CN115124693B - Foaming polyurethane elastomer and preparation method and application thereof - Google Patents

Foaming polyurethane elastomer and preparation method and application thereof Download PDF

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Publication number
CN115124693B
CN115124693B CN202210874036.7A CN202210874036A CN115124693B CN 115124693 B CN115124693 B CN 115124693B CN 202210874036 A CN202210874036 A CN 202210874036A CN 115124693 B CN115124693 B CN 115124693B
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parts
elastomer
component
isocyanate
foam stabilizer
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CN115124693A (en
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王振
苏丽丽
王小东
张永
郑直
石雅琳
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Liming Research Institute of Chemical Industry Co Ltd
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Liming Research Institute of Chemical Industry Co Ltd
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    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
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    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
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    • C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
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    • 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
    • C08G18/71—Monoisocyanates or monoisothiocyanates
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    • C08G18/71—Monoisocyanates or monoisothiocyanates
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    • 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
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    • 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
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/141—Hydrocarbons
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    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/143—Halogen containing compounds
    • C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
    • C08J9/146—Halogen containing compounds containing carbon, halogen and hydrogen only only fluorine as halogen atoms
    • E—FIXED CONSTRUCTIONS
    • E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
    • E01B—PERMANENT WAY; PERMANENT-WAY TOOLS; MACHINES FOR MAKING RAILWAYS OF ALL KINDS
    • E01B9/00—Fastening rails on sleepers, or the like
    • E01B9/68—Pads or the like, e.g. of wood, rubber, placed under the rail, tie-plate, or chair
    • E01B9/681—Pads or the like, e.g. of wood, rubber, placed under the rail, tie-plate, or chair characterised by the material
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    • C08G2110/00—Foam properties
    • C08G2110/0083—Foam properties prepared using water as the sole blowing agent
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    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
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    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3

Abstract

The invention relates to a foaming polyurethane elastomer, a preparation method and application thereof, wherein the elastomer is prepared by reacting a prepolymer I component and a curing agent P component, and the prepolymer I component comprises the following components in parts by weight: 100 parts of mixed polyol, 1-5 parts of polyfunctional isocyanate, 1-8 parts of monofunctional isocyanate, 29-140 parts of diisocyanate and 1 part of foam stabilizer: 1-5 parts; the curing agent P comprises the following components in parts by weight: 0-160 parts of mixed polyol, chain extender and/or cross-linking agent: 4-14 parts of catalyst: 0.1-6 parts of foaming agent: 0.1-5 parts of foam stabilizer 2:0.5-5 parts. According to the invention, the polyurethane material is modified by using the polyfunctional isocyanate and the monofunctional isocyanate, so that the crystallization behavior of polyurethane molecular chains is destroyed, and meanwhile, a plurality of foam stabilizers are adopted for cooperative sharing, so that the obtained foaming polyurethane backing plate has the characteristics of high static rigidity, low dynamic-static ratio, small compression deformation, small product size after fatigue, small rigidity change rate and the like, and can meet the use requirement of the elastic backing plate of the heavy haul railway.

Description

Foaming polyurethane elastomer and preparation method and application thereof
Technical Field
The invention belongs to the field of polyurethane, and particularly relates to a foaming polyurethane elastomer, and a preparation method and application thereof.
Background
Railway pads are a type of shock absorbing elements specifically designed to reduce noise and vibration generated when a vehicle is traveling at high speeds. The vibration and noise reduction effect of the backing plate depends on indexes such as static rigidity and dynamic and static rigidity ratio of the product. Generally, high-speed railways require lower static stiffness, while ordinary lines require higher static stiffness. The closer the dynamic and static stiffness ratio values are, the better the shock absorption and buffering performance is exerted. In addition, the pad material should have low compression set and excellent fatigue resistance to ensure that the track system has good compression characteristics and pad dimensions and performance retention of static stiffness indicators.
The traditional heavy-duty railway rail lower backing plate is made of rubber materials, such as natural rubber, styrene-butadiene rubber, nitrile rubber and the like, and in order to reduce the static rigidity of the solid rubber backing plates, the backing plate structural design is mainly designed by adopting a solid groove, so that indentation damage to a sleeper is easily caused after long-time use, and the comprehensive use and maintenance cost is high. The existing foaming backing plate for the high-speed railway is made of polyurethane microporous materials, but is applied to a heavy-duty railway, and the foaming backing plate also has the problems of rigidity design, dynamic and static rigidity ratio, high and low temperature performance, fatigue durability, mismatching of a processing forming process and the like of the backing plate materials and products, and cannot meet the application requirements of the heavy-duty railway.
