Preparation method and application of polycarbonate block polyol

Abstract

The invention relates to a preparation method of polycarbonate block polyol, which comprises the following steps: preparing polycarbonate polyol from siloxane diol / amine, phosphorus-containing diol, aliphatic diol and / or alicyclic diol, carbonic ester and a catalyst through ester exchange and condensation polymerization, according to the polycarbonate polyol, the polycarbonate block polyol is prepared by initiating a lactone ring-opening polymerization reaction. A polyurethane elastomer prepared from the polycarbonate block polyol is excellent in performance, can be used in the fields of industrial products and civil supplies, such as oil pipes, cables, wheels, belts, sealing elements, leather, adhesives, coatings, printing ink, PUR, PUD, CPUs, shoe glue and the like, and can also be used in the medical field, such as medical catheters, medical balloons, medical injection molding joints, medical injection molding connecting pieces and the like.

Description

Technical Field

[0001] The invention relates to the field of polyols and polyurethanes, and in particular to the preparation of a polycarbonate block polyol and a polyurethane prepared from the polycarbonate block polyol. The polyurethane has the characteristics of low temperature resistance and excellent biocompatibility and can be used in industrial products, medical treatment and other fields. Background Art

[0002] Currently, the polycarbonate diols available on the market are usually homopolymerized hexanediol-type polycarbonate diols, copolypentanediol / hexanediol-type polycarbonate diols and other short-chain diol-type homopolymerized or copolymerized polycarbonate diols. Thanks to its high-energy carbonate bonds, the polycarbonate polyurethane elastomers prepared therefrom have outstanding properties such as heat resistance, oil resistance, hydrolysis resistance, acid resistance, alkali resistance, solvent resistance and excellent biocompatibility, but its poor low-temperature resistance and poor elasticity limit its use in scenarios that require low-temperature resistance, such as shale oil pipes, cables and other outdoor applications. It is usually necessary to improve low-temperature resistance and resilience by physically blending polyesters, polycaprolactones and polyether polyols, but the production process is complicated because it involves blending multiple polyols. Summary of the invention

[0003] The object of the present invention is to provide a method for preparing a polycarbonate block polyol. The polyurethane prepared by using the polycarbonate block polyol has the characteristics of low temperature resistance and good resilience, which solves the shortcomings of polycarbonate polyurethane in the prior art that the low temperature resistance is poor and it cannot be used in extremely cold outdoor application scenarios, thereby broadening the application field of polyurethane. In addition, the polyurethane of the present invention contains silicon and phosphorus elements and has an intrinsic flame retardant effect.

[0004] The technical solution of the present invention is as follows:

[0005] A method for preparing a polycarbonate block polyol comprises:

[0006] (1) preparing polycarbonate polyol by transesterification and polycondensation of siloxane diol / amine, phosphorus-containing diol, aliphatic diol and / or alicyclic diol, carbonate and catalyst;

[0007] (2) Polycarbonate polyol is subjected to a ring-opening polymerization reaction with lactone to prepare polycarbonate block polyol.

[0008] In the present invention, the siloxane diol / amine is one or more of the following structures:

[0009]

[0010]

[0011] Wherein, R1 is any one of the following structures: -OH, C3-C6 alkyl with -OH as the terminal group, C3-C6 alkoxy with -OH as the terminal group, C3-C6 alkyl with -NH2 as the terminal group,

[0012] Any one of the following structures is preferred:

[0013] -OH,

[0014] R2 is -OH.

[0015] In the present invention, the number average molecular weight of the siloxane diol / amine is preferably 300-4000.

[0016] In the present invention, the phosphorus-containing diol is one or more of the following structures:

[0017]

[0018] Among them, R3, R4, and R5 independently represent one or more of C1-C10 straight or branched alkyl groups, C2-C10 aryl groups, R3 and R4 are preferably -CH2-CH2-CH2- and / or -CH2-CH2-CH2-CH2-, and R5 is preferably -CH2-CH(CH3)2.

