High hardness polyurethane and preparation method and application thereof

Abstract

The present application relates to a kind of high hardness polyurethane and its preparation method and application.The phosphorus-containing polyol structural formula is as follows: the phosphorus-containing polyol is prepared by ester exchange reaction using phosphorus-containing diol and dialkyl carbonate.High hardness flame-retardant thermoplastic polyurethane elastomer is prepared from the phosphorus-containing polyol.The phosphorus-containing polyol can decompose phosphoric acid, metaphosphoric acid and other substances during heating, promote the dehydration and carbonization of polyurethane, and form a dense carbon layer that is not easy to burn, thereby achieving excellent flame-retardant effect.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of polyurethane, and particularly relates to a high-hardness polyurethane and a preparation method and application thereof. BACKGROUND

[0002] Thermoplastic polyurethane elastomers are widely used in the fields of wire and cable sheath, film, cable plug, water pipe, fire-fighting water bag, mattress, shoe material, building material, thermal insulation material, etc. However, the thermoplastic polyurethane elastomer has a low limiting oxygen index, and will burn and cause fire when encountering fire, thus threatening the safety of life and property. Therefore, it is of great significance to prepare a flame-retardant thermoplastic polyurethane. The thermoplastic polyurethane material prepared from a phosphorus-containing polyol can decompose phosphoric acid, metaphosphoric acid and other substances during the heating process, promote the dehydration and carbonization of the polyurethane, and form a dense carbon layer that is not easy to burn, thus achieving excellent flame-retardant effect. The thermoplastic polyurethane elastomer with a conventional hardness in the range of 60A-65D has a low strength and modulus, and cannot be applied in the related fields of engineering-grade components with high tensile strength, high tensile modulus, high bending strength and high bending modulus. Chinese Patent CN102276975B reports a high-hardness and high-toughness polyurethane composite material, which realizes the flame-retardant effect by adding a composite flame retardant, but has the problem of migration of the flame retardant, and has a low tensile strength and tear strength. Chinese Patent CN109054352A discloses a high-hardness thermoplastic polyurethane, which realizes the flame-retardant effect by adding nano-magnesium hydroxide and nano-aluminum hydroxide, is not an intrinsic type, also has the problem of migration, and has a Shore hardness greater than 70D but a tensile strength of only 45-52 MPa.

[0003] In summary, the existing high-hardness flame-retardant thermoplastic polyurethane realizes the flame-retardant effect by adding a flame retardant, has the problem of migration and precipitation of the flame retardant, and has a low strength. SUMMARY

[0004] The present application aims to provide a phosphorus-containing polyol, and a high-hardness flame-retardant thermoplastic polyurethane elastomer prepared from the phosphorus-containing polyol. The polyurethane is of an intrinsic type, solves the problem of precipitation of the flame retardant, and the phosphorus-containing polyol can decompose phosphoric acid, metaphosphoric acid and other substances during the heating process, promote the dehydration and carbonization of the polyurethane, and form a dense carbon layer that is not easy to burn, thus achieving excellent flame-retardant effect.

[0005] To achieve the above-mentioned application purposes, the present application adopts the following technical solutions:

[0006] A phosphorus-containing polyol has a structure shown in Formula 1:

[0007]

[0008] wherein R represents oxygen and / or sulfur; R1, R4 independently represent one or more of C1-C10 alkyl, C1-C10 aryl, preferably one or more of isopropyl, tert-butyl, phenyl, methoxyphenyl; R2, R3, R5, R6 independently represent one or more of C1-C10 alkyl, C2-C10 aryl, preferably -CH2-CH2-CH2- and / or -CH2-CH2-CH2-CH2-, and n is an integer of 2-6.

[0009] Another object of the present application is to provide a method for preparing a phosphorus-containing polyol.

