WO2013060088A1 - 刚性聚氨酯的制备方法 - Google Patents

刚性聚氨酯的制备方法 Download PDF

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WO2013060088A1
WO2013060088A1 PCT/CN2012/000338 CN2012000338W WO2013060088A1 WO 2013060088 A1 WO2013060088 A1 WO 2013060088A1 CN 2012000338 W CN2012000338 W CN 2012000338W WO 2013060088 A1 WO2013060088 A1 WO 2013060088A1
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rigid polyurethane
chain extender
prepolymer
polyol
diisocyanate
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PCT/CN2012/000338
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English (en)
French (fr)
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陈海良
张芳
陈伟
陈由亮
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山东东大一诺威聚氨酯有限公司
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Priority to BR112013026720-8A priority Critical patent/BR112013026720B1/pt
Priority to AU2012327770A priority patent/AU2012327770B2/en
Publication of WO2013060088A1 publication Critical patent/WO2013060088A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4202—Two or more polyesters of different physical or chemical nature
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4808—Mixtures of two or more polyetherdiols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group

Definitions

  • the object of the present invention is to provide a method for preparing a rigid polyurethane, which can solve the technical problem of reducing the hardness of the product by high-temperature intermolecular hydrogen bond cleavage and intermolecular force of the rigid polyurethane, and obtaining a normal temperature by the method.
  • the hardness is greater than Shore D60, and the hardness is still greater than the Shore D50 rigid polyurethane at 80 °C.
  • the technical scheme of the present invention is: A method for preparing a rigid polyurethane, which comprises a prepolymer and a chain extender.
  • the prepolymer is obtained by the following preparation method: by weight, by weight of the diisocyanate 24. 5 ⁇ 50% with the polymer polyol 50 ⁇ 75.
  • the diisocyanate is one or more of tolylene diisocyanate or diphenylformamidine diisocyanate.
  • the polymer polyol is one of a polyglycidyl ether polyol, a polytetrahydrofuran ether polyol or a polycaprolactone polyol having a functionality of 2 to 3 and a number average molecular weight of 300 to 3000 or More than one. Among them, the polymer polyol having a functionality of 3 accounts for 10 to 50%, preferably 20 to 40%, based on the total mass of the polymer polyol.
  • the chain extender is an amine chain extender, preferably M0CA, E-300 or M-CDEA.
  • the preparation method of rigid polyurethane is as follows:
  • the chain extender After the chain extender is heated and melted at 100 to 110 ° C, the mixture is reacted with the prepolymer at a mass ratio of 20 to 29. 4:100, the mixing temperature is 60 to 75 ° C, and then poured into a mold at 100 to 110. The mold was vulcanized under a condition of ° C for 30 minutes, and finally vulcanized at 90 to 110 ° C for 8 to 10 hours to obtain a rigid polyurethane.
  • the toluene diisocyanate is preferably TDI-80 or TDI-100, and the diphenylformamidine diisocyanate is preferably MDI-50 or 1-100.
  • the rigid polyurethane product prepared by the invention has a hardness of between D60 and 80, and the hardness of the rigid polyurethane product can be maintained at a temperature greater than Shore D when the temperature is 80 Torr.
  • the beneficial effects of the present invention are as follows: by adding a polymer polyol having a total mass of 10% to 50% of a polymer polyol to a polymer polyol having a functionality of 3, which causes a certain degree of carbamate chemical cross-linking between the rigid polyurethane molecules to compensate The effect of intermolecular hydrogen bond cleavage and intermolecular force reduction at high temperatures ensures the use of rigid polyurethane articles at high temperatures.
  • PPG220 Polypropylene oxide ether diol having a number average molecular weight of 2000
  • PPG330 Polyglycidyl ether triol with a number average molecular weight of 3000
  • PPG210 Polypropylene oxide ether diol having a number average molecular weight of 1000
  • PPG400 Polypropylene oxide ether diol having a number average molecular weight of 400
  • PPG303 Polyepoxypropane ether triol with a number average molecular weight of 300
  • PTMG2000 Polytetrahydrofuran ether diol having a number average molecular weight of 2000
  • PTMG1000 Polytetrahydrofuran ether diol with a number average molecular weight of 1000
  • PCL210 Polycaprolactone diol with a number average molecular weight of 1000
  • PCL220 Polycaprolactone diol with a number average molecular weight of 2000
  • MDI-50 4, 4 '-diphenylformamidine diisocyanate 50%, 2, 4 '-diphenylformamidine diisocyanate 50% MDI-100: 4, 4 '-diphenylformamidine diisocyanate
  • TDI-80 2, 4-toluene diisocyanate 80%, 2, 6-toluene diisocyanate 20%
  • prepolymer Polytetrahydrofuran ether polyol of molecular weight 1000 (PTMG1000) by weight percent 37.75%, a polypropylene oxide ether polyol having a molecular weight of 3000 (PPG330) of 37.75% and a TDI-100 of 24.5%.
  • the reaction was carried out at 80 ° C for 3 hours, and then the bubbles were removed by vacuum (a 0.095 MPa) to obtain a prepolymer having an isocyanate mass content of 7.0%.
  • prepolymer Polytetrahydrofuran ether polyol (PTMG2000) having a molecular weight of 2000, 53% by weight, polyglycidyl ether polyol (PPG303) having a molecular weight of 300, 13%, TDI-80 34% by weight.
  • PTMG2000 Polytetrahydrofuran ether polyol
  • PPG303 polyglycidyl ether polyol
  • the reaction was carried out at 85 ° C for 2 hours, and then the bubbles were removed by vacuum (a 0.095 MPa) to obtain a prepolymer having an isocyanate mass content of 8.5%.
  • PCL210 Polycaprolactone polyol
  • PPG400 polyglycidyl ether polyol
  • TDI-100 35.3% by weight.
  • the reaction was carried out at 85 ° C for 3 hours, and then the bubbles were removed by vacuum (a 0.095 MPa) to obtain a prepolymer having an isocyanate mass content of 8.8%.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Tires In General (AREA)