[0019] In the present invention, the aliphatic diol is a C2-C10 diol, including one or more of ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, diethylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, and 1,10-decanediol, preferably 1,4-butanediol and 1,6-hexanediol;

[0020] The alicyclic diol is 1,4-cyclohexanediol and / or 1,4-cyclohexanedimethanol, preferably 1,4-cyclohexanedimethanol.

[0021] In the present invention, the carbonate includes one or more of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, diphenyl carbonate, and ethylene carbonate.

[0022] In the present invention, the catalyst is one or more of tetraethyl titanate, tetra-n-butyl titanate, tetraisopropyl titanate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin octoate, di-n-butyltin oxide, and stannous octoate; the catalyst addition amount is 30-200ppm of the total feed amount (the sum of the mass of siloxane diol / amine, phosphorus-containing diol, aliphatic diol and / or alicyclic diol, and carbonate), preferably 50-100ppm.

[0023] In the present invention, the lactone includes one or more of caprolactone, valerolactone and butyrolactone.

[0024] In the present invention, the preparation of the polycarbonate polyol, based on the total weight of the raw materials, the proportions of the components are as follows:

[0025] Siloxane diol / amine 40-75%, preferably 45-70%;

[0026] Phosphorus-containing diol 10-40%, preferably 15-35%;

[0027] Aliphatic diol and / or alicyclic diol 5-20%, preferably 6-15%;

[0028] Carbonate 5-30%, preferably 10-20%;

[0029] The present invention also provides a method for preparing the polycarbonate polyol: under nitrogen protection, siloxane diol / amine, phosphorus-containing diol, aliphatic diol and / or alicyclic diol, carbonate and catalyst are added to a reaction kettle, the temperature is raised to 160-250° C., preferably 200-220° C., at normal pressure, and after maintaining the temperature at normal pressure for a period of time (e.g., 10-30 hours), vacuuming is performed to continue the reaction until the hydroxyl value reaches the required value.

[0030] In the present invention, the preparation of the polycarbonate block polyol is based on the total weight of the raw materials, and the proportions of the components are as follows:

[0031] Polycarbonate polyol 10-90%, preferably 70-80%;

[0032] Lactone 90%-10%, preferably 20-30%;

[0033] The present invention also provides a method for preparing the polycarbonate block polyol. Under nitrogen protection, polycarbonate polyol is added to a reaction kettle, heated to 100-130°C, vacuum dehydrated, cooled to below 60°C, lactone is added, the reaction kettle is heated to 160-190°C, a catalyst is added, vacuum is drawn and the reaction is continued until the acid value reaches the requirement; the catalyst can be stannous octoate, tetra-n-butyl titanate, or tetraisopropyl titanate, and the added amount is generally 10-100 ppm.

[0034] The invention also relates to the application of the polycarbonate block polyol for preparing polyurethane elastomer.

[0035] A polyurethane elastomer is prepared by reacting raw materials including the above-mentioned polycarbonate block polyol, diisocyanate and chain extender.

[0036] In the present invention, the diisocyanate is one or more of an aromatic polyisocyanate, an aliphatic polyisocyanate, and an alicyclic polyisocyanate; preferably 4,4'-diphenylmethane diisocyanate, 2,4-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,5-naphthalene diisocyanate, 1,4-phenylene diisocyanate, m-xylylene diisocyanate, diphenylmethane-3,3'-dimethoxy-4,4'-diisocyanate, 1,6-hexamethylene diisocyanate, 1,10-decane diisocyanate, 1,3 -cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, 2,4-hexahydrotoluene diisocyanate, 2,6-hexahydrotoluene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 2,2'-dicyclohexylmethane diisocyanate, 2,4-dicyclohexylmethane diisocyanate, isophorone diisocyanate, lysine diisocyanate, L-lysine diisocyanate, 1,4-butane diisocyanate, 1,5-pentane diisocyanate or more, more preferably 4,4'-diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate and 4,4'-dicyclohexylmethane diisocyanate.

