CN111574685A - Cold-resistant polyurethane cushion plate for heavy haul railway and preparation method thereof - Google Patents

Cold-resistant polyurethane cushion plate for heavy haul railway and preparation method thereof Download PDF

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CN111574685A
CN111574685A CN202010521973.5A CN202010521973A CN111574685A CN 111574685 A CN111574685 A CN 111574685A CN 202010521973 A CN202010521973 A CN 202010521973A CN 111574685 A CN111574685 A CN 111574685A
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polyether polyol
polyol
parts
cold
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CN111574685B (en
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李平
盛兴丰
韩文
朱彦
唐劲松
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Shanghai Huafon New Material Research & Development Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4887—Polyethers containing carboxylic ester groups derived from carboxylic acids other than acids of higher fatty oils or other than resin acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
    • C08G18/725—Combination of polyisocyanates of C08G18/78 with other polyisocyanates
    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • E—FIXED CONSTRUCTIONS
    • E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
    • E01B—PERMANENT WAY; PERMANENT-WAY TOOLS; MACHINES FOR MAKING RAILWAYS OF ALL KINDS
    • E01B19/00—Protection of permanent way against development of dust or against the effect of wind, sun, frost, or corrosion; Means to reduce development of noise
    • E01B19/003—Means for reducing the development or propagation of noise
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0083—Foam properties prepared using water as the sole blowing agent

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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)
  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Civil Engineering (AREA)
  • Structural Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention relates to the technical field of polyurethane materials, in particular to a cold-resistant polyurethane cushion plate for a heavy haul railway and a preparation method thereof. The weight ratio of A component to B component is 100: (91-107) by mass; the component A comprises the following raw materials: 80-120 parts of polyol A, 15-20 parts of chain extender and 0.1-1.8 parts of assistant; the component B comprises the following raw materials in parts by weight: 35-50 parts of polyol B, 50-65 parts of diisocyanate and 0.01-0.02 part of polymerization inhibitor. The cold-resistant polyurethane backing board has excellent mechanical property, lower compression permanent deformation and dynamic-static ratio and better vibration reduction effect. In addition, the polyurethane elastic cushion plate has lower low-temperature brittleness temperature, the static rigidity change rate at minus 30 ℃ is less than 15%, the use requirement is met, the low-temperature resistance is excellent, the polyurethane elastic cushion plate is suitable for being used in an environment at minus 30 ℃, the indexes in the standard Q/CR481-2015 of the China railway general company are completely met, and the polyurethane elastic cushion plate is suitable for the construction of railways in cold regions such as Xinjiang, inner Mongolia and northeast.

Description

Cold-resistant polyurethane cushion plate for heavy haul railway and preparation method thereof
Technical Field
The invention relates to the technical field of polyurethane materials, in particular to a cold-resistant polyurethane cushion plate for a heavy haul railway and a preparation method thereof.
Background
In a railway track structure, an elastic base plate is usually additionally arranged between a steel rail and a sleeper to provide reasonable elasticity for the track and play a role in vibration and noise reduction. Along with the development of high speed and heavy load of railway transportation, the speed, axle weight and transportation capacity of trains are continuously improved, and higher requirements are provided for the performance of the base plate under the rail due to the aggravation of the dynamic action and the increase of the frequency of action of wheel rails. The pad under the rail in China is usually made of rubber, thermoplastic elastomer, nylon and the like. Under the action of the frequent train load of the heavy haul railway, the common rubber cushion is easy to crack, age and the like, and generally needs to be replaced about half a year after being used. Thermoplastic elastomer (TPEE) pads are excellent in wear resistance and oil resistance, but also have the phenomena of large compression set, large rigidity, increased sleeper breakage and the like. The polyurethane material has excellent oil resistance and wear resistance, radiation resistance, good mechanical property, high bearing capacity, good vibration damping effect and wide adjustable range of the formula, and is widely applied to vibration damping structures of railways, bridges and automobiles.
Chinese patent CN 305186256S discloses an appearance design of heavy haul railway elastomer pad (polyurethane microcellular), but does not disclose formulation composition and preparation method of the pad.
Chinese patent CN 105037673B discloses a polyurethane elastic material for heavy-duty turnout, which has the advantages of high strength, good toughness, oil resistance, good wear resistance, etc. But the manufacturing process needs to heat the die to 160-210 ℃, so that the energy consumption is high, the production period is long, and the efficiency is low. And the tensile strength of the base plate is not large enough (less than 24MPa), and the mechanical property requirement of the base plate under the 30-ton axle load heavy haul railway rail is not met. In addition, the polyester prepolymer used in the method is easy to crystallize, has large static rigidity change at low temperature, and is difficult to use in low-temperature environment.
Chinese patent CN 107602817A discloses the cold-resistant polyurethane vibration damping pad and the preparation method thereof. The method selects caprolactone modified polyether polyol, hydroxyl-terminated polybutadiene and primary hydroxyl-terminated siloxane to prepare the combined material, improves the low-temperature resistance of the polyurethane material to a certain extent, but reduces the mechanical property of the material to a great extent, has the highest tensile strength of only 2.67MPa, and is not suitable for a base plate of a heavy haul railway.
Disclosure of Invention
Aiming at the technical problems, the invention provides the polyurethane cushion plate which has good mechanical property, good cold resistance, excellent shock absorption performance and convenient processing.
Specifically, the first aspect of the invention provides a cold-resistant polyurethane cushion plate which is prepared from a component A and a component B in a ratio of 100: (91-107) by mass;
the component A comprises the following raw materials in parts by weight:
80-120 parts of polyol A
15-20 parts of chain extender
0.1-1.8 parts of an auxiliary agent;
the polyol A comprises polyether polyol A, modified polyether polyol B and modified polyether polyol A, and the weight ratio of the polyether polyol A to the modified polyether polyol B is 1: (2-4): (2.5-6);
the component B comprises the following raw materials in parts by weight:
35-50 parts of polyol B
50-65 parts of diisocyanate
0.01-0.02 part of polymerization inhibitor;
the polyol B comprises modified polyether polyol B and polyether polyol B; the modified polyether polyol B accounts for at least 60 wt% of the polyol B;
the modified polyether polyol A is caprolactone modified polyether polyol; the modified polyether polyol B is polyether polyol with a hydrocarbon side chain in the structure.
As a preferred technical solution of the present invention, the modified polyether polyol B has the following structural formula:
Figure BDA0002532406620000021
wherein R is a hydrocarbyl selected from one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, ethenyl and propenyl; m and n are positive integers.
As a preferable technical scheme, m and n in the structural formula of the modified polyether polyol B satisfy that m is more than or equal to 15 and less than or equal to 25, and n is more than or equal to 2 and less than or equal to 8.
In a preferred embodiment of the present invention, the modified polyether polyol B has an average functionality of 2 and a number average molecular weight of 1800 to 2500.
As a preferred technical solution of the present invention, the modified polyether polyol a has the following structural formula:
Figure BDA0002532406620000022
wherein x, y and z are positive integers, and satisfy x + z is more than or equal to 5 and less than or equal to 20, and y is more than or equal to 10 and less than or equal to 18.
In a preferred embodiment of the present invention, x, y and z in the structural formula of the modified polyether polyol a satisfy x + z ═ 9 or 18, and y ═ 14.
As a preferable technical scheme of the invention, the number average molecular weight of the polyether polyol A and the polyether polyol B is 1000-3000.
As a preferred technical solution of the present invention, the diisocyanate comprises 4, 4-diphenylmethane diisocyanate and carbodiimide-modified liquefied MDI; the carbodiimide-modified liquefied MDI accounts for 8-20 wt% of the diisocyanate.
