CN106832203B - Polyurethane resin for tire and preparation method thereof - Google Patents
Polyurethane resin for tire and preparation method thereof Download PDFInfo
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- CN106832203B CN106832203B CN201611272192.7A CN201611272192A CN106832203B CN 106832203 B CN106832203 B CN 106832203B CN 201611272192 A CN201611272192 A CN 201611272192A CN 106832203 B CN106832203 B CN 106832203B
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- 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
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- 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
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/40—High-molecular-weight compounds
- C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
- C08G18/632—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto polyethers
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- 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
- C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6511—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 compounds of group C08G18/3203
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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
- C08G18/65—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
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- 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
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- 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
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- 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
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
- C08J9/06—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 chemical blowing agent
- C08J9/08—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 chemical blowing agent developing carbon dioxide
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- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/02—CO2-releasing, e.g. NaHCO3 and citric acid
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- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
Abstract
The invention discloses polyurethane for a tire and a preparation method thereof, wherein the resin comprises a resin A component, a resin B1 component and a resin B2 component, wherein the resin A component comprises a polyol A, a cross-linking agent, a catalyst, a foaming agent and a foam stabilizer; the resin B1 comprises 1100 parts of isocyanate B, 110-40 parts of polyol B, 0.002-0.010 part of side reaction inhibitor, the resin B2 comprises 2100 parts of isocyanate B, 250-100 parts of polyol B, 0.002-0.010 part of side reaction inhibitor, the isocyanate B1 is diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, toluene diisocyanate or naphthalene diisocyanate, the polyol B1 is a polyester polyol of a polyadipate series, the isocyanate B2 is diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, toluene diisocyanate or naphthalene diisocyanate, and the polyol B2 is polyester polyol of a polyadipate series or polyester polyol of a polyterephthalate series. The invention can prepare polyurethane tires with different hardness.
Description
Technical Field
The invention relates to a polyurethane resin for a tire and a preparation method thereof.
Background
The full-name polyurethane is a general name of macromolecular compounds containing repeated urethane groups on the main chain, and is a macromolecular compound obtained by the interaction of binary or polybasic organic isocyanate and a polyol compound.
The resins used for the production of polyurethane tires are generally two-component raw materials-polyol mixtures and prepolymers (AB material/AB component or black and white material for short).
Polyurethane tires with different performance requirements need different types of AB materials for matching. For polyurethane tire manufacturing enterprises, raw materials of various types and specifications are required to be prepared to meet the production of tires with different performance requirements, and a proofing machine table and a material tank body are required to be cleaned when the raw materials are replaced every time, so that the production cost is high.
Disclosure of Invention
The invention aims to provide a polyurethane resin for a tire and a preparation method thereof, which aim to overcome the defects in the prior art.
The polyurethane resin for the tire comprises a resin A component, a resin B1 component and a resin B2 component;
the resin A component consists of the following components in parts by weight:
the resin B1 comprises the following components in parts by weight:
1100 parts of isocyanate B;
110-40 parts of a polyol B;
0.002-0.010 part of side reaction inhibitor;
the resin B2 comprises the following components in parts by weight:
2100 parts of isocyanate B;
250-100 parts of a polyol B;
0.002-0.010 part of side reaction inhibitor.
Preferably:
the resin A component consists of the following components in parts by weight:
preferably:
the resin B1 comprises the following components in parts by weight:
1100 parts of isocyanate B;
112-20 parts of a polyol B;
0.002-0.010 part of side reaction inhibitor;
preferably:
the resin B2 comprises the following components in parts by weight:
2100 parts of isocyanate B;
250-90 parts of a polyol B;
0.002-0.010 part of side reaction inhibitor.
The polymeric polyol A in the resin A component is a mixture of polyether polyol and polymer polyol, and the mass ratio of the polyether polyol to the polymer polyol is 1: 1-4: 1.
The polyether polyol is polyoxyethylene-propylene oxide triol with the number average molecular weight of 6000-10000;
the polymer polyol is styrene or acrylonitrile graft copolymerization ethylene oxide-propylene oxide trihydric alcohol with the number average molecular weight of 6000-10000, and the solid content is 40-50%.
The cross-linking agent is one or more of ethylene glycol, 1, 4-butanediol, 1, 3-propanediol and 1, 6-butanediol.
