CN106832203A - Tire polyurethane resin and preparation method - Google Patents
Tire polyurethane resin and preparation method Download PDFInfo
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- CN106832203A CN106832203A CN201611272192.7A CN201611272192A CN106832203A CN 106832203 A CN106832203 A CN 106832203A CN 201611272192 A CN201611272192 A CN 201611272192A CN 106832203 A CN106832203 A CN 106832203A
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- polyvalent alcohol
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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
- C08G18/28—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
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
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- 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
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- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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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
- C08G18/28—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
- C08G18/4072—Mixtures of compounds of group C08G18/63 with other macromolecular compounds
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- 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
- C08G18/42—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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- 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
- C08G18/63—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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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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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- C08G18/00—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
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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
- C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
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- 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
- C08G18/74—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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- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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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- 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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/02—CO2-releasing, e.g. NaHCO3 and citric acid
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Engineering & Computer Science (AREA)
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- Polyurethanes Or Polyureas (AREA)
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Abstract
The invention discloses a kind of tire polyurethane and preparation method, the resin includes Resin A component, the component of resin B 1 and the component of resin B 2, and Resin A component includes polyvalent alcohol A, crosslinking agent, catalyst, foaming agent and foam stabilizer；Resin B 1 includes 100 parts of isocyanates B1, 10~40 parts of polyvalent alcohol B1, 0.002~0.010 part of side reaction inhibitor, resin B 2 includes 100 parts of isocyanates B2, 50~100 parts of polyvalent alcohol B2, 0.002~0.010 part of side reaction inhibitor, isocyanates B1 is methyl diphenylene diisocyanate, carbodiimide modified diphenylmethane diisocyanate, toluene di-isocyanate(TDI) or naphthalene diisocyanate, polyvalent alcohol B1 is polyadipate system PEPA, isocyanates B2 is methyl diphenylene diisocyanate, carbodiimide modified diphenylmethane diisocyanate, toluene di-isocyanate(TDI) or naphthalene diisocyanate, polyvalent alcohol B2 is polyadipate system PEPA or poly terephthalic acid system PEPA.The present invention can be obtained different hardness pu tire.
Description
Technical field
The present invention relates to a kind of tire polyurethane resin and preparation method.
Background technology
The full name polyurethanes of polyurethane, is to contain the macromolecular compound for repeating carbamate groups on main chain
It is referred to as, is the macromolecular compound as obtained from binary or polynary organic isocyanate interact with polyol compound.
Resin generally double-component raw material for producing pu tire --- polyol blends and prepolymer are (referred to as
AB material/AB components or black and white material).
The pu tire of different performance requirement needs different types of AB material to use cooperatively.Produced for pu tire
Enterprise is, it is necessary to be equipped with the raw material of various different model different sizes to adapt to the production of the tire of different performance requirement, and often
Secondary replacing raw material needs cleaning to draw a design board and material tank body, and production cost is high.
The content of the invention
It is an object of the invention to provide a kind of tire polyurethane resin and preparation method, to overcome prior art to exist
Defect.
Tire polyurethane resin of the present invention, comprising Resin A component, the component of resin B 1 and the component of resin B 2；
The Resin A component is made up of the component of following parts by weight：
The component of the resin B 1 is made up of the component of following parts by weight：
100 parts of isocyanates B1；
10~40 parts of polyvalent alcohol B1；
0.002~0.010 part of side reaction inhibitor；
The component of the resin B 2 is made up of the component of following parts by weight：
100 parts of isocyanates B2；
50~100 parts of polyvalent alcohol B2；
0.002~0.010 part of side reaction inhibitor.
Preferably：
The Resin A component is made up of the component of following parts by weight：
Preferably：
The component of the resin B 1 is made up of the component of following parts by weight：
100 parts of isocyanates B1；
12~20 parts of polyvalent alcohol B1；
0.002~0.010 part of side reaction inhibitor；
Preferably：
The component of the resin B 2 is made up of the component of following parts by weight：
100 parts of isocyanates B2；
50~90 parts of polyvalent alcohol B2；
0.002~0.010 part of side reaction inhibitor.
Polyvalent alcohol A is the mixture of PPG and polymer polyatomic alcohol in the Resin A component, and the polyethers is more
The mass ratio of first alcohol and polymer polyatomic alcohol is 1: 1~4: 1.
