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WO2017113568A1 - 耐铬酸聚氨酯弹性体及其制备方法 - Google Patents

耐铬酸聚氨酯弹性体及其制备方法 Download PDF

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Publication number
WO2017113568A1
WO2017113568A1 PCT/CN2016/082281 CN2016082281W WO2017113568A1 WO 2017113568 A1 WO2017113568 A1 WO 2017113568A1 CN 2016082281 W CN2016082281 W CN 2016082281W WO 2017113568 A1 WO2017113568 A1 WO 2017113568A1
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Prior art keywords
chromic acid
polyurethane elastomer
resistant polyurethane
component
preparation
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PCT/CN2016/082281
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English (en)
French (fr)
Inventor
徐军
陈海良
刘兆阳
张芳
王维龙
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山东一诺威聚氨酯股份有限公司
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Publication of WO2017113568A1 publication Critical patent/WO2017113568A1/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
    • C08G18/70—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
    • 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
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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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
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    • 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
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    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
    • 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
    • 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
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C08K5/1345—Carboxylic esters of phenolcarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/08—Polyurethanes from polyethers

Definitions

  • the present invention relates to a chromic acid resistant polyurethane elastomer and a preparation method thereof, and belongs to the technical field of polyurethane elastomer application.
  • Polyurethane elastomer is a kind of polymer synthetic material between plastic and rubber. It has excellent wear resistance, good mechanical strength, oil resistance, low temperature resistance, ozone aging resistance, etc. Rolls, oil seals, car tires and other fields. Polyurethane has penetrated into the national economy and people's lives and has become a rapidly developing synthetic material. Polyurethane rubber roller has the advantages of excellent tearing performance, good resilience performance, good wear resistance, long service life, and ability to withstand high pressure and high speed environment. It is widely used in steel mills, paper making and printing industries.
  • An object of the present invention is to provide a chromic acid resistant polyurethane elastomer which has better chromic acid resistance and is immersed in a chromic acid environment for 24 hours, and the product retention rate is good; ⁇ Provides a simple, energy-saving and environmentally friendly preparation method.
  • the chromic acid-resistant polyurethane elastomer of the present invention is composed of an A component and a B component, and the weight ratio of the A and B components is 100: 2.9-6.2, wherein:
  • the A component is a polyurethane prepolymer, which is prepared from the following weight percentages of raw materials:
  • Plasticizer 0 ⁇ 3 ⁇ 4 ⁇ 40 ⁇ 3 ⁇ 4 [0009] Antioxidant (! ⁇ . ⁇ ;
  • Component B is a curing agent, one or two of 1,4-butanediol or trimethylolpropane (TMP)
  • the polytetrahydrofuran ether glycol has a functionality of 2 and a number average molecular weight of from 1,000 to 2,000.
  • the diisocyanate is composed of 2,4-diphenylmethane diisocyanate and 4,4'-diphenylmethane diisocyanate (MDI-50), 4,4'-diphenylmethane diisocyanate (MDI) -100) or carbodiimide modified
  • One or more of MDI (liquefied MDI) is mixed.
  • the plasticizer is dioctyl terephthalate (DOTP), dioctyl phthalate (DOP), dimethyl phthalate (DMEP), phthalic acid Diisobutyl formate (DIBP) or butyl benzyl phthalate (BBP).
  • DOP dioctyl terephthalate
  • DOP dioctyl phthalate
  • DMEP dimethyl phthalate
  • DIBP phthalic acid Diisobutyl formate
  • BBP butyl benzyl phthalate
  • the antioxidant is 1076, 1010, PDP or 1035.
  • the preparation method of the chromic acid resistant polyurethane elastomer comprises the following steps:
  • component A Polytetrahydrofuran ether glycol, diisocyanate, plasticizer and antioxidant are reacted at 70 to 85 ° C for 2 to 3 hours to obtain a polyurethane prepolymer, which isocyanate The acid content is 2.7 ⁇ 6.0%;
  • the raw material polytetrahydrofuran ether glycol is used in combination with MDI to make the product have excellent chromic acid resistance; 1,4-butanediol in the preparation process of the polyurethane elastomer
  • TMP and plasticizers gives the product a lower hardness.
  • the obtained chromic acid-resistant polyurethane elastomer has better chromic acid resistance, and is immersed in a chromic acid environment for 24 hours, and the product retention rate is good;
  • PTMG1000 number average molecular weight 1000, polytetrahydrofuran ether glycol
  • PTMG2000 number average molecular weight 2000, polytetrahydrofuran ether glycol
  • MDI-50 2,4-diphenylmethane diisocyanate and 4,4'-diphenylmethane diisocyanate;
  • MDI-100 4, 4'-diphenylmethane diisocyanate
  • liquefied MDI carbodiimide modified MDI
  • DOTP dioctyl terephthalate
  • BDO 1,4-butanediol
  • TMP trimethylolpropane
  • Antioxidant 1076.
  • the preparation method of the chromic acid resistant polyurethane elastomer comprises the following steps:
  • component A Polytetrahydrofuran ether glycol (PTMG1000) having a molecular weight of 1000 (63.6%), diphenylmethane diisocyanate (MDI-100), 18.1%, carbodiimide-modified MDI (liquefaction) MDI) 18.1 ⁇ 3 ⁇ 4, antioxidant (1076) 0.2% reacted at 70 ° C for 2 hours, vacuum (a 0.095 MPa) to remove bubbles, to obtain a polyurethane prepolymer, the isocyanate content of 6.0%;
  • the preparation method of the chromic acid resistant polyurethane elastomer comprises the following steps:
  • the preparation method of the chromic acid resistant polyurethane elastomer comprises the following steps:
  • component A Polytetrahydrofuran ether glycol having a molecular weight of 2000 (PTMG2000) 75.2% ⁇ Diphenylmethane diisocyanate (MDI-50) 12.2%. Carbonitride diimide modified MDI (liquefaction) MDI) 12.2%, antioxidant (1076) 0.4% reaction at 75 ° C for 2.5 hours, vacuum (a 0.095MPa) to remove bubbles, to obtain a polyurethane prepolymer, the isocyanate content of 4.5%;
  • the preparation method of the chromic acid resistant polyurethane elastomer comprises the following steps:
  • component A Polytetrahydrofuran ether glycol having a molecular weight of 2000 (PTMG2000) 61.1% ⁇ Diphenylmethane diisocyanate (MDI-50) 18.4%, dioctyl terephthalate (DOTP) 20%, antioxidant (1076) 0.5% reacted at 85 ° C for 2 hours, vacuum (a 0.095 MPa) to remove bubbles, to obtain a polyurethane prepolymer, the isocyanate content of 4.5%;
  • the preparation method of the chromic acid resistant polyurethane elastomer comprises the following steps:
  • component A Polytetrahydrofuran ether glycol having a molecular weight of 2000 (PTMG2000) 44 ⁇ 3 ⁇ 4, carbon Diimine modified MDI (liquefied MDI) 15.6%, dioctyl terephthalate (DOTP) 40%, antioxidant (1076) 0.4% reacted at 75 ° C for 2 hours, vacuum (a 0.095 MPa Removing the bubbles to obtain a polyurethane prepolymer having an isocyanate content of 4.5%;