The catalyst is a mixture of a triethylene diamine ethylene glycol solution and a solution prepared from 70 wt% of bis (dimethylaminoethyl) ether and 30 wt% of dipropylene glycol, and the mass ratio of the triethylene diamine ethylene glycol solution to the solution prepared from 70 wt% of bis (dimethylaminoethyl) ether and 30 wt% of dipropylene glycol is 1: 4-1: 1.
The foaming agent is water;
the foam stabilizer is an organic silicon foam stabilizer;
the isocyanate B1 in the component B1 of the resin is one or more of diphenylmethane diisocyanate, carbodiimide modified diphenylmethane diisocyanate, toluene diisocyanate or naphthalene diisocyanate;
in the component B1, the polyester polyol B1 is poly adipic acid polyester polyol, preferably poly adipic acid polyester glycol prepared by condensation copolymerization of adipic acid and one or a mixture of more of ethylene glycol, diethylene glycol and 1, 4-butanediol, and the number average molecular weight is 1000-3000;
the side reaction inhibitor in the component B1 is phosphoric acid;
the isocyanate B2 in the component B2 of the resin is one or more of diphenylmethane diisocyanate, carbodiimide modified diphenylmethane diisocyanate, toluene diisocyanate or naphthalene diisocyanate;
the polyester polyol B2 in the component B2 is poly adipic acid polyester polyol or poly terephthalic acid polyester polyol, preferably one or a mixture of more of ethylene glycol, diethylene glycol and 1, 4-butanediol, and adipic acid or terephthalic acid are subjected to condensation copolymerization to form the polyester polyol B2, and the number average molecular weight is 1000-3000;
the side reaction inhibitor in the component of the resin B2 is phosphoric acid.
The preparation method of the polyurethane resin for the tire comprises the following steps:
(1) reacting a polyol A, a cross-linking agent, a catalyst, a foaming agent and a foam stabilizer at 50-60 ℃ for 1.5-2.5 h, cooling to 40-45 ℃, and mixing for 1.0-1.5 h to obtain a polyurethane resin A component;
(2) reacting isocyanate B1, polyol B1 and a side reaction inhibitor at 65-75 ℃ for 2-3 h to obtain a polyurethane resin B1 component;
(3) and (3) reacting the isocyanate B2, the polyol B2 and the side reaction inhibitor at 65-75 ℃ for 2-3 h to obtain the polyurethane resin B2 component.
The polyurethane resin for a tire, the method for preparing a polyurethane tire, comprises the steps of:
mixing a polyurethane resin A component with the temperature of 35-45 ℃, a polyurethane resin B1 component with the temperature of 35-45 ℃ and a polyurethane resin B2 component with the temperature of 35-45 ℃ in a casting machine, injecting into a mold with the temperature of 35-45 ℃ for reaction for 3-5 min for molding, demolding, standing in a natural environment for 2 days, and curing to obtain the polyurethane tire.
The mass ratio of the polyurethane resin B1 component to the polyurethane resin B2 component is 1: 9-9: 1;
the ratio of the number of moles of active hydrogen of the A component to the number of moles of isocyanate groups of the B1 component and the B2 component together was 1: 1.
The invention has the beneficial effects that:
the polyurethane resin for the tire comprises a resin A component, a resin B1 component and a resin B2 component, and polyurethane tires with different properties can be prepared by adjusting the mass ratio of the B1 component to the B2 component. Compared with the common two-component polyurethane resin, the product of the invention does not need to prepare various different raw materials by manufacturers in the process of producing the polyurethane tire, and only needs to adjust the proportion of the components B1 and B2 when producing the tire with different requirements, thereby saving the production cost, reducing the resource waste and improving the production efficiency, and the polyurethane resin chain segments formed by the mixing reaction of the two prepolymer components (B1 and B2) with different proportions and the component A are more regular and ordered, and the performance of the prepared polyurethane tire is better. The polyurethane tire produced by the invention has wide adjustable range of hardness, good physical property, low compression deformation rate, low cost and high production efficiency, and is more suitable for continuous production operation.
Detailed Description
The following examples are given to illustrate the present invention and should not be construed as limiting the scope of the present invention. The implementation conditions used in the examples may be modified or adjusted according to the conditions and requirements of the particular manufacturer.