The PPG is the polyethylene glycol oxide-propylene oxide trihydroxylic alcohol of number-average molecular weight 6000~10000；
The polymer polyatomic alcohol is styrene or acrylonitrile graft copolymer the oxidation second of number-average molecular weight 6000~10000
Alkene-propylene oxide trihydroxylic alcohol, solid content is 40~50%.
The crosslinking agent is ethylene glycol, BDO, 1,3-PD, one kind or one kind in 1,6- butanediol with
On.
The catalyst for the ethylene glycol solution of triethylene diamine and double (dimethylaminoethyl) ethers of 70wt% with
The mixture of the solution that 30wt% dipropylene glycols are made into, the ethylene glycol solution of the triethylene diamine and 70wt%'s is double
The mass ratio of the mixture of the solution that (dimethylaminoethyl) ether is made into 30wt% dipropylene glycols is 1: 4~1: 1.
The foaming agent is water；
The foam stabilizer is organosilicon foam stabilizer；
Isocyanates B1 is methyl diphenylene diisocyanate, Carbodiimide-Modified diphenyl in the component of the resin B 1
One or more in methane diisocyanate, toluene di-isocyanate(TDI) or naphthalene diisocyanate；
In the component of the resin B 1 polyvalent alcohol B1 be polyadipate system PEPA, preferably ethylene glycol, diethylene glycol,
The polyadipate system polyester diol that one or more mixtures in BDO pass through condensation copolymerization with adipic acid,
Number-average molecular weight is 1000~3000；
Side reaction inhibitor is phosphoric acid in the component of the resin B 1；
Isocyanates B2 is methyl diphenylene diisocyanate, Carbodiimide-Modified diphenyl in the component of the resin B 2
One or more in methane diisocyanate, toluene di-isocyanate(TDI) or naphthalene diisocyanate；
Polyvalent alcohol B2 is polyadipate system PEPA or poly terephthalic acid system polyester in the component of the resin B 2
One or more mixtures and adipic acid or terephthalic acid (TPA) in polyalcohol, preferably ethylene glycol, diethylene glycol, BDO
Formed by condensation copolymerization, number-average molecular weight is 1000~3000；
Side reaction inhibitor is phosphoric acid in the component of the resin B 2.
The preparation method of described tire polyurethane resin, comprises the following steps：
(1) polyvalent alcohol A, crosslinking agent, catalyst, foaming agent and foam stabilizer are reacted into 1.5~2.5h at 50~60 DEG C
Afterwards, 40~45 DEG C are cooled to, mix 1.0~1.5h, obtain described polyurethane resin component A；
(2) isocyanates B1, polyvalent alcohol B1 and side reaction inhibitor are reacted into 2~3h at 65~75 DEG C, obtains final product poly- ammonia
The component of ester resin B 1；
(3) isocyanates B2, polyvalent alcohol B2 and side reaction inhibitor are reacted into 2~3h at 65~75 DEG C, obtains final product poly- ammonia
The component of ester resin B 2.
The tire polyurethane resin, the method for preparing pu tire comprises the following steps：
By polyurethane resin component A that temperature is 35~45 DEG C, the polyurethane resin B1 components that temperature is 35~45 DEG C and
Temperature is 35~45 DEG C of polyurethane resin B2 components, after mixing in the casting machine, reaction 3 in 35~45 DEG C of moulds of injection~
5min is molded, the demoulding, curing in 2 days is placed under natural environment and obtains final product described pu tire.
The mass ratio of polyurethane resin B1 components and polyurethane resin B2 components is 1: 9~9: 1；
Component A reactive hydrogen molal quantity is 1: 1 with the ratio between B1 components and the total isocyanate groups molal quantity of B2 components.
Present invention has the advantages that：
Tire of the present invention includes Resin A component, the component of resin B 1 and the component of resin B 2 with polyurethane resin, by adjusting B1
The mass ratio of component and B2 components, can be obtained the pu tire of different performance.Compared to common dual-component polyurethane resin,
Product of the present invention manufacturer during pu tire is produced need not configure various different materials, and production is different to require tire
When, it is only necessary to the proportioning of B1 and B2 components is adjusted, production cost is saved, the wasting of resources, improve production efficiency is reduced, and utilize not
Two kinds of performed polymer components (B1 and B2) in proportion are more regular with the polyurethane resin segment that component A hybrid reaction is formed to be had
Sequence, obtained pu tire performance is more preferably.Pu tire hardness adjustable extent using present invention production is wide, physical property is good,
Compression deformation rate is low, is more suitable for continuous production operation, and low cost, production efficiency is high.