[0010] A method for preparing a phosphorus-containing polyol, the method comprising: subjecting a phosphorus-containing diol of Formula 2 and / or a phosphorus-containing diol of Formula 3 to an ester exchange reaction with a dialkyl carbonate under the condition of a catalyst to obtain a target product:

[0011]

[0012]

[0013] wherein R represents oxygen and / or sulfur; R1, R4 independently represent one or more of C1-C10 alkyl, C1-C10 aryl, preferably one or more of isopropyl, tert-butyl, phenyl, methoxyphenyl; R2, R3, R5, R6 independently represent one or more of C1-C10 alkyl, C2-C10 aryl, preferably -CH2-CH2-CH2- and / or -CH2-CH2-CH2-CH2-.

[0014] In the present application, the phosphorus-containing diol of Formula 2 accounts for 0%-100% of the mass percentage of the phosphorus-containing diols of Formula 2 and Formula 3.

[0015] Another object of the present application is to provide a thermoplastic high-hardness polyurethane elastomer.

[0016] A thermoplastic high-hardness polyurethane elastomer, which employs the phosphorus-containing polyol described above, or the phosphorus-containing polyol prepared by the method described above, is prepared by using raw materials in the following proportions:

[0017] (a) polyisocyanate 40-80 wt%, preferably 45-75 wt%;

[0018] (b) polyol 0-35 wt%, preferably 0-30 wt%;

[0019] (c) chain extender 0-60 wt%, preferably 1-55 wt%.

[0020] In the present application, the polyol includes phosphorus-containing polyol and phosphorus-free polyol; preferably, the phosphorus-containing polyol is the polyol of formula 1, and the phosphorus-free polyol is one or more of polyether polyol, polyester polyol, polycarbonate polyol.

[0021] In the present application, the polyisocyanate is one or more of aromatic polyisocyanate, aliphatic polyisocyanate, alicyclic polyisocyanate; preferably, the polyisocyanate is 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 one or more of 4,4'-diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate.

[0022] In the present application, the chain extender is aliphatic diol and / or alicyclic diol, 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; the alicyclic diol is 1,4-cyclohexanediol and / or 1,4-cyclohexanedimethanol, preferably 1,4-cyclohexanedimethanol.

[0023] In the present application, the polyurethane elastomer is further added with a catalyst, and the catalyst is tin compound, preferably one or more of stannous acetate, stannous octoate, stannous laurate, dialkyl tin salt of organic carboxylic acid, wherein the dialkyl tin salt of organic carboxylic acid is preferably one or more of dibutyl tin diacetate, dibutyl tin dilaurate, dioctyl tin diacetate, and the catalyst is more preferably stannous octoate, dibutyl tin dilaurate.

[0024] In the present application, the polyurethane elastomer is further added with an antioxidant, an ultraviolet absorber and a light stabilizer, the antioxidant is one or more of hindered phenol, aromatic secondary amine, sulfur ester and phosphite ester antioxidant, the ultraviolet absorber is benzotriazole and / or benzophenone ultraviolet absorber, and the light stabilizer is hindered amine light stabilizer.

[0025] In the present application, the polyisocyanate, polyol, chain extender, antioxidant, ultraviolet absorber, light stabilizer and catalyst are added into a reactor and fully mixed to prepare.

[0026] Another purpose of the present application is to provide a use of the phosphorus-containing polyol.

[0027] A use of the phosphorus-containing polyol, which is the phosphorus-containing polyol described above or prepared by the preparation method described above, is used in the field of high-hardness polyurethane with flame-retardant requirements.

[0028] Compared with the prior art, the present application has the following beneficial effects:

[0029] (1) The polyurethane of the present application has a hardness of ≥70D, a tensile strength of ≥50MPa and a bending strength of ≥30MPa.

[0030] (2) The polyurethane of the present application has a low limiting oxygen index and a flame-retardant effect by introducing the phosphorus-containing polyol. DETAILED DESCRIPTION

[0031] 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.

