A method for preparing and using a polycarbonate block polyol

Abstract

The present application relates to a kind of preparation methods of polycarbonate block polyol, comprising: by siloxane diol / amine, phosphorus-containing diol, aliphatic diol and / or alicyclic diol, carbonate, catalyst is prepared by ester exchange and polycondensation reaction polycarbonate polyol, the polycarbonate polyol is prepared by initiating lactone ring-opening polymerization polycarbonate block polyol.The polycarbonate block polyol prepared by polyurethane elastomer is excellent in performance, can be used in industrial products, civilian product field, such as oil pipe, cable, wheel, belt, seal, leather, adhesive, paint, ink, PUR, PUD, CPU, shoe rubber etc., can also be used in medical field, such as medical catheter, medical balloon, medical injection joint, medical injection connecting piece etc..

Description

TECHNICAL FIELD

[0001] The present application relates to the field of polyols and polyurethane, in particular to a preparation method of polycarbonate block polyol and a polyurethane prepared from the polycarbonate block polyol, which has the characteristics of low temperature resistance and excellent biocompatibility, and can be used in industrial products, medical and other fields. BACKGROUND

[0002] Currently, commercially available polycarbonate diols are generally homopolymerization hexanediol type polycarbonate diols, copolymerization pentanediol / hexanediol type polycarbonate diols and other short carbon chain diol type homopolymerization or copolymerization polycarbonate diols. Due to the high bond energy of the carbonate bond, the polycarbonate type polyurethane elastomer prepared therefrom has outstanding heat resistance, oil resistance, hydrolysis resistance, acid resistance, alkali resistance, solvent resistance and excellent biocompatibility, but its low temperature resistance and elasticity are poor, which limits its application in outdoor application fields such as shale oil pipes and cables that require low temperature resistance. It is usually necessary to improve the low temperature resistance and resilience by physically blending polyester, polycaprolactone and polyether polyol, but the production process is complex due to the involvement of multiple polyol blending. SUMMARY

[0003] The present application aims to provide a preparation method of polycarbonate block polyol, and the polyurethane prepared from the polycarbonate block polyol has the characteristics of low temperature resistance and good resilience, which solves the shortcomings of poor low temperature resistance of polycarbonate type polyurethane in the prior art and cannot be used in extremely cold outdoor application scenarios, thereby widening the application field of polyurethane. In addition, the polyurethane of the present application contains silicon and phosphorus elements, which has intrinsic flame retardant effect.

[0004] The technical scheme of the present application is as follows:

[0005] A preparation method of polycarbonate block polyol, comprising:

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

[0007] (2) preparing a polycarbonate block polyol by ring-opening polymerization reaction of the polycarbonate polyol and lactone.

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

[0009]

[0010]

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

[0012] R1 is any one of the following structures: -OH, C3-C6 alkyl with -OH as the end group, C3-C6 alkoxy with -OH as the end group, C3-C6 alkyl with -NH2 as the end group,

[0013] R1 is any one of the following structures: -OH, C3-C6 alkyl with -OH as the end group, C3-C6 alkoxy with -OH as the end group, C3-C6 alkyl with -NH2 as the end group,

[0014] R1 is any one of the following structures: -OH, C3-C6 alkyl with -OH as the end group, C3-C6 alkoxy with -OH as the end group, C3-C6 alkyl with -NH2 as the end group,

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

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

[0017]

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

[0019] In the present application, the aliphatic diol is C2-C10 diol, including one or more of ethylene glycol, 1,3-propanediol, 1,2-propanediol, 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, 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 application, the carbonate includes one or more of dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, ethylene carbonate, diphenyl carbonate, and ethylene carbonate.

[0022] In the present application, the catalyst is one or more of tetraethyl titanate, tetra-n-butyl titanate, tetraisopropyl titanate, dibutyl tin diacetate, dibutyl tin dilaurate, dibutyl tin octoate, di-n-butyl tin oxide, and stannous octoate; the catalyst is added in an amount of 30-200 ppm, preferably 50-100 ppm, based on the total amount of the siloxane diol / amine, the phosphorus-containing diol, the aliphatic diol and / or the alicyclic diol, and the carbonate.

[0023] In this invention, the lactone includes one or more of caprolactone, valproic acid lactone, and butyrolactone.

[0024] In this invention, the preparation of the polycarbonate polyol is based on the total weight of the raw materials, and the proportions of each component are as follows:

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

[0026] Contains 10-40% phosphorus diol, preferably 15-35%;

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

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

[0029] This 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 vessel, the temperature is raised to 160-250℃, preferably 200-220℃, under normal pressure, and the temperature is maintained at normal pressure for a period of time (e.g., 10-30h), and then the reaction is continued under vacuum until the hydroxyl value reaches the required value.