The second aspect of the present invention provides a method for preparing the cold-resistant polyurethane mat as described above, which comprises the steps of:
(1) preparation of component A: adding the polyol A, the chain extender and the auxiliary agent into a container according to the proportion and mixing to obtain the component A;
(2) preparation of the component B: adding diisocyanate and a polymerization inhibitor into a reaction kettle according to a ratio, stirring and mixing, then adding polyol B, raising the temperature of the reaction kettle to 70-80 ℃, and reacting for 1.5-2.5 h to obtain a component B;
(3) curing and forming: preheating the component A and the component B, preheating the component A to 40-50 ℃, preheating the component B to 40-45 ℃, mixing the component A and the component B according to the proportion, injecting the mixture into a mold at 60-90 ℃, curing for 8-15 min, and discharging and post-treating to obtain the high-temperature-resistant high-strength high-toughness high-strength high-toughness high-.
The third aspect of the present invention provides the use of the cold-resistant polyurethane slab as described above in the technical field of railway rails.
Has the advantages that: the cold-resistant polyurethane backing plate has excellent mechanical properties, and compared with the conventional polyurethane backing plate, the cold-resistant polyurethane backing plate has the advantages of lower compression permanent deformation and dynamic-static ratio and better vibration reduction effect. In terms of cold resistance, the polyurethane elastic backing plate E 'of the present invention'-30℃/E′25℃The lower value shows that the dependence of the performance of the material on the temperature in the range of-30 ℃ to 25 ℃ is low, and the material has better stability. The polyurethane elastic cushion plate has lower low-temperature brittleness temperature, the static rigidity change rate at minus 30 ℃ is less than 15 percent, the use requirement is met, the low-temperature resistance is excellent, and the polyurethane elastic cushion plate is suitable for being used in an environment at minus 30 ℃. In addition, the polyurethane elastic base plate completely meets the performance index of the standard Q/CR 481-2015' 30T elastic VII-type fastener for axle load heavy haul railway of China railway general company, and is suitable for the construction field of railways in cold regions such as Xinjiang, inner Mongolia and northeast.
Detailed Description
The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
When an amount, concentration, amount, or other value or parameter is expressed as a range, preferred range, or as a range of values, with a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
The indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.
In addition, the molecular weight average number average molecular weight described in the present invention is measured by a conventional method well known to those skilled in the art, such as end titration. The functionality of the polyol in the present invention means the number of moles of hydroxyl groups capable of reacting with isocyanate per mole of molecular chain, for example, the functionality of ethylene glycol is 2.
The invention provides the polyurethane cushion plate which has good mechanical property, good cold resistance, excellent damping property and convenient processing.
Specifically, the first aspect of the invention provides a cold-resistant polyurethane cushion plate which is prepared from a component A and a component B in a ratio of 100: (91-107) by mass;
the component A comprises the following raw materials in parts by weight:
80-120 parts of polyol A
15-20 parts of chain extender
0.1-1.8 parts of an auxiliary agent;
the polyol A comprises polyether polyol A, modified polyether polyol B and modified polyether polyol A, and the weight ratio of the polyether polyol A to the modified polyether polyol B is 1: (2-4): (2.5-6);
the component B comprises the following raw materials in parts by weight:
35-50 parts of polyol B
50-65 parts of diisocyanate
0.01-0.02 part of polymerization inhibitor;
the polyol B comprises modified polyether polyol B and polyether polyol B; the modified polyether polyol B accounts for at least 60 wt% of the polyol B; further, the content of the modified polyether polyol B is not more than 85 wt% of the polyol B;
the modified polyether polyol A is caprolactone modified polyether polyol; the modified polyether polyol B is polyether polyol with a hydrocarbon side chain in the structure.
The polyol A and the polyol B are conventional components for preparing polyurethane materials, and various polyester polyols or polyether polyols which are well known to those skilled in the art can be selected. The polyester polyol is a polycondensate obtained by reacting a low-molecular-weight polyol (preferably a diol) with a polybasic acid (preferably a dibasic acid), and the specific components and structure are not particularly limited. The polyether polyol is a compound prepared by carrying out addition polymerization reaction on an initiator containing an active hydrogen group and ethylene oxide, propylene oxide, butylene oxide and the like in the presence of a catalyst or carrying out dehydration condensation reaction on a polyol in the presence of a catalyst.
In some embodiments, the polyol a and the polyol B are selected from polyether polyols.
In some preferred embodiments, the polyol A comprises, by weight, 50-60 parts of modified polyether polyol A, B20-40 parts of modified polyether polyol B and 10-20 parts of polyether polyol A.
In some preferred embodiments, the polyol B comprises 25-35 parts by weight of modified polyether polyol B and 10-15 parts by weight of polyether polyol B.
<Modified polyether polyol B>
The modified polyether polyol B is the copolymerized polyether obtained after copolymerization of at least two monomers. Wherein at least one of the monomer structures contains a branch or a pendant group.
In some embodiments, tetrahydrofuran is included in the raw materials for preparing the modified polyether polyol B.
In some preferred embodiments, the modified polyether polyol B has the following structural formula:
Figure BDA0002532406620000061
wherein R is a hydrocarbon group, and m and n are positive integers.
In the present invention, the above-mentioned groups are not particularly limited, and include, but are not limited to, saturated aliphatic hydrocarbon groups, saturated aromatic hydrocarbon groups, unsaturated aliphatic hydrocarbon groups, and aromatic hydrocarbon groups.
In some preferred embodiments, the hydrocarbyl group is selected from one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, ethenyl, propenyl;
further preferably, the hydrocarbyl group is methyl.
Furthermore, m and n in the structural formula of the modified polyether polyol B satisfy that m is more than or equal to 15 and less than or equal to 25 and n is more than or equal to 2 and less than or equal to 8.
Preferably, the modified polyether polyol B has a structure in which m and n satisfy m-22 and n-5.
In some preferred embodiments, the modified polyether polyol B has an average functionality of 2 and a number average molecular weight of 1800 to 2500.
Preferably, the modified polyether polyol B has an average functionality of 2 and a number average molecular weight of 2000.
The modified polyether polyols described above in the present invention can be prepared by methods well known to those skilled in the art. The structure of the modified polyether polyol B can be regulated and controlled by adjusting parameters such as the molar ratio of the prepared monomers, the reaction temperature, other reaction conditions and the like, and the specific structure of the modified polyether polyol B is characterized and confirmed by means such as nuclear magnetic hydrogen spectrum/nuclear magnetic carbon spectrum, infrared spectrum and the like.
In a preferred embodiment, the preparation method of the modified polyether polyol B comprises the following steps: cooling in an ice salt bath to-5 ℃ in a reaction kettle provided with an electric stirrer and a thermometer, sequentially adding a certain amount of tetrahydrofuran, 2-methyltetrahydrofuran, glycol and boron trifluoride diethyl etherate, quickly stirring, reacting for 3 hours to obtain crude polyether, and washing, neutralizing, filtering, vacuumizing and the like to obtain refined polyether polyol B. Wherein the molar ratio of tetrahydrofuran to 2-methyltetrahydrofuran is 22: 5.
<modified polyether polyol A>
The modified polyether polyol A is copolymerized polyether obtained by copolymerization of at least two monomers, wherein one monomer is caprolactone.
In some embodiments, the modified polyether polyol A is a caprolactone-modified polytetrahydrofuran polyol having an average functionality of 2 and a molecular weight of 2000 to 3000.
In some preferred embodiments, the modified polyether polyol a has the following structural formula:
Figure BDA0002532406620000062
wherein x, y and z are positive integers, and satisfy x + z is more than or equal to 5 and less than or equal to 20, and y is more than or equal to 10 and less than or equal to 18.
Further preferably, the modified polyether polyol a has a structural formula in which x, y and z satisfy x + z ═ 9 or 18, and y ═ 14.