[0032] Raw material sources:

[0033] 4,4'-diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, polybutylene adipate glycol WHP-104, number average molecular weight 1000g / mol, Wanhua Chemical Group Co., Ltd., industrial grade.

[0034] Polytetrahydrofuran diol 1000, number average molecular weight 1000g / mol, BASF, industrial grade.

[0035] Polycaprolactone diol PCL 210N, number average molecular weight 1000g / mol, Daicel, industrial grade.

[0036] Tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]pentaerythritol ester, 2-(2'-hydroxy-3',5'-di-tert-amylphenyl)benzotriazole, Bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, Tris(2,4-di-tert-butylphenyl) phosphite, 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-amylphenyl)benzotriazole, Taiwan Double Bond, technical grade.

[0037] Diethyl carbonate, Ube, technical grade.

[0038] Equipment information and test standards:

[0039] NMR, Bruker Fourier 300.

[0040] Tensile strength test equipment, Shimadzu tensile testing machine, test standard ASTM D 638.

[0041] Bending strength test equipment, Shimadzu tensile testing machine, test standard ASTM D 790.

[0042] Limiting oxygen index test equipment, Oxygen Index Tester, Model JF-5, JiaLei Instrument Equipment, test standard ASTM D2863.

[0043] Preparation of phosphorus-containing polyols

[0044] Example 1

[0045] Preparation of phosphorus-containing polyol A.

[0046] Under nitrogen protection, 10.0 kg of dimethyl carbonate and 19 kg of isobutyl bis-hydroxypropyl phosphine oxide were added to a reaction kettle, and the temperature was raised to 200°C for reaction. When the acid value was reduced to 15 mg KOH / g, 2.0 g of n-butyl titanate was added, vacuum was extracted to -0.09 MPaG, and the temperature was raised to 220°C for continuous reaction. When the acid value was less than 1.5 mg KOH / g and the hydroxyl value was 112 mg KOH / g, the reaction was stopped, and the number average molecular weight was 1000 g / mol.

[0047] 1H NMR (DMSO-d6, TMS), δ (ppm): [4.7, -COO-CH2-CH2-CH2-P(=O)(-CH2-CH2-CH2-OOC)(-CH2-CH(CH3)2)], [4.5, -COO-CH2-CH2-CH2-P(=O)(-CH2-CH2-CH2-OOC)(-CH2-CH(CH3)2)], [1.0, -COO-CH2-CH2-CH2-P(=O)(-CH2-CH2-CH2-OOC)(-CH2-CH(CH3)2)].

[0048] Example 2

[0049] Preparation of phosphorus-containing polyol B.

[0050] Under the protection of nitrogen, 10.0 kg of diethyl carbonate and 15.94 kg of phenyl bis-hydroxymethyl phosphine oxide were added into a reaction kettle, and the temperature was raised to 200°C for reaction. When the acid value was reduced to 15 mg KOH / g, 2.0 g of n-butyl titanate was added, vacuum was extracted to -0.09 MPaG, and the temperature was raised to 220°C for continuous reaction. When the acid value was less than 1.5 mg KOH / g and the hydroxyl value was 112 mg KOH / g, the reaction was stopped, and the corresponding number average molecular weight was 1000 g / mol.

[0051] 1 H NMR (DMSO-d6, TMS), δ (ppm): [4.8, -COO-CH2-P(=O)(-CH2-OOC)(Ph)], [7.3-7.8, -COO-CH2-P(=O)(-CH2-OOC)(Ph)].

[0052] Example 3

[0053] Preparation of phosphorus-containing polyol C.

[0054] Under the protection of nitrogen, 10.0 kg of diethyl carbonate and 15.94 kg of phenyl bis-hydroxymethyl phosphine oxide were added into a reaction kettle, and the temperature was raised to 200°C for reaction. When the acid value was reduced to 15 mg KOH / g, 2.0 g of n-butyl titanate was added, vacuum was extracted to -0.09 MPaG, and the temperature was raised to 220°C for continuous reaction. When the acid value was less than 1.5 mg KOH / g and the hydroxyl value was 112 mg KOH / g, the reaction was stopped, and the corresponding number average molecular weight was 1000 g / mol.