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

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

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

[0033] This invention also provides a method for preparing the polycarbonate block polyol. Under nitrogen protection, the polycarbonate polyol is added to a reaction vessel, heated to 100-130°C, dehydrated under vacuum, cooled to below 60°C, and lactone is added. The reaction vessel is then heated to 160-190°C, a catalyst is added, and the reaction continues under vacuum until the acid value meets the requirements. The catalyst can be stannous octoate, tetrabutyl titanate, or tetraisopropyl titanate, and the amount added is generally 10-100 ppm.

[0034] This invention also relates to the application of the aforementioned polycarbonate block polyols in the preparation of polyurethane elastomers.

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

[0036] In the present application, the diisocyanate is one or more of aromatic polyisocyanate, aliphatic polyisocyanate, alicyclic polyisocyanate; preferably one or more of 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, more preferably 4,4'-diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate and 4,4'-dicyclohexylmethane diisocyanate.

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

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

[0039] Polycarbonate block polyol 30%-80%, preferably 40-75%, for example 50%, 55%, 60%, 65%, 70% and the like;

[0040] Chain extender 4%-30%, preferably 5-20%, for example 10%, 15%, 20%, 25% and the like;

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

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

[0043] Advantages of the present application:

[0044] In the prior art, polycarbonate type polyurethane has poor low temperature resistance, and usually needs to be optimized for low temperature resistance by blending polycaprolactone, polyether and other polyols, and needs to be stirred and mixed with multiple polyols in the production process, thereby increasing the process flow. The present application solves the defects of the above prior art and provides a novel preparation method of polycarbonate block polyol, which introduces siloxane flexible chains into the polyol to improve the low temperature flexibility. Moreover, the present application prepares polycarbonate-block-polyestolactone by copolymerizing estolactone, and connects the two polyols by covalent bond, thereby solving the problem of complex production process of physical blending of the two polyols. In addition, the polyurethane of the present application contains silicon and phosphorus elements, and has intrinsic flame retardant effect. DETAILED DESCRIPTION

[0045] The present application will be further described in detail below in combination with specific examples, but the scope of the present application is not limited to these examples. Various substitutions or changes made according to ordinary technical knowledge and conventional means in the art without departing from the method idea of the present application should be included in the scope of the present application.

[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 Boji.

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

[0052] If not specified, the raw materials used in the examples or comparative examples are obtained from commercial channels.

[0053] Test Method:

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

[0055] Limiting oxygen index test equipment, oxygen index tester, model JF-5, Jia Lei instrument equipment, test standard ASTM D2863.

[0056] Example 1

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

[0058]

[0059] Preparation of polycarbonate polyol: 1000 g of dimethyl carbonate, 4498 g of siloxane diol, 2000 g of isobutyl bis-hydroxypropyl phosphine oxide, 1063 g of 1,6-hexanediol, and 0.26 g of tetrabutyl titanate catalyst are mixed and added to a reaction kettle, the reaction kettle is gradually heated to 190°C, after 20 h of reaction, the vacuum is slowly extracted to 6 KPa, and vacuum reaction is continued for 20 h, the temperature is lowered, and the product is discharged, to obtain a polycarbonate polyol. The hydroxyl value is 56.24 mgKOH / g, the acid value is 0.1 mgKOH / g, and the molecular weight is 2000.

[0060] Preparation of polycarbonate block polycaprolactone polyol: 1000 g of the above polycarbonate polyol is added to a reaction kettle under nitrogen protection, heated to 120°C, vacuum dehydrated for half an hour, cooled to below 60°C, 250 g of caprolactone is added, the reaction kettle is heated to 175°C, 0.05 g of stannous octoate catalyst is added, after 4 hours, the acid value is tested by sampling, vacuum extraction, and subsequent sampling and testing of the acid value every 1 h until the acid value is <0.1 mgKOH / g, the temperature is lowered and the product is discharged, and the molecular weight is 2500.

[0061] Preparation of polyurethane:

[0062] 680 g of the polycarbonate block polycaprolactone polyol prepared in the above step is added to a reactor, heated to 130°C, 66 g of 1,4-butanediol is added and stirred to mix uniformly, 254 g of 4,4'-diphenyl methane diisocyanate and 0.06 g of stannous octoate are sequentially added, high-speed stirring is adopted by using a stirrer, after 1 min of sufficient reaction, it is quickly poured into a Teflon cloth mold, and placed in a 100°C oven for 12 h of curing to prepare a thermoplastic polyurethane elastomer. The physical properties of the thermoplastic polyurethane elastomer after 24 h under standard temperature 23°C and low temperature resistance -40°C conditions are compared and tested.