CN 101058629B discloses a method for manufacturing railway tie plates, which adopts a specially designed mixing device to disperse inert gas in a mixed solidified substance of polyurethane prepolymer, polyol and chain extender component, and the foaming molding process is complex, and has higher requirements on mechanical equipment and high equipment cost. In addition, the static rigidity of the disclosed backing plate is low, and the backing plate is not suitable for the application of heavy haul railways.
CN 101942786B discloses a method for manufacturing a microporous polyurethane elastomer rail pad, which adopts water as a foaming agent, the static rigidity of the obtained rail pad is 23kN/mm, the static rigidity ratio is less than or equal to 1.4, and the dimensional change rate of the pad after fatigue test is less than or equal to 20%. The static rigidity of the backing plate material is low, and the size change rate index of the backing plate after fatigue cannot meet the performance requirement of a heavy haul railway.
Disclosure of Invention
The invention aims to solve the technical problems in the background art, and provides a foaming polyurethane elastomer, a preparation method and application thereof, wherein the foaming polyurethane elastomer is prepared by modifying polyurethane materials by using polyfunctional isocyanate and monofunctional isocyanate to destroy the crystallization behavior of polyurethane molecular chains, and simultaneously two foam stabilizers are adopted for cooperative sharing.
In order to solve the technical problems, the invention adopts the following technical scheme:
the invention provides a foaming polyurethane elastomer, which is prepared from a prepolymer I component and a curing agent P component in a mass ratio of 100: (5-187) and a reaction product,
(1) The prepolymer I component comprises the following components in parts by weight:
mixing polyol: 100 parts of
Polyfunctional isocyanates: 1-5 parts
Monofunctional isocyanates: 1-8 parts
A diisocyanate: 29-140 parts
Foam stabilizer 1:1-5 parts
(2) The curing agent P comprises the following components in parts by weight:
mixing polyol: 0-160 parts
Chain extenders and/or crosslinkers: 4-14 parts
Catalyst: 0.1-6 parts
Foaming agent: 0.1-5 parts
Foam stabilizer 2:0.5-5 parts
The mixed polyol is polytetrahydrofuran ether glycol and polyether polyol with the functionality of 2-3.
Preferably, the mixed polyol is a mixture of polytetrahydrofuran ether glycol having a molecular weight of 1000-2000 and a functionality of 2 and a polyether polyol having a molecular weight of 1000-8000 and a functionality of 2-3, preferably in a mass ratio of 20/80 to 80/20.
Preferably, the polyfunctional isocyanate is a modified diphenylmethane diisocyanate MDI having a functionality of greater than 2 and less than or equal to 3, preferably one or more of the Wannate MDI-100HL, wannate 8319, wannate8617 and Dow chemical Isonate 143L, and the NCO is 21% -32%.
Preferably, the monofunctional isocyanate is one or more of p-toluenesulfonyl isocyanate, ethyl isocyanate, dodecyl isocyanate, cyclohexyl isocyanate, isopropyl isocyanate, phenyl isocyanate and p-nitrophenyl isocyanate.
Preferably, the diisocyanate is one or more of MDI, TDI, PPDI, NDI, TODI.
Preferably, the foam stabilizer 1 is a hydroxyl-containing polysiloxane foam stabilizer, further preferably one or more of the following, conning DC193, yingzheng TEGOSTAB B8930, and Maillard M8804; foam stabilizer 2 is a hydroxyl-free polysiloxane foam stabilizer, further preferably one or more of the commercial grades Dow Corning DC190, maillard M88710.
Preferably, the curing agent P component can contain mixed polyol in the prepolymer I component, and the dosage of the mixed polyol in the P component and the mixing proportion of the I, P component can be adjusted according to the requirements of the product forming process, the forming equipment and other conditions.
