CN115124693A - Foamed polyurethane elastomer and preparation method and application thereof - Google Patents

Foamed polyurethane elastomer and preparation method and application thereof Download PDF

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Publication number
CN115124693A
CN115124693A CN202210874036.7A CN202210874036A CN115124693A CN 115124693 A CN115124693 A CN 115124693A CN 202210874036 A CN202210874036 A CN 202210874036A CN 115124693 A CN115124693 A CN 115124693A
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parts
component
isocyanate
elastomer
foam stabilizer
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CN115124693B (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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    • C08G18/28—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
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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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    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
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    • C08G18/71—Monoisocyanates or monoisothiocyanates
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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
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    • 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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    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
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  • Polymers & Plastics (AREA)
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  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention relates to a foaming polyurethane elastomer and a preparation method and application thereof, wherein the elastomer is obtained 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 component comprises the following components in parts by weight: 0-160 parts of mixed polyol, a chain extender and/or a 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 multifunctional and monofunctional isocyanate modified polyurethane material is used to destroy the crystallization behavior of polyurethane molecular chains, and multiple foam stabilizers are cooperatively used, so that the obtained foamed polyurethane cushion plate has the characteristics of high static rigidity, low dynamic-static ratio, small compression deformation, small size of a product after fatigue, small rigidity change rate and the like, and can meet the use requirements of the elastic cushion plate of the heavy haul railway.

Description

Foamed polyurethane elastomer and preparation method and application thereof
Technical Field
The invention belongs to the field of polyurethane, and particularly relates to a foamed polyurethane elastomer, and a preparation method and application thereof.
Background
Railway tie plates are a type of shock absorbing elements specifically designed to reduce noise and vibration generated when vehicles travel at high speeds. The vibration and noise reduction effect of the base plate depends on indexes such as static rigidity, dynamic rigidity ratio and static rigidity ratio of the product. Generally, high-speed railways require low static rigidity, while ordinary lines require high static rigidity. The closer the dynamic stiffness ratio value and the static stiffness ratio value are, the better the damping and buffering performance is exerted. In addition, the backing plate material also needs to have lower compression set and excellent fatigue resistance so as to ensure that the rail system has better compression characteristics and backing plate size and performance retention rate of static rigidity index.
The backing plate material is mostly rubber materials under traditional heavy haul railway rail, like natural rubber, butadiene styrene rubber, nitrile rubber etc. for the quiet rigidity that reduces these solid rubber backing plates, the solid slot design is adopted to backing plate structural design more, causes the indentation damage to the sleeper after using for a long time easily, and the comprehensive use maintenance cost is higher. The existing foamed backing plate for the high-speed railway is a polyurethane microporous material, but when the foamed backing plate is applied to a heavy-duty railway, the problems of rigidity design, dynamic-static rigidity ratio, high and low temperature performance, fatigue durability, unmatched processing and forming processes and the like of the backing plate material and a product exist, and the application requirement of the heavy-duty railway cannot be met.
CN 101058629B discloses a method for manufacturing a railway tie plate, in which an inert gas is dispersed in a mixed cured product of a polyurethane prepolymer, a polyol and a chain extender through a specially designed mixing device, the foaming molding process is complicated, the requirement on mechanical equipment is high, and the equipment cost is high. In addition, the disclosed tie plate has low static rigidity and is not suitable for application of heavy haul railways.
CN 101942786B discloses a manufacturing method of 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 ratio of the static rigidity to the dynamic rigidity is less than or equal to 1.4, and the size change rate of the pad after a fatigue test is less than or equal to 20%. The material of the base plate has lower static rigidity, and the size change rate index of the base plate after fatigue can not meet the performance requirement of a heavy haul railway.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects in the background technology and provide a foamed polyurethane elastomer and a preparation method and application thereof, wherein a multifunctional isocyanate and a monofunctional isocyanate are used for modifying a polyurethane material to destroy the crystallization behavior of a polyurethane molecular chain, and two foam stabilizers are cooperatively used at the same time, so that the obtained foamed polyurethane elastomer has the characteristics of high static rigidity, low dynamic-static ratio, small compression deformation, small size of a product after fatigue, small rigidity change rate and the like, and can meet the use requirement of an elastic backing plate of a heavy-load railway.