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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)

Abstract

提供了一种耐铬酸聚氨酯弹性体，由A组分和B组分组成，A、B组分的重量比为100：2.9-6.2，其中A组分为聚氨酯预聚物，由聚四氢呋喃醚二醇、二异氰酸酯、抗氧剂和任选增塑剂组成，B组分为固化剂，为1，4-丁二醇或三羟甲基丙烷中的一种或两种。所述聚四氢呋喃醚二醇的官能度为2，数均分子量为1000-2000。所述聚氨酯弹性体具有较好的耐铬酸性能，在铬酸的环境中浸泡24小时，产品的性能保持率较好。同时提供了一种简单易行、节能环保的耐铬酸聚氨酯弹性体的制备方法。

Description

耐铬酸聚氨酯弹性体及其制备方法 技术领域
[0001] 本发明涉及一种耐铬酸聚氨酯弹性体及其制备方法， 属于聚氨酯弹性体应用技 术领域。
背景技术
[0002] 聚氨酯弹性体是介于塑料与橡胶之间的一种高分子合成材料， 具有优良的耐磨 性、 良好的力学强度及耐油、 耐低温、 耐臭氧老化等性能， 因而广泛用于胶辊 、 油封、 汽车轮胎等领域。 聚氨酯已深入到国民经济和人民生活中， 成为一种 发展迅速的合成材料。 聚氨酯胶辊具有撕裂性能优、 回弹性能好， 耐磨性能佳 ， 使用寿命长， 能够承受高压力、 高转速的环境等优势， 广泛应用于钢厂、 造 纸、 印刷行业。 但对于一些特殊环境的应用， 例如用在有铬酸环境中的胶辊， 因铬酸具有酸性和氧化性， 一般的聚氨酯材料在铬酸的环境中分解很快， 性能 下降较多， 导致产品的性能保持率低。 研究幵发耐铬酸聚氨酯弹性体是应对市 场需求助推弹性体技术进步的需要。
技术问题
[0003] 本发明的目的是提供一种耐铬酸聚氨酯弹性体， 其具有较好的耐铬酸性能， 在 铬酸的环境中浸泡 24小吋， 产品的性能保持率较好； 本发明同吋提供了简单易 行、 节能环保的制备方法。
问题的解决方案
技术解决方案
[0004] 本发明所述的耐铬酸聚氨酯弹性体， 由 A组分和 B组分组成， A、 B组分的重量 比为 100: 2.9-6.2, 其中：
[0005] (1) A组分为聚氨酯预聚物， 由以下重量百分含量的原料制成：
[0006] 聚四氢呋喃醚二醇 44<¾〜75.2<¾
[0007] 二异氰酸酯 15.6<¾〜36.2<¾
[0008] 增塑剂 0<¾〜40<¾ [0009] 抗氧剂 （！ ^〜。^^;
[0010] (2) B组分为固化剂， 为 1,4-丁二醇或三羟甲基丙烷 （TMP) 中的一种或两种
[0011] 所述聚四氢呋喃醚二醇的官能度为 2， 数均分子量为 1000-2000。
[0012] 所述的二异氰酸酯由 2， 4-二苯基甲烷二异氰酸酯与 4， 4'-二苯基甲烷二异氰酸 酯 （MDI-50) 、 4， 4'-二苯基甲烷二异氰酸酯 （MDI-100) 或碳化二亚胺改性的
MDI (液化 MDI) 中的一种或者多种混合而成。
[0013] 所述的增塑剂为对苯二甲酸二辛酯 （DOTP) 、 邻苯二甲酸二辛酯 （DOP) 、 邻苯二甲酸二甲基乙二醇酯 （DMEP) 、 邻苯二甲酸二异丁酯 （DIBP) 或邻苯 二甲酸丁苄酯 (BBP) 。
[0014] 所述的抗氧剂为 1076、 1010、 PDP或 1035。
[0015] 所述的耐铬酸聚氨酯弹性体的制备方法， 包括以下步骤：
