WO2013091271A1 - Microporous polyurethane elastomer composition with excellent dynamic performance and method for preparing same - Google Patents

Microporous polyurethane elastomer composition with excellent dynamic performance and method for preparing same Download PDF

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Publication number
WO2013091271A1
WO2013091271A1 PCT/CN2012/000341 CN2012000341W WO2013091271A1 WO 2013091271 A1 WO2013091271 A1 WO 2013091271A1 CN 2012000341 W CN2012000341 W CN 2012000341W WO 2013091271 A1 WO2013091271 A1 WO 2013091271A1
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Prior art keywords
polyurethane elastomer
polyol
component
elastomer composition
dynamic performance
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PCT/CN2012/000341
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French (fr)
Chinese (zh)
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李健
孙清峰
孙兆任
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山东东大一诺威聚氨酯有限公司
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Priority to BR112013026700A priority Critical patent/BR112013026700A2/en
Publication of WO2013091271A1 publication Critical patent/WO2013091271A1/en

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08Processes
    • C08G18/10Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08Processes
    • C08G18/10Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12Prepolymer 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
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30Low-molecular-weight compounds
    • C08G18/32Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203Polyhydroxy compounds
    • C08G18/3206Polyhydroxy compounds aliphatic
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30Low-molecular-weight compounds
    • C08G18/32Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3271Hydroxyamines
    • C08G18/3275Hydroxyamines containing two hydroxy groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/42Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269Lactones
    • C08G18/4277Caprolactone and/or substituted caprolactone
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/48Polyethers
    • C08G18/4825Polyethers containing two hydroxy groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/48Polyethers
    • C08G18/4854Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group

Definitions

  • the invention belongs to the field of polyurethane elastomer synthesis, and in particular relates to the preparation of a microcellular polyurethane elastomer composition excellent in dynamic properties.
  • the microporous polyurethane elastomer is a novel material between the elastomer and the foam material, and the cell diameter is generally 0.1 to 10 ⁇ ⁇ , the cells are fine and uniform, and the density is lower than the solid elastomer material.
  • the mechanical properties are significantly higher than the common foam materials. Therefore, the microcellular polyurethane elastomer has the advantages of light weight, comfort and high strength of the elastomer material and good mechanical properties. It has good cushioning performance and excellent fatigue resistance. It is an elastic material with excellent comprehensive performance. It has broad application potential in some special fields, such as the application of high-speed rail cushions and the preparation of high-speed car shock absorbers.
  • the conventional railway cushion plate is made of rubber material.
  • the elastic recovery is relatively slow, and the dynamic and static stiffness ratio can reach 1.5 or more. It is difficult to meet the development requirements of high-speed railway.
  • the method of partial grooving is often used to reduce the dynamic stiffness of the material, which results in the stress concentration at the root of the groove and the early destruction of the material, and the life is shortened.
  • the microporous polyurethane elastomer can easily reduce the dynamic and static stiffness ratio of the material due to the regularity of the molecular structure and the strong molecular design.
  • the conventional common polyether is obtained by ring-opening polymerization of propylene oxide and epoxy oxime.
  • the molecular structure contains a large number of pendant methyl groups. Although the molecular structure is relatively regular, when subjected to alternating external forces, the molecular chain The motion is affected by the steric hindrance of the side base, and the deformation is lagging behind the change of stress. The energy loss becomes larger, and the dynamic and static stiffness ratio becomes larger. Therefore, the dynamic and static stiffness is also difficult to achieve the dynamic and static stiffness of the current high-speed railway pad. More than the requirements of 1.35.
  • Patent CN100506871C reports on a preparation method of NDI-based polyurethane microcellular elastomer. It is well known that polyurethane materials prepared by NDI have excellent dynamic performance, low damping property and high resilience, and are specially suitable for dynamic load and heat resistance. However, this material has a higher melting point, is complicated in the preparation of the polyurethane material, and has poor storage stability, and the prepared prepolymer has a storage stability time of only a few small crucibles.
  • Patent CN101469054B reports a preparation method of PPDI-based polyurethane microcellular elastomer, which has better dynamic performance and better storage stability of prepolymer, but PPEI has higher melting point and complicated processing technology; CN101380442B reports a T0DI base.
  • the preparation method of the polyurethane microporous elastomer has good processing performance, and the prepared polyurethane microporous elastomer material is excellent in heat resistance, wear resistance and dynamic fatigue property.
  • the isocyanates used in the above patents are all special isocyanates, and the raw material cost is relatively high; on the other hand,
  • the above patents all use the prepolymer method to prepare the microporous elastomer, the chain extension is carried out by using a small molecule mixture, the viscosity of the prepolymer component is large, the viscosity difference between the two components is large, the material mixing temperature is high, and the mass of the two components is high. The problem is larger than the gap, it is not easy to mix evenly, and the product quality is not easy to control stably.
  • the object of the present invention is to provide a microcellular polyurethane elastomer composition excellent in dynamic performance and a preparation method thereof, and the microporous elastomer material prepared according to the composition provided by the invention has excellent dynamic performance and resilience, dynamic and static stiffness ratio 1. 35, 3 million fatigue test after appearance without damage, impact resilience 75%, can be used for the preparation of high-speed rail cushions and automotive shock absorber components.
  • microporous polyurethane elastomer composition excellent in dynamic performance comprises the following two components:
  • Component A comprising a polymer polyol, a chain extender, a blowing agent, a catalyst A, a catalyst B, a foam stabilizer, and an antioxidant, wherein the other raw materials account for polymerization based on 100% by weight of the total of the polymer polyol.
  • the percentage of the total weight of the polyol is: 5% to 12% of the chain extender, 0. 1% ⁇ 0. 3%, the catalyst ⁇ . 3 ⁇ 1.
  • 0%, the catalyst B 0. 01% ⁇ 0 6%; 6%; 2%; 0%, antioxidants 0. 3 ⁇ 0. 6%;
  • Component B a modified isocyanate component, a mixture of a NC0 group-terminated urethane-modified isocyanate and an isocyanate prepared by reacting a polymer polyol with an isocyanate;
  • component A and component B are mixed at a mass ratio of 100: 90 to 110.
  • the temperature of component A is 30 V to 45 ° C
  • the temperature of component B is 40 ° C to 50 ° C.
  • the mass ratio of the component A to the component B is preferably 100: 93 to 100, more preferably 100: 95 to 97.
  • the component A temperature is preferably from 33 ° C to 37 ° C
  • the component B temperature is preferably from 43 ° C to 47 ° C.
  • the polyether polyol or the average functionality of the polymer polyol is preferably from 1.8 to 4, preferably from 2 to 3, and the number average molecular weight is from 1000 to 8000, preferably from 2000 to 6000. 3, preferably 2 to 2. 5, a mixture of one or two of the polyester polyols having a number average molecular weight of from 1,000 to 6,000, preferably from 1,500 to 3,000, in any ratio.
  • the polyether polyol is preferably one or a mixture of one or more of a polypropylene oxide ether polyol, a propylene oxide-ethylene oxide copolyether polyol, and a polytetrahydrofuran ether polyol, more preferably a polytetrahydrofuran ether.