[0055] Preparation of high-hardness polyurethane

[0056] Example 4

[0057] A reactor was charged with 200 g of phosphorus-containing polyol A having a number average molecular weight of 1000 g / mol, 200 g of polytetrahydrofuran diol having a number average molecular weight of 1000 g / mol, 1208 g of 4,4'-diphenylmethane diisocyanate, 390 g of 1,4-butanediol, 10 g of tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentaerythritol ester, 2 g of 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2 g of bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, stirred at 800 rpm for 2 min, and then poured into a polytetrafluoroethylene mold after the reaction, and cured in an oven for 12 h to produce a thermoplastic polyurethane elastomer. The hardness, tensile strength, bending strength, and limiting oxygen index were measured.

[0058] Example 5

[0059] A reactor was charged with 40 g of phosphorus-containing polyol A having a number average molecular weight of 1000 g / mol, 1342 g of 4,4'-diphenylmethane diisocyanate, 618 g of 1,6-hexanediol, 9 g of tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentaerythritol ester, 5 g of tris(2,4-di-tert-butylphenyl)phosphite, 3 g of 2-(2'-hydroxy-3',5'-di-tert-pentylphenyl)benzotriazole, 4 g of bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, stirred at 800 rpm for 2 min, and then poured into a polytetrafluoroethylene mold after the reaction, and cured in an oven for 12 h to produce a thermoplastic polyurethane elastomer. The hardness, tensile strength, bending strength, and limiting oxygen index were measured.

[0060] Example 6

[0061] A reactor was charged with 100 g of phosphorus-containing polyol A having a number average molecular weight of 1000 g / mol, 1132 g of 1,6-hexanediisocyanate, 768 g of 1,6-hexanediol, 3 g of tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentaerythritol ester, 1 g of 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 1 g of bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, stirred at 800 rpm for 2 min, and then poured into a polytetrafluoroethylene mold after the reaction, and cured in an oven for 12 h to produce a thermoplastic polyurethane elastomer. The hardness, tensile strength, bending strength, and limiting oxygen index were measured.

[0062] Example 7

[0063] A reactor was charged with 150 g of phosphorus-containing polyol A having a number average molecular weight of 1000 g / mol, 150 g of polycaprolactone diol having a number average molecular weight of 1000 g / mol, 1292 g of 4,4'-dicyclohexylmethane diisocyanate, 408 g of 1,4-butanediol, 6 g of tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentaerythritol ester, 3 g of 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 3 g of bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, stirred at 800 rpm for 2 min, and then poured into a polytetrafluoroethylene mold after the reaction, and cured in an oven for 12 h to produce a thermoplastic polyurethane elastomer. The hardness, tensile strength, bending strength, and limiting oxygen index were measured.

[0064] Example 8

[0065] A reactor was charged with 100 g of phosphorus-containing polyol A having a number average molecular weight of 1000 g / mol, 1380 g of 4,4'-diphenylmethane diisocyanate, 346 g of 1,4-butanediol, 173 g of 1,6-hexanediol, 3 g of tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentaerythritol ester, 1 g of 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 1 g of bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, stirred at 800 rpm for 2 min, and then poured into a polytetrafluoroethylene mold after the reaction, and cured in an oven for 12 h to produce a thermoplastic polyurethane elastomer. The hardness, tensile strength, bending strength, and limiting oxygen index were measured.