[0063] Example 2

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

[0065]

[0066] Polycarbonate polyol: 1000 g of dimethyl carbonate, 4668 g of siloxane diol, 3112 g of isobutyl bis-hydroxypropyl phosphine oxide, 552 g of 1,6-hexanediol, and 0.39 g of tetrabutyl titanate catalyst were mixed and added to a reaction kettle, the reaction kettle was gradually heated to 190°C, and after reaction for 20 h, vacuum was slowly drawn to 6 KPa, and vacuum reaction was continued for 20 h, and then the reaction kettle was cooled and discharged to obtain a polycarbonate polyol. The hydroxyl value was 56.32 mgKOH / g, the acid value was 0.1 mgKOH / g, and the molecular weight was 2000.

[0067] Polycarbonate block polycaprolactone polyol: 1000 g of the above polycarbonate polyol was added to a reaction kettle under nitrogen protection, heated to 120°C, vacuum dehydrated for half an hour, cooled to below 60°C, and 250 g of caprolactone was added. The reaction kettle was heated to 175°C, 0.05 g of stannous octoate catalyst was added, and after 4 h, the acid value was tested by sampling. Vacuum was drawn, and the acid value was tested by sampling every 1 h until the acid value was <0.1 mgKOH / g. The reaction kettle was cooled and discharged, and the molecular weight was 2500.

[0068] Preparation of polyurethane

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

[0070] Example 3

[0071] The siloxane diol has the following structure, and the number average molecular weight is 1000.

[0072]

[0073] Polycarbonate polyol: 1000 g of dimethyl carbonate, 6913 g of siloxane diol, 1537 g of isobutyl bis-hydroxypropyl phosphine oxide, 720 g of 1,5-pentanediol, and 0.31 g of tetrabutyl titanate catalyst were mixed and added to a reaction kettle, the reaction kettle was gradually heated to 190°C, and after reaction for 20 h, vacuum was slowly drawn to 6 KPa, vacuum reaction was continued for 20 h, and after cooling and discharging, a polycarbonate polyol was obtained. The hydroxyl value was 56.17 mgKOH / g, the acid value was 0.1 mgKOH / g, and the molecular weight was 2000.

[0074] Polycarbonate block polycaprolactone polyol: 1000 g of the above polycarbonate polyol was added to a reaction kettle under nitrogen protection, heated to 120°C, vacuum dehydrated for half an hour, cooled to below 60°C, and 250 g of caprolactone was added. The reaction kettle was heated to 175°C, 0.05 g of stannous octoate catalyst was added, after 4 hours, the acid value was tested by sampling, vacuum was drawn, and the acid value was tested by sampling every 1 h subsequently until the acid value was <0.1 mgKOH / g, and the product was discharged after cooling. The molecular weight was 2500.

[0075] Preparation of polyurethane

[0076] 700 g of the polycarbonate block polycaprolactone polyol prepared in the above step was added to a reactor, heated to 130°C, 87.5 g of 1,4-butanediol was added and stirred to mix uniformly, 212 g of 1,6-hexamethylene diisocyanate and 0.06 g of dibutyl tin dilaurate were added in sequence, high-speed stirring was adopted, and after 2 min of sufficient reaction, it was quickly poured into a Teflon cloth mold, and placed in a 100°C oven for 12 h of curing to prepare a thermoplastic polyurethane elastomer. The physical properties of the thermoplastic polyurethane elastomer after 24 h under standard temperature 23°C and low-temperature resistance -40°C conditions were compared and tested.

[0077] Example 4

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

[0079]

[0080] Polycarbonate polyol: 1000 g of dimethyl carbonate, 2721 g of siloxane diol, 1378 g of isobutyl bis-hydroxypropyl phosphine oxide, 894 g of 1,4-cyclohexane dimethanol, and 0.18 g of tetrabutyl titanate catalyst were mixed and added to a reaction kettle, the reaction kettle was gradually heated to 190°C, and after reaction for 20 h, vacuum was slowly drawn to 6 KPa, vacuum reaction was continued for 20 h, and after cooling and discharging, a polycarbonate polyol was obtained. The hydroxyl value was 74.82 mgKOH / g, the acid value was 0.2 mgKOH / g, and the molecular weight was 1500.