  • polyester polyols preferably from polycaprolactone polyols, polycarbonate polyols, polyadipate-1,4 butanediol ester polyols, polyadipates-1,6-hexanediol esters One or more of the polyols, more preferably a polycaprolactone polyol.
  • the chain extender is preferably selected from the group consisting of ethylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol or 3,3-dichloro-4, 4- One or more of diphenyltoluenediamine.
  • the blowing agent is preferably one or more selected from the group consisting of water, formic acid, acetic acid or monofluorodichloroethane, more preferably water.
  • the catalyst A is preferably selected from a tertiary amine catalyst, and may be selected from triethylene glycol of triethylenediamine having a solid content of 33%.
  • Catalyst B is preferably one or more selected from the group consisting of an organotin catalyst, an organic ruthenium catalyst or an organozinc catalyst, and dibutyltin dilaurate may be used.
  • the foam stabilizer is preferably selected from the group consisting of a silicone surfactant, which may be selected from DC3043 (manufacturer of the US Gas Chemical), 8444 (manufacturer of Shanghai Gao Shimet Chemical) or AK7703 (manufacturer Nanjing Demei Shichuang). One or more.
  • the antioxidant is preferably a hindered phenolic antioxidant, and may be selected from BHT264 (2,6-di-tert-butyl-4-methylphenol), ChinoxlOlO (manufacturer is Taiwan Double Bond Chemical) or Irganoxl035 (manufacturer) One or more of Ciba Specialty Chemicals).
  • the isocyanate in the modified isocyanate component is preferably 4,4'-diphenylmethyl modified from 4,4'-diphenylmethane diisocyanate (pure MDI) or carbonized diimine-uretonimide. ⁇ Diisocyanate (liquefied MDI), p-phenylene diisocyanate ⁇ ?01), 1,5-naphthalene diisocyanate (1) or 3,3 '-dimethyl-4,4'-biphenyldiisocyanate (T0DI) One or more.
  • the modified isocyanate component is preferably from 11% to 14% by weight, more preferably from 12% to 12% by weight, more preferably from 2% to 25%, more preferably from 2 to 2, more preferably from 2 to 2.
  • the invention has the following advantages: (1) The invention adopts a semi-prepolymer method to prepare a microporous polyurethane elastomer material, the two components have similar viscosity, the mixing mass ratio is similar, the mixing temperature is low, and the material is easy to be uniformly mixed, the process The control conditions are simple and easy to operate. (2) The microporous polyurethane elastomer material prepared by the composition provided by the invention has a dynamic-static stiffness ratio of 1.35, impact resilience of 75%, no damage after 3 million fatigue tests, and a dimensional change rate of 20%, which can be used for high-speed rail Preparation of high performance products such as cushions and automotive shock absorbers. .
  • the temperature of component A is maintained at 35 ° C
  • the temperature of component B is maintained at 45 ° C
  • the two components are quickly mixed uniformly at a weight ratio of 100: 110, and poured into a mold which is pre-55 ° C, 85 After aging for 10 minutes in the drying tunnel of °C, the mold was opened to obtain a polyurethane microcellular elastomer material.
  • PTMG2000 polytetrahydrofuran ether polyol
  • the component A temperature at 35 when in use The temperature of C and B components is maintained at 45 V.
  • the two components are quickly mixed evenly at a weight ratio of 100:90.
  • the mixture is poured into a mold that is pre-55 ° C. After curing for 10 minutes in a drying oven at 85 ° C, the mold is opened. A polyurethane microcellular elastomer material is obtained.
  • PTMG2000 polytetrahydrofuran ether polyol
  • the moisture content is less than 0.05%, the moisture content is less than 0. 05%, the moisture content is less than 0. 05%, the moisture content is less than 0. 05%, the moisture content is less than 0. 05%, 5 ⁇ 13 ⁇
  • the temperature was reduced to 50 ° C, the addition of 72.5 parts of pure MDI, slowly heated to 75 times the incubation reaction 1. 5 hours, adding 15 parts of liquefied MDI, stirring 0. 5 hours, sampling test, - NC0 mass content of 13. 1%, cooled to 50 ° C discharge, sealed and stored.
  • the temperature of component A is maintained at 35 ° C
  • the temperature of component B is maintained at 45 ° C
  • the two components are quickly mixed uniformly at a weight ratio of 100: 92, poured into a mold of 55 ⁇ , and baked at 85 ⁇ . After the mold is aged for 10 minutes, the mold is opened, and a polyurethane microporous elastomer material is obtained.
  • PTMG2000 polytetrahydrofuran ether polyol
  • component A When used, the temperature of component A was maintained at 35 ° C and the temperature of component B was maintained at 45. C, the two components are quickly mixed uniformly according to the weight ratio of 100 : 95, poured into a mold of 55 ⁇ , and the mold is opened after being aged for 10 minutes in an 85 ⁇ drying tunnel to obtain a polyurethane microcellular elastomer material.

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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)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention relates to the preparation of a microporous polyurethane elastomer composition with excellent dynamic performance, consisting of a component A and a component of modified isocyanate. The component A comprises a polymer of polyol, a chain extender, a foaming agent, a catalyst A, a catalyst B, a foam stabiliser, and an anti-oxidant. The present invention has the following advantages: (1) the present invention is a microporous polyurethane elastomer material prepared by semi-prepolymerisation, and the two groups of fractional materials have similar viscosity and mixed mass ratio, a low mixture temperature; the materials are easy to mix, and the conditions for controlling the process are simple and easy to operate. (2) The microporous polyurethane elastomer material prepared from the composition provided by the present invention has a ratio of dynamic to static stiffness of ≤1.35, an impact resilience of ≥75%, a rate of change in size of ≤20%, without damage to appearance after 3 million fatigue tests, and can be used in the preparation of high performance products such as vibration-damping blocks for high speed railways and vibration-damping elements in vehicles.

Description

动态性能优异的微孔聚氨酯弹性体组合物及其制备方法 技术领域  Microporous polyurethane elastomer composition excellent in dynamic performance and preparation method thereof
本发明属于聚氨酯弹性体合成领域,特别涉及一种动态性能优异的微孔聚氨酯弹性体 组合物的制备。  The invention belongs to the field of polyurethane elastomer synthesis, and in particular relates to the preparation of a microcellular polyurethane elastomer composition excellent in dynamic properties.