In order to solve the technical problem, 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) reacting to obtain the compound,
(1) the prepolymer I component comprises the following components in parts by weight:
mixing polyol: 100 portions of
Polyfunctional isocyanates: 1-5 parts of
Monofunctional isocyanate: 1 to 8 portions of
Diisocyanate: 29-140 parts of
Foam stabilizer 1: 1 to 5 portions of
(2) The curing agent P component comprises the following components in parts by weight:
mixing polyol: 0 to 160 portions of
Chain extenders and/or crosslinkers: 4 to 14 portions of
Catalyst: 0.1 to 6 portions
Foaming agent: 0.1 to 5 portions
Foam stabilizer 2: 0.5 to 5 portions of
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 with a molecular weight of 1000-2000 and a functionality of 2 and polyether polyol with a molecular weight of 1000-8000 and a functionality of 2-3, preferably in a mass ratio of 20/80-80/20.
Preferably, the polyfunctional isocyanate is a modified diphenylmethane diisocyanate, MDI, having a functionality of greater than 2 and equal to or less than 3, preferably one or more of Wannate MDI-100HL, Wannate 8319, Wannate8617 and Dow Isonate 143L, in the order of 21% to 32% NCO.
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 and TODI.
Preferably, the foam stabilizer 1 is a polysiloxane foam stabilizer containing hydroxyl, and more preferably one or more of Dow Corning DC193, Yingchuang TEGOSTAB B8930 and Maillard M8804; foam stabilizer 2 is a polysiloxane foam stabilizer containing no hydroxyl group, and more preferably one or more of Dow Corning DC190 and Maillard M88710.
Preferably, the curing agent P component can contain the mixed polyol in the prepolymer I component, and the amount of the mixed polyol in the P component and the mixing ratio of the I, P component can be adjusted according to the requirements of conditions such as product forming process, forming equipment and the like.
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 is 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 catalyst and metal catalyst, and the amine catalyst is preferably one or more of triethylene diamine, bis (dimethylaminoethyl) ether, tetramethylethylenediamine and dimethylethanolamine; the metal catalyst is one or more of organic tin and organic bismuth, such as one or more of catalysts dibutyltin dilaurate (T12), stannous octoate (T9), dibutyltin diacetate and bismuth isooctanoate.
The foaming agent is one or more of water, hydro-fluoro-chloro-hydrocarbon, low-boiling-point fluoride and alkane; the hydro-chlorofluorocarbon 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 blowing agent is water.
Preferably, the P component also comprises 0-2 parts of pigment.
Preferably, the P component also comprises 0-2 parts of antioxidant.
Preferably, the I-component has an NCO% content of 4.5% to 18%, more preferably, an NCO% content of 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 functionality of 2-3 as mixed polyol and a foam stabilizer 1, performing vacuum dehydration, 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 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 curing agent P component;
(3) uniformly mixing the prepolymer I component and the curing agent P component according to the mass ratio, pouring the mixture 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 high-performance polyurethane adhesive.