The modified polyether polyol A in the invention can be prepared by taking polytetrahydrofuran as an initiator and carrying out ring-opening polymerization on caprolactone, and the specific preparation method is not particularly limited and can be prepared according to a method well known by a person skilled in the art. The modified polyether polyol A (caprolactone-modified polytetrahydrofuran polyol) in the invention can also be selected from commercial products, such as products with corresponding brands of Japanese xylonite. The structure of the modified polyether polyol A can be regulated and controlled by changing the molar ratio of polytetrahydrofuran to caprolactone monomers, and the specific structure of the modified polyether polyol A is characterized and confirmed by means of nuclear magnetic hydrogen spectrum/nuclear magnetic carbon spectrum, infrared spectrum and the like.
<Polyether polyol A>
The polyether polyol A in the present invention is a polyether polyol having an average functionality of 2.
In some preferred embodiments, the polyether polyol A has a number average molecular weight of 1000 to 3000; preferably, the number average molecular weight is 1000 or 3000.
Further preferably, the polyether polyol a is polytetrahydrofuran diol (PTMG).
<Polyether polyol B>
In the present invention, the polyether polyol B is a polyether polyol having an average functionality of 2.
In some preferred embodiments, the polyether polyol B has a number average molecular weight of 1000 to 3000; preferably, it has a number average molecular weight of 1000 or 2000.
Further preferably, the polyether polyol B is polytetrahydrofuran diol (PTMG).
<Chain extender>
The chain extender is a high-activity compound containing hydroxyl, amino and the like, which can react with isocyanate groups to expand molecular chains of the isocyanate-terminated prepolymer and increase molecular weight.
As the amino group-containing compound, a diamine may be mentioned, and specific examples include, but are not limited to, ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 3 '-dichloro-4, 4' -diaminodiphenylmethane (moka), dimethylthiotoluenediamine, and the like.
As the hydroxyl group-containing compound, there may be mentioned a diol, specific examples include, but are not limited to, ethylene glycol, propylene glycol, 1, 4-butanediol, 1, 3-butanediol, 1, 2-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, diethylene glycol, neopentyl glycol, alkane (7 to 22) diols, diethylene glycol, triethylene glycol, dipropylene glycol, 3-methyl-1, 5-pentanediol, alkane-1, 2-diols (C17 to 20), 1, 3-or 1, 4-cyclohexanedimethanol and mixtures thereof, 1, 4-cyclohexanediol, hydrogenated bisphenol A, 1, 4-dihydroxy-2-butene, 2, 6-dimethyl-1-octene-3, 8-diol, bisphenol A, hydroquinone dihydroxyethyl ether, and the like. Diols of symmetrical linear structure, such as 1, 4-butanediol or ethylene glycol, are preferred.
<Auxiliary agent>
The auxiliary agent comprises a catalyst, a foaming agent and a foam stabilizer.
In some embodiments, the auxiliary agent comprises 0.1 to 0.2 parts by weight of catalyst, 0.8 to 1.5 parts by weight of foam stabilizer, and 0.1 to 0.16 parts by weight of foaming agent.
The catalyst is a component for the reaction of the polyol A in the component A and the isocyanate-terminated prepolymer in the component B, and comprises a tertiary amine catalyst, an organic metal catalyst and the like.
In some preferred embodiments, the catalyst is a mixture of a tertiary amine-based catalyst and an organometallic-based catalyst.
The tertiary amine catalyst in the present invention includes, but is not limited to, triethylenediamine, bis (dimethylaminoethyl) ether, N-methylmorpholine, N-methylimidazole, N, N-dimethylcyclohexylamine, N, N, N ', N ' -tetramethylalkylenediamine, N, N-dimethylbenzylamine, N-ethylmorpholine, triethanolamine, N, N ' -dimethylpyridine, and the like.
The organometallic catalysts used in the present invention include, but are not limited to, bismuth laurate, bismuth neodecanoate, bismuth naphthenate, stannous octoate (T9), dibutyltin dilaurate (T12), zinc isooctanoate, and the like.
In some embodiments, the tertiary amine catalyst is at least one of triethylenediamine, bis (dimethylaminoethyl) ether, N-methylmorpholine, N-methylimidazole; the organic metal catalyst is at least one of stannous octoate, dibutyltin dilaurate (T12) and zinc isooctanoate.
Preferably, the catalyst is a catalyst compounded by triethylenediamine and dibutyltin dilaurate (T12).
The foaming agent in the invention is a component which can foam in the forming and curing process after the component A and the component B are mixed in the process of preparing the polyurethane cushion plate. Preferably, water is used as the blowing agent.
The foam stabilizer is a component for stabilizing foam generated in the curing and forming process of the backing plate, and the specific component of the foam stabilizer is a surfactant. In some embodiments, the foam stabilizer is a silicone surfactant.
In some embodiments, the silicone surfactant includes, but is not limited to, DABCO DC2585 (U.S. air chemical), L1501 (U.S. mezzanine), DC 5604 (dow chemical), DC 5585 (dow chemical), DC 5350 (dow chemical), DC 5098 (dow chemical), and the like.
Preferably, DABCO DC2585 (American air chemical) is selected as the foam stabilizer.
In addition, on the premise of not affecting the comprehensive performances of mechanical property, cold resistance, shock absorption and the like of the cold-resistant polyurethane cushion plate, other auxiliary agents can be selected, including but not limited to flame retardants, antioxidants, ultraviolet absorbers, heat stabilizers, weather-resistant agents, plasticizers, antistatic agents and the like. Among them, examples of the flame retardant include, but are not limited to, guanidine phosphate, ammonium phosphate, melamine phosphate, triphenyl phosphate, tris (2, 3-dichloropropyl) phosphate, ammonium polyphosphate, phosphate ester, tricresyl phosphate, trichloroethyl phosphoric acid, and the like; examples of the antioxidant include, but are not limited to, phosphorus compounds such as copper compounds, organic or inorganic halogen compounds, hindered phenols, hindered amines, hydrazines, sulfur compounds, sodium hypophosphite, potassium hypophosphite, calcium hypophosphite, and magnesium hypophosphite; examples of the ultraviolet absorber include, but are not limited to, benzotriazole-based ultraviolet absorbers such as 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-butylphenyl) benzotriazole, 2- (2-hydroxy-5-octylphenyl) benzotriazole, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, and 2- (3, 5-di-tert-amyl-2-hydroxyphenyl) benzotriazole; benzophenone-based ultraviolet absorbers such as 2-hydroxy-4-methoxybenzophenone and 2-hydroxy-4-n-octyloxybenzophenone; triazine-based ultraviolet absorbers such as 2- [4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazin-2-yl ] -5- (octyloxy) phenol and 2- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -5- (hexyloxy) phenol; salicylate-based ultraviolet absorbers such as p-tert-butylphenyl salicylate and phenyl salicylate; as the heat stabilizer, there may be exemplified, but not limited to, heat stabilizers including basic lead salts (e.g., dibasic lead stearate, tribasic lead sulfate, dibasic lead phthalate, dibasic lead phosphite, tribasic lead maleate, basic lead carbonate, basic lead sulfate, basic lead sulfite, lead silicate, coprecipitated basic lead silicate-lead sulfate, coprecipitated lead orthosilicate-silica gel, lead chlorosilicate complex, lead chlorophthalic silicate, basic lead sulfophosphite complex, basic lead chlorosilicate-lead sulfate complex, basic thioester lead phthalate, lead tetrafumarate, lead salicylate, etc.), metallic soaps, organotins, organic compounds and polyhydric alcohols, composite stabilizers, etc.; examples of the plasticizer include, but are not limited to, phthalates, glutarates, adipates, azelates, sebacates, phosphates, stearates, laurates, citrates, oleates, trimellitates, epoxy derivatives, sulfonic acid derivatives, polyol derivatives, maleates, fumarates, itaconates, and the like; as the antistatic agent, there may be mentioned, but not limited to, stearamidopropyl dimethyl-beta-hydroxyethylammonium nitrate, (3-lauramidopropyl) trimethylammonium methyl sulfate, N-bis (2-hydroxyethyl) -N- (3 ' -dodecyloxy-2 ' -hydroxypropyl) methyl sulfate, N- (3-dodecyloxy-2-hydroxypropyl) ethanolamine, triethylmethylammonium methyl sulfate, stearamidopropyl dimethyl-beta-hydroxyethylammonium dihydrogenphosphate, alkylphosphate diethanolamine salt, N-bis (2-hydroxyethyl) alkylamine, N-hexadecylethylmorpholine ethyl sulfate, octadecyldimethylhydroxyethylquaternary ammonium nitrate, N-hexadecyl ethylmorpholine ethyl sulfate, octadecyldimethylhydroxyethylquaternary ammonium nitrate, N-dodecylamidopropyl dimethyl-beta-hydroxyethylammonium sulfate, N-dodecyloxy-2 ' -hydroxypropyl) methyl sulfate, N- (3-dodecyloxy-2-hydroxypropyl) methyl sulfate, HZ-1 antistatic agent, HKD-300, HKD-311, HBT-5 type antistatic agent, ECH type antistatic agent, etc.