[0037] In the present invention, the chain extender is an aliphatic diol and / or an alicyclic diol with a molecular weight of 60-200 g / mol; preferably, the aliphatic diol is one or more of ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, diethylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, neopentyl glycol, and 1,6-hexanediol, preferably 1,4-butanediol and 1,6-hexanediol; the alicyclic diol is 1,4-cyclohexanediol and / or 1,4-cyclohexanedimethanol, preferably 1,4-cyclohexanedimethanol.

[0038] A polyurethane elastomer, based on the total weight of raw materials, the proportions of each component are as follows:

[0039] Polycarbonate block polyol 30%-80%, preferably 40-75%, such as 50%, 55%, 60%, 65%, 70%, etc.;

[0040] Chain extender 4%-30%, preferably 5-20%, such as 10%, 15%, 20%, 25%, etc.;

[0041] Diisocyanate 15-60%, preferably 20-50%, for example 20%, 25%, 30%, 35%, 40%, etc.

[0042] The polyurethane elastomer can be used in the fields of industrial products and civilian products, such as oil pipes, cables, wheels, belts, seals, leather, adhesives, coatings, inks, PUR, PUD, CPU, shoe glue, etc. It can also be used in the medical field, such as medical catheters, medical balloons, medical injection molding joints, medical injection molding connectors, etc.

[0043] Beneficial effects of the present invention:

[0044] In the prior art, polycarbonate polyurethane has a low temperature resistance difference, and usually needs to be optimized by blending polyols such as polycaprolactone and polyether for low temperature resistance. In the production process, it is necessary to stir and mix multiple polyols, which increases the process flow. The present invention solves the defects of the above prior art, provides a novel preparation method of polycarbonate block polyol, introduces siloxane flexible chain into polyol, and improves low temperature flexibility. Moreover, the present invention prepares polycarbonate-block polylactone by copolymerizing lactone, connects two polyols by covalent bonds, and solves the problem of complex production process of two polyol physical blending. In addition, polyurethane of the present invention contains silicon and phosphorus elements, and has intrinsic flame retardant effect. DETAILED DESCRIPTION

[0045] Below we further elaborate the present invention in detail with reference to specific embodiments, but the scope of the present invention is not limited to these embodiments. Without departing from the above method concept of the present invention, various substitutions or changes made according to common technical knowledge and customary means in the art should be included in the scope of the present invention.

[0046] Source of raw materials:

[0047] Dimethyl carbonate, 1,4-butanediol, 4,4'-diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, homopolymer 1,6-hexanediol type polycarbonate diol HD200 (molecular weight 2000), copolymer 1,5-pentanediol and 1,6-hexanediol type polycarbonate diol CD200 (molecular weight 2000), Wanhua Chemical Group Co., Ltd., industrial grade.

[0048] Isobutyl bis(hydroxypropyl)phosphine oxide, Solvay.

[0049] 1,6-Hexanediol, Yuanli Chemical Group Co., Ltd., industrial grade.

[0050] 1,5-Pentanediol, Zhejiang Boju.

[0051] 1,4-Cyclohexanedimethanol, SK chemicals, Korea, industrial grade.

[0052] Unless otherwise specified, the raw materials used in the examples or comparative examples were obtained from commercial channels.

[0053] Test method:

[0054] Tensile strength testing equipment, Shimadzu tensile testing machine, testing standard ASTM D 412.

[0055] Limiting oxygen index test equipment, oxygen index tester, model JF-5, Jionglei Instruments, test standard ASTMD2863.

[0056] Example 1

[0057] The structure of siloxane diol is as follows, and the number average molecular weight is 1000 g / mol.