The third aspect of the invention provides the use of the 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 the common rubber base plate, the foamed polyurethane elastomer provided by the invention has the characteristics that the surface is not required to be grooved, the service life is long, and the maintenance cost is low;
(2) according to the invention, by analyzing the formula of the polyurethane material substrate, the monofunctional isocyanate is used for modifying the polytetrahydrofuran ether glycol and polyether polyol soft segment material, the crystallization behavior of a polyurethane molecular chain is destroyed, and meanwhile, the polyfunctional isocyanate is used for making up the defect of insufficient crosslinking of a polyurethane material hard segment, so that the performances of large static compression deformation and high dynamic-static ratio of the polyurethane material are improved. Compared with the low-rigidity elastic base plate for the existing high-speed railway, the invention has the characteristics of high static rigidity, low dynamic-static ratio and small compression deformation;
(3) according to the analysis of the backing plate product forming and foaming process, the low-rigidity elastic backing plate for the high-speed railway obtains a corresponding cell structure through mechanical foaming or water foaming, and mechanical foaming equipment is high in cost and inconvenient to use; when the foam is foamed by water or by low-boiling-point fluoride, alkane and the like, the cell structure is not compact and uniform enough, because the coordination of various foam stabilizers is not exerted. In the initial stage of mixing, the excellent stabilizer combination can enable two components of materials to be quickly mixed and emulsified uniformly, then bubble cores and bubbles are more easily and uniformly generated, and finally the effects of stabilizing foams and preventing the bubbles from being combined and becoming large are achieved. The invention adopts polysiloxane foam stabilizer containing hydroxyl to react with isocyanate firstly, so that the foam stabilizer is connected to the component I of isocyanate prepolymer, and the foam stabilizer has certain internal emulsification; then mixing with a component P of polysiloxane foam stabilizer without hydroxyl, so that the two foam stabilizers generate synergistic action, and the cell structure of the polyurethane material is improved.
Therefore, through the material formula adjustment and the foaming process adjustment, the size change rate of the prepared cushion plate product after 300 ten thousand times of fatigue is less than 5%, the rigidity stability of the product can be maintained for a long time, and the use requirement of the elastic cushion plate of the heavy haul railway can be met.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the scope of the present invention, and it should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of 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 disclosure.
The examples of the invention and the comparative examples used the following raw materials:
polytetrahydrofuran ether glycol: PTMEG1000, PTMEG2000, BASF, germany;
polyether polyol DL 1000: functionality of 2, molecular weight of 1000, Shandong Lanxindong chemical industry, Inc.;
polyether polyol EP 3600: functionality of 3, molecular weight of 6000, Shandong Lanxindong chemical industry, LLC;
polyfunctional isocyanates: wannate MDI-100HL, Van der Waals Chemicals; wannate8617, wanwawa chemistry;
monofunctional isocyanate: p-toluenesulfonyl isocyanate, isopropyl isocyanate, p-nitrophenyl isocyanate;
diisocyanate: MDI100, wanhua chemistry; 1, 5-Naphthalene Diisocyanate (NDI), BAYER;
foam stabilizer 1: dow corning DC193, maillard M8804;
foam stabilizer 2: dow corning DC190, maillard M88710;
chain extender: 1, 4-butanediol, 1, 6-hexanediol;
a 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 serving as mixed polyol and 2 parts of foam stabilizer 1 (DC 193), performing vacuum dehydration, controlling the moisture 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 the NCO = 5%;
(2) preparation of curing agent P component: stirring and uniformly mixing 5 parts of chain extender 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 the component P;
(3) preheating the I, P two components to 45-50 ℃, and then mixing the components according to the proportion of I: p = 100: 16, pouring the mixture into a mold at the temperature of between 55 and 65 ℃, demolding after 8 minutes, curing the product for 16 hours at the temperature of between 70 and 80 ℃, and standing for 7 days at normal temperature to obtain the foamed polyurethane cushion plate.