Preferably, the molecular weight of the chain extender is less than 500, the molecular weight is preferably 90-150, the chain extender is preferably one or more of ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol and 1, 6-hexanediol, and further preferably 1, 4-butanediol; the molecular weight of the cross-linking agent is less than 500, the molecular weight is preferably 90-150, and the cross-linking agent is preferably one or more of trimethylolpropane, trimethylolethane, glycerol, 1,2, 6-hexanetriol and triethanolamine.
The catalyst is one or more of amine catalysts and metal catalysts, and the amine catalysts are preferably one or more of triethylenediamine, bis (dimethylaminoethyl) ether, tetramethyl ethylenediamine and dimethylethanolamine; the metal catalyst is one or more of organic tin and organic bismuth, such as one or more of dibutyl tin dilaurate (T12), stannous octoate (T9), dibutyl tin diacetate and bismuth isooctanoate.
The foaming agent is one or more of water, hydrogenated fluorochlorohydrocarbon, low-boiling point fluoride and alkane; the hydrochlorofluorocarbon can be HCFC-141b, the low boiling point fluoride is preferably one or more of pentafluoropropane and hexafluorobutane, and the alkane is preferably one or more of cyclopentane, n-pentane, n-hexane and n-heptane; further preferably, the foaming agent is water.
Preferably, the P component also comprises 0-2 parts of pigment.
Preferably, the component P also comprises 0-2 parts of antioxidant.
Preferably, the NCO% content of the I component is 4.5% to 18%, more preferably, the NCO% content is 5% to 9%.
The second aspect of the present invention provides a method for preparing the foamed polyurethane elastomer, comprising the steps of:
(1) Preparation of prepolymer I component: mixing polytetrahydrofuran ether glycol and polyether polyol with the functionality of 2-3 as mixed polyol and foam stabilizer 1, vacuum dehydrating, controlling the water content to be less than 300ppm, cooling to 40-60 ℃, adding monofunctional isocyanate, reacting for 3-5 hours at 70-90 ℃, cooling to 40-60 ℃ after NCO groups of the monofunctional isocyanate are fully reacted, adding diisocyanate and polyfunctional isocyanate, reacting for 2-3 hours at 65-100 ℃, and cooling to 45-55 ℃ to obtain a prepolymer I component;
(2) Preparation of a curing agent P component: uniformly stirring and mixing the mixed polyol, the chain extender and/or the cross-linking agent, the catalyst, the foaming agent and the foam stabilizer 2 to obtain a component P of the curing agent;
(3) Uniformly mixing the component I and the component P of the prepolymer according to the mass ratio, pouring into a mold at 45-80 ℃, demolding after 8-15 minutes, curing the product at 60-85 ℃ for 10-16 hours, and standing at normal temperature for 5-7 days to obtain the polyurethane foam.
In a third aspect the invention provides the use of said foamed polyurethane elastomer in a tie plate, preferably a heavy haul railway tie plate.
Compared with the prior art, the invention has the beneficial effects that:
(1) Compared with a common rubber cushion plate, the foaming polyurethane elastomer provided by the invention has the characteristics of no need of grooving design on the surface, long service life and low maintenance cost;
(2) According to the invention, the single-functionality isocyanate is used for modifying the polytetrahydrofuran ether glycol and polyether polyol soft segment material, so that the crystallization behavior of polyurethane molecular chains is destroyed, and meanwhile, the defect of insufficient hard segment crosslinking of the polyurethane material is overcome by using the multi-functionality isocyanate, so that the performances of high static compression deformation and high dynamic-static ratio of the polyurethane material are improved. Compared with the existing low-rigidity elastic cushion plate for the high-speed railway, the invention has the characteristics of high static rigidity, low dynamic-static ratio and small compression deformation;
(3) The low-rigidity elastic cushion plate for the high-speed railway is obtained by mechanical foaming or water foaming to obtain a corresponding cell structure from the analysis of the molding foaming process of the cushion plate product, and the mechanical foaming equipment has high cost and is inconvenient to use; foaming with water or foaming with low boiling point fluorides, alkanes, etc., is insufficient in cell structure to be dense and uniform, because the coordination of various foam stabilizers is not well developed. In the initial stage of mixing, the excellent stabilizer combination can enable the two component materials to be quickly mixed and emulsified uniformly, then bubble cores and bubbles are easier to be uniformly generated, and finally the effect of stabilizing the foam and preventing the bubbles from being combined and becoming large is achieved. The invention adopts a hydroxyl-containing polysiloxane foam stabilizer to react with isocyanate firstly, so that the foam stabilizer is connected into an isocyanate prepolymer I component, and has certain internal emulsification; and then mixing the polyurethane foam stabilizer with a component P of the polysiloxane foam stabilizer without hydroxyl, so that the two foam stabilizers produce synergistic effect, and the cell structure of the polyurethane material is improved.