背景技术 Background technique
微孔聚氨酯弹性体是一种介于弹性体和泡沫材料之间的新型材料,其泡孔直径一般在 0. 1〜10 μ πι, 泡孔细密均匀, 密度低于实心的弹性体材料, 而力学性能要明显高于常见的 泡沫材料, 因此微孔聚氨酯弹性体兼备了泡沫材料的质轻、舒适和弹性体材料强度高、机 械性能好的双重优点, 具有缓冲性能好, 耐疲劳性能优异的特点, 是一种综合性能优异的 弹性材料, 在一些特殊领域具有广阔的应用潜力, 例如在高铁减震垫方面的应用以及高档 轿车减震原件的制备等方面, 具有显著的优势。  The microporous polyurethane elastomer is a novel material between the elastomer and the foam material, and the cell diameter is generally 0.1 to 10 μ πι, the cells are fine and uniform, and the density is lower than the solid elastomer material. The mechanical properties are significantly higher than the common foam materials. Therefore, the microcellular polyurethane elastomer has the advantages of light weight, comfort and high strength of the elastomer material and good mechanical properties. It has good cushioning performance and excellent fatigue resistance. It is an elastic material with excellent comprehensive performance. It has broad application potential in some special fields, such as the application of high-speed rail cushions and the preparation of high-speed car shock absorbers.
随着高速铁路运营速度的不断提高, 车辆在运行中产生的震动和噪音也不断增加, 为 了减少提速所带来的负面影响,在铁路轨道铺设时需要在水泥枕木和钢轨之间加一弹性垫 板来减少刚性材料之间产生的震动和噪音。 传统的铁路减震垫板是采用橡胶材料来制备 的,这种橡胶材料在受到交变外力作用时,弹性回复比较慢,动静刚度比可达到 1. 5以上, 难以满足高速铁路的发展要求, 实际应用中常采用局部开槽的方法来降低材料的动刚度, 如此一来就会导致槽根部位容易产生应力集中而使材料及早破坏, 寿命缩短。而微孔聚氨 酯弹性体由于分子结构的规整性和极强的分子可设计性,因此可以较容易的降低材料的动 静刚度比。传统的普通聚醚多是由环氧丙烷和环氧乙垸开环聚合而得到, 分子结构上含有 大量的侧甲基基团, 虽然分子结构比较规整, 但是当受到交替外力作用时, 分子链运动受 到侧基的位阻影响, 其形变也就越滞后于应力的变化, 能量损耗变大, 动静刚度比也就明 显变大, 因此, 其动静刚度也较难达到当前高速铁路垫板动静刚度比 1. 35的要求。  As the operation speed of high-speed railways continues to increase, the vibration and noise generated by the vehicles are also increasing. In order to reduce the negative impact of speed increase, it is necessary to add an elastic pad between the cement sleepers and the rails when laying the railway tracks. Plates to reduce vibration and noise generated between rigid materials. The conventional railway cushion plate is made of rubber material. When the rubber material is subjected to alternating external force, the elastic recovery is relatively slow, and the dynamic and static stiffness ratio can reach 1.5 or more. It is difficult to meet the development requirements of high-speed railway. In practical applications, the method of partial grooving is often used to reduce the dynamic stiffness of the material, which results in the stress concentration at the root of the groove and the early destruction of the material, and the life is shortened. The microporous polyurethane elastomer can easily reduce the dynamic and static stiffness ratio of the material due to the regularity of the molecular structure and the strong molecular design. The conventional common polyether is obtained by ring-opening polymerization of propylene oxide and epoxy oxime. The molecular structure contains a large number of pendant methyl groups. Although the molecular structure is relatively regular, when subjected to alternating external forces, the molecular chain The motion is affected by the steric hindrance of the side base, and the deformation is lagging behind the change of stress. The energy loss becomes larger, and the dynamic and static stiffness ratio becomes larger. Therefore, the dynamic and static stiffness is also difficult to achieve the dynamic and static stiffness of the current high-speed railway pad. More than the requirements of 1.35.
专利 CN100506871C报道了一种 NDI基聚氨酯微孔弹性体的制备方法, 众所周知, 采 用 NDI制备的聚氨酯材料具有优异的动态性能、 阻尼性小, 回弹性高, 特备适用于动态载 荷和耐热性场合, 但是这种材料熔点较高, 在制备聚氨酯材料时工艺复杂, 而且储存稳定 性很差,制得的预聚体只有几个小吋的储存稳定时间。专利 CN101469054B报道了一种 PPDI 基聚氨酯微孔弹性体的制备方法, 具有较好的动态性能, 预聚体储存稳定性较好, 但是 PPDI熔点较高,加工工艺复杂; CN101380442B报道了一种 T0DI基聚氨酯微孔弹性体的制 备方法,加工性能较好, 制备的聚氨酯微孔弹性体材料耐热性、 耐磨性和动态疲劳性能优 异。但是上述专利所采用的异氰酸酯全部为特种异氰酸酯,原料成本相对太高;另一方面, 上述专利均采用预聚体的方法制备微孔弹性体, 采用小分子混合物进行扩链,存在预聚体 组份粘度大, 两组份料粘度差别大, 物料混合温度高, 两组份料质量比差距大, 不易混合 均匀等问题, 产品质量不易稳定控制。 Patent CN100506871C reports on a preparation method of NDI-based polyurethane microcellular elastomer. It is well known that polyurethane materials prepared by NDI have excellent dynamic performance, low damping property and high resilience, and are specially suitable for dynamic load and heat resistance. However, this material has a higher melting point, is complicated in the preparation of the polyurethane material, and has poor storage stability, and the prepared prepolymer has a storage stability time of only a few small crucibles. Patent CN101469054B reports a preparation method of PPDI-based polyurethane microcellular elastomer, which has better dynamic performance and better storage stability of prepolymer, but PPEI has higher melting point and complicated processing technology; CN101380442B reports a T0DI base. The preparation method of the polyurethane microporous elastomer has good processing performance, and the prepared polyurethane microporous elastomer material is excellent in heat resistance, wear resistance and dynamic fatigue property. However, the isocyanates used in the above patents are all special isocyanates, and the raw material cost is relatively high; on the other hand, The above patents all use the prepolymer method to prepare the microporous elastomer, the chain extension is carried out by using a small molecule mixture, the viscosity of the prepolymer component is large, the viscosity difference between the two components is large, the material mixing temperature is high, and the mass of the two components is high. The problem is larger than the gap, it is not easy to mix evenly, and the product quality is not easy to control stably.
发明内容 Summary of the invention
本发明的目的在于提供一种动态性能优异的微孔聚氨酯弹性体组合物及其制备方法, 根据本发明提供的组合物制备的微孔弹性体材料具有优异的动态性能和回弹性,动静刚度 比 1. 35, 300万次疲劳实验后外观无破损, 冲击回弹性 75%, 可用于高铁减震垫块和 汽车减震元件的制备。  The object of the present invention is to provide a microcellular polyurethane elastomer composition excellent in dynamic performance and a preparation method thereof, and the microporous elastomer material prepared according to the composition provided by the invention has excellent dynamic performance and resilience, dynamic and static stiffness ratio 1. 35, 3 million fatigue test after appearance without damage, impact resilience 75%, can be used for the preparation of high-speed rail cushions and automotive shock absorber components.