Abstract

公开了一种刚性聚氨酯的制备方法。将扩链剂在100〜110°C加热熔化，与预聚物以质量比20〜29.4：100混合反应，混合温度为60〜75°C，然后浇注到模具中在100〜110°C条件下硫化30分钟脱模，最后在90〜110°C条件下硫化8〜10小时，得到刚性聚氨酯。以重量百分数计，预聚物由二异氰酸酯24.5〜50%与聚合物多元醇50〜75.5%在80〜85°C反应2〜3小时，得到异氰酸根质量含量为7〜10%的预聚物。扩链剂选用胺类扩链剂。解决了刚性聚氨酯在高温下由于分子间氢键断裂和分子间作用力降低而使制品硬度降低的问题，获得一种常温时硬度大于邵氏D60，在80°C下硬度仍然大于邵氏D50的刚性聚氨酯。

Description

说 明 书 刚性聚氨酯的制备方法
技术领域
本发明涉及一种聚氨酯的制备方法， 具体涉及一种刚性聚氨酯的制备方法。
背景技术
聚氨酯具有独特的软硬段嵌段共聚物的结构， 这赋予了其制品具有优良的机械性能， 同时制品的硬度可调节的范围宽，这些优异的综合性能是其他很多种商品化橡胶和塑料所 不具备的。聚氨酯既可以生产具有优良的回弹性的聚氨酯弹性体， 也可以用于生产硬度大 于邵氏 D60的刚性材料。这些刚性聚氨酯材料常用于承担载荷很重的工作场合和使用温度 较高的工作环境，这就要求聚氨酯制品必须具有较高的硬度，通常要求硬度大于邵氏 D60, 并且在 80Ό高温下使用硬度大于邵氏 D50。常规的聚氨酯高低温硬度变化很大， 常温下容 易达到硬度大于邵氏 D60， 但在 8CTC下由于高温分子间氢键断裂和分子间作用力的降低， 制品硬度降低很快， 通常只有不到邵氏 D40的硬度， 由于硬度的降低不能够承担更多的载 荷， 因此满足不了使用要求。
发明内容
本发明的目的是提供一种刚性聚氨酯的制备方法，能够解决刚性聚氨酯高温分子间氢 键断裂和分子间作用力的降低， 而使制品硬度降低的技术问题， 并借助此方法获得一种常 温时硬度大于邵氏 D60, 在 80°C下硬度仍然大于邵氏 D50的刚性聚氨酯。 本发明的技术方案是： 一种刚性聚氨酯的制备方法， 由预聚物和扩链剂组成。 预聚物 按照如下制备方法得到： 以重量百分数计， 由二异氰酸酯 24. 5〜50%与聚合物多元醇 50〜 75. 5 %在 80〜85'C反应 2〜3小时， 得到异氰酸根质量含量为 7〜10 %的预聚物。所述二异 氰酸酯为甲苯二异氰酸酯或二苯基甲垸二异氰酸酯中的一种或一种以上。 所述聚合物多元 醇采用官能度为 2〜3， 数均分子量在 300〜3000范围内的聚环氧丙垸醚多元醇、 聚四氢呋 喃醚多元醇或聚己内酯多元醇中的一种或一种以上。 其中， 官能度为 3的聚合物多元醇占 聚合物多元醇总质量的 10〜50%，优选 20〜40%。扩链剂选用胺类扩链剂，优选 M0CA、 E-300 或 M- CDEA。 刚性聚氨酯的制备方法如下：
将扩链剂在 100〜110°C加热熔化后，与预聚物以质量比 20〜29. 4： 100进行混合反应， 混合温度为 60〜75'C， 然后浇注到模具中在 100〜110°C条件下硫化 30分钟脱模， 最后在 90〜110°C条件下硫化 8〜10小时， 得到刚性聚氨酯。 甲苯二异氰酸酯优选用 TDI-80或 TDI- 100, 二苯基甲垸二异氰酸酯优选用 MDI-50或 1-100。
本发明制备得到的刚性聚氨酯制品的硬度在邵氏 D60〜80之间，该刚性聚氨酯制品 使用温度 80Ό时， 硬度能够保持在大于邵氏 D50。
本发明的有益效果在于： 通过加入聚合物多元醇总质量 10%〜50%的官能度为 3的聚 合物多元醇， _使刚性聚氨酯分子间产生一定的氨基甲酸酯化学交联， 从弥补高温下分子间 氢键断裂和分子间作用力的降低的影响， 保证刚性聚氨酯制品在高温下使用。
具体实施方式
以下结合实施例对本发明做进一步说明。
实施例所用材料如下：
PPG220: 数均分子量 2000的聚环氧丙烷醚二元醇
PPG330: 数均分子量 3000的聚环氧丙垸醚三元醇
PPG210: 数均分子量 1000的聚环氧丙烷醚二元醇
PPG400: 数均分子量 400的聚环氧丙烷醚二元醇
PPG303: 数均分子量 300的聚环氧丙垸醚三元醇
PTMG2000: 数均分子量 2000的聚四氢呋喃醚二元醇
PTMG1000: 数均分子量 1000的聚四氢呋喃醚二元醇
PCL210: 数均分子量 1000的聚己内酯二元醇
PCL220: 数均分子量 2000的聚己内酯二元醇