Specific embodiment
The present invention is specifically described below by embodiment, is served only for being further described the present invention, no
It is understood that to be limiting the scope of the present invention.The implementation condition used in embodiment can according to the condition of specific producer and
It is required that doing some nonessential modifications and adaptations.
Embodiment 1
The polyethylene glycol oxide of 221.7kg-propylene oxide trihydroxylic alcohol (number-average molecular weight is 6000), the styrene of 55.4kg connects
Branch copolymerization ethylene oxide-propylene oxide trihydroxylic alcohol (number-average molecular weight is 6000), 1.39kg ethylene glycol, the triethylene two of 0.22kg
The ethylene glycol solution of amine, double (dimethylaminoethyl) ethers of the 70wt% of 0.89kg are molten with what 30wt% dipropylene glycols were made into
After liquid, 2.77kg water and 0.28kg organosilicons foam stabilizer react 2.5h at 50 DEG C, 40 DEG C are cooled to, mix 1.5h, gathered
Urethane Resin A component.
By the methyl diphenylene diisocyanate of 45.4kg, the isocyanide of Carbodiimide-Modified diphenyl methane two of 15.1kg
Acid esters, the polyadipate ethylene glycol butyl glycol ester diol (number-average molecular weight is 1000) of 0.76kg and the phosphoric acid of 0.0015kg are 65
DEG C reaction 3h, obtain final product polyurethane resin B1 components.
By the methyl diphenylene diisocyanate of 4.54kg, (number is equal for the polyethylene terephthalate glycol of 2.28kg
Molecular weight is that the phosphoric acid 1000) with 0.0002kg reacts 3h at 65 DEG C, obtains final product polyurethane resin B2 components.
It is 35 by polyurethane resin component A, the polyurethane resin B1 components that temperature is 35 DEG C and temperature that temperature is 35 DEG C
DEG C polyurethane resin B2 components, after mixing in the casting machine, 5min shapings, the demoulding, natural ring are reacted in 35 DEG C of moulds of injection
Curing in 2 days is placed under border and obtains final product pu tire.
Embodiment 2
The polyethylene glycol oxide of 221.7kg-propylene oxide trihydroxylic alcohol (number-average molecular weight is 6000), the styrene of 55.4kg connects
Branch copolymerization ethylene oxide-propylene oxide trihydroxylic alcohol (number-average molecular weight is 6000), 1.39kg ethylene glycol, the triethylene two of 0.22kg
The ethylene glycol solution of amine, double (dimethylaminoethyl) ethers of the 70wt% of 0.89kg are molten with what 30wt% dipropylene glycols were made into
After liquid, 2.77kg water and 0.28kg organosilicons foam stabilizer react 2.5h at 50 DEG C, 40 DEG C are cooled to, mix 1.5h, gathered
Urethane Resin A component.
By the methyl diphenylene diisocyanate of 7.46kg, the isocyanide of Carbodiimide-Modified diphenyl methane two of 2.48kg
Acid esters, the polyadipate ethylene glycol butyl glycol ester diol (number-average molecular weight is 1000) and the phosphoric acid of 0.00032kg of 0.12kg exist
65 DEG C of reaction 3h, obtain final product polyurethane resin B1 components.
By the methyl diphenylene diisocyanate of 60.4kg, (number is equal for the polyethylene terephthalate glycol of 30.2kg
Molecular weight is that the phosphoric acid 1000) with 0.002kg reacts 3h at 65 DEG C, obtains final product polyurethane resin B2 components.
It is 35 by polyurethane resin component A, the polyurethane resin B1 components that temperature is 35 DEG C and temperature that temperature is 35 DEG C
DEG C polyurethane resin B2 components, after mixing in the casting machine, 5min shapings, the demoulding, natural ring are reacted in 35 DEG C of moulds of injection
Curing in 2 days is placed under border and obtains final product pu tire.
Embodiment 3
The polyethylene glycol oxide of 101.0kg-propylene oxide trihydroxylic alcohol (number-average molecular weight is 10000), the acrylonitrile of 101.0kg
Graft copolymerization ethylene oxide-propylene oxide trihydroxylic alcohol (number-average molecular weight is 10000), 2.02kg ethylene glycol, three second of 1.01kg
The ethylene glycol solution of alkene diamines, double (dimethylaminoethyl) ethers of the 70wt% of 1.01kg are made into 30wt% dipropylene glycols
Solution, after 3.03kg water and 4.04kg organosilicons foam stabilizer react 1.5h at 60 DEG C, be cooled to 45 DEG C, mix 1.0h, obtain
To described polyurethane resin component A.
