WO2016150209A1 - 一种高速铁路用聚氨酯微孔弹性体的制备方法 - Google Patents

一种高速铁路用聚氨酯微孔弹性体的制备方法 Download PDF

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WO2016150209A1
WO2016150209A1 PCT/CN2015/097891 CN2015097891W WO2016150209A1 WO 2016150209 A1 WO2016150209 A1 WO 2016150209A1 CN 2015097891 W CN2015097891 W CN 2015097891W WO 2016150209 A1 WO2016150209 A1 WO 2016150209A1
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preparing
elastomer
polyurethane
preparation
speed railway
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魏昌林
吴夕虎
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江苏兴华胶带股份有限公司
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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
    • 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
    • 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
    • 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

Definitions

  • the invention relates to the field of manufacturing of polymer materials, in particular to a preparation method of polyurethane microporous elastomer for high-speed railway.
  • the elastic damping pad is the key damping component on the ballastless track, providing the necessary elasticity for the ballastless track to make the load distribution on the rail more reasonable, thus reducing the damage caused by the vibration inside the car.
  • the main material of the domestic rail transit line damping pad was made of EPDM rubber, styrene butadiene rubber, natural rubber, etc.
  • the product has defects such as high temperature static stiffness change rate, large dynamic and static stiffness ratio and poor durability.
  • the derailment factor of the high-speed train during operation reduces the safety of train operation.
  • polyurethane microcellular elastomer Compared with general rubber, polyurethane microcellular elastomer has excellent mechanical properties, good oil resistance and fatigue resistance. At the same hardness, polyurethane material has high strength and good toughness, and the compressive stress transmission is uniform and stable under high strain conditions. The most outstanding feature is its excellent impact absorption properties, which is widely used in the manufacture of anti-vibration cushioning products. At present, the low-temperature static stiffness change rate, the dynamic stiffness ratio and the fatigue resistance of the elastic pad produced in China need to be further optimized.
  • the technical problem to be solved by the present invention is to provide a high-performance preparation method of a polyurethane microcellular elastomer for high-speed railway.
  • the technical solution of the present invention is: a method for preparing a polyurethane microporous elastomer for high-speed railway, which is innovative in that the method is to prepare a polyurethane microporous elastomer for high-speed railway by semi-prepolymerization. .
  • the metered A component parts by weight are polyester polyol 40-60, butylated hydroxy polyol 10-20, chain extender: 4-20, foam stabilizer 0.2-2.5, catalyst 0.2-10.
  • the metered B component parts by weight are diisocyanate 45 to 75, polyester polyol 24 to 45, and side reaction inhibitor 10 to 130 ppm.
  • the invention has the advantages that the preparation method of the polyurethane microporous elastomer for high-speed railway of the invention can prepare a microporous structure rubber elastic body with a completely closed pore structure, and can produce high elasticity, small compression set and high damping. Rubber with excellent wear resistance and mechanical properties Products can be applied to high-speed railway and urban track line rubber shock absorbers, elevator shock absorbers and automotive vibration damping parts.
  • the invention relates to a method for preparing a polyurethane microporous elastomer for high-speed railway, which comprises preparing a polyurethane microcellular elastomer for high-speed railway by semi-prepolymerization, and the specific steps are as follows:
  • composition of the composition in parts by weight, 40 parts of polyester polyol, 10 parts of butylated hydroxy polyol, 4 parts of chain extender, 0.2 parts of foaming agent, 0.2 parts by weight of catalyst added to the mixture In the reaction kettle, mix well at 35 ° C, and seal the composition for use;
  • the second step the preparation of the prepolymer: in parts by weight, 45 parts of diisocyanate, 24 parts of polyester polyol, 10 ppm of side reaction inhibitor, dehydrated at 105 ° C under vacuum for 2 h, then cooled to 45 ° C, the most And the molten MDI I is rapidly added under rapid stirring, reacted at 85 ° C for 2.5 h under uniform stirring, and then defoamed for 30 min under vacuum, sealed and stored for use;
  • the third step is the preparation of the microcellular elastomer: the metered prepolymer and the composite material are thoroughly mixed with the mixing head of the casting machine, and then preheated to an aluminum mold of 70, and the casting is ultrasonically oscillated and molded for 10 minutes. After demolding, the sample was aged in a 100 ° C oven for 3 h, and the product was tested at room temperature for 1 week.
  • the first step the configuration of the composition: in parts by weight, 52 parts of polyester polyol, 12 parts of butylated hydroxy polyol, 6 parts of chain extender, 1.2 parts of the foaming agent, and 4 parts by weight of the catalyst are added to the mixture.
  • the reaction kettle mix well at 38 ° C, and seal the composition for storage;
  • the second step, preparation of the prepolymer 56 parts of diisocyanate, 30 parts of polyester polyol, 10 ppm of side reaction inhibitor at 110 ° C, dehydrated under vacuum for 2.4 h, and then cooled to 48 ° C, in terms of parts by weight
  • the most melted MDII is rapidly added under rapid stirring, reacted at 86 ° C for 2.5 h under uniform stirring, and then defoamed by vacuum for 30 min, sealed and stored for use;
  • the third step is to prepare the microcellular elastomer: the metered prepolymer and the composite material are thoroughly mixed with the mixing head of the casting machine, and then preheated to an aluminum mold of 70 ⁇ 3° C., and the pouring is performed by ultrasonic vibration. After molding for 10 minutes, the mold was released, and the sample was aged in a 100 ° C oven for 3 hours, and the product was tested at room temperature for 1 week.
  • the invention relates to a method for preparing a polyurethane microporous elastomer for high-speed railway, which comprises preparing a polyurethane microcellular elastomer for high-speed railway by semi-prepolymerization, and the specific steps are as follows:
  • the composition of the composition 60 parts of polyester polyol, 20 parts of butylated hydroxy polyol, 20 parts of chain extender, 2.5 parts of foam stabilizer, and 10 parts of catalyst are added to the mixing reactor. , thoroughly mix at 42 ° C, the composition is sealed and stored for use;
  • the second step the preparation of the prepolymer: in parts by weight, 75 parts of diisocyanate, 45 parts of polyester polyol, 130 ppm of side reaction inhibitor, mixed and under vacuum at 135 ° C Dehydrated for 3h, then cooled to 55 ° C, the most melted MDII was quickly added under rapid stirring, reacted under uniform stirring conditions at 90 ° C for 2.5 h, then vacuum defoamed for 30 min, sealed and stored for use;
  • the third step is to prepare the microcellular elastomer: the metered prepolymer and the composite material are thoroughly mixed with the mixing head of the casting machine, and then preheated to an aluminum mold of 70 ⁇ 3° C., and the pouring is performed by ultrasonic vibration. After molding for 10 minutes, the mold was released, and the sample was aged in a 100 ° C oven for 3 hours, and the product was tested at room temperature for 1 week.