Therefore, the dimensional change rate of the prepared backing plate product after 300 times of fatigue is less than 5 percent through the material formula adjustment and the foaming process adjustment, the rigidity stability of the product can be maintained for a long time, and the use requirement of the elastic backing plate of the heavy haul railway can be met.
Detailed Description
The present invention is further described below with reference to examples, but the present invention is not limited to the examples, and it should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., fall within the scope of the present invention and the scope of disclosure.
The raw materials used in the examples and comparative examples of the present invention are as follows:
polytetrahydrofuran ether glycol: PTMEG1000, PTMEG2000, BASF, germany;
polyether polyol DL1000: functionality is 2, molecular weight is 1000, shandong blue star Dong Dacron chemical industry Limited liability company;
polyether polyol EP3600: functionality is 3, molecular weight is 6000, shandong blue star Dong Dajingxiao Limited liability company;
polyfunctional isocyanates: wannate MDI-100HL, vancomic chemistry; wannate8617, wanhua chemistry;
monofunctional isocyanates: p-toluenesulfonyl isocyanate, isopropyl isocyanate, p-nitrophenyl isocyanate;
a diisocyanate: MDI100, vancomic chemistry; 1, 5-Naphthalene Diisocyanate (NDI), BAYER, germany;
foam stabilizer 1: dow Corning DC193, maillard M8804;
foam stabilizer 2: dow Corning DC190, maillard M88710;
chain extender: 1, 4-butanediol, 1, 6-hexanediol;
crosslinking agent: trimethylolpropane, triethanolamine;
foaming agent: water, hexafluorobutane, cyclopentane;
catalyst: triethylenediamine, bis (dimethylaminoethyl) ether, dibutyltin dilaurate (T12), stannous octoate (T9).
Example 1
(1) Preparation of prepolymer I component: mixing 20 parts of polytetrahydrofuran ether glycol (PTMEG 2000) and 80 parts of polyether polyol EP3600 as mixed polyol and 2 parts of foam stabilizer 1 (DC 193), vacuum dehydrating, controlling the water content to be less than 300ppm, then cooling to 45-50 ℃, slowly adding 1 part of p-toluenesulfonyl isocyanate, reacting for 3.5 hours at 75-80 ℃, cooling to 45-55 ℃ after NCO groups are fully reacted, then adding 29 parts of MDI100 and 1 part of Wannate MDI-100HL, reacting for 2.5 hours at 70-75 ℃, then cooling to 50 ℃ to obtain a prepolymer I component, wherein NCO=5%;
(2) Preparation of a curing agent P component: uniformly stirring and mixing 5 parts of 1, 4-butanediol, 3 parts of catalyst triethylene diamine, 3 parts of T12, 2 parts of water and 3 parts of foam stabilizer 2 (DC 190) to obtain a component P;
(3) Preheating the two components I, P to 45-50 ℃, and then carrying out the following steps: p=100: 16, pouring into a mould at 55-65 ℃ for 8 minutes, demoulding, curing the product at 70-80 ℃ for 16 hours, and standing at normal temperature for 7 days to obtain the foaming polyurethane backing plate.
Example 2
Preparation of prepolymer I component: mixing 80 parts of polytetrahydrofuran ether glycol (PTMEG 2000) and 20 parts of polyether polyol EP3600 as mixed polyol and 3 parts of foam stabilizer 1 (M8804), vacuum dehydrating, controlling the water content to be less than 300ppm, then cooling to 45-50 ℃, slowly adding 8 parts of isopropyl isocyanate, reacting for 3.5 hours at 75-80 ℃, cooling to 45-55 ℃ after NCO groups are fully reacted, then adding 140 parts of MDI100 and 5 parts of Wannate8617, reacting for 2.5 hours at 70-75 ℃, and then cooling to 50 ℃ to obtain a prepolymer I component, wherein NCO=18%;
(2) Preparation of a curing agent P component: 130 parts of polytetrahydrofuran ether glycol (PTMEG 2000) and 30 parts of polyether polyol EP3600 as mixed polyol, 14 parts of triethanolamine as a chain extender, 1.5 parts of catalyst triethylene diamine and 1.5 parts of T9, 5 parts of hexafluorobutane and 5 parts of foam stabilizer 2 (M88710) are uniformly stirred and mixed to obtain a P component;
(3) Preheating the two components I, P to 45-55 ℃, and then carrying out the following steps: p=100: 187, pouring the mixture into a die at 55-65 ℃ for 8 minutes, demolding, curing the product at 70-80 ℃ for 16 hours, and standing at normal temperature for 7 days to obtain the foaming polyurethane backing plate.
