0099] The present invention can be better understood according to the following examples. However, it is easy for those skilled in the art to understand that the contents described in the examples are only used to illustrate the present invention, and should not and will not limit the present invention described in detail in the claims.

[0100] The experimental methods described in the following examples are conventional methods unless otherwise specified; the reagents and materials described are commercially available unless otherwise specified.

[0101] The nuclear magnetic resonance hydrogen spectra involved in the following examples were measured using a Bruker AscendTM-400 nuclear magnetic resonance hydrogen spectrometer produced by Bruker Corporation, and the deuterated reagent used was deuterated chloroform (CDCl 3 ) and deuterated dimethyl sulfoxide (DMSO-d 6 ).

[0102] The polycarbonate diol used in the examples of the present invention has an acid value of 0.2 mg KOH / g, a hydroxyl value of 30 mg KOH / g, and a number average molecular weight of 2000 g / mol, and was purchased from Xuzhou Yihuiyang New Materials Co., Ltd.

[0103] The triethylamine used in the embodiments of the present invention has a chemical structural formula of

[0104] Triphenylamine used in the embodiment of the present invention has the chemical structural formula:

[0105] Triphenylphosphine used in the embodiment of the present invention has the chemical structural formula:

[0106] The diethyl phosphate used in the embodiments of the present invention has the chemical structural formula:

[0107] Example 1: Using iodine and triethylamine as polyurethane elastomer catalyst

[0108] 100g polycarbonate diol (PCDL), 12.5g 4,4-diphenylmethane diisocyanate (MDI), 0.8g polyurethane elastomer catalyst (iodine and triethylamine, wherein the molar ratio of iodine and triethylamine is 1:1) were mixed, and the prepolymerization reaction was carried out at 65°C for 4h, and then 0.45g 1,4-butanediol (BDO) was added, and then the final polymerization reaction was carried out at 65°C for 4h. At this time, there were many small bubbles in the product, which needed to be defoamed by a high-speed centrifuge (6000r / min, 3min); then the defoamed polyurethane product was poured into a mold and placed in a constant temperature drying oven at 55°C for 10 hours to cure it. After taking it out, the specimen was tested for performance.

[0109] The polyurethane elastomer obtained in Example 1 was subjected to nuclear magnetic resonance detection, and the nuclear magnetic resonance hydrogen spectrum (400 MHz, DMSO-d 6 ) Figure 1 As shown, carbon NMR spectrum (101MHz, DMSO-d 6 )like Figure 2 shown.

[0110] The polyurethane elastomer obtained in Example 1 was 3D printed, and the obtained dumbbell-shaped spline was as shown in the figure. Figure 3 shown.

[0111] Example 2: Using iodine and triphenylamine as polyurethane elastomer catalyst

[0112] 100g of polycarbonate diol (PCDL), 12.5g of 4,4-diphenylmethane diisocyanate (MDI), and 1.25g of polyurethane elastomer catalyst (iodine and triphenylamine, wherein the molar ratio of iodine and triphenylamine is 1:1) were mixed, and the prepolymerization reaction was carried out at 65°C for 4h, and then 0.45g of 1,4-butanediol (BDO) was added, and then the final polymerization reaction was carried out at 65°C for 4h. At this time, there were many small bubbles in the product, which needed to be defoamed by a high-speed centrifuge (6000r / min, 3min); then the defoamed polyurethane product was poured into a mold, placed in a constant temperature drying oven at 55°C for aging for 10 hours, and cured. After taking out, the specimen was tested for performance.

[0113] Example 3: Using iodine and triphenylphosphine as polyurethane elastomer catalyst

[0114] 100g of polycarbonate diol (PCDL), 12.5g of 4,4-diphenylmethane diisocyanate (MDI), and 1.3g of polyurethane elastomer catalyst (iodine and triphenylphosphine, wherein the molar ratio of iodine and triphenylphosphine is 1:1) were mixed, and the prepolymerization reaction was carried out at 65°C for 4h, and then 0.45g of 1,4-butanediol (BDO) was added, and then the final polymerization reaction was carried out at 65°C for 4h. At this time, there were many small bubbles in the product, which needed to be defoamed by a high-speed centrifuge (6000r / min, 3min); then the defoamed polyurethane product was poured into a mold and placed in a constant temperature drying oven at 55°C for 10 hours to cure it. After taking it out, the specimen was tested for performance.