[0016] (1) 制备 A组分： 将聚四氢呋喃醚二醇、 二异氰酸酯、 增塑剂和抗氧剂在 70〜 85°C反应 2〜3小吋， 得到聚氨酯预聚物， 其异氰酸根含量为 2.7〜6.0%；
[0017] (2) 制备聚氨酯弹性体： 将聚氨酯预聚物加热至 80〜90°C， 再将其与加热至 5 0〜60°C的固化剂混合， 然后将混合物浇注到 100~150°C的模具中， 6~10h后脱模 ， 将脱模后的制品在 100〜120°C下硫化 8〜10小吋， 得到耐铬酸聚氨酯弹性体， 其硬度为邵 A 35〜70。
[0018] 本发明在制备 A组分的过程中， 原料聚四氢呋喃醚二醇与 MDI的搭配使用， 使 产品具有优异的耐铬酸性能； 聚氨酯弹性体的制备过程中 1,4-丁二醇、 TMP和增 塑剂的使用使产品具有较低的硬度。
发明的有益效果
有益效果
[0019] (1) 制得的耐铬酸聚氨酯弹性体， 具有较好的耐铬酸性能， 在铬酸的环境中 浸泡 24小吋， 产品的性能保持率较好；
[0020] (2) 所述的耐铬酸聚氨酯弹性体的制备方法， 不但节能环保， 而且简单易行 具体实施方式
[0021] 下面结合实施例对本发明作进一步的说明， 但其并不限制本发明的实施。
[0022] 实施例中所用材料如下：
[0023] PTMG1000: 数均分子量 1000， 聚四氢呋喃醚二醇；
[0024] PTMG2000: 数均分子量 2000， 聚四氢呋喃醚二醇；
[0025] MDI-50: 2， 4-二苯基甲烷二异氰酸酯与 4， 4'-二苯基甲烷二异氰酸酯；
[0026] MDI-100: 4， 4'-二苯基甲烷二异氰酸酯；
[0027] 液化 MDI: 碳化二亚胺改性的 MDI;
[0028] DOTP: 对苯二甲酸二辛酯；
[0029] BDO: 1,4-丁二醇；
[0030] TMP: 三羟甲基丙烷；
[0031] 抗氧剂： 1076。
[0032] 以下实施例中的百分数均指质量百分数。
[0033] 实施例 1
[0034] 所述的耐铬酸聚氨酯弹性体的制备方法， 包括以下步骤：
[0035] (1) 制备 A组分： 将分子量 1000的聚四氢呋喃醚二醇 （PTMG1000) 63.6%、 二苯基甲烷二异氰酸酯 （MDI-100) 18.1%、 碳化二亚胺改性的 MDI (液化 MDI ) 18.1<¾、 抗氧剂 （1076) 0.2%在 70°C反应 2小吋， 真空 （一 0.095MPa) 脱除气 泡， 得到聚氨酯预聚物， 其异氰酸根含量为 6.0%;
[0036] (2) 制备聚氨酯弹性体： 将聚氨酯预聚物加热至 80°C， 再将其与加热至 50°C 的固化剂 （BDO与 TMP的质量比为 4:1) 混合， 聚氨酯预聚物与固化剂的质量比 为 100:6.2， 然后将混合物浇注到 130°C的模具中， 6h后脱模， 将脱模后的制品在 120°C下硫化 10小吋， 得到耐铬酸聚氨酯弹性体， 其硬度为邵 A 70。
[0037] 实施例 2
[0038] 所述的耐铬酸聚氨酯弹性体的制备方法， 包括以下步骤：