本发明所述的一种动态性能优异的微孔聚氨酯弹性体组合物, 由以下两种组份组成: The microporous polyurethane elastomer composition excellent in dynamic performance according to the present invention comprises the following two components:
A组份: 包括聚合物多元醇、 扩链剂、 发泡剂、 催化剂 A、 催化剂 B、 泡沫稳定剂以及 抗氧剂, 其中, 以聚合物多元醇总重量为 100%计, 其它原料占聚合物多元醇总重量的百分 数分别为: 扩链剂 5%〜12%, 发泡剂 0. 1%〜0. 3%, 催化剂 ΑΌ. 3〜1. 0%, 催化剂 B 0. 01%〜 0. 06%, 泡沬稳定剂 0. 2〜1. 0%, 抗氧剂 0. 3〜0. 6%; Component A: comprising a polymer polyol, a chain extender, a blowing agent, a catalyst A, a catalyst B, a foam stabilizer, and an antioxidant, wherein the other raw materials account for polymerization based on 100% by weight of the total of the polymer polyol. The percentage of the total weight of the polyol is: 5% to 12% of the chain extender, 0. 1%~0. 3%, the catalyst ΑΌ. 3~1. 0%, the catalyst B 0. 01%~ 0 6%; 6%; 2%; 0%, antioxidants 0. 3~0. 6%;
B组份: 改性异氰酸酯组份, 由聚合物多元醇与异氰酸酯反应制得的 NC0基团封端的 氨酯改性异氰酸酯与异氰酸酯的混合物;  Component B: a modified isocyanate component, a mixture of a NC0 group-terminated urethane-modified isocyanate and an isocyanate prepared by reacting a polymer polyol with an isocyanate;
使用时, A组份和 B组份按照质量比为 100: 90〜 110混合,混合时 A组份的温度为 30 V〜 45 °C , B组份温度为 40°C〜50°C。  When used, component A and component B are mixed at a mass ratio of 100: 90 to 110. When mixed, the temperature of component A is 30 V to 45 ° C, and the temperature of component B is 40 ° C to 50 ° C.
本发明所述的组合物在使用时, A组份和 B组份的质量比优选为 100: 93〜100, 更优 选 100: 95〜97。两组份混合时, A组份温度优选为 33°C〜37°C, B组份温度优选为 43°C〜 47°C。  When the composition of the present invention is used, the mass ratio of the component A to the component B is preferably 100: 93 to 100, more preferably 100: 95 to 97. When the two components are mixed, the component A temperature is preferably from 33 ° C to 37 ° C, and the component B temperature is preferably from 43 ° C to 47 ° C.
所述的聚合物多元醇优选自平均官能度为 1. 8〜4, 优选 2〜3, 数均相对分子质量为 1000〜8000, 优选 2000〜6000的聚醚多元醇或平均官能度为 2〜3, 优选 2〜2. 5, 数均相 对分子质量 1000〜6000, 优选 1500〜3000的聚酯多元醇中的一种或两种任意比例混合的 混合物。其中, 聚醚多元醇优选自聚环氧丙烷醚多元醇、环氧丙垸-环氧乙烷共聚醚多元醇 和聚四氢呋喃醚多元醇中的一种或一种以上的混合物, 更优选聚四氢呋喃醚多元醇; 聚酯 多元醇优选自聚己内酯多元醇、聚碳酸酯多元醇、聚己二酸- 1, 4 丁二醇酯多元醇、聚己二 酸 -1, 6-己二醇酯多元醇中的一种或多种, 更优选聚己内酯多元醇。  The polyether polyol or the average functionality of the polymer polyol is preferably from 1.8 to 4, preferably from 2 to 3, and the number average molecular weight is from 1000 to 8000, preferably from 2000 to 6000. 3, preferably 2 to 2. 5, a mixture of one or two of the polyester polyols having a number average molecular weight of from 1,000 to 6,000, preferably from 1,500 to 3,000, in any ratio. Wherein, the polyether polyol is preferably one or a mixture of one or more of a polypropylene oxide ether polyol, a propylene oxide-ethylene oxide copolyether polyol, and a polytetrahydrofuran ether polyol, more preferably a polytetrahydrofuran ether. Polyols; polyester polyols preferably from polycaprolactone polyols, polycarbonate polyols, polyadipate-1,4 butanediol ester polyols, polyadipates-1,6-hexanediol esters One or more of the polyols, more preferably a polycaprolactone polyol.
所述的扩链剂优选自乙二醇、 一缩二乙二醇、 一缩二丙二醇、 1,4-丁二醇、 1, 6-己二 醇或 3, 3-二氯 4, 4-二苯基甲苯二胺中的一种或多种。  The chain extender is preferably selected from the group consisting of ethylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol or 3,3-dichloro-4, 4- One or more of diphenyltoluenediamine.
所述的发泡剂优选自水、 甲酸、 乙酸或一氟二氯乙烷中的一种或多种, 更优选水。 所述的催化剂 A优选自叔胺类催化剂, 可以选用固含量 33%的三乙烯二胺的二乙二醇 溶液; 催化剂 B优选自有机锡类催化剂、 有机铋类催化剂或有机锌类催化剂中的一种或多 种, 可以选用二月桂酸二丁基锡。 The blowing agent is preferably one or more selected from the group consisting of water, formic acid, acetic acid or monofluorodichloroethane, more preferably water. The catalyst A is preferably selected from a tertiary amine catalyst, and may be selected from triethylene glycol of triethylenediamine having a solid content of 33%. Solution; Catalyst B is preferably one or more selected from the group consisting of an organotin catalyst, an organic ruthenium catalyst or an organozinc catalyst, and dibutyltin dilaurate may be used.
所述的泡沫稳定剂优选自有机硅表面活性剂, 可以选用 DC3043 (生产厂家为美国气体 化工)、 8444 (生产厂家为上海高施米特化工) 或 AK7703 (生产厂家南京德美世创) 中的 一种或多种。  The foam stabilizer is preferably selected from the group consisting of a silicone surfactant, which may be selected from DC3043 (manufacturer of the US Gas Chemical), 8444 (manufacturer of Shanghai Gao Shimet Chemical) or AK7703 (manufacturer Nanjing Demei Shichuang). One or more.
所述的抗氧剂优选自受阻酚类抗氧剂,可以选用 BHT264 (2, 6-二叔丁基- 4-甲基苯酚)、 ChinoxlOlO (生产厂家为台湾双键化工)或 Irganoxl035 (生产厂家为 Ciba特殊化学品公 司) 中的一种或多种。  The antioxidant is preferably a hindered phenolic antioxidant, and may be selected from BHT264 (2,6-di-tert-butyl-4-methylphenol), ChinoxlOlO (manufacturer is Taiwan Double Bond Chemical) or Irganoxl035 (manufacturer) One or more of Ciba Specialty Chemicals).
所述的改性异氰酸酯组份中的异氰酸酯优选自 4, 4' -二苯基甲烷二异氰酸酯 (纯 MDI )、炭化二亚胺-脲酮亚胺改性的 4, 4' -二苯基甲垸二异氰酸酯 (液化 MDI)、对苯二异氰 酸酯^?01)、 1,5-萘二异氰酸酯( 1)或3, 3 ' -二甲基- 4, 4' -联苯二异氰酸酯 (T0DI)中的 一种或多种。  The isocyanate in the modified isocyanate component is preferably 4,4'-diphenylmethyl modified from 4,4'-diphenylmethane diisocyanate (pure MDI) or carbonized diimine-uretonimide.垸Diisocyanate (liquefied MDI), p-phenylene diisocyanate ^?01), 1,5-naphthalene diisocyanate (1) or 3,3 '-dimethyl-4,4'-biphenyldiisocyanate (T0DI) One or more.