[0115] Example 4: Using iodine and diethyl phosphate as polyurethane elastomer catalyst

[0116] 100g of polycarbonate diol (PCDL), 12.5g of 4,4-diphenylmethane diisocyanate (MDI), and 1.1g of polyurethane elastomer catalyst (iodine and diethyl phosphate, wherein the molar ratio of iodine and diethyl phosphate is 1:1) were mixed, and the prepolymerization reaction was carried out at 65°C for 4h, and then 0.45g of 1,4-butanediol (BDO) was added, and then the final polymerization reaction was carried out at 65°C for 4h. At this time, there were many small bubbles in the product, which needed to be defoamed by a high-speed centrifuge (6000r / min, 3min); then the defoamed polyurethane product was poured into a mold and placed in a constant temperature drying oven at 55°C for 10 hours to cure it. After taking it out, the specimen was tested for performance.

[0117] Comparative Example 1: Using iodine as a catalyst for polyurethane elastomer

[0118] The experimental method is the same as that of Example 1, except that iodine is used as the polyurethane elastomer catalyst.

[0119] 100g polycarbonate diol (PCDL), 12.5g 4,4-diphenylmethane diisocyanate (MDI), and 1.27g polyurethane elastomer catalyst (iodine element) were mixed and stirred at 65°C for prepolymerization for 4h, and then 0.45g 1,4-butanediol (BDO) was added, followed by stirring at 65°C for final polymerization for 4h. At this time, there were many small bubbles in the product, which needed to be defoamed using a high-speed centrifuge (6000r / min, 3min); then the defoamed polyurethane product was poured into a mold and placed in a constant temperature drying oven at 55°C for 10 hours to cure and shape it. After taking it out, the specimen was tested for performance.

[0120] Comparative Example 2: Using triethylamine as polyurethane elastomer catalyst

[0121] The experimental method is the same as that of Example 1, except that triethylamine is used as the polyurethane elastomer catalyst.

[0122] 100g polycarbonate diol (PCDL), 12.5g 4,4-diphenylmethane diisocyanate (MDI), and 0.5g polyurethane elastomer catalyst (triethylamine) were mixed and stirred at 65°C for prepolymerization for 4h, and then 0.45g 1,4-butanediol (BDO) was added, followed by stirring at 65°C for final polymerization for 4h. At this time, there were many small bubbles in the product, which needed to be defoamed using a high-speed centrifuge (6000r / min, 3min); then the defoamed polyurethane product was poured into a mold and placed in a constant temperature drying oven at 55°C for 10 hours to cure and shape it. After taking it out, the specimen was tested for performance.

[0123] Comparative Example 3: Using dibutyltin dilaurate as polyurethane elastomer catalyst

[0124] The experimental method is the same as that of Example 1, except that dibutyltin dilaurate is used as the polyurethane elastomer catalyst.

[0125] 100g polycarbonate diol (PCDL), 12.5g 4,4-diphenylmethane diisocyanate (MDI), 3.2g polyurethane elastomer catalyst (dibutyltin dilaurate) were mixed, stirred at 65°C for prepolymerization for 4h, and then 0.45g 1,4-butanediol (BDO) was added, followed by stirring at 65°C for final polymerization for 4h. At this time, there were many small bubbles in the product, which needed to be defoamed using a high-speed centrifuge (6000r / min, 3min); then the defoamed polyurethane product was poured into a mold and placed in a constant temperature drying oven at 55°C for 10 hours to cure and shape it. After taking it out, the specimen was tested for performance.

[0126] Comparative Example 4: Using triethyl lead as polyurethane elastomer catalyst

[0127] The experimental method is the same as that of Example 1, except that triethyl lead is used as the polyurethane elastomer catalyst.

[0128] 100g of polycarbonate diol (PCDL), 12.5g of 4,4-diphenylmethane diisocyanate (MDI), and 1.5g of polyurethane elastomer catalyst (triethyl lead) were mixed and stirred at 65°C for prepolymerization for 4h, and then 0.45g of 1,4-butanediol (BDO) was added, followed by stirring at 65°C for final polymerization for 4h. At this time, there were many small bubbles in the product, which needed to be defoamed using a high-speed centrifuge (6000r / min, 3min); then the defoamed polyurethane product was poured into a mold and placed in a constant temperature drying oven at 55°C for 10 hours to cure and shape it. After taking it out, the specimen was tested for performance.