<Polymerization inhibitor>
The polymerization inhibitor of the present invention is a component for adjusting the degree of reaction between the raw materials in the system, and acids or acyl chloride compounds can be selected as the polymerization inhibitor of the polyurethane mat of the present invention, including but not limited to hydrogen chloride gas, phosphoric acid, benzoyl chloride, adipoyl chloride, and the like. Phosphoric acid is preferably used.
<Diisocyanate>
The diisocyanate in the present invention is an isocyanate having a functionality of 2, and the specific type is not particularly limited, and various diisocyanates known to those skilled in the art, including aliphatic diisocyanate, alicyclic diisocyanate, and aromatic diisocyanate, can be used.
The aliphatic diisocyanate includes, but is not limited to, propylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, 1, 6-hexamethylene diisocyanate, 1, 2-propylene diisocyanate, 1, 2-butylene diisocyanate, 2, 3-butylene diisocyanate, 1, 3-butylene diisocyanate, 2,4, 4-or 2,2, 4-trimethyl 1, 6-hexamethylene diisocyanate, methyl 2, 6-diisocyanatohexanoate, and the like.
As the alicyclic diisocyanate, there may be mentioned, but not limited to, 1, 3-cyclopentane diisocyanate, 1, 4-cyclohexane diisocyanate, 1, 3-cyclohexane diisocyanate, 3-isocyanatomethyl-3, 5, 5-trimethylcyclohexane isocyanate (alias: isophorone diisocyanate), 4' -methylenebis (cyclohexyl isocyanate), methyl-2, 4-cyclohexane diisocyanate, methyl-2, 6-cyclohexane diisocyanate, 1, 3-bis (isocyanatomethyl) cyclohexane, 1, 3-bis (isocyanatoethyl) cyclohexane, 1, 4-bis (isocyanatoethyl) cyclohexane, 2, 5-or 2, 6-bis (isocyanatomethyl) Norbornane (NBDI), mixtures thereof and the like.
The aromatic diisocyanate includes, but is not limited to, 2, 4-tolylene diisocyanate and 2, 6-tolylene diisocyanate, and isomer mixtures of the tolylene diisocyanates, 4' -diphenylmethane diisocyanate, 2,4' -diphenylmethane diisocyanate and 2,2' -diphenylmethane diisocyanate, and arbitrary isomer mixtures of the diphenylmethane diisocyanates, tolylene diisocyanate, p-phenylene diisocyanate, naphthalene diisocyanate, and the like.
In some preferred embodiments, the diisocyanate comprises 4, 4-diphenylmethane diisocyanate and carbodiimide-modified liquefied MDI; the carbodiimide-modified liquefied MDI accounts for 8-20 wt% of the diisocyanate.
Preferably, MDI-100 is selected as the 4, 4-diphenylmethane diisocyanate; the carbodiimide modified liquefied MDI is 143L.
The carbodiimide-modified liquefied MDI is carbodiimide-uretonimine-modified 4,4' -diphenylmethane diisocyanate and has an OCN-R ═ N-C-N-R-NCO molecular structure. Due to the introduction of carbodiimide groups in the molecular structure, the crystallization caused by ordered accumulation of molecules is effectively avoided. The polyether polyol is in a liquid state at normal temperature, and the reaction activity is not reduced, so that the polyether polyol can be reacted with components such as polyether polyol in a system more stably and fully.
The A component and the B component of the raw materials for preparing the polyurethane cushion board comprise specially compounded polyols, the A component and the B component comprise tetrahydrofuran and modified polyether polyol with alkyl side chain tetrahydrofuran copolymerization modification, and meanwhile, enough caprolactone modified tetrahydrofuran polyol is added into the A component. In the process of completing the invention, the applicant finds that the mechanical strength such as tensile strength, compression deformation, aging resistance and the like of the polyurethane backing plate can be effectively improved and the cold resistance and the vibration reduction effect at low temperature can be obviously improved by compounding the polyol components in the component A and the component B. On one hand, the regularity of a polyurethane molecular chain segment structure is damaged by utilizing the difference between polyester and polyether structures, so that the crystallization is prevented from becoming brittle, and the polyurethane can still keep good elasticity at lower temperature; on the other hand, the high cohesive energy density of the polyester chain segment in the caprolactone modified polyether polyol structure is utilized to further improve the aggregation state and the density of the polyurethane molecular chain segment, so that the polyurethane molecular chain segment has higher strength and meets the heavy-load requirement. Meanwhile, on one hand, the lower activation energy of the alkyl side chain in the structure of the tetrahydrofuran copolymerization modified polyether polyol is utilized, so that the polyurethane molecular chain segment can still rotate or migrate the side group at lower temperature, and the stress applied from the outside is consumed by the sufficient extension of the side group, so that the polyurethane molecular chain segment still has better elasticity at very low temperature on the premise of not using components such as organosiloxane and the like. On the other hand, the introduction of the alkyl side chain can also damage the regularity of the chain segment, avoid the ordered arrangement of the polyurethane chain segment to form crystals, improve the elasticity of the base plate and contribute to avoiding the reduction of the elasticity of the base plate caused by the caprolactone chain segment.
In addition, the applicant found that the addition of the polyether polyol modified by copolymerization of tetrahydrofuran and the conventional tetrahydrofuran polyol having a specific molecular weight to both the a-component and the B-component contributes to the improvement of the mechanical properties and the shock absorption effect of the polyurethane mat. Sufficient tetrahydrofuran copolymerization modified polyether glycol is added into the component B to react with diisocyanate to form a prepolymer, and then the prepolymer reacts with the compound polyol and the chain extender in the component A to form long-chain polyurethane molecules. On one hand, after diisocyanate in the component B reacts with the polyol B, the content of NCO groups in the component B can be adjusted, so that the reaction between the diisocyanate and the polyol B and the chain extender in the component A are more uniform and stable, the foaming agent, the foam stabilizer and other components in the system can fully play a role, and a foam structure which is uniformly distributed and has a more stable size structure is obtained. On the other hand, when the polyol in the component B reacts with diisocyanate to form a urethane bond hard segment, a part of the tetrahydrofuran copolymerization modified polyether polyol soft segment connected with the polyol is ensured to have good flexibility, and under the synergistic action of the tetrahydrofuran copolymerization modified polyether polyol soft segment, the caprolactone modified polyether polyol in the component A and other polyether polyols, the good compactness and strength are ensured, and meanwhile, the temperature sensitivity of the obtained base plate at low temperature is effectively reduced, so that the base plate has a good vibration damping effect at low temperature.