[0058]

[0059] Preparation of polycarbonate polyol: Under nitrogen protection, 1000g dimethyl carbonate, 4498g siloxane diol, 2000g isobutyl dihydroxypropyl phosphine oxide, 1063g 1,6-hexanediol, and 0.26g tetrabutyl titanate catalyst were mixed and added to the reactor, and the reactor was gradually heated to 190°C. After reacting for 20 hours, the reactor was slowly evacuated to 6KPa, and the vacuum reaction was continued for 20 hours. The temperature was lowered and the material was discharged to obtain polycarbonate polyol. The hydroxyl value was 56.24mgKOH / g, the acid value was 0.1mgKOH / g, and the molecular weight was 2000.

[0060] Preparation of polycarbonate block polycaprolactone polyol: Under nitrogen protection, 1000g of the above polycarbonate polyol was added to the reactor, heated to 120°C, vacuum dehydrated for half an hour, cooled to below 60°C, 250g of caprolactone was added, the reactor was heated to 175°C, 0.05g of stannous octoate catalyst was added, and after 4 hours, samples were taken to test the acid value, vacuumed, and samples were taken every 1h to test the acid value until the acid value was <0.1mgKOH / g, and the material was cooled and discharged, with a molecular weight of 2500.

[0061] Preparation of polyurethane:

[0062] 680g of polycarbonate block polycaprolactone polyol prepared in the above steps was added to the reactor, heated to 130°C, 66g of 1,4-butanediol was added and stirred to mix evenly, 254g of 4,4'-diphenylmethane diisocyanate and 0.06g of stannous octoate were added in sequence, stirred at high speed with a stirrer, and after fully reacting for 1min, it was quickly poured into a Teflon cloth mold and placed in a 100°C oven for aging for 12h to obtain a thermoplastic polyurethane elastomer. The physical properties of the thermoplastic polyurethane elastomer after 24h at the standard temperature of 23°C and the low temperature resistance of -40°C were compared and tested.

[0063] Example 2

[0064] The structure of siloxane diol is as follows, and the number average molecular weight is 1000 g / mol.

[0065]

[0066] Polycarbonate polyol: Under nitrogen protection, 1000g dimethyl carbonate, 4668g siloxane diol, 3112g isobutyl dihydroxypropyl phosphine oxide, 552g 1,6-hexanediol, and 0.39g tetrabutyl titanate catalyst were mixed and added to the reactor. The reactor was gradually heated to 190°C. After reacting for 20h, it was slowly evacuated to 6KPa, and the vacuum reaction was continued for 20h. The temperature was lowered and the material was discharged to obtain polycarbonate polyol. The hydroxyl value was 56.32mgKOH / g, the acid value was 0.1mgKOH / g, and the molecular weight was 2000.

[0067] Polycarbonate block polycaprolactone polyol: Under nitrogen protection, add 1000g of the above polycarbonate polyol into the reactor, heat to 120°C, vacuum dehydrate for half an hour, cool to below 60°C, add 250g of caprolactone, heat the reactor to 175°C, add 0.05g of stannous octoate catalyst, take samples to test the acid value after 4 hours, evacuate, and subsequently take samples to test the acid value every 1h until the acid value is <0.1mgKOH / g, cool and discharge, with a molecular weight of 2500.

[0068] Preparation of polyurethane

[0069] 720 g of the polycarbonate block polycaprolactone polyol prepared in the above steps was added to the reactor and heated to 130° C., 54.5 g of 1,4-butanediol was added and stirred to mix evenly, 226 g of 4,4'-diphenylmethane diisocyanate and 0.06 g of stannous octoate were added in sequence, and stirred at high speed using a stirrer. After fully reacting for 1 min, the mixture was quickly poured into a Teflon cloth mold and placed in an oven at 100° C. for aging for 12 h to obtain a thermoplastic polyurethane elastomer. The physical properties of the thermoplastic polyurethane elastomer were compared and tested at a standard temperature of 23° C. and at a low temperature of -40° C. after 24 h.

[0070] Example 3

[0071] The structure of siloxane diol is as follows, and the number average molecular weight is 1000.