所述的改性异氰酸酯组份的异氰酸根质量含量优选为 11%〜14%, 更优选 12%〜12. 5%, 平均官能度优选为 2〜3, 更优选为 2〜2. 2。  2。 The modified isocyanate component is preferably from 11% to 14% by weight, more preferably from 12% to 12% by weight, more preferably from 2% to 25%, more preferably from 2 to 2, more preferably from 2 to 2.
本发明具有以下优点: (1 )本发明是采用半预聚体法制备微孔聚氨酯弹性体材料, 两 组份料粘度相近, 混合质量比相近, 混料温度较低, 物料容易混合均匀, 工艺控制条件简 单,易操作。(2 )用本发明提供的组合物制备的微孔聚氨酯弹性体材料动静刚度比 1. 35, 冲击回弹性 75%, 300万次疲劳实验后外观无破损, 尺寸变化率 20%, 可用于高铁减震 垫块和汽车减震元件等高性能产品的制备。 .  The invention has the following advantages: (1) The invention adopts a semi-prepolymer method to prepare a microporous polyurethane elastomer material, the two components have similar viscosity, the mixing mass ratio is similar, the mixing temperature is low, and the material is easy to be uniformly mixed, the process The control conditions are simple and easy to operate. (2) The microporous polyurethane elastomer material prepared by the composition provided by the invention has a dynamic-static stiffness ratio of 1.35, impact resilience of 75%, no damage after 3 million fatigue tests, and a dimensional change rate of 20%, which can be used for high-speed rail Preparation of high performance products such as cushions and automotive shock absorbers. .
具体实施方式 Detailed ways
以下结合实施例对本发明做进一步说明。  The invention will be further described below in conjunction with the embodiments.
实施例 1 : Example 1
A组份: 分别称取 50 份平均官能度 =2, 数均分子量 =2000 的聚四氢呋喃醚多元醇 (PTMG2000, 巴斯夫产品)、 50份平均官能度 =2, 数均分子量 =1000的聚四氢呋喃醚多元 醇 ( PTMG1000, 巴斯夫产品)、 8份 1, 4-丁二醇、 0. 25g水、 0. 5份 AK- 7703、 0. 8份固含 量 33%的三乙烯二胺的二乙二醇溶液、 0. 03份二月桂酸二丁基锡、 0. 35份 BHT264于混合 器中, 搅拌均匀, 真空脱除气泡, 密封保存。  Component A: Weigh 50 parts of polytetrahydrofuran ether polyol (PTMG2000, BASF product) with average functionality = 2, number average molecular weight = 2000, 50 parts of polytetrahydrofuran ether with average functionality = 2, number average molecular weight = 1000 Polyol (PTMG1000, BASF product), 8 parts of 1,4-butanediol, 0.25g water, 0.5 parts AK-7703, 0.8 parts of triethylene glycol diethylene glycol with 33% solid content The solution, 0.03 parts of dibutyltin dilaurate, 0.33 parts of BHT264 in a mixer, stirred evenly, vacuum removed bubbles, sealed and stored.
B组份:将 80份平均官能度 =2,数均分子量 =2000的聚四氢呋喃醚多元醇(PTMG2000, 巴斯夫产品)和 20份平均官能度 =3, 数均分子量 =6000的聚醚多元醇(EP- 3600, 山东蓝 星东大化学有限公司产品)于 110Ό下真空(- 0. 09MPa)脱水 2小时, 保证水分含量小于 0. 05%, 然后降温至 50T:, 加入 70. 4份的纯MDI, 缓慢升温至 75°C下保温反应 1. 5小时, 加入 15份液化 MDI, 搅拌 0.5小时, 取样检测, -NC0的质量含量 13.0%, 降温至 50°C出 料, 密封保存。 Component B: 80 parts of polytetrahydrofuran ether polyol (PTMG2000, BASF product) having an average functionality = 2, number average molecular weight = 2000, and 20 parts of a polyether polyol having an average functionality = 3 and a number average molecular weight = 6000 (份份,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, 5小时,,,,,,,,,,,,,,,, Add 15 parts of liquefied MDI, stir for 0.5 hours, sample and test, -NC0 mass content of 13.0%, cool down to 50 ° C discharge, sealed and stored.
使用时, 将 A组份温度维持在 35°C, B组份温度维持在 45°C, 两组份按 100: 110的 重量比快速混合均匀, 浇注至预至 55°C的模具中, 85°C的烘道中熟化 10分钟后开模, 即 得聚氨酯微孔弹性体材料。  When used, the temperature of component A is maintained at 35 ° C, the temperature of component B is maintained at 45 ° C, and the two components are quickly mixed uniformly at a weight ratio of 100: 110, and poured into a mold which is pre-55 ° C, 85 After aging for 10 minutes in the drying tunnel of °C, the mold was opened to obtain a polyurethane microcellular elastomer material.
实施例 2: Example 2:
A 组份: 分别称取 80 份平均官能度 =2, 数均分子量 =2000 的聚四氢呋喃醚多元醇 (PTMG2000,巴斯夫产品)、20份平均官能度 =3,数均分子量 =6000的聚醚多元醇(EP- 3600, 山东蓝星东大化学有限公司产品)、 7份 1, 4-丁二醇、 0.25g水、 0.5份 AK- 7703、 1.0份 固含量 33%的三乙烯二胺的二乙二醇溶液、 0.03份二月桂酸二丁基锡、 0.35份 BHT264于 混合器中, 搅拌均匀, 真空脱除气泡, 密封保存。  Component A: Weigh 80 parts of polytetrahydrofuran ether polyol (PTMG2000, BASF product) with average functionality = 2, number average molecular weight = 2000, 20 parts of polyether polyol with average functionality = 3, number average molecular weight = 6000 Alcohol (EP-3600, Shandong Bluestar Dongda Chemical Co., Ltd.), 7 parts of 1,4-butanediol, 0.25g of water, 0.5 parts of AK-7703, 1.0 part of 33% solids of triethylenediamine The ethylene glycol solution, 0.03 parts of dibutyltin dilaurate, and 0.35 parts of BHT264 were mixed in a mixer, and the bubbles were removed by vacuum, and sealed and stored.