[0066] Example 9

[0067] A reactor was charged with 150 g of phosphorus-containing polyol B having a number average molecular weight of 1000 g / mol, 150 g of polybutylene adipate diol having a number average molecular weight of 1000 g / mol, 1276 g of 4,4'-diphenylmethane diisocyanate, 424 g of 1,4-butanediol, 4 g of tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentaerythritol ester, 2 g of 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 3 g of bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, stirred at 800 rpm for 2 min, and then poured into a polytetrafluoroethylene mold after the reaction, and cured in an oven for 12 h to produce a thermoplastic polyurethane elastomer. The hardness, tensile strength, bending strength, and limiting oxygen index were measured.

[0068] Example 10

[0069] A reactor was charged with 200 g of phosphorus-containing polyol C having a number average molecular weight of 1000 g / mol, 160 g of polybutylene adipate diol having a number average molecular weight of 1000 g / mol, 1236 g of 4,4'-diphenylmethane diisocyanate, 404 g of 1,4-butanediol, 4 g of tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentaerythritol ester, 2 g of 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 3 g of bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, and the mixture was stirred at 800 rpm for 2 min. After the reaction, the mixture was quickly poured into a polytetrafluoroethylene mold, and the mold was placed in an oven for 12 h to cure. A thermoplastic polyurethane elastomer was obtained. The hardness, tensile strength, bending strength, and limiting oxygen index were tested.

[0070] Comparative Example 1

[0071] The comparative example does not contain a phosphorus-containing polyol.

[0072] A reactor was charged with 400 g of polytetramethylene glycol having a number average molecular weight of 1000 g / mol, 1208 g of 4,4'-diphenylmethane diisocyanate, 390 g of 1,4-butanediol, 10 g of tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentaerythritol ester, 2 g of 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2 g of bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, and the mixture was stirred at 800 rpm for 2 min. After the reaction, the mixture was quickly poured into a polytetrafluoroethylene mold, and the mold was placed in an oven for 12 h to cure. A thermoplastic polyurethane elastomer was obtained. The hardness, tensile strength, bending strength, and limiting oxygen index were tested.

[0073] The data of the examples and comparative examples of the high-hardness polyurethane elastomer are shown in Table 1.

[0074] Table 1 Properties of the high-hardness polyurethane elastomer

[0075]

[0076]

[0077] The high-hardness thermoplastic polyurethane elastomer of the present application has high tensile strength and bending strength. As shown by the comparative examples and the comparative examples, the high-hardness thermoplastic polyurethane elastomer of the present application has good flame retardant effect and low limiting oxygen index.

Claims

1. A phosphorus-containing polyol, characterized by, The phosphorus-containing polyol has a structure shown in Formula 1: wherein R represents oxygen and / or sulfur; R1, R4 independently represent one or more of C1-C10 alkyl, C1-C10 aryl; R2, R3, R5, R6 independently represent one or more of C2-C10 alkylene, C2-C10 arylene, and n is an integer of 2-6.

2. The polyol of claim 1, wherein, In the structure of the phosphorus-containing polyol, R1, R4 independently represent one or more of isopropyl, tert-butyl, phenyl; R2, R3, R5, R6 independently represent -CH2-CH2-CH2- and / or -CH2-CH2-CH2-CH2-.

3. A process for the preparation of the phosphorus-containing polyol of claim 1, characterized in that, The preparation method is that the phosphorus-containing diol of Formula 2 and / or the phosphorus-containing diol of Formula 3 is subjected to ester exchange reaction with a dialkyl carbonate under catalyst conditions to obtain the target product. wherein R represents oxygen and / or sulfur; R1, R4 independently represent one or more of C1-C10 alkyl, C1-C10 aryl; R2, R3, R5, R6 independently represent one or more of C1-C10 alkylene, C2-C10 arylene.

4. The production method according to claim 3, characterized by, In the structure of the phosphorus-containing diol in the preparation method, R1, R4 independently represent one or more of isopropyl, tert-butyl, phenyl; R2, R3, R5, R6 independently represent -CH2-CH2-CH2- and / or -CH2-CH2-CH2-CH2-.