Example 3
Preparation of prepolymer I component: mixing 80 parts of polytetrahydrofuran ether glycol (PTMEG 1000) and 20 parts of polyether polyol DL1000 as mixed polyol and 5 parts of foam stabilizer 1 (DC 193), vacuum dehydrating, controlling the water content to be less than 300ppm, then cooling to 45-50 ℃, slowly adding 5 parts of p-nitrophenyl isocyanate, reacting for 3.5 hours at 75-80 ℃, cooling to 45-55 ℃ after NCO groups are fully reacted, then adding 71 parts of MDI100 and 3 parts of Wannate MDI-100HL, reacting for 2.5 hours at 70-75 ℃, and then cooling to 50 ℃ to obtain a prepolymer I component, wherein NCO=9%;
(2) Preparation of a curing agent P component: uniformly stirring and mixing 10 parts of 1, 6-hexanediol, 2.5 parts of catalyst triethylene diamine, 2.5 parts of T12, 5 parts of cyclopentane and 5 parts of foam stabilizer 2 (DC 190) to obtain a P component;
(3) Preheating the two components I, P to 45-55 ℃, and then carrying out the following steps: p=100: 25, pouring into a mould at 55-65 ℃ for 8 minutes, demoulding, curing the product at 70-80 ℃ for 16 hours, and standing at normal temperature for 7 days to obtain the foaming polyurethane backing plate.
Example 4
(1) Preparation of prepolymer I component: mixing 40 parts of polytetrahydrofuran ether glycol (PTMEG 1000) and 60 parts of polyether polyol EP3600 as mixed polyol and 5 parts of foam stabilizer 1 (DC 193), vacuum dehydrating, controlling the water content to be less than 300ppm, then cooling to 45-50 ℃, slowly adding 5 parts of p-toluenesulfonyl isocyanate, reacting for 3.5 hours at 75-80 ℃, cooling to 45-55 ℃ after NCO groups are fully reacted, then adding 29 parts of NDI and 3 parts of Wannate MDI-100HL, reacting for 2.5 hours at 90-95 ℃, then cooling to 50 ℃ to obtain a prepolymer I component, wherein NCO=4.5%;
(2) Preparation of a curing agent P component: 3 parts of chain extender, 1, 4-butanediol, 1 part of cross-linking agent, 0.2 part of bis (dimethylaminoethyl) ether, 0.1 part of water and 0.5 part of foam stabilizer 2 (DC 190) are stirred and mixed uniformly to obtain a component P;
(3) Preheating the two components I, P to 45-50 ℃, and then carrying out the following steps: p=100: 5, pouring into a die at 55-65 ℃ for 15 minutes, demolding, curing the product at 70-80 ℃ for 10 hours, and standing at normal temperature for 5 days to obtain the foaming polyurethane backing plate.
Comparative example 1
Preparation of prepolymer I component: mixing 20 parts of polytetrahydrofuran ether glycol (PTMEG 2000), 80 parts of polyether polyol EP3600 and 2 parts of foam stabilizer 1 (DC 193), vacuum dehydrating, controlling the water content to be less than 300ppm, cooling to 45-50 ℃, adding 29 parts of MDI100, reacting for 2.5 hours at 70-75 ℃, and cooling to 50 ℃ to obtain a prepolymer I component, wherein NCO=5%;
(2) Preparation of a curing agent P component: uniformly stirring and mixing 5 parts of 1, 4-butanediol, 3 parts of catalyst triethylene diamine, 3 parts of T12, 2 parts of water and 3 parts of foam stabilizer 2 (DC 190) to obtain a component P;
(3) Preheating the two components I, P to 45-50 ℃, and then carrying out the following steps: p=100: 16, pouring into a mould at 55-65 ℃ for 8 minutes, demoulding, curing the product at 70-80 ℃ for 16 hours, and standing at normal temperature for 7 days to obtain the foaming polyurethane backing plate.