B组份:将 100份平均官能度 =2,数均分子量 =2000的聚四氢呋喃醚多元醇(PTMG2000, 巴斯夫产品) 于 110'C下真空 (- 0.09MPa) 脱水 2小时, 保证水分含量小于 0.05°/。, 然后 降温至 50Ό , 加入 72.5份的纯MDI, 缓慢升温至 75Ό下保温反应 1.5小时, 加入 15份 液化 MDI, 搅拌 0.5小时, 取样检测, -NC0的质量含量 13.0%, 降温至 50°C出料, 密封保 存。  Component B: 100 parts of polytetrahydrofuran ether polyol (PTMG2000, BASF product) with an average functionality = 2 and a number average molecular weight = 2000 were dehydrated at 110 ° C under vacuum (- 0.09 MPa) for 2 hours to ensure a moisture content of less than 0.05. °/. Then, cool down to 50 Ό, add 72.5 parts of pure MDI, slowly heat up to 75 Torr for 1.5 hours, add 15 parts of liquefied MDI, stir for 0.5 hours, sample and test, -NC0 mass content of 13.0%, cool down to 50 °C Material, sealed and stored.
使用时, 将 A组份温度维持在 35。C, B组份温度维持在 45 V, 两组份按 100: 90的 重量比快速混合均匀, 浇注至预至 55°C的模具中, 85°C的烘道中熟化 10分钟后开模, 即 得聚氨酯微孔弹性体材料。  Maintain the component A temperature at 35 when in use. The temperature of C and B components is maintained at 45 V. The two components are quickly mixed evenly at a weight ratio of 100:90. The mixture is poured into a mold that is pre-55 ° C. After curing for 10 minutes in a drying oven at 85 ° C, the mold is opened. A polyurethane microcellular elastomer material is obtained.
实施例 3: Example 3:
A 组份: 分别称取 80 份平均官能度 =2, 数均分子量 =2000 的聚四氢呋喃醚多元醇 (PTMG2000,巴斯夫产品〉、20份平均官能度 =3,数均分子量 =6000的聚醚多元醇(EP-3600, 山东蓝星东大化学有限公司产品)、 8.0份 1, 4-丁二醇、 0.25g水、 0.5份 DC3043、 1.0份 固含量 33%的三乙烯二胺的二乙二醇溶液、 0.03份二月桂酸二丁基锡、 0.35份 BHT264于 混合器中, 搅拌均匀, 真空脱除气泡, 密封保存。  Component A: Weigh 80 parts of polytetrahydrofuran ether polyol with average functionality = 2 and number average molecular weight = 2000 (PTMG2000, BASF product), 20 parts of average functionality = 3, number average molecular weight = 6000 polyether Alcohol (EP-3600, Shandong Bluestar Dongda Chemical Co., Ltd.), 8.0 parts of 1,4-butanediol, 0.25g of water, 0.5 parts of DC3043, 1.0 part of triethylenediamine with a solid content of 33% The alcohol solution, 0.03 parts of dibutyltin dilaurate, and 0.35 parts of BHT264 were mixed in a mixer, and the bubbles were removed by vacuum, and sealed and stored.
B组份:将 100份平均官能度 =2,数均分子量 =2000的聚四氢呋喃醚多元醇(PTMG2000, 巴斯夫产品)于 110Ό下真空 (-0.09MPa) 脱水 2小时, 保证水分含量小于 0.05%, 然后 降温至 5CTC,加入 28.1份的纯 MDI和 28.1份的 PPDI,升温至 85'C下保温反应 1.5小时, 取样检测, - NC0的质量含量 12.8%, 降温至 50Ό出料, 密封保存。  Component B: 100 parts of polytetrahydrofuran ether polyol (PTMG2000, BASF product) with an average functionality = 2 and a number average molecular weight = 2000 were dehydrated under vacuum (-0.09 MPa) at 110 Torr for 2 hours to ensure a moisture content of less than 0.05%. Then, the temperature was lowered to 5 CTC, and 28.1 parts of pure MDI and 28.1 parts of PPDI were added, and the temperature was raised to 85 ° C for 1.5 hours. The sample was tested, and the mass content of -NC0 was 12.8%, and the temperature was lowered to 50 Ό, and sealed and stored.
使用时, 将 A组份温度维持在 35°C, B组份温度维持在 45Ό, 两组份按 100: 93的 重量比快速混合均匀, 浇注至预至 55°C的模具中, 85°C的珙道中熟化 10分钟后开模, 即 得聚氨酯微孔弹性体材料。 When using, maintain the temperature of component A at 35 ° C, maintain the temperature of component B at 45 Ό, and quickly mix the two components in a weight ratio of 100: 93, and pour it into a mold that is pre-55 ° C, 85 ° C. Molding in the ramp for 10 minutes, then open the mold, ie A polyurethane microcellular elastomer material is obtained.
实施例 4:  Example 4:
A组份:分别称取 100份平均官能度 =2,数均分子量 =2000的聚己内酯多元醇 (CAPA2200: 英国苏威公司产品), 5份乙二醇、 0. 27g水、 0. 5份 DC3043、 1. 0份固含量 33%的三乙烯 二胺的二乙二醇溶液、 0. 03份二月桂酸二丁基锡、 0. 35份 BHT264于混合器中,搅拌均匀, 真空脱除气泡, 密封保存。 A component: 100 parts of polycaprolactone polyol having an average functionality = 2, number average molecular weight = 2000 (CAPA2200 : British Solvay product), 5 parts of ethylene glycol, 0. 27 g of water, 0. 5 parts DC3043, 1.0 part solid solution 33% triethylenediamine diethylene glycol solution, 0.03 parts dibutyltin dilaurate, 0.33 parts BHT264 in a mixer, stirred evenly, vacuum removal Bubbles, sealed and preserved.
B组份: 将 100份平均官能度 =2, 数均分子量二 2000的聚己内酯多元醇于 110'C下真 空 (- 0. 09MPa)脱水 2小时, 保证水分含量小于 0. 05%, 然后降温至 50°C, 加入 72. 5份 的纯 MDI, 缓慢升温至 75 下保温反应 1. 5小时, 加入 15份液化 MDI , 搅拌 0. 5小时, 取样检测, - NC0的质量含量 13. 1%, 降温至 50°C出料, 密封保存。  05%, the moisture content is less than 0.05%, the moisture content is less than 0. 05%, the moisture content is less than 0. 05%, the moisture content is less than 0. 05%, 5小时进行质量质量13。 Then, the temperature was reduced to 50 ° C, the addition of 72.5 parts of pure MDI, slowly heated to 75 times the incubation reaction 1. 5 hours, adding 15 parts of liquefied MDI, stirring 0. 5 hours, sampling test, - NC0 mass content of 13. 1%, cooled to 50 ° C discharge, sealed and stored.
使用时, 将 A组份温度维持在 35°C, B组份温度维持在 45°C , 两组份按 100: 92的 重量比快速混合均匀, 浇注至预至 55Ό的模具中, 85Ό的烘道中熟化 10分钟后开模, 即 得聚氨酯微孔弹性体材料。  When used, the temperature of component A is maintained at 35 ° C, the temperature of component B is maintained at 45 ° C, and the two components are quickly mixed uniformly at a weight ratio of 100: 92, poured into a mold of 55 预, and baked at 85 Ό. After the mold is aged for 10 minutes, the mold is opened, and a polyurethane microporous elastomer material is obtained.