Example 1
221.7kg of polyoxyethylene-propylene oxide triol (number average molecular weight is 6000), 55.4kg of styrene graft copolymerization ethylene oxide-propylene oxide triol (number average molecular weight is 6000), 1.39kg of ethylene glycol, 0.22kg of ethylene glycol solution of triethylene diamine, 0.89kg of solution prepared by 70 wt% of bis (dimethylaminoethyl) ether and 30 wt% of dipropylene glycol, 2.77kg of water and 0.28kg of silicone foam stabilizer react at 50 ℃ for 2.5h, then the temperature is reduced to 40 ℃, and the mixture is mixed for 1.5h to obtain the polyurethane resin A component.
45.4kg of diphenylmethane diisocyanate, 15.1kg of carbodiimide-modified diphenylmethane diisocyanate, 0.76kg of polyethylene glycol butanediol adipate glycol (with the number average molecular weight of 1000) and 0.0015kg of phosphoric acid are reacted for 3 hours at 65 ℃ to obtain a polyurethane resin B1 component.
4.54kg of diphenylmethane diisocyanate, 2.28kg of polyethylene terephthalate glycol (number average molecular weight 1000) and 0.0002kg of phosphoric acid were reacted at 65 ℃ for 3 hours to obtain a polyurethane resin B2 component.
Mixing the polyurethane resin A component with the temperature of 35 ℃, the polyurethane resin B1 component with the temperature of 35 ℃ and the polyurethane resin B2 component with the temperature of 35 ℃ in a casting machine, injecting into a mold with the temperature of 35 ℃ for reaction for 5min for molding, demolding, standing in a natural environment for 2 days, and curing to obtain the polyurethane tire.
Example 2
221.7kg of polyoxyethylene-propylene oxide triol (number average molecular weight is 6000), 55.4kg of styrene graft copolymerization ethylene oxide-propylene oxide triol (number average molecular weight is 6000), 1.39kg of ethylene glycol, 0.22kg of ethylene glycol solution of triethylene diamine, 0.89kg of solution prepared by 70 wt% of bis (dimethylaminoethyl) ether and 30 wt% of dipropylene glycol, 2.77kg of water and 0.28kg of silicone foam stabilizer react at 50 ℃ for 2.5h, then the temperature is reduced to 40 ℃, and the mixture is mixed for 1.5h to obtain the polyurethane resin A component.
7.46kg of diphenylmethane diisocyanate, 2.48kg of carbodiimide-modified diphenylmethane diisocyanate, 0.12kg of polyethylene glycol butanediol adipate glycol (number average molecular weight is 1000) and 0.00032kg of phosphoric acid are reacted for 3 hours at 65 ℃ to obtain a component B1 of polyurethane resin.
60.4kg of diphenylmethane diisocyanate, 30.2kg of polyethylene terephthalate glycol (number average molecular weight of 1000) and 0.002kg of phosphoric acid were reacted at 65 ℃ for 3 hours to obtain a component B2 of polyurethane resin.
Mixing the polyurethane resin A component with the temperature of 35 ℃, the polyurethane resin B1 component with the temperature of 35 ℃ and the polyurethane resin B2 component with the temperature of 35 ℃ in a casting machine, injecting into a mold with the temperature of 35 ℃ for reaction for 5min for molding, demolding, standing in a natural environment for 2 days, and curing to obtain the polyurethane tire.
Example 3
101.0kg of polyoxyethylene-propylene oxide triol (with the number average molecular weight of 10000), 101.0kg of acrylonitrile graft copolymerization ethylene oxide-propylene oxide triol (with the number average molecular weight of 10000), 2.02kg of ethylene glycol, 1.01kg of ethylene glycol solution of triethylene diamine, 1.01kg of solution prepared by 70 weight percent of bis (dimethylaminoethyl) ether and 30 weight percent of dipropylene glycol, 3.03kg of water and 4.04kg of organic silicon foam stabilizer react at 60 ℃ for 1.5h, then the temperature is reduced to 45 ℃, and the mixture is mixed for 1.0h to obtain the component A of the polyurethane resin.
48.3g of diphenylmethane diisocyanate, 12.1kg of carbodiimide-modified diphenylmethane diisocyanate, 12.1kg of polyethylene glycol butanediol adipate glycol (number average molecular weight of 2000) and 0.002kg of phosphoric acid were reacted at 75 ℃ for 2 hours to obtain a component B1 of polyurethane resin.