[0072]

[0073] Polycarbonate polyol: Under nitrogen protection, 1000g dimethyl carbonate, 6913g siloxane diol, 1537g isobutyl dihydroxypropyl phosphine oxide, 720g 1,5-pentanediol, and 0.31g tetrabutyl titanate catalyst were mixed and added to the reactor, and the reactor was gradually heated to 190°C. After reacting for 20 hours, the reactor was slowly evacuated to 6KPa, and the vacuum reaction was continued for 20 hours. The temperature was lowered and the material was discharged to obtain polycarbonate polyol. The hydroxyl value was 56.17mgKOH / g, the acid value was 0.1mgKOH / g, and the molecular weight was 2000.

[0074] Polycarbonate block polycaprolactone polyol: Under nitrogen protection, add 1000g of the above polycarbonate polyol into the reactor, heat to 120°C, vacuum dehydrate for half an hour, cool to below 60°C, add 250g of caprolactone, heat the reactor to 175°C, add 0.05g of stannous octoate catalyst, take samples to test the acid value after 4 hours, evacuate, and subsequently take samples to test the acid value every 1h until the acid value is <0.1mgKOH / g, cool and discharge, with a molecular weight of 2500.

[0075] Preparation of polyurethane

[0076] 700 g of the polycarbonate block polycaprolactone polyol prepared in the above steps was added to the reactor and heated to 130° C., 87.5 g of 1,4-butanediol was added and stirred to mix evenly, 212 g of 1,6-hexamethylene diisocyanate and 0.06 g of dibutyltin dilaurate were added in sequence, and stirred at high speed using a stirrer. After fully reacting for 2 minutes, the mixture was quickly poured into a Teflon cloth mold and placed in an oven at 100° C. for aging for 12 hours to obtain a thermoplastic polyurethane elastomer. The physical properties of the thermoplastic polyurethane elastomer were compared and tested at a standard temperature of 23° C. and at a low temperature of -40° C. after 24 hours.

[0077] Example 4

[0078] The structure of siloxane diol is as follows: polydimethylsiloxane-co-diphenylsiloxane, number average molecular weight 439.

[0079]

[0080] Polycarbonate polyol: Under nitrogen protection, 1000g dimethyl carbonate, 2721g siloxane diol, 1378g isobutyl dihydroxypropyl phosphine oxide, 894g 1,4-cyclohexanedimethanol, and 0.18g tetrabutyl titanate catalyst were mixed and added to the reactor. The reactor was gradually heated to 190°C. After reacting for 20h, it was slowly evacuated to 6KPa, and the vacuum reaction was continued for 20h. The temperature was lowered and the material was discharged to obtain polycarbonate polyol. The hydroxyl value was 74.82mgKOH / g, the acid value was 0.2mgKOH / g, and the molecular weight was 1500.

[0081] Polycarbonate block polycaprolactone polyol: Under nitrogen protection, add 1000g of the above polycarbonate polyol into the reactor, heat to 120°C, vacuum dehydrate for half an hour, cool to below 60°C, add 333g of caprolactone, heat the reactor to 175°C, add 0.05g of stannous octoate catalyst, take samples to test the acid value after 4 hours, evacuate, and then take samples every 1h to test the acid value until the acid value is <0.1mgKOH / g, cool and discharge, with a molecular weight of 2000.

[0082] Preparation of polyurethane

[0083] 600 g of the polycarbonate block polycaprolactone polyol prepared in the above steps was added to the reactor and heated to 130° C., 82 g of 1,4-butanediol was added and stirred to mix evenly, 318 g of 4,4'-dicyclohexylmethane diisocyanate and 0.12 g of dibutyltin dilaurate were added in sequence, and stirred at high speed using a stirrer. After fully reacting for 2 minutes, the mixture was quickly poured into a Teflon cloth mold and placed in an oven at 100° C. for aging for 12 hours to obtain a thermoplastic polyurethane elastomer. The physical properties of the thermoplastic polyurethane elastomer were compared and tested at a standard temperature of 23° C. and at a low temperature of -40° C. after 24 hours.