MDI-50: 4, 4 ' -二苯基甲垸二异氰酸酯 50%, 2, 4 ' -二苯基甲垸二异氰酸酯 50% MDI-100: 4, 4 ' -二苯基甲垸二异氰酸酯
TDI-100: 2， 4-甲苯二氰酸酯
TDI-80: 2， 4-甲苯二氰酸酯 80%， 2， 6-甲苯二异氰酸酯 20%
M-CDEA: 4, 4 ' -亚甲基-双 _ (3-氯- 2， 6-二乙二基苯胺）
M0CA: 3, 3 ' -二氯- 4, 4' -二氨基二苯基甲烷
E-300: 二甲硫基甲苯二胺。
实施例 1 :
制备预聚物： 按照重量百分数计， 分子量 1000的聚四氢呋喃醚多元醇 （PTMG1000) 37.75%， 分子量 3000的聚环氧丙烷醚多元醇（ PPG330) 37.75%, TDI-100 24.5%。 在 80°C反应 3小时， 然后真空 （一 0.095MPa) 脱除气泡， 得到异氰酸根质量含量为 7.0%的 预聚物。
制备刚性聚氨酯： 上述制得的预聚物和熔化后的 M- CDEA以 100: 29.4的质量比混合 反应，混合温度为 65 °C，然后浇注到模具中在 100°C条件下硫化 30分钟脱模，最后在 110°C 条件下硫化 8小时， 得到 25°C时硬度邵氏 D60的刚性聚氨酯制品。
实施例 2:
制备预聚物： 按照重量百分数计， 分子量 2000的聚四氢呋喃醚多元醇 （PTMG2000) 53%, 分子量 300的聚环氧丙垸醚多元醇 （PPG303) 13%, TDI- 80 34%。 在 85°C反应 2 小时， 然后真空 （一 0.095MPa) 脱除气泡， 得到异氰酸根质量含量为 8.5%的预聚物。
制备刚性聚氨酯：上述制得的预聚物和熔化后的 E- 300以 100: 20的质量比混合反应， 混合温度为 6(TC， 然后浇注到模具中在 10CTC条件下硫化 30分钟脱模， 最后在 11CTC条 件下硫化 8小时， 得到 25°C时硬度邵氏 D70的刚性聚氨酯制品。
实施例 3:
制备预聚物： 按照重量百分数计， 分子量 1000的聚己内酯多元醇 （PCL210) 25%, 分子量 2000的聚己内酯多元醇 （PCL220) 15%， 分子量 300的聚环氧丙垸醚 （PPG303) 10%, MDI-50 40.3%, MDI- 100 9.7%。 在 80°C反应 3小时， 然后真空 (-0.095MPa) 脱 除气泡， 得到异氰酸根质量含量为 10%的预聚物。 .
制备刚性聚氨酯： 上述制得的预聚物和熔化后的 M0CA以 100: 28.5的质量比混合反 应，混合温度为 75。C， 然后浇注到模具中在 11(TC条件下硫化 30分钟脱模， 最后在 11CTC 条件下硫化 8小时， 得到 25°C时硬度邵氏 D80的刚性聚氨酯制品。
实施例 4:
制备预聚物： 按照重量百分数计，分子量 1000的聚环氧丙烷醚多元醇（PPG210) 25.5 %, 分子量 2000的聚环氧丙烷醚多元醇 （PPG220) 25.5%, 分子量 300的聚环氧丙垸醚 (PPG303) 12.7%, TDI-100 30.3%, TDI- 80 6% 。 在 85°C反应 3小时， 然后真空 (― 0.095MPa) 脱除气泡， 得到异氰酸根质量含量为 8.8%的预聚物。
制备刚性聚氨酯： 上述制得的预聚物和熔化后的 M0CA以 100: 25.5的质量比混合反 应，混合温度为 75°C， 然后浇注到模具中在 110Ό条件下硫化 30分钟脱模， 最后在 11CTC 条件下硫化 8小时， 得到 25°C时硬度邵氏 D75的刚性聚氨酯制品。 对比例 1:
制备预聚物： 按照重量百分数计， 分子量 1000的聚己内酯多元醇（PCL210) 45.0%, 分子量 400的聚环氧丙垸醚多元醇 （PPG400) 19.7%, TDI-100 35.3%。 在 85°C反应 3 小时， 然后真空 （一 0.095MPa) 脱除气泡， 得到异氰酸根质量含量为 8.8%的预聚物。
制备刚性聚氨酯： 上述制得的预聚物和熔化后的 M0CA以 100: 25.5的质量比混合反 应， 混合温度为 75°C， 然后浇注到模具中在 110Ό条件下硫化 30分钟脱模， 最后在 11CTC 条件下硫化 8小时， 得到 25Ό时硬度邵氏 D75的刚性聚氨酯制品。
上述各实施例和对比例所制得刚性聚氣酯制品性能如下表:
Figure imgf000005_0001