[0129] Comparative Example 5: Using triethylenediamine as polyurethane elastomer catalyst

[0130] The experimental method is the same as that of Example 1, except that triethylenediamine is used as the polyurethane elastomer catalyst.

[0131] 100g of polycarbonate diol (PCDL), 12.5g of 4,4-diphenylmethane diisocyanate (MDI), and 0.6g of polyurethane elastomer catalyst (triethylenediamine) were mixed and stirred at 65°C for prepolymerization for 4h, and then 0.45g of 1,4-butanediol (BDO) was added, followed by stirring at 65°C for final polymerization for 4h. At this time, there were many small bubbles in the product, which needed to be defoamed using a high-speed centrifuge (6000r / min, 3min); then the defoamed polyurethane product was poured into a mold and placed in a constant temperature drying oven at 55°C for 10 hours to cure and shape it. After taking it out, the specimen was tested for performance.

[0132] Comparative Example 6: Using BDMA as a polyurethane elastomer catalyst

[0133] The experimental method is the same as that of Example 1, except that BDMA is used as the polyurethane elastomer catalyst.

[0134] 100g polycarbonate diol (PCDL), 12.5g 4,4-diphenylmethane diisocyanate (MDI), 0.7g polyurethane elastomer catalyst (BDMA, N,N-dimethylbenzylamine) were mixed, stirred at 65°C for prepolymerization for 4h, and then 0.45g 1,4-butanediol (BDO) was added, followed by stirring at 65°C for final polymerization for 4h. At this time, there were many small bubbles in the product, which needed to be defoamed using a high-speed centrifuge (6000r / min, 3min); then the defoamed polyurethane product was poured into a mold and placed in a constant temperature drying oven at 55°C for 10 hours to cure and shape it. After taking it out, the specimen was tested for performance.

[0135] Embodiment 5:

[0136] The polyurethane elastomers prepared in Examples 1 to 4 and Comparative Examples 1 to 6 were tested for tensile strength, tensile elastic modulus, tensile strain at break, nominal strain at break, maximum displacement, maximum force and other data of the samples according to the national light industry standard "QBT2710-2005". The results are shown in Table 1.

[0137] Table 1 Determination of tensile properties of polyurethane elastomers

[0138]

[0139] It can be seen from the above results that the polyurethane elastomer catalyst provided by Examples 1 to 4 has a higher catalytic activity and, under certain reaction conditions, the polymerization reaction of isocyanate and polycarbonate diol is completed faster; and while ensuring the catalytic activity, the prepared polyurethane elastomer has excellent physical properties and better tensile strength.

[0140] Embodiment 6:

[0141] The polyurethane elastomers prepared in Examples 1 to 4 and Comparative Examples 1 to 6 were tested for elongation at break according to the national standard GB / T6344-86, for shear strength according to the national standard GB / T7124-1986, for compressive strength and elastic modulus according to the national standard GB / T12954-1991, and for shrinkage according to the standard HG / T2380-1992 of the Ministry of Chemical Industry. The results are shown in Table 2.

[0142] Table 2

[0143]

[0144]

[0145] It can be seen from the above results that the polyurethane elastomer adhesive prepared using the polyurethane elastomer catalyst provided in Examples 1 to 4 has excellent physical properties: the compressive strength, elastic modulus and shear strength are all maintained at a high level, the shrinkage rate is small, the elongation at break is high, and it has excellent bonding effect on porous materials such as foam plastics, wood, and leather.

[0146] It is worth noting that the numerical range described in the present invention includes not only the point values ​​listed above, but also any point values ​​between the above numerical ranges that are not listed. Due to the limited space and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range. The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise range or value, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed in this article.

[0147] The present invention provides a polyurethane elastomer catalyst and its application in the preparation of polyurethane elastomer. There are many methods and ways to implement the technical solution. The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the protection scope of the present invention. All components not specified in this embodiment can be implemented by existing technologies.

Claims

1. A polyurethane elastomer catalyst, characterized in that: The polyurethane elastomer catalyst is a composition of iodine and an organic base; Wherein, the organic base is any one or a combination of the compound represented by the following formula I-1, the compound represented by the following formula I-2, the compound represented by the following formula I-3, the compound represented by the following formula II-1, the compound represented by the following formula II-2 and the compound represented by the following formula II-3; in, R1, R2, and R3 are independently selected from hydroxy, substituted or unsubstituted C1-C4 alkyl, substituted or unsubstituted C1-C4 alkoxy, or substituted or unsubstituted phenyl; R is selected from hydroxy, amino, carboxyl, or substituted or unsubstituted C1-C4 alkyl.