Comparative example 2
(1) Preparation of prepolymer I component: vacuum dehydrating 20 parts of polytetrahydrofuran ether glycol (PTMEG 2000) and 80 parts of polyether polyol EP3600 as mixed polyol, controlling the water content to be less than 300ppm, then cooling to 45-50 ℃, slowly adding 1 part of p-toluenesulfonyl isocyanate, reacting for 3.5 hours at 75-80 ℃, cooling to 45-55 ℃ after NCO groups are fully reacted, then adding 29 parts of MDI100 and 1 part of Wannate MDI-100HL, reacting for 2.5 hours at 70-75 ℃, and cooling to 50 ℃ to obtain a prepolymer I component, wherein NCO=5%;
(2) Preparation of a curing agent P component: uniformly stirring and mixing 5 parts of 1, 4-butanediol, 3 parts of catalyst triethylene diamine, 3 parts of T12, 2 parts of water and 3 parts of foam stabilizer 2 (DC 190) to obtain a component P;
(3) Preheating the two components I, P to 45-50 ℃, and then carrying out the following steps: p=100: 16, pouring into a mould at 55-65 ℃ for 8 minutes, demoulding, curing the product at 70-80 ℃ for 16 hours, and standing at normal temperature for 7 days to obtain the foaming polyurethane backing plate.
The properties of the pads of examples 1-4 and comparative examples 1-2, such as static stiffness, compression type deformation, dynamic-static ratio, size after fatigue, static stiffness change, etc., are shown in the following table.
Table 1 comparative backing plate Performance
Test item Index requirements Example 1 Example 2 Example 3 Example 4 Comparative example 1 Comparative example 2
Static stiffness (kN/mm) 90-100 91 95 98 96 91 91
Compression set (%) ≤5 4.5 4.7 4.9 4.8 12.6 4.4
Dynamic-static ratio ≤1.50 1.40 1.49 1.50 1.45 1.64 1.65
Post-fatigue dimensional change rate (%) ≤10 4.6 4.1 5.6 4.5 8.6 13.3
Rate of change in static stiffness after fatigue (%) ≤10 5.1 6.1 6.5 5.2 15.8 18.7
As can be seen from the table, the formula of the comparative example 1 is not added with monofunctional isocyanate and polyfunctional isocyanate, the formula of the comparative example 2 is not added with the foam stabilizer 1 containing hydroxyl, the compression deformation of the cushion plate material is large, the dynamic-static ratio is high, and the dimensional change rate and the static stiffness change rate after fatigue exceed the index requirements.

Claims (24)

1. A foaming polyurethane elastomer comprises a prepolymer I component and a curing agent P component in a mass ratio of 100: (5-187) and a reaction product,
(1) The prepolymer I component comprises the following components in parts by weight:
mixing polyol: 100 parts of
Polyfunctional isocyanates: 1-5 parts
Monofunctional isocyanates: 1-8 parts
A diisocyanate: 29-140 parts
Foam stabilizer 1:1-5 parts
(2) The curing agent P comprises the following components in parts by weight:
mixing polyol: 0-160 parts
Chain extenders and/or crosslinkers: 4-14 parts
Catalyst: 0.1-6 parts
Foaming agent: 0.1-5 parts
Foam stabilizer 2:0.5-5 parts
The mixed polyol is polytetrahydrofuran ether glycol and polyether polyol with the functionality of 2-3;
the foam stabilizer 1 is a hydroxyl-containing polysiloxane foam stabilizer, and the foam stabilizer 2 is a hydroxyl-free polysiloxane foam stabilizer.
2. The elastomer of claim 1 wherein the polytetrahydrofuran ether glycol has a molecular weight of 1000 to 2000 and a functionality of 2; the molecular weight of the polyether polyol is 1000-8000.
3. The elastomer according to claim 1 or 2, characterized in that the mass ratio of polytetrahydrofuran ether glycol to polyether polyol is 20/80 to 80/20.