4.34kg of diphenylmethane diisocyanate, 3.74kg of polydiethylene glycol adipate glycol (number average molecular weight 2000) and 0.0002kg of phosphoric acid were reacted at 75 ℃ for 2 hours to obtain a component B2 of polyurethane resin.
Mixing the component A of polyurethane resin at the temperature of 45 ℃, the component B1 of polyurethane resin at the temperature of 45 ℃ and the component B2 of polyurethane resin at the temperature of 45 ℃ in a casting machine, injecting into a 45 ℃ box bubble for reaction for 3min for molding, demolding, standing for 2 days in a natural environment for curing, and obtaining the polyurethane tire.
Example 4
101.0kg of polyoxyethylene-propylene oxide triol (with the number average molecular weight of 10000), 101.0kg of acrylonitrile graft copolymerization ethylene oxide-propylene oxide triol (with the number average molecular weight of 10000), 2.02kg of ethylene glycol, 1.01kg of ethylene glycol solution of triethylene diamine, 1.01kg of solution prepared by 70 weight percent of bis (dimethylaminoethyl) ether and 30 weight percent of dipropylene glycol, 3.03kg of water and 4.04kg of organic silicon foam stabilizer react at 60 ℃ for 1.5h, then the temperature is reduced to 45 ℃, and the mixture is mixed for 1.0h to obtain the component A of the polyurethane resin.
8.01kg of diphenylmethane diisocyanate, 2.00kg of carbodiimide-modified diphenylmethane diisocyanate, 2.00kg of polyethylene glycol butanediol adipate glycol (number average molecular weight of 2000) and 0.002kg of phosphoric acid were reacted at 75 ℃ for 2 hours to obtain a component B of a polyurethane resin.
57.7kg of diphenylmethane diisocyanate, 50.1kg of polydiethylene glycol adipate (number average molecular weight 2000) and 0.009kg of phosphoric acid were reacted at 75 ℃ for 2 hours to obtain a component B2 of polyurethane resin.
Mixing the polyurethane resin A component with the temperature of 45 ℃, the polyurethane resin B1 component with the temperature of 45 ℃ and the polyurethane resin B2 component with the temperature of 45 ℃ in a casting machine, injecting into a 45 ℃ box bubble for reaction for 3min for molding, demolding, standing in a natural environment for 2 days, and curing to obtain the polyurethane tire.
Example 5
290.1kg of polyoxyethylene-propylene oxide triol (the number average molecular weight is 9000), 145.1kg of styrene graft copolymerization ethylene oxide-propylene oxide triol (the number average molecular weight is 9000), 21.8kg of ethylene glycol, 1.31kg of ethylene glycol solution of triethylene diamine, 2.61kg of solution prepared by 70 wt% of bis (dimethylaminoethyl) ether and 30 wt% of dipropylene glycol, 5.66kg of water and 4.35kg of organosilicon foam stabilizer react at 60 ℃ for 1.5h, then the temperature is reduced to 45 ℃, and the mixture is mixed for 1.0h to obtain the component A of the polyurethane resin.
83.6kg of diphenylmethane diisocyanate, 11.5kg of polyethylene glycol adipate glycol (number average molecular weight of 3000) and 0.008kg of phosphoric acid are reacted at 65 ℃ for 3 hours to obtain a component B of polyurethane resin.
28.5kg of diphenylmethane diisocyanate, 23.7kg of carbodiimide-modified diphenylmethane diisocyanate, 43.0kg of polybutylene adipate glycol (number average molecular weight of 3000) and 0.008kg of phosphoric acid were reacted at 65 ℃ for 3 hours to obtain a component B2 of polyurethane resin.
Mixing the polyurethane resin A component with the temperature of 45 ℃, the polyurethane resin B1 component with the temperature of 45 ℃ and the polyurethane resin B2 component with the temperature of 45 ℃ in a casting machine, injecting into a 45 ℃ box bubble for reaction for 3min for molding, demolding, standing in a natural environment for 2 days, and curing to obtain the polyurethane tire.
Example 6
200.0kg of polyoxyethylene-propylene oxide triol (number average molecular weight 8000), 160.0kg of styrene graft copolymerization ethylene oxide-propylene oxide triol (number average molecular weight 8000), 36.0kg of 1, 4-butanediol, 1.08kg of ethylene glycol solution of triethylene diamine, 2.16kg of solution prepared by 70 wt% of bis (dimethylaminoethyl) ether and 30 wt% of dipropylene glycol, 4.32kg of water and 4.68kg of organosilicon foam stabilizer react at 50 ℃ for 2.5h, then the temperature is reduced to 40 ℃, and the mixture is mixed for 1.5h to obtain the polyurethane resin A component.