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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

本发明涉及一种高速铁路用聚氨酯微孔弹性体的制备方法，所述方法为采用半预聚法制备高速铁路用聚氨酯微孔弹性体，具体步骤如下：第一步，组合料的配置：将计量的A组分加人到混合反应釜中，在35-42℃充分混合均匀，将组合料密封保存待用；第二步预聚体的制备：将计量的B组分在105～135℃、真空下脱水2-3h，然后冷却至45-55℃，将计最并熔化的MDII在快速搅拌下迅速加人，在均匀搅拌条件下于85-90℃反应2.5h，再真空脱泡30min，密封保存待用；第三步微孔弹性体制备。本发明的高速铁路用聚氨酯微孔弹性体的制备方法，可生产具有高弹性、压缩永久变形小、高阻尼、耐磨性和力学性能优良的橡胶制品。

Description

一种高速铁路用聚氨酯微孔弹性体的制备方法 技术领域
本发明涉及高分子材料制造领域，特别涉及一种高速铁路用聚氨酯微孔弹性体的制备方法。
背景技术
随着我国铁路运营时速的不断提升，无碴轨道因其优秀的综合性能在高速铁路上大量铺设，成为现代铁路的发展趋势。弹性减振垫是无碴轨道上的关键减振部件，为无碴轨道提供必要的弹性能使钢轨上的载荷分配更合理，从而降低车内振动带来的危害。
在此之前国内轨道交通线路减振垫板主体材料多采用三元乙丙橡胶、丁苯橡胶、天然橡胶等，产品存在低温静刚度变化率大、动静刚度比大和耐久性差等缺陷，增大了高速列车在运行中的脱轨系数，降低了列车运行安全性。
聚氨酯微孔弹性体与一般橡胶相比，其力学性能优异，耐油和耐疲劳性好，在相同硬度时，聚氨酯材料强度高、韧性好，在高应变条件下压缩应力传递均匀平稳，这种材料的最突出的特点是具有优异的吸收冲击性能，因而广泛用于制造防振缓冲产品。目前国内生产的弹性垫板低温静刚度变化率、动朴刚度比及耐疲劳等性能指标有待进一步优化。
发明内容
本发明要解决的技术问题是提供一种高性能的高速铁路用聚氨酯微孔弹性体的制备方法。
为解决上述技术问题，本发明的技术方案为：一种高速铁路用聚氨酯微孔弹性体的制备方法，其创新点在于：所述方法为采用半预聚法制备高速铁路用聚氨酯微孔弹性体。
进一步地，所述方法的具体步骤如下：
(1)组合料的配置：将计量的A组分加人到混合反应釜中，在35-42℃充分混合均匀，将组合料密封保存待用；
(2)预聚体的制备：将计量的B组分在105～135℃、真空下脱水2-3h，然后冷却至45-55℃，将计最并熔化的MDII在快速搅拌下迅速加人，在均匀搅拌条件下于85-90℃反应2.5h，再真空脱泡30min，密封保存待用；
(3)微孔弹性体制备：将计量的预聚体与组合料输送到浇注机的混合头充分混合后注人预热至70±3℃的铝模中，浇注是使用超声震荡，合模成型10min后脱模，样品放人100℃烘箱内熟化3h，室温放置l周后进行性能检测。
进一步地，所述计量的A组分重量份为聚酯多元醇40～60、丁羟多元醇10～20、扩链剂：4～20、匀泡剂0.2～2.5、催化剂0.2～10。
进一步地，所述计量的B组分重量份为二异氰酸酯45～75、聚酯多元醇24～45、副反应阻止剂10～130ppm。