[0039] (1) 制备 A组分： 将分子量 2000的聚四氢呋喃醚二醇 （PTMG2000) 74%、 二 苯基甲烷二异氰酸酯 （MDI-50) 25.7%、 抗氧剂 （1076) 0.3%在 85°C反应 3小吋 [0040] (2) 制备聚氨酯弹性体： 将聚氨酯预聚物加热至 80°C， 再将其与加热至 60°C 的固化剂 （TMP) 混合， 聚氨酯预聚物与固化剂的质量比为 100:5.7， 然后将混 合物浇注到 100°C的模具中， 7h后脱模， 将脱模后的制品在 120°C下硫化 10小吋， 得到耐铬酸聚氨酯弹性体， 其硬度为邵 A 65。
[0041] 实施例 3
[0042] 所述的耐铬酸聚氨酯弹性体的制备方法， 包括以下步骤：
[0043] (1) 制备 A组分： 将分子量 2000的聚四氢呋喃醚二醇 （PTMG2000) 75.2% ^ 二苯基甲烷二异氰酸酯 （MDI-50) 12.2%. 碳化二亚胺改性的 MDI (液化 MDI) 12.2%、 抗氧剂 (1076) 0.4%在 75°C反应 2.5小吋， 真空 (一 0.095MPa) 脱除气 泡， 得到聚氨酯预聚物， 其异氰酸根含量为 4.5%;
[0044] (2) 制备聚氨酯弹性体： 将聚氨酯预聚物加热至 85°C， 再将其与加热至 60°C 的固化剂 （BDO与 TMP的质量比为 3:7) 混合， 聚氨酯预聚物与固化剂的质量比 为 100:4.7， 然后将混合物浇注到 130°C的模具中， 8h后脱模， 将脱模后的制品在 110°C下硫化 10小吋， 得到耐铬酸聚氨酯弹性体， 其硬度为邵 A 55。
[0045] 实施例 4
[0046] 所述的耐铬酸聚氨酯弹性体的制备方法， 包括以下步骤：
[0047] (1) 制备 A组分： 将分子量 2000的聚四氢呋喃醚二醇 （PTMG2000) 61.1%^ 二苯基甲烷二异氰酸酯 （MDI-50) 18.4%、 对苯二甲酸二辛酯 （DOTP) 20%、 抗氧剂 （1076) 0.5%在 85°C反应 2小吋， 真空 （一 0.095MPa) 脱除气泡， 得到聚 氨酯预聚物， 其异氰酸根含量为 4.5%;
[0048] (2) 制备聚氨酯弹性体： 将聚氨酯预聚物加热至 90°C， 再将其与加热至 60°C 的固化剂 （BDO与 TMP的质量比为 3:7) 混合， 聚氨酯预聚物与固化剂的质量比 为 100:3.8， 然后将混合物浇注到 140°C的模具中， 9h后脱模， 将脱模后的制品在 120°C下硫化 8小吋， 得到耐铬酸聚氨酯弹性体， 其硬度为邵 A 45。
[0049] 实施例 5
[0050] 所述的耐铬酸聚氨酯弹性体的制备方法， 包括以下步骤：
[0051] (1) 制备 A组分： 将分子量 2000的聚四氢呋喃醚二醇 （PTMG2000) 44<¾、 碳 化二亚胺改性的 MDI (液化 MDI) 15.6%、 对苯二甲酸二辛酯 （DOTP) 40%、 抗 氧剂 (1076) 0.4%在 75°C反应 2小吋， 真空 (一 0.095MPa) 脱除气泡， 得到聚氨 酯预聚物， 其异氰酸根含量为 4.5%;
(2) 制备聚氨酯弹性体： 将聚氨酯预聚物加热至 90°C， 再将其与加热至 50°C 的固化剂 （BDO与 TMP的质量比为 4:1) 混合， 聚氨酯预聚物与固化剂的质量比 为 100:2.9， 然后将混合物浇注到 150°C的模具中， 10h后脱模， 将脱模后的制品 在 120°C下硫化 9小吋， 得到耐铬酸聚氨酯弹性体， 其硬度为邵 A 35。
[0053] 由实施例所得的聚氨酯弹性体的性能见表 1。
[0054] 表 1实施例 1-5所得的聚氨酯弹性体的性能
Figure imgf000006_0001
[0055]