The second aspect of the present invention provides a method for preparing the cold-resistant polyurethane mat as described above, which comprises the steps of:
(1) preparation of component A: adding the polyol A, the chain extender and the auxiliary agent into a container according to the proportion and mixing to obtain the component A;
(2) preparation of the component B: adding diisocyanate and a polymerization inhibitor into a reaction kettle according to a ratio, stirring and mixing, then adding polyol B, raising the temperature of the reaction kettle to 70-80 ℃, and reacting for 1.5-2.5 h to obtain a component B;
(3) curing and forming: preheating the component A and the component B, preheating the component A to 40-50 ℃, preheating the component B to 40-45 ℃, mixing the component A and the component B according to the proportion, injecting the mixture into a mold at 60-90 ℃, curing for 8-15 min, and discharging and post-treating to obtain the high-temperature-resistant high-strength high-toughness high-strength high-toughness high-.
Further, the preparation method of the cold-resistant polyurethane cushion plate comprises the following steps:
(1) preparation of component A: uniformly mixing modified polyether polyol A, modified polyether polyol B, polyether polyol, a chain extender, a catalyst, a foam stabilizer and a foaming agent in a container to obtain a component A of the polyol composition;
(2) preparation of the component B: adding MDI, carbodiimide modified liquefied MDI and a polymerization inhibitor into a reaction kettle, stirring and mixing uniformly, adding modified polyether polyol B and polyether polyol, slowly heating, reacting at 70-80 ℃ for 1.5-2.5 h, testing the NCO content, and when the NCO content reaches a required value, sealing and storing;
(3) curing and forming: respectively adding the component A and the component B into an A, B tank of a low-pressure casting machine for preheating, wherein the component A is preheated to 40-50 ℃, and the component B is preheated to 40-45 ℃; a, B components are mixed at a high speed according to a proportion, injected into a mold at the temperature of 60-90 ℃, cured for 8-15 minutes after the mold is closed, and placed at room temperature for more than 7 days after being demoulded to prepare the polyurethane elastic backing plate.
The third aspect of the present invention provides the use of the cold-resistant polyurethane slab as described above in the technical field of railway rails.
The present invention will be specifically described below by way of examples. It is to be noted that the following examples are only intended to illustrate the present invention and should not be construed as limiting the scope of the present invention.
Examples
Example 1: provided is a cold-resistant polyurethane mat which is prepared from a component A and a component B in a ratio of 100:91.8, and mixing the components according to the mass ratio;
the component A comprises the following raw materials in parts by weight:
Figure BDA0002532406620000131
the component B comprises the following raw materials in parts by weight:
Figure BDA0002532406620000132
the modified polyether polyol B has the following structural formula:
Figure BDA0002532406620000133
wherein R is methyl, m is 22, n is 5; the preparation method comprises the following steps:
cooling in an ice salt bath to-5 ℃ in a reaction kettle provided with an electric stirrer and a thermometer, sequentially adding a certain amount of tetrahydrofuran, 2-methyltetrahydrofuran, glycol and boron trifluoride diethyl etherate, quickly stirring, reacting for 3 hours to obtain crude polyether, and washing, neutralizing, filtering, vacuumizing and the like to obtain refined polyether polyol B. Wherein the molar ratio of tetrahydrofuran to 2-methyltetrahydrofuran is 22: 5.
the modified polyether polyol A is caprolactone modified polyether polyol and has the following structural formula:
Figure BDA0002532406620000141
wherein x + z is 9 and y is 14.
The polyether polyol A is polytetrahydrofuran polyol (the functionality is 2, and the molecular weight is 2000); the polyether polyol B is polytetrahydrofuran polyol (the functionality is 2, and the molecular weight is 2000); the catalyst is a mixture of Dabco33-LV (American air chemical industry) and T12 (mass ratio is 4: 1); the foam stabilizer is DABCO DC2585 (American air chemical); the foaming agent is water; the polymerization inhibitor is phosphoric acid; the carbodiimide-modified liquefied MDI was 143L.
The preparation method of the cold-resistant polyurethane cushion plate comprises the following steps:
(1) preparation of component A: 50 parts of the modified polyether polyol A (with the functionality of 2 and the molecular weight of about 2000), 40 parts of the modified polyether polyol B (with the functionality of 2 and the molecular weight of about 2000), 10 parts of polytetrahydrofuran polyol (with the functionality of 2 and the molecular weight of 2000), 15 parts of 1, 4-butanediol, 0.1 part of water, 1 part of foam stabilizer DABCO DC2585 (American air chemical industry), 0.08 part of Dabco33-LV (American air chemical industry) and 120.02 parts of T are uniformly mixed in a container and are sealed for storage, so that the component A is obtained.
(2) Preparation of the component B: adding 45 parts of MDI-100 and 10 parts of 143L into a reaction kettle, adding 0.01 part of polymerization inhibitor phosphoric acid, stirring and mixing uniformly, adding 35 parts of modified polyether polyol B (with the functionality of 2 and the molecular weight of about 2000) and 10 parts of polytetrahydrofuran polyol (with the functionality of 2 and the molecular weight of 2000), slowly heating, reacting for 2 hours at 75 +/-5 ℃, measuring the NCO content to be 17.85%, and sealing and storing to obtain the component B.
(3) Respectively adding the component A and the component B into an A, B tank of a low-pressure casting machine for preheating, wherein the component A is preheated to 50 ℃, and the component B is preheated to 40 ℃. And (3) mixing the component A and the component B at a high speed according to the mass ratio of 100:91.8, injecting into a mold at 70 ℃, curing for 10 minutes after mold closing, and standing at room temperature for 7 days after mold stripping to obtain the polyurethane elastic cushion plate.
Example 2: provided is a cold-resistant polyurethane mat which is prepared from a component A and a component B in a ratio of 100:107 in a mass ratio;
the component A comprises the following raw materials in parts by weight:
Figure BDA0002532406620000142
Figure BDA0002532406620000151
the component B comprises the following raw materials in parts by weight:
Figure BDA0002532406620000152
the modified polyether polyol B has the following structural formula:
Figure BDA0002532406620000153
wherein R is methyl, m is 22, n is 5; the preparation method comprises the following steps:
cooling in an ice salt bath to-5 ℃ in a reaction kettle provided with an electric stirrer and a thermometer, sequentially adding a certain amount of tetrahydrofuran, 2-methyltetrahydrofuran, glycol and boron trifluoride diethyl etherate, quickly stirring, reacting for 3 hours to obtain crude polyether, and washing, neutralizing, filtering, vacuumizing and the like to obtain refined polyether polyol B. Wherein the molar ratio of tetrahydrofuran to 2-methyltetrahydrofuran is 22: 5.
the modified polyether polyol A is caprolactone modified polyether polyol and has the following structural formula:
Figure BDA0002532406620000154
wherein x + z is 9 and y is 14.
The polyether polyol A is polytetrahydrofuran polyol (the functionality is 2, and the molecular weight is 3000); the polyether polyol B is polytetrahydrofuran polyol (the functionality is 2, and the molecular weight is 1000); the catalyst is a mixture of Dabco33-LV (American air chemical industry) and T12 (mass ratio is 5: 1); the foam stabilizer is DABCO DC2585 (American air chemical); the foaming agent is water; the polymerization inhibitor is phosphoric acid; the carbodiimide-modified liquefied MDI was 143L.