实施例 5:  Example 5
A组份: 分别称取 100份平均官能度 =2, 数均分子量 =2000的的聚四氢呋喃醚多元醇 (PTMG2000, 巴斯夫产品)、 9份一缩二乙二醇、 0. 25g水、 0. 5份 AK- 7703、 1. 0份固含 量 33%的三乙烯二胺的二乙二醇溶液、 0. 03份二月桂酸二丁基锡、 0. 35份 BHT264于混合 器中, 搅拌均匀, 真空脱除气泡, 密封保存。  A component: 100 parts of polytetrahydrofuran ether polyol (PTMG2000, BASF product) having an average functionality = 2, number average molecular weight = 2000, 9 parts of diethylene glycol, 0.25 g of water, 0. 5 parts AK-7703, 1.0 part solid solution 33% triethylenediamine diethylene glycol solution, 0.03 part dibutyltin dilaurate, 0.33 parts BHT264 in a mixer, stir evenly, vacuum Remove the bubbles and store them in a sealed form.
B组份:将 100份平均官能度 =2,数均分子量 =2000的聚四氢呋喃醚多元醇(PTMG2000, 巴斯夫产品) 于 11CTC下真空 (- 0. 09MPa) 脱水 2小时, 保证水分含量小于 0. 05%, 然后 降温至 5CTC , 加入 58. 7份的纯 MDI和 25. 2份的 T0DI, 缓慢升温至 85Ό下保温反应 1. 5 小时,, 取样检测, - NC0的质量含量 12. 6%, 降温至 50°C出料, 密封保存。  Component B: 100 parts of polytetrahydrofuran ether polyol (PTMG2000, BASF product) with an average functionality = 2 and a number average molecular weight = 2000 were dehydrated under vacuum at 11 CTC (-0.09 MPa) for 2 hours to ensure a moisture content of less than 0. 0 重量,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, Cool down to 50 ° C discharge, sealed and stored.
使用时, 将 A组份温度维持在 35°C, B组份温度维持在 45。C, 两组份按 100: 95的 重量比快速混合均匀, 浇注至预至 55Ό的模具中, 85Ό的烘道中熟化 10分钟后开模, 即 得聚氨酯微孔弹性体材料。 When used, the temperature of component A was maintained at 35 ° C and the temperature of component B was maintained at 45. C, the two components are quickly mixed uniformly according to the weight ratio of 100 : 95, poured into a mold of 55 预, and the mold is opened after being aged for 10 minutes in an 85 烘 drying tunnel to obtain a polyurethane microcellular elastomer material.
实施例 1〜5所制得的聚氨酯微孔弹性体材料的性能指标如下:  The performance indexes of the polyurethane microcellular elastomer materials obtained in Examples 1 to 5 are as follows:
Figure imgf000006_0001
Figure imgf000007_0001
Figure imgf000006_0001
Figure imgf000007_0001

Claims

1、一种动态性能优异的微孔聚氨酯弹性体组合物,其特征在于,由以下两种组份组成: A组份: 包括聚合物多元醇、 扩链剂、 发泡剂、 催化剂 A、 催化剂 B、 泡沬稳定剂以及 抗氧剂, 其中, 以聚合物多元醇总重量为 100%计, 其它原料占聚合物多元醇总重量的百分 数分别为: 扩链剂 5%〜12%, 发泡剂 0. 1%〜0. 3%, 催化剂 A O. 3〜1. 0%, 催化剂 B 0. 01%〜 0. 06%, 泡沫稳定剂 0. 2〜1. 0%, 抗氧剂 0. 3〜0. 6%; A microcellular polyurethane elastomer composition excellent in dynamic performance, which is characterized by being composed of the following two components: Component A: comprising a polymer polyol, a chain extender, a foaming agent, a catalyst A, a catalyst B, a foam stabilizer and an antioxidant, wherein, based on 100% by weight of the total weight of the polymer polyol, the percentage of other raw materials in the total weight of the polymer polyol is: 5% to 12% of the chain extender, foaming 2%1 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 . 3~0. 6%;
B组份: 改性异氰酸酯组份, 由聚合物多元醇与异氰酸酯反应制得的 NC0基团封端的 氨酯改性异氰酸酯与异氰酸酯的混合物;  Component B: a modified isocyanate component, a mixture of a NC0 group-terminated urethane-modified isocyanate and an isocyanate prepared by reacting a polymer polyol with an isocyanate;
使用时 , A组份和 B组份按照质量比为 100: 90〜110混合,混合时 A组份的温度为 30Ό〜 45 °C, B组份温度为 40°C〜50°C。  When used, the components A and B are mixed according to a mass ratio of 100: 90 to 110, and the temperature of the component A is 30 Ό to 45 ° C when mixed, and the temperature of the component B is 40 ° C to 50 ° C.
2、根据权利要求 1所述的动态性能优异的微孔聚氨酯弹性体组合物, 其特征在于, 所 述聚合物多元醇选自平均官能度为 1. 8〜4, 优选 2〜3, 数均相对分子质量为 1000〜8000, 优选 2000〜6000 的聚醚多元醇或平均官能度为 2〜3, 优选 2〜2. 5, 数均相对分子质量 1000〜6000, 优选 1500〜3000的聚酯多元醇中的一种或两种任意比例混合的混合物。  The average functionality is 1. 8~4, preferably 2~3, and the average number of the polymer polyols. a polyether polyol having a relative molecular mass of from 1000 to 8000, preferably from 2000 to 6000, or an average functionality of from 2 to 3, preferably from 2 to 2. 5, a number average molecular weight of from 1000 to 6000, preferably from 1500 to 3,000. One or two mixtures of alcohols in any ratio.
3、根据权利要求 2所述的动态性能优异的微孔聚氨酯弹性体组合物, 其特征在于, 所 述聚醚多元醇选自聚环氧丙垸醚多元醇、环氧丙垸 -环氧乙垸共聚醚多元醇和聚四氢呋喃醚 多元醇中的一种或一种以上的混合物, 优选聚四氢呋喃醚多元醇; 所述聚酯多元醇选自聚 己内酯多元醇、 聚碳酸酯多元醇、 聚己二酸- 1, 4-丁二醇酯多元醇、 聚己二酸- 1, 6-己二 醇酯多元醇中的一种或多种, 优选聚己内酯多元醇。  The microcellular polyurethane elastomer composition excellent in dynamic performance according to claim 2, wherein the polyether polyol is selected from the group consisting of polyglycidyl ether polyols, epoxidizer-epoxy a mixture of one or more of a ruthenium copolyether polyol and a polytetrahydrofuran ether polyol, preferably a polytetrahydrofuran ether polyol; the polyester polyol is selected from the group consisting of polycaprolactone polyols, polycarbonate polyols, poly One or more of adipic acid-1,4-butylene glycol ester polyol, polyhexamethylenedicarboxylic acid-1,6-hexanediol polyol, preferably polycaprolactone polyol.