Example 2
Preparation of prepolymer I component: mixing 80 parts of polytetrahydrofuran ether glycol (PTMEG 2000) and 20 parts of polyether polyol EP3600 serving as mixed polyol and 3 parts of foam stabilizer 1 (M8804), performing vacuum dehydration, controlling the moisture content to be less than 300ppm, then cooling to 45-50 ℃, slowly adding 8 parts of isopropyl isocyanate, reacting at 75-80 ℃ for 3.5 hours, cooling to 45-55 ℃ after NCO groups are fully reacted, then adding 140 parts of MDI100 and 5 parts of Wannate8617, reacting at 70-75 ℃ for 2.5 hours, then cooling to 50 ℃ to obtain a prepolymer I component, wherein NCO = 18%;
(2) preparation of curing agent P component: uniformly stirring and mixing 130 parts of polytetrahydrofuran ether glycol (PTMEG 2000) and 30 parts of polyether polyol EP3600 serving as mixed polyol, 14 parts of triethanolamine serving as a chain extender, 1.5 parts of catalyst triethylene diamine, 1.5 parts of T9, 5 parts of hexafluorobutane and 5 parts of foam stabilizer 2 (M88710) to obtain a P component;
(3) preheating the I, P two components to 45-55 ℃, and then mixing the components according to the proportion of I: p = 100: 187, pouring the mixture into a mold at 55-65 ℃, demolding after 8 minutes, curing the product at 70-80 ℃ for 16 hours, and standing at normal temperature for 7 days to obtain the foamed polyurethane cushion 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), performing vacuum dehydration, controlling the moisture content to be less than 300ppm, then cooling to 45-50 ℃, slowly adding 5 parts of p-nitrobenzene 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 curing agent P component: stirring and uniformly mixing 10 parts of chain extender, namely 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 component P;
(3) preheating the I, P two components to 45-55 ℃, and then mixing the components according to the proportion of I: p = 100: and (2) uniformly mixing the components according to the ratio of 25, pouring the mixture into a mold at the temperature of 55-65 ℃, demolding after 8 minutes, curing the product for 16 hours at the temperature of 70-80 ℃, and standing for 7 days at normal temperature to obtain the foamed polyurethane cushion 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 serving as mixed polyol and 5 parts of foam stabilizer 1 (DC 193), performing vacuum dehydration, controlling the moisture 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 ℃, and then cooling to 50 ℃ to obtain a prepolymer I component, wherein NCO = 4.5%;
(2) preparation of curing agent P component: uniformly stirring and mixing 3 parts of chain extender, 1 part of 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) to obtain the P component;
(3) preheating the I, P two components to 45-50 ℃, and then mixing the components according to the proportion of I: p = 100: 5, pouring the mixture into a mold at the temperature of between 55 and 65 ℃, demolding after 15 minutes, curing the product for 10 hours at the temperature of between 70 and 80 ℃, and then standing for 5 days at normal temperature to obtain the foamed polyurethane cushion 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), performing vacuum dehydration, controlling the moisture content to be less than 300ppm, cooling to 45-50 ℃, adding 29 parts of MDI100, reacting for 2.5 hours at the temperature of 70-75 ℃, cooling to 50 ℃ to obtain a prepolymer I component, wherein the NCO = 5%;
(2) preparation of curing agent P component: stirring and uniformly mixing 5 parts of chain extender, 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 I, P two components to 45-50 ℃, and then mixing the components according to the proportion of I: p = 100: 16, pouring the mixture into a mold at the temperature of between 55 and 65 ℃, demolding after 8 minutes, curing the product for 16 hours at the temperature of between 70 and 80 ℃, and standing for 7 days at normal temperature to obtain the foamed polyurethane cushion 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 serving 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 then cooling to 50 ℃ to obtain a prepolymer I component, wherein NCO = 5%;
(2) preparation of curing agent P component: stirring and uniformly mixing 5 parts of chain extender, 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) two components I, P were preheated to 45-50 ℃ and then mixed as follows: p = 100: 16, pouring the mixture into a mold at the temperature of between 55 and 65 ℃, demolding after 8 minutes, curing the product for 16 hours at the temperature of between 70 and 80 ℃, and standing for 7 days at normal temperature to obtain the foamed polyurethane cushion plate.
The properties of the pads of examples 1 to 4 and comparative examples 1 to 2, such as static stiffness, compression set, dynamic-static ratio, and change in size and static stiffness after fatigue, are shown in the following table.
TABLE 1 comparison of pad Properties
Test item Index requirement Example 1 Example 2 Example 3 Practice ofExample 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
Percentage change in dimension after fatigue (%) ≤10 4.6 4.1 5.6 4.5 8.6 13.3
Static rigidity Change Rate after fatigue (%) ≤10 5.1 6.1 6.5 5.2 15.8 18.7
As can be seen from the above table, the formulation of comparative example 1 does not add monofunctional isocyanate and polyfunctional isocyanate, and the formulation of comparative example 2 does not add foam stabilizer 1 containing hydroxyl, the compression deformation of the cushion material is large, the dynamic-static ratio is high, and the dimensional change rate and static rigidity change rate after fatigue exceed the index requirements.