[0084] Comparative Example 1

[0085] 680 g of polycarbonate polyol HD200 with a molecular weight of 2000 was added to the reactor and heated to 130°C. 62.2 g of 1,4-butanediol was added and stirred to mix evenly. 258 g of 4,4'-diphenylmethane diisocyanate and 0.06 g of stannous octoate were added in sequence and stirred at high speed using a stirrer. After fully reacting for 1 minute, the mixture was quickly poured into a Teflon cloth mold and placed in a 100°C oven for aging for 12 hours to obtain a thermoplastic polyurethane elastomer. The physical properties of the thermoplastic polyurethane elastomer were compared and tested after 24 hours at a standard temperature of 23°C and at a low temperature resistance of -40°C.

[0086] Comparative Example 2

[0087] 720 g of polycarbonate polyol CD200 with a molecular weight of 2000 was added to the reactor and heated to 130°C. 50.3 g of 1,4-butanediol was added and stirred to mix evenly. 230 g of 4,4'-diphenylmethane diisocyanate and 0.06 g of stannous octoate were added in sequence and stirred at high speed using a stirrer. After fully reacting for 1 minute, the mixture was quickly poured into a Teflon cloth mold and placed in a 100°C oven for aging for 12 hours to obtain a thermoplastic polyurethane elastomer. The physical properties of the thermoplastic polyurethane elastomer were compared and tested after 24 hours at a standard temperature of 23°C and at a low temperature of -40°C.

[0088] The examples and comparative examples of polyurethane elastomer are shown in Table 1.

[0089] Table 1 Polyurethane elastomer properties

[0090]

[0091] According to the test results in Table 1, the elongation of the thermoplastic polyurethane elastomer of the embodiment does not change significantly under the standard temperature of 23°C and the low temperature resistance of -40°C for 24 hours, and both retain a high elongation, indicating that the elastomer has good elasticity under both the standard temperature and low temperature resistance conditions. Although the thermoplastic polyurethane elastomer of the comparative example has a high elongation at the standard temperature of 23°C, after being low-temperature resistant at -40°C for 24 hours, the elongation is significantly reduced, the elasticity decreases, and the low temperature resistance is poor. The limiting oxygen index of the embodiment of the present invention is significantly lower than that of the comparative example, and has an intrinsic flame retardant effect.

[0092] The above embodiments are merely examples for the purpose of clear explanation and do not mean that the present invention is limited thereto. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation methods here. However, the obvious changes or modifications derived therefrom are still within the protection scope of the present invention.

Claims

1. A method for preparing a polycarbonate block polyol, characterized in that: include: (1) preparing polycarbonate polyol by transesterification and polycondensation of siloxane diol / amine, phosphorus-containing diol, aliphatic diol and / or alicyclic diol, carbonate and catalyst; (2) Polycarbonate polyol is subjected to a ring-opening polymerization reaction with lactone to prepare polycarbonate block polyol.

2. The preparation method according to claim 1, characterized in that: The siloxane diol / amine is one or more of the following structures: Wherein, R1 is any one of the following structures: -OH, C3-C6 alkyl with -OH as the terminal group, C3-C6 alkoxy with -OH as the terminal group, C3-C6 alkyl with -NH2 as the terminal group, Any one of the following structures is preferred: -OH、 R2 is -OH; Preferably, the number average molecular weight of the siloxane diol / amine is 300-4000.

3. The preparation method according to claim 1, characterized in that: The phosphorus-containing diol is one or more of the following structures: Among them, R3, R4, and R5 independently represent one or more of C1-C10 straight or branched alkyl groups, C2-C10 aryl groups, R3 and R4 are preferably -CH2-CH2-CH2- and / or -CH2-CH2-CH2-CH2-, and R5 is preferably -CH2-CH(CH3)2.

4. The preparation method according to claim 1, characterized in that: The aliphatic diol is a C2-C10 diol, including one or more of ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, diethylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, and 1,10-decanediol, preferably 1,4-butanediol and 1,6-hexanediol; The alicyclic diol is 1,4-cyclohexanediol and / or 1,4-cyclohexanedimethanol, preferably 1,4-cyclohexanedimethanol.