172.5kg of diphenylmethane diisocyanate, 10.05kg of polyethylene glycol adipate glycol (number average molecular weight of 2000) and 0.010kg of phosphoric acid were reacted at 75 ℃ for 2 hours to obtain a polyurethane resin component B.
20.3kg of diphenylmethane diisocyanate, 14.2kg of carbodiimide-modified diphenylmethane diisocyanate, 26.4kg of polyethylene glycol terephthalate (number average molecular weight 2000) and 0.005kg of phosphoric acid were reacted at 75 ℃ for 2 hours to obtain a polyurethane resin B2 component.
Mixing the polyurethane resin A component with the temperature of 35 ℃, the polyurethane resin B1 component with the temperature of 35 ℃ and the polyurethane resin B2 component with the temperature of 35 ℃ in a casting machine, injecting into a 35 ℃ box bubble for reaction for 5min for molding, demolding, standing in a natural environment for 2 days, and curing to obtain the polyurethane tire.
Comparative example 1
221.7kg of polyoxyethylene-propylene oxide triol (number average molecular weight is 6000), 55.4kg of styrene graft copolymerization ethylene oxide-propylene oxide triol (number average molecular weight is 6000), 1.39kg of ethylene glycol, 0.22kg of ethylene glycol solution of triethylene diamine, 0.89kg of solution prepared by 70 wt% of bis (dimethylaminoethyl) ether and 30 wt% of dipropylene glycol, 2.77kg of water and 0.28kg of silicone foam stabilizer react at 50 ℃ for 2.5h, then the temperature is reduced to 40 ℃, and the mixture is mixed for 1.5h to obtain the polyurethane resin A component.
49.94kg of diphenylmethane diisocyanate, 15.1kg of carbodiimide-modified diphenylmethane diisocyanate, 0.76kg of polyethylene glycol butanediol adipate glycol (number average molecular weight of 1000), 2.28kg of polyethylene glycol terephthalate glycol (number average molecular weight of 1000) and 0.0017kg of phosphoric acid are reacted for 3 hours at 65 ℃, so that the component B of the polyurethane resin is obtained.
Mixing the polyurethane resin A component with the temperature of 35 ℃ and the polyurethane resin B component with the temperature of 35 ℃ in a casting machine, injecting into a 35 ℃ box bubble for reaction for 5min for molding, demolding, standing for 2 days in a natural environment for curing to obtain the polyurethane tire. Comparative example 2
101.0kg of polyoxyethylene-propylene oxide triol (with the number average molecular weight of 10000), 101.0kg of acrylonitrile graft copolymerization ethylene oxide-propylene oxide triol (with the number average molecular weight of 10000), 2.02kg of ethylene glycol, 1.01kg of ethylene glycol solution of triethylene diamine, 1.01kg of solution prepared by 70 weight percent of bis (dimethylaminoethyl) ether and 30 weight percent of dipropylene glycol, 3.03kg of water and 4.04kg of organic silicon foam stabilizer react at 60 ℃ for 1.5h, then the temperature is reduced to 45 ℃, and the mixture is mixed for 1.0h to obtain the component A of the polyurethane resin.
52.64kg of diphenylmethane diisocyanate, 12.1kg of carbodiimide modified diphenylmethane diisocyanate, 12.1kg of polyethylene glycol butanediol adipate glycol (number average molecular weight of 2000), 4.34kg of polyethylene glycol adipate glycol (number average molecular weight of 2000) and 0.0022kg of phosphoric acid are reacted for 2 hours at 75 ℃ to obtain the component B of the polyurethane resin.
Mixing the polyurethane resin A component with the temperature of 45 ℃ and the polyurethane resin B component with the temperature of 45 ℃ in a casting machine, injecting into a 45 ℃ box bubble for reaction for 3min for molding, demolding, standing for 2 days in a natural environment for curing to obtain the polyurethane tire.