Claims
权利要求书
一种耐铬酸聚氨酯弹性体， 其特征在于： 由 A组分和 B组分组成， A 、 B组分的重量比为 100: 2.9-6.2, 其中：
(1) A组分为聚氨酯预聚物， 由以下重量百分含量的原料制成： 聚四氢呋喃醚二醇 44%〜75.2%
二异氰酸酯 15.
6%〜36.2<¾
增塑剂 （^。〜 (^。
抗氧剂 。^^〜。^^；
(2) B组分为固化剂， 为 1,4-丁二醇或三羟甲基丙烷中的一种或两种 所述聚四氢呋喃醚二醇的官能度为 2， 数均分子量为 1000-2000。
根据权利要求 1所述的耐铬酸聚氨酯弹性体， 其特征在于： 二异氰酸 酯由 2， 4-二苯基甲烷二异氰酸酯与 4， 4'-二苯基甲烷二异氰酸酯、 4 ， 4'-二苯基甲烷二异氰酸酯或碳化二亚胺改性的 MDI中的一种或者 多种混合而成。
根据权利要求 1所述的耐铬酸聚氨酯弹性体， 其特征在于： 增塑剂为 对苯二甲酸二辛酯、 邻苯二甲酸二辛酯、 邻苯二甲酸二甲基乙二醇酯 、 邻苯二甲酸二异丁酯或邻苯二甲酸丁苄酯。
根据权利要求 1所述的耐铬酸聚氨酯弹性体， 其特征在于： 抗氧剂为 1 076、 1010、 PDP或 1035。
一种权利要求 1所述的耐铬酸聚氨酯弹性体的制备方法， 其特征在于 包括以下步骤：
(1) 制备 A组分： 将聚四氢呋喃醚二醇、 二异氰酸酯、 增塑剂和抗 氧剂在 70〜85°C反应 2〜3小吋， 得到聚氨酯预聚物；
(2) 制备聚氨酯弹性体： 将聚氨酯预聚物加热至 80〜90°C， 再将其 与加热至 50〜60°C的固化剂混合， 然后将混合物浇注到 100~150°C的 模具中， 6~10h后脱模， 将脱模后的制品在 100〜120°C下硫化 8〜10小 吋， 得到耐铬酸聚氨酯弹性体。 [权利要求 6] 根据权利要求 5所述的耐铬酸聚氨酯弹性体的制备方法， 其特征在于
： 聚氨酯预聚物的异氰酸根含量为 2.7〜6.0%。
[权利要求 7] 根据权利要求 5所述的耐铬酸聚氨酯弹性体的制备方法， 其特征在于
： 制得的耐铬酸的聚氨酯弹性体的硬度为邵 A 35〜70。
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