4. The elastomer of claim 1 wherein the polyfunctional isocyanate is a modified diphenylmethane diisocyanate MDI having a functionality of greater than 2 and less than or equal to 3; the monofunctional isocyanate is one or more of p-toluenesulfonyl isocyanate, ethyl isocyanate, dodecyl isocyanate, cyclohexyl isocyanate, isopropyl isocyanate, phenyl isocyanate and p-nitrophenyl isocyanate.
5. The elastomer of claim 1, wherein the foam stabilizer is one or more of 1 dakangning DC193, winning TEGOSTAB 8930, mesid M8804; the foam stabilizer 2 is one or more of Dow Corning DC190 and Maillard M88710.
6. The elastomer of claim 1 wherein the diisocyanate is one or more of MDI, TDI, PPDI, NDI, TODI; the molecular weight of the chain extender is less than 500; the molecular weight of the cross-linking agent is less than 500.
7. The elastomer of claim 1 or 6, wherein the chain extender has a molecular weight of 90 to 150.
8. The elastomer of claim 1 or 6, wherein the chain extender is one or more of ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol.
9. The elastomer of claim 1 or 6, wherein the chain extender is 1, 4-butanediol.
10. The elastomer of claim 1 or 6, wherein the cross-linking agent has a molecular weight of 90 to 150.
11. The elastomer of claim 1 or 6, wherein the cross-linking agent is one or more of trimethylolpropane, trimethylolethane, glycerol, 1,2, 6-hexanetriol, triethanolamine.
12. The elastomer of claim 1, wherein the catalyst is one or more of an amine catalyst and a metal catalyst.
13. The elastomer of claim 12 wherein the amine catalyst is one or more of triethylenediamine, bis (dimethylaminoethyl) ether, tetramethylethylenediamine, dimethylethanolamine.
14. The elastomer of claim 12 wherein the metal based catalyst is one or more of organotin and organobismuth.
15. The elastomer of claim 12, wherein the metal-based catalyst is one or more of dibutyltin dilaurate (T12), stannous octoate, dibutyltin diacetate, bismuth isooctanoate.
16. The elastomer of claim 1 wherein the blowing agent is one or more of water, a hydro fluorochlorocarbon, a low boiling point fluoride, an alkane.
17. The elastomer of claim 16 wherein the hydro fluorochlorocarbon is HCFC-141b.
18. The elastomer of claim 16 wherein the low boiling point fluoride is one or more of pentafluoropropane and hexafluorobutane.
19. The elastomer of claim 16 wherein the alkane is one or more of cyclopentane, n-pentane, n-hexane, n-heptane.
20. The elastomer of claim 1, wherein the P component comprises 0-2 parts of pigment and/or 0-2 parts of antioxidant; the NCO% content of the component I is 4.5% -18%.
21. An elastomer as claimed in claim 1 or claim 20 wherein the nco% content of the I component is from 5% to 9%.
22. A process for preparing the elastomer of any one of claims 1 to 21, comprising the steps of:
(1) Preparation of prepolymer I component: mixing polytetrahydrofuran ether glycol and polyether polyol with the functionality of 2-3 as mixed polyol and foam stabilizer 1, vacuum dehydrating, controlling the water content to be less than 300ppm, cooling to 40-60 ℃, adding monofunctional isocyanate, reacting for 3-5 hours at 70-90 ℃, cooling to 40-60 ℃ after NCO groups of the monofunctional isocyanate are fully reacted, adding diisocyanate and polyfunctional isocyanate, reacting for 2-3 hours at 65-100 ℃, and cooling to 45-55 ℃ to obtain a prepolymer I component;
(2) Preparation of a curing agent P component: uniformly stirring and mixing the mixed polyol, the chain extender and/or the cross-linking agent, the catalyst, the foaming agent and the foam stabilizer 2 to obtain a component P of the curing agent;
(3) Uniformly mixing the component I and the component P of the prepolymer according to the mass ratio, pouring into a mold at 45-80 ℃, demolding after 8-15 minutes, curing the product at 60-85 ℃ for 10-16 hours, and standing at normal temperature for 5-7 days to obtain the polyurethane foam.
23. Use of an elastomer according to any of claims 1 to 21 in a backing plate.
24. The use of the elastomer as claimed in claim 23, wherein the elastomer is used in heavy duty railway pads.
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