4、根据权利要求 1所述的动态性能优异的微孔聚氨酯弹性体组合物, 其特征在于, 所 述扩链剂选自乙二醇、 一缩二乙二醇、 一缩二丙二醇、 1,4-丁二醇、 1, 6-己二醇或 3, 3 -二 氯 4, 4-二苯基甲苯二胺中的一种或多种。  The microcellular polyurethane elastomer composition excellent in dynamic performance according to claim 1, wherein the chain extender is selected from the group consisting of ethylene glycol, diethylene glycol, dipropylene glycol, and 1, One or more of 4-butanediol, 1,6-hexanediol or 3,3-dichloro-4,4-diphenyltoluenediamine.
5、根据权利要求 1所述的动态性能优异的微孔聚氨酯弹性体组合物, 其特征在于, 所 述发泡剂选自水、 甲酸、 乙酸或一氟二氯乙烷中的一种或多种, 优选水。 '  The microcellular polyurethane elastomer composition excellent in dynamic performance according to claim 1, wherein the foaming agent is one or more selected from the group consisting of water, formic acid, acetic acid or monofluorodichloroethane. Kind of, preferably water. '
6、根据权利要求 1所述的动态性能优异的微孔聚氨酯弹性体组合物, 其特征在于, 所 述催化剂 A选自叔胺类催化剂; 所述催化剂 B选自有机锡类催化剂、 有机铋类催化剂或有 机锌类催化剂中的一种或多种。  The microcellular polyurethane elastomer composition excellent in dynamic performance according to claim 1, wherein the catalyst A is selected from the group consisting of tertiary amine catalysts; and the catalyst B is selected from the group consisting of organotin catalysts and organic hydrazines. One or more of a catalyst or an organozinc catalyst.
7、根据权利要求 1所述的动态性能优异的微孔聚氨酯弹性体组合物, 其特征在于, 所 述泡沫稳定剂选自有机硅表面活性剂, 优选 DC3043、 8444或 AK7703中的一种或多种。  The microcellular polyurethane elastomer composition excellent in dynamic performance according to claim 1, wherein the foam stabilizer is selected from the group consisting of silicone surfactants, preferably one or more of DC3043, 8444 or AK7703. Kind.
8、根据权利要求 1所述的动态性能优异的微孔聚氨酯弹性体组合物, 其特征在于, 所 述抗氧剂选自受阻酚类抗氧剂,优选用 BHT264、 ChinoxlOlO或 IrganoX1035中的一种或多 种。 The microcellular polyurethane elastomer composition excellent in dynamic performance according to claim 1, wherein the antioxidant is selected from the group consisting of hindered phenol antioxidants, preferably BHT264, ChinoxlO10 or Ir ga no X 1035. One or more of them.
9、根据权利要求 1所述的动态性能优异的微孔聚氨酯弹性体组合物, 其特征在于, 所 述改性异氰酸酯组份中的异氰酸酯选自 4, 4' -二苯基甲垸二异氰酸酯、 炭化二亚胺 -脲酮 亚胺改性的 4, 4 ' -二苯基甲烷二异氰酸酯、对苯二异氰酸酯、 1, 5-萘二异氰酸酯或 3, 3' - 二甲基 -4, 4' -联苯二异氰酸酯中的一种或多种。 The microcellular polyurethane elastomer composition excellent in dynamic performance according to claim 1, wherein the isocyanate in the modified isocyanate component is selected from the group consisting of 4,4'-diphenylformamidine diisocyanate, Carbonized diimine-ureido ketimine modified 4,4 '-diphenylmethane diisocyanate, p-phenylene diisocyanate, 1, 5-naphthalene diisocyanate or 3, 3'-dimethyl-4, 4' One or more of biphenyl diisocyanate.
10、 根据权利要求 1所述的动态性能优异的微孔聚氨酯弹性体组合物, 其特征在于, 所述改性异氰酸酯组份的异氰酸根质量含量为 11%〜14%,优选 12%〜12. 5%,平均官能度为 2〜3, 优选为 2〜2. 2。  The microcellular polyurethane elastomer composition excellent in dynamic performance according to claim 1, wherein the modified isocyanate component has an isocyanate mass content of 11% to 14%, preferably 12% to 12%. 5%。 The average functionality is 2~3, preferably 2~2.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1534051A (en) * 2003-03-28 2004-10-06 上海凯众聚氨酯有限公司 Polyurethane microporous elastic body production method
CN1986592A (en) * 2005-12-23 2007-06-27 华峰集团有限公司 Method for raising mechanical performace of microporous polyether-type polyurethane elastomer
CN101165094A (en) * 2007-09-29 2008-04-23 山东东大一诺威聚氨酯有限公司 Urethane micro-pore elastomer composite material adapated for insole and preparation method thereof
CN101942786A (en) * 2010-08-25 2011-01-12 北京科聚化工新材料有限公司 Rail tie plate and preparation method thereof
CN102212180A (en) * 2011-04-29 2011-10-12 黎明化工研究院 Microcellular polyurethane elastomer and preparation method thereof
CN102250313A (en) * 2011-06-03 2011-11-23 山东东大一诺威聚氨酯有限公司 Self-skinning microporous elastomer composite for polyurethane foam tire
CN102585162A (en) * 2011-12-23 2012-07-18 山东东大一诺威聚氨酯有限公司 Microporous polyurethane elastomer compound with excellent dynamic performance and preparation method thereof

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3602669A1 (en) * 1986-01-31 1987-07-30 Japan National Railway SPRING COVER FOR A DIRECT CONNECTION THRESHOLD
CN1189499C (en) * 2003-04-30 2005-02-16 中国科学院山西煤炭化学研究所 Prepn of polyether-type polyurethane as shoe sole material
CN101519485B (en) * 2008-11-08 2011-05-11 中国工程物理研究院化工材料研究所 Wide temperature domain damping polyurethane micropore elastomer material and preparation method thereof
CN101486788B (en) * 2008-12-30 2011-09-14 浙江华峰新材料股份有限公司 Low density high hardness polyurethane micropore elastomer and preparation thereof
CN101948616B (en) * 2010-09-13 2012-07-18 安徽大学 Microporous polyurethane elastomer shock absorption element for high-speed railway and preparation method thereof
CN101962473B (en) * 2010-10-28 2012-03-21 苏州新纶超净技术有限公司 Method for preparing wear-resisting, anti-hydrolysis and antistatic polyurethane materials and shoe material prepared by polyurethane materials
CN102250306B (en) * 2011-04-29 2012-09-05 黎明化工研究院 Polyurethane microporous elastomer prepared from mixed acid type polyester and preparation method thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1534051A (en) * 2003-03-28 2004-10-06 上海凯众聚氨酯有限公司 Polyurethane microporous elastic body production method
CN1986592A (en) * 2005-12-23 2007-06-27 华峰集团有限公司 Method for raising mechanical performace of microporous polyether-type polyurethane elastomer
CN101165094A (en) * 2007-09-29 2008-04-23 山东东大一诺威聚氨酯有限公司 Urethane micro-pore elastomer composite material adapated for insole and preparation method thereof
CN101942786A (en) * 2010-08-25 2011-01-12 北京科聚化工新材料有限公司 Rail tie plate and preparation method thereof
CN102212180A (en) * 2011-04-29 2011-10-12 黎明化工研究院 Microcellular polyurethane elastomer and preparation method thereof
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