The preparation method of the cold-resistant polyurethane cushion plate comprises the following steps:
(1) preparation of component A: 60 parts of the modified polyether polyol A (with the functionality of 2 and the molecular weight of about 2000), 20 parts of the modified polyether polyol B (with the functionality of 2 and the molecular weight of about 2000), 20 parts of polytetrahydrofuran polyol (with the functionality of 2 and the molecular weight of 3000), 20 parts of 1, 4-butanediol, 0.16 part of water, 1.5 parts of foam stabilizer DABCO DC2585 (American air chemical industry), 0.1 part of Dabco33-LV (American air chemical industry) and 120.02 parts of T are uniformly mixed in a container and are sealed for storage, so that the component A is obtained.
(2) Preparation of the component B: putting 55 parts of MDI-100 and 5 parts of 143L into a reaction kettle, adding 0.01 part of polymerization inhibitor phosphoric acid, stirring and mixing uniformly, adding 25 parts of modified polyether polyol B (with the functionality of 2 and the molecular weight of about 2000) and 15 parts of polytetrahydrofuran polyol (with the functionality of 2 and the molecular weight of 1000), slowly heating, reacting for 2 hours at 75 +/-5 ℃, measuring the NCO content to be 17.64%, sealing and storing to obtain the component B.
(3) Respectively adding the component A and the component B into an A, B tank of a low-pressure casting machine for preheating, wherein the component A is preheated to 48 ℃, and the component B is preheated to 43 ℃. A, B components are mixed at a high speed according to the mass ratio of 100:107, injected into a mold at 80 ℃, cured for 12 minutes after mold closing, and placed at room temperature for 7 days after mold stripping to prepare the polyurethane elastic backing plate.
Example 3: provided is a cold-resistant polyurethane mat which is prepared from a component A and a component B in a ratio of 100:98 by mass ratio;
the component A comprises the following raw materials in parts by weight:
Figure BDA0002532406620000161
the component B comprises the following raw materials in parts by weight:
Figure BDA0002532406620000162
the modified polyether polyol B has the following structural formula:
Figure BDA0002532406620000171
wherein R is methyl, m is 22, n is 5; the preparation method comprises the following steps:
cooling in an ice salt bath to-5 ℃ in a reaction kettle provided with an electric stirrer and a thermometer, sequentially adding a certain amount of tetrahydrofuran, 2-methyltetrahydrofuran, glycol and boron trifluoride diethyl etherate, quickly stirring, reacting for 3 hours to obtain crude polyether, and washing, neutralizing, filtering, vacuumizing and the like to obtain refined polyether polyol B. Wherein the molar ratio of tetrahydrofuran to 2-methyltetrahydrofuran is 22: 5.
the modified polyether polyol A is caprolactone modified polyether polyol and has the following structural formula:
Figure BDA0002532406620000172
wherein x + z is 18, and y is 14.
The polyether polyol A is polytetrahydrofuran polyol (the functionality is 2, and the molecular weight is 3000); the polyether polyol B is polytetrahydrofuran polyol (the functionality is 2, and the molecular weight is 1000); the catalyst is a mixture of Dabco33-LV (American air chemical industry) and T12 (mass ratio is 4: 1); the foam stabilizer is DABCO DC2585 (American air chemical); the foaming agent is water; the polymerization inhibitor is phosphoric acid; the carbodiimide-modified liquefied MDI was 143L.
The preparation method of the cold-resistant polyurethane cushion plate comprises the following steps:
(1) preparation of component A: 54 parts of the modified polyether polyol A (with the functionality of 2 and the molecular weight of about 3000), 32 parts of the modified polyether polyol B (with the functionality of 2 and the molecular weight of about 2000), 14 parts of polytetrahydrofuran polyol (with the functionality of 2 and the molecular weight of 3000), 16 parts of 1, 4-butanediol, 0.15 part of water, 0.8 part of foam stabilizer DABCO DC2585 (American air chemical), 0.16 part of Dabco33-LV (American air chemical) and T120.04 parts are uniformly mixed in a container and are sealed for storage, so that the component A is obtained.
(2) Preparation of the component B: adding 52 parts of MDI-100 and 6 parts of 143L into a reaction kettle, adding 0.02 part of polymerization inhibitor phosphoric acid, stirring and mixing uniformly, adding 30 parts of modified polyether polyol B (with the functionality of 2 and the molecular weight of about 2000) and 12 parts of polytetrahydrofuran polyol (with the functionality of 2 and the molecular weight of 1000), slowly heating, reacting for 2 hours at 75 +/-5 ℃, measuring the NCO content to be 17%, and sealing and storing to obtain a component B.
(3) Respectively adding the component A and the component B into an A, B tank of a low-pressure casting machine for preheating, wherein the component A is preheated to 42 ℃, and the component B is preheated to 45 ℃. A, B components are mixed at high speed according to the mass ratio of 100:98, injected into a mold at 85 ℃, cured for 10 minutes after mold closing, and placed at room temperature for 7 days after mold stripping to prepare the polyurethane elastic cushion plate.
Example 4: provided is a cold-resistant polyurethane mat which is prepared from a component A and a component B in a ratio of 100:102 is prepared by mixing;
the component A comprises the following raw materials in parts by weight:
Figure BDA0002532406620000181
the component B comprises the following raw materials in parts by weight:
Figure BDA0002532406620000182
the modified polyether polyol B has the following structural formula:
Figure BDA0002532406620000183
wherein R is methyl, m is 22, n is 5; the preparation method comprises the following steps:
cooling in an ice salt bath to-5 ℃ in a reaction kettle provided with an electric stirrer and a thermometer, sequentially adding a certain amount of tetrahydrofuran, 2-methyltetrahydrofuran, glycol and boron trifluoride diethyl etherate, quickly stirring, reacting for 3 hours to obtain crude polyether, and washing, neutralizing, filtering, vacuumizing and the like to obtain refined polyether polyol B. Wherein the molar ratio of tetrahydrofuran to 2-methyltetrahydrofuran is 22: 5.
the modified polyether polyol A is caprolactone modified polyether polyol and has the following structural formula:
Figure BDA0002532406620000191
wherein x + z is 18, and y is 14.
The polyether polyol A is polytetrahydrofuran polyol (the functionality is 2, and the molecular weight is 2000); the polyether polyol B is polytetrahydrofuran polyol (the functionality is 2, and the molecular weight is 2000); the catalyst is a mixture of Dabco33-LV (American air chemical industry) and T12 (mass ratio is 4: 1); the foam stabilizer is DABCO DC2585 (American air chemical); the foaming agent is water; the polymerization inhibitor is phosphoric acid; the carbodiimide-modified liquefied MDI was 143L.
The preparation method of the cold-resistant polyurethane cushion plate comprises the following steps:
(1) preparation of component A: 56 parts of the modified polyether polyol A (with the functionality of 2 and the molecular weight of about 3000), 36 parts of the modified polyether polyol B (with the functionality of 2 and the molecular weight of about 2000), 8 parts of polytetrahydrofuran polyol (with the functionality of 2 and the molecular weight of 2000), 18 parts of 1, 4-butanediol, 0.12 part of water, 1 part of foam stabilizer DABCO DC2585 (American air chemical), 0.12 part of Dabco33-LV (American air chemical) and T120.03 parts are uniformly mixed in a container and are sealed for storage, so that the component A is obtained.
(2) Preparation of the component B: adding 50 parts of MDI-100 and 8 parts of 143L into a reaction kettle, adding 0.01 part of polymerization inhibitor phosphoric acid, stirring and mixing uniformly, adding 28 parts of modified polyether polyol B (with the functionality of 2 and the molecular weight of about 2000) and 14 parts of polytetrahydrofuran polyol (with the functionality of 2 and the molecular weight of 2000), slowly heating, reacting for 2 hours at 75 +/-5 ℃, measuring the NCO content to be 17.38%, sealing and storing to obtain the component B.