The polyurethane tires prepared in examples 1 to 4 and comparative examples 1 to 2 were tested for each property as follows:
TABLE I
From the embodiment 1, the embodiment 2, the embodiment 3 and the embodiment 4, on the premise that the component A of the polyurethane resin is not changed, the polyurethane tires with different hardness, different physical properties and different compression deformation ratios can be prepared by simply adjusting the proportion of the component B1 to the component B2, so that the production efficiency is improved, and meanwhile, the energy consumption and the production cost are saved. By comparing example 1 with comparative example 1, and example 3 with comparative example 2, it is understood that a polyurethane tire having a higher hardness and a lower compression set, or having a lower hardness and a lower compression set can be more easily obtained by using the polyurethane resin for a tire of the present invention.
Although the embodiments of the present invention have been described in detail, the technical aspects of the present invention are not limited to the embodiments, and equivalent changes or modifications made to the contents of the claims of the present invention should fall within the technical scope of the present invention without departing from the spirit and the spirit of the present invention.
Claims (8)
1. A polyurethane resin for a tire characterized by comprising a resin a component, a resin B1 component and a resin B2 component;
the resin A component comprises the following components in parts by weight:
the polymeric polyol A is a mixture of polyether polyol and polymer polyol; the mass ratio of the polyether polyol to the polymer polyol is 1: 1-4: 1;
the polyether polyol is polyoxyethylene-propylene oxide triol with the number average molecular weight of 6000-10000;
the polymer polyol is styrene or acrylonitrile graft copolymerization ethylene oxide-propylene oxide trihydric alcohol with the number average molecular weight of 6000-10000, and the solid content is 40-50%;
the cross-linking agent is one or more of ethylene glycol, 1, 4-butanediol, 1, 3-propanediol and 1, 6-butanediol;
the resin B1 component comprises the following components in parts by weight:
1100 parts of isocyanate B;
110-40 parts of a polyol B;
0.002-0.010 part of side reaction inhibitor;
the resin B2 comprises the following components in parts by weight:
2100 parts of isocyanate B;
250-100 parts of a polyol B;
0.002-0.010 part of side reaction inhibitor;
the isocyanate B1 is selected from one or more of diphenylmethane diisocyanate, carbodiimide modified diphenylmethane diisocyanate, toluene diisocyanate or naphthalene diisocyanate;
the polyol B1 is formed by condensation copolymerization of one or a mixture of more of ethylene glycol, diethylene glycol and 1, 4-butanediol and adipic acid, and the number average molecular weight is 1000-3000;
the isocyanate B2 is one or more of diphenylmethane diisocyanate, carbodiimide modified diphenylmethane diisocyanate, toluene diisocyanate or naphthalene diisocyanate;
the polyol B2 is prepared by condensation copolymerization of one or a mixture of more of ethylene glycol, diethylene glycol and 1, 4-butanediol and adipic acid or terephthalic acid, and has a number average molecular weight of 1000-3000.
2. The polyurethane resin for a tire as claimed in claim 1, wherein the resin a component is composed of:
the resin A component consists of the following components in parts by weight:
3. the polyurethane resin for a tire as claimed in claim 1, wherein the resin B1 component is composed of the following components in parts by weight:
1100 parts of isocyanate B;
112-20 parts of a polyol B;
0.002-0.010 part of side reaction inhibitor;
the resin B2 comprises the following components in parts by weight:
2100 parts of isocyanate B;
250-90 parts of a polyol B;
0.002-0.010 part of side reaction inhibitor;
the isocyanate B1 is selected from one or more of diphenylmethane diisocyanate, carbodiimide modified diphenylmethane diisocyanate, toluene diisocyanate or naphthalene diisocyanate;
the isocyanate B2 is one or more of diphenylmethane diisocyanate, carbodiimide modified diphenylmethane diisocyanate, toluene diisocyanate or naphthalene diisocyanate;
the side reaction inhibitor is phosphoric acid.
4. The polyurethane resin for a tire according to claim 1,
the catalyst is a mixture of a triethylene diamine ethylene glycol solution and a solution prepared from 70 wt% of bis (dimethylaminoethyl) ether and 30 wt% of dipropylene glycol, and the mass ratio of the triethylene diamine ethylene glycol solution to the solution prepared from 70 wt% of bis (dimethylaminoethyl) ether and 30 wt% of dipropylene glycol is 1: 4-1: 1;
the foaming agent is water;
the foam stabilizer is an organic silicon foam stabilizer.