5. The preparation method according to claim 3, characterized in that, The mass percentage of the phosphorus-containing diol of Formula 2 in the phosphorus-containing diols of Formula 2 and Formula 3 is 0%-100%.

6. A thermoplastic high hardness polyurethane elastomer comprising the phosphorus-containing polyol of claim 1 or 2, or the phosphorus-containing polyol prepared by the method of any one of claims 3-5, characterized in that, The elastomer is prepared by using raw materials in the following proportions: (a) polyisocyanate 40-80 wt%; (b) polyol 0-35 wt%; (c) chain extender 0-60 wt%; wherein the polyol content is not 0.

7. The polyurethane elastomer according to claim 6, wherein The elastomer is prepared by using raw materials in the following proportions: (a) polyisocyanate 45-75 wt%; (b) polyol 0-30 wt%; (c) chain extender 1-55 wt%; wherein the polyol content is not 0.

8. The polyurethane elastomer according to claim 6, wherein The polyol includes a phosphorus-containing polyol and a polyol not containing phosphorus.

9. The polyurethane elastomer according to claim 8, wherein, The phosphorus-containing polyol is a polyol of Formula 1, and the polyol not containing phosphorus is one or more of a polyether polyol, a polyester polyol, and a polycarbonate polyol.

10. The polyurethane elastomer according to claim 6 or 7, wherein The polyisocyanate is one or more of an aromatic polyisocyanate, an aliphatic polyisocyanate, and a cycloaliphatic polyisocyanate.

11. The polyurethane elastomer according to claim 10, wherein The polyisocyanate is 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, and 1,5-pentane diisocyanate.

12. The polyurethane elastomer of claim 11, wherein, The polyisocyanate is one or more of 4,4'-diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate.

13. The polyurethane elastomer of claim 6, wherein, The chain extender is an aliphatic diol and / or a cycloaliphatic diol, 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, and 1,6-hexanediol; and the cycloaliphatic diol is 1,4-cyclohexanediol and / or 1,4-cyclohexanedimethanol.

14. The polyurethane elastomer of claim 13, wherein, The aliphatic diol is 1,4-butanediol; and the cycloaliphatic diol is 1,4-cyclohexanedimethanol.

15. The polyurethane elastomer of claim 6, wherein, The polyurethane elastomer is further added with a catalyst, and the catalyst is a tin compound.

16. The polyurethane elastomer of claim 15, wherein, The catalyst is one or more of stannous acetate, stannous octoate, stannous laurate, and a dialkyl tin salt of an organic carboxylic acid.

17. The polyurethane elastomer of claim 16, wherein, In the catalyst, the dialkyl tin salt of an organic carboxylic acid is one or more of dibutyl tin diacetate, dibutyl tin dilaurate, and dioctyl tin diacetate.

18. The polyurethane elastomer according to claim 16 or 17, wherein The catalyst is stannous octoate and dibutyl tin dilaurate.

19. The polyurethane elastomer of claim 6, wherein, The polyurethane elastomer is further added with an antioxidant, an ultraviolet absorber, and a light stabilizer, the antioxidant is one or more of a hindered phenol antioxidant, an aromatic secondary amine antioxidant, a sulfur ester antioxidant, and a phosphite antioxidant; the ultraviolet absorber is a benzotriazole ultraviolet absorber and / or a benzophenone ultraviolet absorber; and the light stabilizer is a hindered amine light stabilizer.

20. The polyurethane elastomer of claim 6, wherein, The polyisocyanate, the polyol, the chain extender, the antioxidant, the ultraviolet absorber, the light stabilizer, and the catalyst are added to a reactor and mixed to prepare.

21. Use of a phosphorus-containing polyol, which is the phosphorus-containing polyol of claim 1 or 2, or which is the phosphorus-containing polyol prepared by the preparation process of any one of claims 3 to 5, characterized in that The phosphorus-containing polyol is used in the field of high-hardness polyurethane with flame-retardant requirements.

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