[0081] Polycarbonate block polycaprolactone polyol: 1000 g of the above polycarbonate polyol was added into a reactor under nitrogen protection, heated to 120°C, vacuum dewatering for half an hour, cooled to below 60°C, 333 g of caprolactone was added, the reactor was heated to 175°C, 0.05 g of stannous octoate catalyst was added, after 4 hours, the sample was tested for acid value, vacuum was applied, and the sample was tested for acid value every 1 h, until the acid value was <0.1 mg KOH / g, the temperature was lowered and the product was discharged, molecular weight 2000.

[0082] Preparation of polyurethane

[0083] 600 g of the polycarbonate block polycaprolactone polyol prepared in the above step was added into a reactor, heated to 130°C, 82 g of 1,4-butanediol was added and stirred to mix uniformly, 318 g of 4,4'-dicyclohexylmethane diisocyanate and 0.12 g of dibutyltin dilaurate were added in sequence, high-speed stirring was adopted, after 2 min of sufficient reaction, it was quickly poured into a Teflon cloth mold, and placed in a 100°C oven for 12 h of curing, to obtain a thermoplastic polyurethane elastomer, the physical properties of the thermoplastic polyurethane elastomer after 24 h under standard temperature 23°C and low-temperature resistance -40°C conditions were compared and tested.

[0084] Comparative Example 1

[0085] 680 g of polycarbonate polyol HD200 with a molecular weight of 2000 was added into a reactor, heated to 130°C, 62.2 g of 1,4-butanediol was added and stirred to mix uniformly, 258 g of 4,4'-diphenylmethane diisocyanate and 0.06 g of stannous octoate were added in sequence, high-speed stirring was adopted, after 1 min of sufficient reaction, it was quickly poured into a Teflon cloth mold, and placed in a 100°C oven for 12 h of curing, to obtain a thermoplastic polyurethane elastomer, the physical properties of the thermoplastic polyurethane elastomer after 24 h under standard temperature 23°C and low-temperature resistance -40°C conditions were compared and tested.

[0086] Comparative Example 2

[0087] 720 g of polycarbonate polyol CD200 with a molecular weight of 2000 was added into a reactor, heated to 130°C, 50.3 g of 1,4-butanediol was added and stirred to mix uniformly, 230 g of 4,4'-diphenylmethane diisocyanate and 0.06 g of stannous octoate were added in sequence, high-speed stirring was adopted, after 1 min of sufficient reaction, it was quickly poured into a Teflon cloth mold, and placed in a 100°C oven for 12 h of curing, to obtain a thermoplastic polyurethane elastomer, the physical properties of the thermoplastic polyurethane elastomer after 24 h under standard temperature 23°C and low-temperature resistance -40°C conditions were compared and tested.

[0088] The example and comparative example data of the polyurethane elastomer are shown in Table 1.

[0089] Table 1 Properties of polyurethane elastomers

[0090]

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

[0092] The above examples are merely examples for the purpose of clarity and do not mean that the present application is limited to this. For those skilled in the art, other different forms of changes or variations can be made on the basis of the above description. It is not necessary and impossible to exhaust all the embodiments. The obvious changes or variations derived therefrom are still within the protection scope of the present application.

Claims

1. A method for preparing a polycarbonate block polyol, characterized in that, include: (1) Polycarbonate polyols are prepared by transesterification and polycondensation reactions of siloxane diols / amines, phosphorus-containing diols, aliphatic diols and / or alicyclic diols, carbonates, and catalysts; (2) Polycarbonate block polyols are prepared by ring-opening polymerization of polycarbonate polyols and lactones; The siloxane diol / amine has one or more of the following structures: 、 、 、 、 Wherein, R1 is any of the following structures: -OH, -OH as a terminal C3-C6 alkyl, -OH as a terminal C3-C6 alkoxy, -NH2 as a terminal C3-C6 alkyl; R2 is -OH.

2. The preparation method according to claim 1, characterized in that, R1 can be any of the following structures: -OH、 、 。 3. The preparation method according to claim 1, characterized in that, The number-average molecular weight of the siloxane diol / amine is 300-4000.

4. The preparation method according to claim 1, characterized in that, The phosphorus-containing diol has one or more of the following structures: ， Wherein, R3, R4, and R5 independently represent one or more of C1-C10 straight-chain or branched alkyl groups and C2-C10 aryl groups.

5. The preparation method according to claim 4, characterized in that, R3 and R4 are selected from -CH2-CH2-CH2- and / or -CH2-CH 2- CH2-CH2-, R5 is -CH2-CH(CH3)2.