5. The polyurethane resin for a tire as claimed in claim 1, wherein the mass ratio of the polyurethane resin B1 component to the polyurethane resin B2 component is 1: 9 to 9: 1; the ratio of the number of moles of active hydrogen of the A component to the number of moles of isocyanate groups of the B1 component and the B2 component together was 1: 1.
6. A method for producing a polyurethane resin for a tire as claimed in any one of claims 1 to 5, characterized by comprising the steps of:
(1) reacting a polyol A, a cross-linking agent, a catalyst, a foaming agent and a foam stabilizer at 50-60 ℃ for 1.5-2.5 h, cooling to 40-45 ℃, and mixing for 1.0-1.5 h to obtain a polyurethane resin A component;
(2) reacting isocyanate B1, polyol B1 and a side reaction inhibitor at 65-75 ℃ for 2-3 h to obtain a polyurethane resin B1 component;
(3) and (3) reacting the isocyanate B2, the polyol B2 and the side reaction inhibitor at 65-75 ℃ for 2-3 h to obtain the polyurethane resin B2 component.
7. Use of the polyurethane resin for a tire according to any one of claims 1 to 5 for producing a polyurethane tire.
8. Use according to claim 7, characterized in that the method of application comprises the steps of: mixing a polyurethane resin A component with the temperature of 35-45 ℃, a polyurethane resin B1 component with the temperature of 35-45 ℃ and a polyurethane resin B2 component with the temperature of 35-45 ℃ in a casting machine, injecting into a mold with the temperature of 35-45 ℃ for reaction for 3-5 min for molding, demolding, standing in a natural environment for 2 days, and curing to obtain the polyurethane tire.
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| CN108973534A (en) * | 2018-07-20 | 2018-12-11 | 滁州市玉林聚氨酯有限公司 | A kind of suction ground antiskid polyurethane tire and preparation method thereof |
| CN109265974B (en) * | 2018-08-02 | 2021-03-26 | 江苏唯源橡塑制品有限公司 | Water-resistant high-temperature-resistant PU tire for wheelchair and preparation method thereof |
| CN111169060A (en) * | 2018-11-12 | 2020-05-19 | 广州科济化学材料有限公司 | Manufacturing process for pouring polyurethane foaming inflation-free wheel in outer tire |
| CN110372842A (en) * | 2019-07-30 | 2019-10-25 | 青岛双星轮胎工业有限公司 | Non-inflatable tyre formula with fluorescent effect and preparation method thereof |
| CN110746562A (en) * | 2019-11-11 | 2020-02-04 | 湖北可兴鞋业有限公司 | Synthetic rubber and preparation method thereof |
| CN111518381A (en) * | 2020-05-29 | 2020-08-11 | 叶正芬 | Two-component polyurethane stock solution for engineering tires and preparation method thereof |
| CN113512286A (en) * | 2021-04-25 | 2021-10-19 | 苏州频发机电科技有限公司 | High-wear-resistance and anti-aging polyurethane tire |
| CN113292764B (en) * | 2021-05-07 | 2023-03-31 | 湖北祥源新材科技股份有限公司 | Compression-resistant polyurethane foam and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103030781A (en) * | 2011-09-29 | 2013-04-10 | 拜耳材料科技(中国)有限公司 | Microcellular polyurethane elastomer, its preparation method and application |
| CN105001394A (en) * | 2015-06-29 | 2015-10-28 | 山东一诺威聚氨酯股份有限公司 | Self-skinning compound material for heat-resistant polyurethane foaming tyre and preparation method thereof |
| CN105949434A (en) * | 2016-06-16 | 2016-09-21 | 旭川化学（昆山）有限公司 | B component isocyanate prepolymer and polyurethane double components for preparing microcellular polyurethane elastomer and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103030781A (en) * | 2011-09-29 | 2013-04-10 | 拜耳材料科技(中国)有限公司 | Microcellular polyurethane elastomer, its preparation method and application |
| CN105001394A (en) * | 2015-06-29 | 2015-10-28 | 山东一诺威聚氨酯股份有限公司 | Self-skinning compound material for heat-resistant polyurethane foaming tyre and preparation method thereof |
| CN105949434A (en) * | 2016-06-16 | 2016-09-21 | 旭川化学（昆山）有限公司 | B component isocyanate prepolymer and polyurethane double components for preparing microcellular polyurethane elastomer and application |
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