(3) Respectively adding the component A and the component B into an A, B tank of a low-pressure casting machine for preheating, wherein the component A is preheated to 42 ℃, and the component B is preheated to 45 ℃. A, B components are mixed at a high speed according to the mass ratio of 100:102, injected into a mold at 90 ℃, cured for 9 minutes after mold closing, and placed at room temperature for 7 days after mold stripping to prepare the polyurethane elastic cushion plate.
Comparative example 1: provided is a cold-resistant polyurethane mat which is prepared from a component A and a component B in a ratio of 100:96 in a mass ratio;
the component A comprises the following raw materials in parts by weight:
Figure BDA0002532406620000192
Figure BDA0002532406620000201
the component B comprises the following raw materials in parts by weight:
Figure BDA0002532406620000202
the modified polyether polyol B has the following structural formula:
Figure BDA0002532406620000203
wherein R is methyl, m is 22, n is 5; the preparation method comprises the following steps:
cooling in an ice salt bath to-5 ℃ in a reaction kettle provided with an electric stirrer and a thermometer, sequentially adding a certain amount of tetrahydrofuran, 2-methyltetrahydrofuran, glycol and boron trifluoride diethyl etherate, quickly stirring, reacting for 3 hours to obtain crude polyether, and washing, neutralizing, filtering, vacuumizing and the like to obtain refined polyether polyol B. Wherein the molar ratio of tetrahydrofuran to 2-methyltetrahydrofuran is 22: 5.
the polyether polyol A is polytetrahydrofuran polyol (the functionality is 2, and the molecular weight is 3000); the polyether polyol B is polytetrahydrofuran polyol (the functionality is 2, and the molecular weight is 1000); the catalyst is a mixture of Dabco33-LV (American air chemical industry) and T12 (mass ratio is 4: 1); the foam stabilizer is DABCO DC2585 (American air chemical); the foaming agent is water; the polymerization inhibitor is phosphoric acid; the carbodiimide-modified liquefied MDI was 143L.
The preparation method of the cold-resistant polyurethane cushion plate comprises the following steps:
(1) preparation of component A: 52 parts of the modified polyether polyol B (functionality of 2 and molecular weight of about 2000), 48 parts of polytetrahydrofuran polyol (functionality of 2 and molecular weight of 3000), 16 parts of 1, 4-butanediol, 0.15 part of water, 0.8 part of foam stabilizer DABCO DC2585 (American air chemical industry), 0.16 part of Dabco33-LV (American air chemical industry) and T120.04 parts are uniformly mixed in a container and sealed for storage, so that the component A is obtained.
(2) Preparation of the component B: adding 52 parts of MDI-100 and 6 parts of 143L into a reaction kettle, adding 0.02 part of polymerization inhibitor phosphoric acid, stirring and mixing uniformly, adding 30 parts of modified polyether polyol B (with the functionality of 2 and the molecular weight of about 2000) and 12 parts of polytetrahydrofuran polyol (with the functionality of 2 and the molecular weight of 1000), slowly heating, reacting for 2 hours at 75 +/-5 ℃, measuring the NCO content to be 17%, and sealing and storing to obtain a component B.
(3) Respectively adding the component A and the component B into an A, B tank of a low-pressure casting machine for preheating, wherein the component A is preheated to 45 ℃, and the component B is preheated to 45 ℃. A, B components are mixed at a high speed according to the mass ratio of 100:96, injected into a mold at 80 ℃, cured for 10 minutes after mold closing, and placed at room temperature for 7 days after mold stripping to prepare the polyurethane elastic cushion plate.
Comparative example 2: provided is a cold-resistant polyurethane mat which is prepared from a component A and a component B in a ratio of 100:98.8, and mixing the components according to the mass ratio;
the component A comprises the following raw materials in parts by weight:
Figure BDA0002532406620000211
the component B comprises the following raw materials in parts by weight:
Figure BDA0002532406620000212
the modified polyether polyol B has the following structural formula:
Figure BDA0002532406620000213
wherein R is methyl, m is 22, n is 5; the preparation method comprises the following steps:
cooling in an ice salt bath to-5 ℃ in a reaction kettle provided with an electric stirrer and a thermometer, sequentially adding a certain amount of tetrahydrofuran, 2-methyltetrahydrofuran, glycol and boron trifluoride diethyl etherate, quickly stirring, reacting for 3 hours to obtain crude polyether, and washing, neutralizing, filtering, vacuumizing and the like to obtain refined polyether polyol B. Wherein the molar ratio of tetrahydrofuran to 2-methyltetrahydrofuran is 22: 5.
the modified polyether polyol A is caprolactone modified polyether polyol and has the following structural formula:
Figure BDA0002532406620000221
wherein x + z is 9 and y is 14.
The polyether polyol A is polytetrahydrofuran polyol (the functionality is 2, and the molecular weight is 2000); the polyether polyol B is polytetrahydrofuran polyol (the functionality is 2, and the molecular weight is 1000); the catalyst is a mixture of Dabco33-LV (American air chemical industry) and T12 (mass ratio is 4: 1); the foam stabilizer is DABCO DC2585 (American air chemical); the foaming agent is water; the polymerization inhibitor is phosphoric acid; the carbodiimide-modified liquefied MDI was 143L.
The preparation method of the cold-resistant polyurethane cushion plate comprises the following steps:
(1) preparation of component A: 40 parts of the modified polyether polyol A (with the functionality of 2 and the molecular weight of about 2000), 60 parts of polytetrahydrofuran polyol (with the functionality of 2 and the molecular weight of 2000), 16 parts of 1, 4-butanediol, 0.12 part of water, 1 part of foam stabilizer DABCO DC2585 (American air chemical industry), 0.12 part of Dabco33-LV (American air chemical industry) and T120.03 parts are uniformly mixed in a container and sealed for storage, so that the component A is obtained.
(2) Preparation of the component B: adding 52 parts of MDI-100 and 6 parts of 143L into a reaction kettle, adding 0.02 part of polymerization inhibitor phosphoric acid, stirring and mixing uniformly, adding 30 parts of modified polyether polyol B (with the functionality of 2 and the molecular weight of about 2000) and 12 parts of polytetrahydrofuran polyol (with the functionality of 2 and the molecular weight of 1000), slowly heating, reacting for 2 hours at 75 +/-5 ℃, measuring the NCO content to be 17%, and sealing and storing to obtain a component B.
(3) Respectively adding the component A and the component B into an A, B tank of a low-pressure casting machine for preheating, wherein the component A is preheated to 45 ℃, and the component B is preheated to 45 ℃. A, B components are mixed at high speed according to the mass ratio of 100:98.8, then injected into a mold at 80 ℃, cured for 10 minutes after mold closing, and placed for 7 days at room temperature after mold stripping to prepare the polyurethane elastic backing plate.
Comparative example 3: provided is a cold-resistant polyurethane mat which is prepared from a component A and a component B in a ratio of 100:98 by mass ratio;
the component A comprises the following raw materials in parts by weight:
Figure BDA0002532406620000231
the component B comprises the following raw materials in parts by weight:
Figure BDA0002532406620000232
the modified polyether polyol B has the following structural formula:
Figure BDA0002532406620000233
wherein R is methyl, m is 22, n is 5; the preparation method comprises the following steps:
cooling in an ice salt bath to-5 ℃ in a reaction kettle provided with an electric stirrer and a thermometer, sequentially adding a certain amount of tetrahydrofuran, 2-methyltetrahydrofuran, glycol and boron trifluoride diethyl etherate, quickly stirring, reacting for 3 hours to obtain crude polyether, and washing, neutralizing, filtering, vacuumizing and the like to obtain refined polyether polyol B. Wherein the molar ratio of tetrahydrofuran to 2-methyltetrahydrofuran is 22: 5.
the modified polyether polyol A is hexaninAn ester-modified polyether polyol having the formula:
Figure BDA0002532406620000234
wherein x + z is 18, and y is 14.