Claims (10)

1. A foamed polyurethane elastomer is prepared from a prepolymer I component and a curing agent P component in a mass ratio of 100: (5-187) reacting to obtain the compound,
(1) the prepolymer I component comprises the following components in parts by weight:
mixing polyol: 100 portions of
Polyfunctional isocyanates: 1-5 parts of
Monofunctional isocyanate: 1-8 parts of
Diisocyanate: 29-140 parts of
Foam stabilizer 1: 1-5 parts of
(2) The curing agent P component comprises the following components in parts by weight:
mixing polyol: 0 to 160 portions of
Chain extenders and/or crosslinkers: 4 to 14 portions of
Catalyst: 0.1 to 6 portions
Foaming agent: 0.1 to 5 portions
Foam stabilizer 2: 0.5 to 5 portions of
The mixed polyol is polytetrahydrofuran ether glycol and polyether polyol with the functionality of 2-3.
2. The elastomer of claim 1 wherein the polytetrahydrofuran ether glycol has a molecular weight of 1000-; the molecular weight of the polyether polyol is 1000-; the preferred mass ratio of polytetrahydrofuran ether glycol to polyether polyol is from 20/80 to 80/20.
3. An elastomer as claimed in claim 1, characterised in that said polyfunctional isocyanate is a modified diphenylmethane diisocyanate, MDI, having a functionality of greater than 2 and not greater than 3; the monofunctional isocyanate is one or more of p-toluenesulfonyl isocyanate, ethyl isocyanate, dodecyl isocyanate, cyclohexyl isocyanate, isopropyl isocyanate, phenyl isocyanate and p-nitrobenzene isocyanate.
4. The elastomer of claim 1 wherein foam stabilizer 1 is a hydroxyl-containing polysiloxane foam stabilizer, preferably one or more of dow corning DC193, winning tegostat B8930, maillard M8804; foam stabilizer 2 is a polysiloxane foam stabilizer containing no hydroxyl group, preferably one or more of Dow Corning DC190 and Maillard M88710.
5. 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 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 the chain extender is 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.
6. The elastomer of claim 1, wherein the catalyst is one or more of an amine-based catalyst, a metal-based catalyst;
the amine catalyst is preferably one or more of triethylene diamine, bis (dimethylaminoethyl) ether, tetramethylethylenediamine and dimethylethanolamine;
the metal catalyst is preferably one or more of organic tin and organic bismuth, and more preferably one or more of dibutyltin dilaurate (T12), stannous octoate, dibutyltin diacetate and bismuth isooctanoate.
7. The elastomer of claim 1, wherein the blowing agent is one or more of water, hydro fluorochlorocarbon, low boiling point fluorides, alkanes;
a hydrochlorofluorocarbon, preferably HCFC-141 b;
the low-boiling fluoride is preferably one or more of pentafluoropropane and hexafluorobutane;
the alkane is preferably one or more of cyclopentane, n-pentane, n-hexane and n-heptane; further preferably, the blowing agent is water.
8. The elastomer of claim 1, wherein the P component comprises 0 to 2 parts of a pigment and/or 0 to 2 parts of an antioxidant;
the NCO% content of the component I is 4.5% -18%, and the NCO% content is preferably 5% -9%.
9. A process for preparing the elastomer of any of claims 1-8, 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 a foam stabilizer 1, then performing vacuum dehydration, controlling the moisture content to be less than 300ppm, then cooling to 40-60 ℃, adding monofunctional isocyanate, reacting for 3-5 hours at 70-90 ℃, cooling to 40-60 ℃ after NCO groups of 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 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 curing agent P component;
(3) uniformly mixing the prepolymer I component and the curing agent P component according to the mass ratio, pouring the mixture 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 high-performance polyurethane adhesive.
10. Use of the elastomer according to any of claims 1 to 8 in a tie plate, preferably in a tie plate for heavy haul railway.
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CN117487122B (en) * 2023-12-28 2024-04-30 巴斯夫新材料有限公司 Polyurethane foaming system, heat-recoverable polyurethane foam and preparation method thereof

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