本发明的优点在于：本发明的高速铁路用聚氨酯微孔弹性体的制备方法，制备出一种完全闭孔结构的微孔结构橡胶弹性体，可生产具有高弹性、压缩永久变形小、高阻尼、耐磨性和力学性能优良的橡胶 制品，可应用于高速铁路和城市轨道线路橡胶减震制品、电梯减振缓冲件和汽车减振件上。
具体实施方式
下面结合具体实施例对本发明的技术方案作详细说明。
实施例1
一种高速铁路用聚氨酯微孔弹性体的制备方法，该方法为采用半预聚法制备高速铁路用聚氨酯微孔弹性体，具体步骤如下：
第一步，组合料的配置：以重量份计算，聚酯多元醇40份、丁羟多元醇10份、扩链剂4份、匀泡剂0.2份、催化剂0.2份的重量份加人到混合反应釜中，在35℃充分混合均匀，将组合料密封保存待用；
第二步，预聚体的制备：以重量份计算，二异氰酸酯45份、聚酯多元醇24份、副反应阻止剂10ppm在105℃、真空下脱水2h，然后冷却至45℃，将计最并熔化的MDI I在快速搅拌下迅速加人，在均匀搅拌条件下于85℃反应2.5h，再真空脱泡30min，密封保存待用；
第三步，微孔弹性体制备：将计量的预聚体与组合料输送到浇注机的混合头充分混合后注人预热至70的铝模中，浇注是使用超声震荡，合模成型10min后脱模，样品放人100℃烘箱内熟化3h，室温放置l周后进行性能检测。
实施例2
一种高速铁路用聚氨酯微孔弹性体的制备方法，该方法为采用半 预聚法制备高速铁路用聚氨酯微孔弹性体，具体步骤如下：
第一步，组合料的配置：以重量份计算，聚酯多元醇52份、丁羟多元醇12份、扩链剂6份、匀泡剂1.2份、催化剂4份的重量份加人到混合反应釜中，在38℃充分混合均匀，将组合料密封保存待用；
第二步，预聚体的制备：以重量份计算，二异氰酸酯56份、聚酯多元醇30份、副反应阻止剂10ppm在110℃、真空下脱水2.4h，然后冷却至48℃，将计最并熔化的MDII在快速搅拌下迅速加人，在均匀搅拌条件下于86℃反应2.5h，再真空脱泡30min，密封保存待用；
第三步，微孔弹性体制备：将计量的预聚体与组合料输送到浇注机的混合头充分混合后注人预热至70±3℃的铝模中，浇注是使用超声震荡，合模成型10min后脱模，样品放人100℃烘箱内熟化3h，室温放置l周后进行性能检测。
实施例1
一种高速铁路用聚氨酯微孔弹性体的制备方法，该方法为采用半预聚法制备高速铁路用聚氨酯微孔弹性体，具体步骤如下：
第一步，组合料的配置：以重量份计算，聚酯多元醇60份、丁羟多元醇20份、扩链剂20份、匀泡剂2.5份、催化剂10份加人到混合反应釜中，在42℃充分混合均匀，将组合料密封保存待用；
第二步，预聚体的制备：以重量份计算，二异氰酸酯75份、聚酯多元醇45份、副反应阻止剂130ppm，混合并在135℃、真空下 脱水3h，然后冷却至55℃，将计最并熔化的MDII在快速搅拌下迅速加人，在均匀搅拌条件下于90℃反应2.5h，再真空脱泡30min，密封保存待用；
第三步，微孔弹性体制备：将计量的预聚体与组合料输送到浇注机的混合头充分混合后注人预热至70±3℃的铝模中，浇注是使用超声震荡，合模成型10min后脱模，样品放人100℃烘箱内熟化3h，室温放置l周后进行性能检测。
以上显示和描述了本发明的基本原理和主要特征和本发明的优点。本行业的技术人员应该了解，本发明不受上述实施例的限制，上述实施例和说明书中描述的只是说明本发明的原理，在不脱离本发明精神和范围的前提下，本发明还会有各种变化和改进，这些变化和改进都落入要求保护的本发明范围内。本发明要求保护范围由所附的权利要求书及其等效物界定。