6. The preparation method according to claim 1, characterized in that, The aliphatic diol is a C2-C10 diol; The alicyclic diol is 1,4-cyclohexanediol and / or 1,4-cyclohexanediol.

7. The preparation method according to claim 6, characterized in that, The aliphatic diol is one or more selected from ethylene glycol, 1,3-propanediol, 1,2-propanediol, diethylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, neopentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, and 1,10-decanediol.

8. The preparation method according to claim 1, characterized in that, The carbonate includes one or more of dimethyl carbonate, diethyl carbonate, methyl ethyl 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 octanoate, di-n-butyltin oxide, and stannous octanoate.

9. The preparation method according to any one of claims 1-8, characterized in that, The preparation of the polycarbonate polyol, based on the total weight of the raw materials, is carried out with the following proportions of each component: Siloxane diol / amine 40-75%; Contains 10-40% phosphodiol; Aliphatic diols and / or alicyclic diols 5-20%; Carbonate content: 5-30%.

10. The preparation method according to claim 9, characterized in that, The preparation of the polycarbonate polyol, based on the total weight of the raw materials, is carried out with the following proportions of each component: Siloxane diol / amine 45-70%; Contains 15-35% phosphorus diol; Aliphatic diols and / or alicyclic diols 6-15%; Carbonate content: 10-20%.

11. The preparation method according to any one of claims 1-8, characterized in that, The preparation of the polycarbonate polyol includes: under nitrogen protection, adding siloxane diol / amine, phosphorus-containing diol, aliphatic diol and / or alicyclic diol, carbonate and catalyst to a reaction vessel, heating to 160-250℃ under normal pressure, maintaining the temperature at normal pressure for a period of time, and then continuing the reaction under vacuum until the hydroxyl value reaches the required level.

12. The preparation method according to claim 11, characterized in that, The preparation of the polycarbonate polyol includes: under nitrogen protection, adding siloxane diol / amine, phosphorus-containing diol, aliphatic diol and / or alicyclic diol, carbonate and catalyst to a reaction vessel, heating to 200-220℃ under normal pressure, maintaining the temperature at normal pressure for 10-30 hours, and then continuing the reaction under vacuum until the hydroxyl value reaches the required level.

13. The preparation method according to any one of claims 1-7, characterized in that, The preparation of the polycarbonate block polyol, based on the total weight of the raw materials, is carried out with the following proportions of each component: Polycarbonate polyols: 10-90%; Lactone 90%-10%.

14. The preparation method according to claim 13, characterized in that, The preparation of the polycarbonate block polyol, based on the total weight of the raw materials, is carried out with the following proportions of each component: Polycarbonate polyols: 70-80%; Lactone 20-30%.

15. The preparation method according to claim 13, characterized in that, The preparation method of the polycarbonate block polyol includes: under nitrogen protection, adding polycarbonate polyol to a reaction vessel, heating to 100-130°C, vacuum dehydration, cooling to below 60°C, adding lactone, heating the reaction vessel to 160-190°C, adding catalyst, and continuing the reaction under vacuum until the acid value reaches the required level.

16. A polyurethane elastomer, said polyurethane elastomer being prepared by reacting a polycarbonate block polyol, a diisocyanate, and a chain extender obtained by the preparation method according to any one of claims 1-15.

17. The polyurethane elastomer according to claim 16, characterized in that, The diisocyanate is one or more of aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates; The chain extender is an aliphatic diol and / or alicyclic diol with a molecular weight of 60-200 g / mol.

18. The polyurethane elastomer according to claim 17, characterized in that, The diisocyanate is 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, isophthalimide diisocyanate, diphenylmethane-3,3'-dimethoxy-4,4'-diisocyanate, 1,6-hexamethylene diisocyanate, or 1,10-decane diisocyanate. One or more of the following: 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-butanediisocyanate, and 1,5-pentanediisocyanate; The aliphatic diol is one or more selected from ethylene glycol, 1,3-propanediol, 1,2-propanediol, diethylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, neopentanediol, and 1,6-hexanediol; the alicyclic diol is 1,4-cyclohexanediol and / or 1,4-cyclohexanediol.

19. The polyurethane elastomer according to any one of claims 16-18, wherein the proportions of each component are as follows, based on the total weight of the raw materials: Polycarbonate block polyols 30%-80%; Chain extender 4%-30%; Diisocyanate 15-60%.

20. The polyurethane elastomer according to claim 19, wherein the proportions of each component are as follows, based on the total weight of the raw materials: 40-75% polycarbonate block polyols; Chain extender 5-20%; Diisocyanate 20-50%.

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