The polyether polyol A is polytetrahydrofuran polyol (the functionality is 2, and the molecular weight is 3000); the polyether polyol B is polytetrahydrofuran polyol (the functionality is 2, and the molecular weight is 2000); the catalyst is a mixture of Dabco33-LV (American air chemical industry) and T12 (mass ratio is 4: 1); the foam stabilizer is DABCO DC2585 (American air chemical); the foaming agent is water; the polymerization inhibitor is phosphoric acid; the carbodiimide-modified liquefied MDI was 143L.
The preparation method of the cold-resistant polyurethane cushion plate comprises the following steps:
(1) preparation of component A: 54 parts of the modified polyether polyol A (with the functionality of 2 and the molecular weight of about 3000), 32 parts of the modified polyether polyol B (with the functionality of 2 and the molecular weight of about 2000), 14 parts of polytetrahydrofuran polyol (with the functionality of 2 and the molecular weight of 3000), 16 parts of 1, 4-butanediol, 0.15 part of water, 0.8 part of foam stabilizer DABCO DC2585 (American air chemical), 0.16 part of Dabco33-LV (American air chemical) and T120.04 parts are uniformly mixed in a container and are sealed for storage, so that the component A is obtained.
(2) Preparation of the component B: accurately weighing 50.8 parts of MDI-100 and 6 parts of liquefied MDI 143L, putting into a reaction kettle, adding 0.05 part of polymerization inhibitor phosphoric acid, stirring and mixing uniformly, adding 43.2 parts of polytetrahydrofuran polyol (the functionality is 2 and the molecular weight is 2000), slowly heating, reacting for 2 hours at 75 +/-5 ℃, measuring the NCO content to be 17%, sealing and storing to obtain the component B.
(3) Respectively adding the component A and the component B into an A, B tank of a low-pressure casting machine for preheating, wherein the component A is preheated to 42 ℃, and the component B is preheated to 45 ℃. A, B components are mixed at high speed according to the mass ratio of 100:98, injected into a mold at 85 ℃, cured for 10 minutes after mold closing, and placed at room temperature for 7 days after mold stripping to prepare the polyurethane elastic cushion plate.
The applicant tested the relevant properties of the above examples and comparative examples according to the standard on the 30T elastic VII type fastener for heavy haul railway of axle weight of China general railway company Standard Q/CR481-2015, and the results are shown in Table 1 below.
TABLE 1 Properties of materials of examples and comparative examples
Figure BDA0002532406620000241
Figure BDA0002532406620000251
Comparing the detection result with the performance index of the lower rail pad in the standard Q/CR 481-2015' 30T elastic VII-type fastener for heavy haul railway with axle load of China railway general company, the polyurethane elastic pad disclosed by the invention completely meets the performance index in the standard.
As can be seen from Table 1, the basic mechanical properties of the polyurethane elastic backing plate are equivalent to those of the comparative example, and compared with the comparative example, the polyurethane elastic backing plate has lower dynamic-static ratio and better vibration damping effect. In terms of cold resistance, the polyurethane elastic backing plate E 'of the present invention'-30℃/E′25℃The lower value shows that the dependence of the performance of the material on the temperature in the range of-30 ℃ to 25 ℃ is low, and the material has better stability. The polyurethane elastic cushion plate has lower low-temperature brittleness temperature, the static rigidity change rate at minus 30 ℃ is less than 15 percent, the use requirement is met, the low-temperature resistance is excellent, and the polyurethane elastic cushion plate is suitable for being used in an environment at minus 30 ℃.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in other forms, and any person skilled in the art may modify or change the technical content disclosed above into an equivalent embodiment with equivalent changes, but all those simple modifications, equivalent changes and modifications made on the above embodiment according to the technical spirit of the present invention still belong to the protection scope of the present invention.

Claims (10)

1. The cold-resistant polyurethane cushion plate is characterized by comprising a component A and a component B, wherein the weight ratio of the component A to the component B is 100: (91-107) by mass;
the component A comprises the following raw materials in parts by weight:
80-120 parts of polyol A
15-20 parts of chain extender
0.1-1.8 parts of an auxiliary agent;
the polyol A comprises polyether polyol A, modified polyether polyol B and modified polyether polyol A, and the weight ratio of the polyether polyol A to the modified polyether polyol B is 1: (2-4): (2.5-6);
the component B comprises the following raw materials in parts by weight:
35-50 parts of polyol B
50-65 parts of diisocyanate
0.01-0.02 part of polymerization inhibitor;
the polyol B comprises modified polyether polyol B and polyether polyol B; the modified polyether polyol B accounts for at least 60 wt% of the polyol B;
the modified polyether polyol A is caprolactone modified polyether polyol; the modified polyether polyol B is polyether polyol with a hydrocarbon side chain in the structure.
2. The cold-resistant polyurethane mat as recited in claim 1, wherein the modified polyether polyol B has the following structural formula:
Figure FDA0002532406610000011
wherein R is a hydrocarbyl selected from one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, ethenyl and propenyl; m and n are positive integers.
3. The cold-resistant polyurethane mat as recited in claim 2, wherein m and n in the structural formula of the modified polyether polyol B satisfy 15. ltoreq. m.ltoreq.25, and 2. ltoreq. n.ltoreq.8.
4. The cold-resistant polyurethane mat as recited in claim 2, wherein the modified polyether polyol B has an average functionality of 2 and a number average molecular weight of 1800 to 2500.
5. The cold-resistant polyurethane mat as recited in any one of claims 1 to 4, wherein the modified polyether polyol A has the following structural formula:
Figure FDA0002532406610000012
wherein x, y and z are positive integers, and satisfy x + z is more than or equal to 5 and less than or equal to 20, and y is more than or equal to 10 and less than or equal to 18.
6. The cold-resistant polyurethane mat as recited in claim 5, wherein x, y and z in the structural formula of the modified polyether polyol A satisfy x + z-9 or 18, and y-14.
7. The cold-resistant polyurethane mat as recited in claim 1, wherein the polyether polyol A and the polyether polyol B have a number average molecular weight of 1000 to 3000.
8. The cold-resistant polyurethane mat as recited in any one of claims 1 to 4, wherein the diisocyanate comprises 4, 4-diphenylmethane diisocyanate and carbodiimide-modified liquefied MDI; the carbodiimide-modified liquefied MDI accounts for 8-20 wt% of the diisocyanate.
9. The preparation method of the cold-resistant polyurethane mat as claimed in any one of claims 1 to 8, which is characterized by comprising the following steps:
(1) preparation of component A: adding the polyol A, the chain extender and the auxiliary agent into a container according to the proportion and mixing to obtain the component A;
(2) preparation of the component B: adding diisocyanate and a polymerization inhibitor into a reaction kettle according to a ratio, stirring and mixing, then adding polyol B, raising the temperature of the reaction kettle to 70-80 ℃, and reacting for 1.5-2.5 h to obtain a component B;
(3) curing and forming: preheating the component A and the component B, preheating the component A to 40-50 ℃, preheating the component B to 40-45 ℃, mixing the component A and the component B according to the proportion, injecting the mixture into a mold at 60-90 ℃, curing for 8-15 min, and discharging and post-treating to obtain the high-temperature-resistant high-strength high-toughness high-strength high-toughness high-.
10. The application of the cold-resistant polyurethane cushion plate of any one of claims 1 to 8 in the technical field of heavy haul railway tracks.
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