Claims

权 利 要 求 书
1、 一种刚性聚氨酯的制备方法， 其特征在于， 由预聚物和扩链剂组成：
. 所述预聚物按照如下制备方法得到：
以重量百分数计， 由二异氰酸酯 24. 5〜50%与聚合物多元醇 50〜75. 5 %在 80〜85°C 反应 2〜3小时， 得到异氰酸根质量含量为 7〜10%的预聚物，
所述二异氰酸酯为甲苯二异氰酸酯或二苯基甲垸二异氰酸酯中的一种或一种以上， 所述聚合物多元醇采用官能度为 2〜3， 数均分子量在 300〜3000范围内的聚环氧丙烷 醚多元醇、 聚四氢呋喃醚多元醇或聚己内酯多元醇中的一种或一种以上， 其中， 官能度为
3的聚合物多元醇占聚合物多元醇总质量的 10〜50%;
所述扩链剂选用胺类扩链剂；
制备方法如下：
将所述扩链剂在 100〜110°C加热熔化后， 与所述预聚物以质量比 20〜29. 4: 100进行 混合反应， 混合温度为 60〜75°C， 然后浇注到模具中在 100〜11(TC条件下硫化 30分钟脱 模， 最后在 90〜11(TC条件下硫化 8〜10小时， 得到所述刚性聚氨酯。
2、根据权利要求 1所述的刚性聚氨酯的制备方法， 其特征在于， 所述官能度为 3的聚 合物多元醇占聚合物多元醇总质量的 20〜40%。
3、根据权利要求 1所述的刚性聚氨酯的制备方法， 其特征在于， 所述甲苯二异氰酸酯 选用 TDI- 80或 TDI- 100。
4、根据权利要求 1所述的刚性聚氨酯的制备方法， 其特征在于， 所述二苯基甲垸二异 氰酸酯选用 MDI- 50或 MDI- 100。
5、根据权利要求 1所述的刚性聚氨酯的制备方法， 其特征在于， 所述胺类扩链剂选用 M0CA、 E- 300或 M- CDEAo
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