Claims (4)

  1. 一种高速铁路用聚氨酯微孔弹性体的制备方法，其特征在于：所述方法为采用半预聚法制备高速铁路用聚氨酯微孔弹性体。
  2. 根据权利要求1所述的高速铁路用聚氨酯微孔弹性体的制备方法，其特征在于：所述方法的具体步骤如下：
    (1)组合料的配置：将计量的A组分加人到混合反应釜中，在35-42℃充分混合均匀，将组合料密封保存待用；
    (2)预聚体的制备：将计量的B组分在105～135℃、真空下脱水2-3h，然后冷却至45-55℃，将计最并熔化的MDII在快速搅拌下迅速加人，在均匀搅拌条件下于85-90℃反应2.5h，再真空脱泡30min，密封保存待用；
    (3)微孔弹性体制备：将计量的预聚体与组合料输送到浇注机的混合头充分混合后注人预热至70±3℃的铝模中，浇注是使用超声震荡，合模成型10min后脱模，样品放人100℃烘箱内熟化3h，室温放置l周后进行性能检测。
  3. 根据权利要求1所述的高速铁路用聚氨酯微孔弹性体的制备方法，其特征在于：所述计量的A组分重量份为聚酯多元醇40～60、丁羟多元醇10～20、扩链剂：4～20、匀泡剂0.2～2.5、催化剂0.2～10。
  4. 根据权利要求1所述的高速铁路用聚氨酯微孔弹性体的制备方法，其特征在于：所述计量的B组分重量份为二异氰酸酯45～75、聚酯多元醇24～45、副反应阻止剂10～130ppm。
PCT/CN2015/097891 2015-03-24 2015-12-18 一种高速铁路用聚氨酯微孔弹性体的制备方法 WO2016150209A1 (zh)

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