5. The preparation method according to claim 1, characterized in that: The carbonate comprises one or more of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, diphenyl carbonate, and ethylene carbonate; and / or The catalyst is one or more of tetraethyl titanate, tetra-n-butyl titanate, tetraisopropyl titanate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin octoate, di-n-butyltin oxide, and stannous octoate.

6. The preparation method according to any one of claims 1 to 5, characterized in that: The preparation of the polycarbonate polyol, based on the total weight of the raw materials, the proportions of the components are as follows: Siloxane diol / amine 40-75%, preferably 45-70%; Phosphorus-containing diol 10-40%, preferably 15-35%; Aliphatic diol and / or alicyclic diol 5-20%, preferably 6-15%; Carbonate 5-30%, preferably 10-20%.

7. The preparation method according to any one of claims 1 to 6, characterized in that: The preparation of the polycarbonate polyol comprises: adding siloxane diol / amine, phosphorus-containing diol, aliphatic diol and / or alicyclic diol, carbonate and catalyst into a reaction kettle under nitrogen protection, heating to 160-250° C., preferably 200-220° C., at normal pressure, keeping the temperature at normal pressure for a period of time (e.g., 10-30 hours), and then evacuating the reaction vessel to continue the reaction until the hydroxyl value reaches the required value.

8. The preparation method according to any one of claims 1 to 7, characterized in that: The preparation of the polycarbonate block polyol, based on the total weight of the raw materials, the proportions of the components are as follows: Polycarbonate polyol 10-90%, preferably 70-80%; Lactone 90%-10%, preferably 20-30%; Preferably, the preparation method of the polycarbonate block polyol comprises: under nitrogen protection, adding polycarbonate polyol into a reaction kettle, heating to 100-130°C, vacuum dehydration, cooling to below 60°C, adding lactone, heating the reaction kettle to 160-190°C, adding a catalyst, vacuumizing and continuing the reaction until the acid value reaches the requirement.

9. A polyurethane elastomer, which is prepared by reacting a polycarbonate block polyol prepared by the preparation method according to any one of claims 1 to 8, a diisocyanate and a chain extender; Preferably, the diisocyanate is one or more of an aromatic polyisocyanate, an aliphatic polyisocyanate, and an alicyclic polyisocyanate; preferably 4,4'-diphenylmethane diisocyanate, 2,4-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,5-naphthalene diisocyanate, 1,4-phenylene diisocyanate, m-xylylene diisocyanate, diphenylmethane-3,3'-dimethoxy-4,4'-diisocyanate, 1,6-hexamethylene diisocyanate, 1,10-decane diisocyanate, 1,3 - one or more of cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, 2,4-hexahydrotoluene diisocyanate, 2,6-hexahydrotoluene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 2,2'-dicyclohexylmethane diisocyanate, 2,4-dicyclohexylmethane diisocyanate, isophorone diisocyanate, lysine diisocyanate, L-lysine diisocyanate, 1,4-butane diisocyanate, 1,5-pentane diisocyanate, more preferably 4,4'-diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate and 4,4'-dicyclohexylmethane diisocyanate; Preferably, the chain extender is an aliphatic diol and / or an alicyclic diol with a molecular weight of 60-200 g / mol; preferably, the aliphatic diol is one or more of ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, diethylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, neopentyl glycol, and 1,6-hexanediol, preferably 1,4-butanediol and 1,6-hexanediol; the alicyclic diol is 1,4-cyclohexanediol and / or 1,4-cyclohexanedimethanol, preferably 1,4-cyclohexanedimethanol.

10. The polyurethane elastomer according to claim 9, based on the total weight of the raw materials, the proportions of the components are as follows: Polycarbonate block polyol 30%-80%, preferably 40-75%; Chain extender 4%-30%, preferably 5-20%; Diisocyanate 15-60%, preferably 20-50%.

Images