2. The polyurethane elastomer catalyst according to claim 1, characterized in that R1, R2, and R3 are independently selected from hydroxy, substituted or unsubstituted C1-C2 alkyl, substituted or unsubstituted C1-C2 alkoxy, or substituted or unsubstituted phenyl; Preferably, R1, R2, R3 are independently selected from hydroxy, ethyl, ethoxy or phenyl.

3. Use of the polyurethane elastomer catalyst according to claim 1 in the preparation of polyurethane elastomer.

4. A polyurethane elastomer, characterized in that Prepared from polyol, diisocyanate, the polyurethane elastomer catalyst according to claim 1 or 2, and a chain extender as raw materials; Wherein, the weight parts of each raw material are as follows: Polyol, 10-100 parts; Diisocyanate, 1 to 10 parts; Polyurethane elastomer catalyst, 0.1-1.0 part; Chain extender, 0.1 to 1.0 parts.

5. The polyurethane elastomer according to claim 4, characterized in that The polyol is any one of polyether polyol and polyester polyol or a combination of two thereof; and / or, the polyester polyol is polycarbonate diol; and / or, the acid value of the polyol is less than 1.0 mg KOH / g; and / or, the hydroxyl value of the polyol is 26-62 mg KOH / g; and / or, the diisocyanate is any one of 4,4-diphenylmethane diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, 4,4-dicyclohexylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, meta-xylylene diisocyanate and 1,5-naphthalene diisocyanate or a combination thereof; and / or, the chain extender is any one of 1,4-butanediol, polyether diamine, polyester diamine, 1,4-butanediamine and 1,6-hexanediamine or a combination thereof.

6. The polyurethane elastomer catalyst according to claim 1 or the polyurethane elastomer according to claim 4, characterized in that: The polyurethane elastomer catalyst is a composition of iodine and an organic base, and the molar ratio of the iodine and the organic base is (0.5-5.0):1.

0.

7. The polyurethane elastomer according to claim 4, characterized in that: The raw material of the polyurethane elastomer further includes a solvent; and / or, the raw material of the polyurethane elastomer further includes a solvent, and the solvent is any one or a combination of several of ethyl acetate, acetone, cyclohexanone, dioxane, tetrahydrofuran, benzene, toluene, xylene, dichloromethane, chloroform, tetrachloromethane, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide and acetonitrile; And / or, when the raw materials of the polyurethane elastomer also include a solvent, the polyurethane elastomer is prepared from polyol, diisocyanate, the polyurethane elastomer catalyst according to claim 1 or 2, a chain extender and a solvent as raw materials; Wherein, the weight parts of each raw material are as follows: Polyol, 10-100 parts; Diisocyanate, 1 to 10 parts; Polyurethane elastomer catalyst, 0.1-1.0 part; Chain extender, 0.1-1.0 part; Solvent, 0.1 to 5.0 parts.

8. The method for preparing a polyurethane elastomer according to any one of claims 4 to 7, characterized in that: The steps include: The polyol, diisocyanate and the polyurethane elastomer catalyst according to claim 1 or 2 are mixed in the above weight proportions, stirred to carry out a prepolymerization reaction, and then a chain extender is added, and the final polymerization reaction is carried out by continuing to stir. After the reaction is completed, the polyurethane elastomer is obtained by removing bubbles and aging. or, The polyol, diisocyanate, the polyurethane elastomer catalyst according to claim 1 or 2 and the solvent in the above-mentioned weight proportions are mixed and stirred for prepolymerization reaction, and then a chain extender is added and stirred continuously for final polymerization reaction. After the reaction is completed, the polyurethane elastomer is obtained by degassing and ripening.

9. The preparation method according to claim 8, characterized in that: The reaction temperature of the prepolymerization reaction is 25°C to 90°C; and / or, the reaction time of the prepolymerization reaction is 2h to 24h; and / or, the reaction temperature of the final polymerization reaction is 25°C to 90°C; and / or, the reaction time of the final polymerization reaction is 2h to 24h.

10. Use of the polyurethane elastomer according to any one of claims 4 to 7 in biomedical materials and / or plastic packaging materials.

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