By the methyl diphenylene diisocyanate of 48.3g, the isocyanide of Carbodiimide-Modified diphenyl methane two of 12.1kg
Acid esters, the polyadipate ethylene glycol butyl glycol ester diol (number-average molecular weight is 2000) of 12.1kg and the phosphoric acid of 0.002kg are 75
DEG C reaction 2h, obtain final product polyurethane resin B1 components.
By the methyl diphenylene diisocyanate of 4.34kg, the polydiethylene glycol adipate glycol of 3.74kg (divide equally by number
Son amount reacts 2h for the phosphoric acid 2000) with 0.0002kg at 75 DEG C, obtains final product polyurethane resin B2 components.
It is 45 by the cruel Resin A component of poly- ammonia, the polyurethane resin B1 components that temperature is 45 DEG C and temperature that temperature is 45 DEG C
DEG C polyurethane resin B2 components, after mixing in the casting machine, 3min shapings, the demoulding, natural ring are reacted in 45 DEG C of casees bubbles of injection
Curing in 2 days is placed under border and obtains final product pu tire.
Embodiment 4
The polyethylene glycol oxide of 101.0kg-propylene oxide trihydroxylic alcohol (number-average molecular weight is 10000), the acrylonitrile of 101.0kg
Graft copolymerization ethylene oxide-propylene oxide trihydroxylic alcohol (number-average molecular weight is 10000), 2.02kg ethylene glycol, three second of 1.01kg
The ethylene glycol solution of alkene diamines, double (dimethylaminoethyl) ethers of the 70wt% of 1.01kg are made into 30wt% dipropylene glycols
Solution, after 3.03kg water and 4.04kg organosilicons foam stabilizer react 1.5h at 60 DEG C, be cooled to 45 DEG C, mix 1.0h, obtain
To described polyurethane resin component A.
By the methyl diphenylene diisocyanate of 8.01kg, the isocyanide of Carbodiimide-Modified diphenyl methane two of 2.00kg
Acid esters, the polyadipate ethylene glycol butyl glycol ester diol (number-average molecular weight is 2000) of 2.00kg and the phosphoric acid of 0.002kg are 75
DEG C reaction 2h, obtain final product polyurethane resin B component.
By the methyl diphenylene diisocyanate of 57.7kg, the polydiethylene glycol adipate glycol of 50.1kg (divide equally by number
Son amount reacts 2h for the phosphoric acid 2000) with 0.009kg at 75 DEG C, obtains final product polyurethane resin B2 components.
It is 45 by polyurethane resin component A, the polyurethane resin B1 components that temperature is 45 DEG C and temperature that temperature is 45 DEG C
DEG C polyurethane resin B2 components, after mixing in the casting machine, 3min shapings, the demoulding, natural ring are reacted in 45 DEG C of casees bubbles of injection
Curing in 2 days is placed under border and obtains final product pu tire.
Embodiment 5
The polyethylene glycol oxide of 290.1kg-propylene oxide trihydroxylic alcohol (number-average molecular weight is 9000), the styrene of 145.1kg
Graft copolymerization ethylene oxide-propylene oxide trihydroxylic alcohol (number-average molecular weight is 9000), 21.8kg ethylene glycol, the triethylene of 1.31kg
The ethylene glycol solution of diamines, what double (dimethylaminoethyl) ethers and the 30wt% dipropylene glycols of the 70wt% of 2.61kg were made into
After solution, 5.66kg water and 4.35kg organosilicons foam stabilizer react 1.5h at 60 DEG C, 45 DEG C are cooled to, mix 1.0h, obtained
Polyurethane resin component A.
By the methyl diphenylene diisocyanate of 83.6kg, polyethylene glycol adipate glycol (the equal molecule of number of 11.5kg
Measure as the phosphoric acid 3000) with 0.008kg reacts 3h at 65 DEG C, obtain final product polyurethane resin B component.
By the methyl diphenylene diisocyanate of 28.5kg, the isocyanide of Carbodiimide-Modified diphenyl methane two of 23.7kg
Acid esters, the polybutylene glyool adipate (number-average molecular weight is 3000) of 43.0kg and the phosphoric acid of 0.008kg are in 65 DEG C of reactions
3h, obtains final product polyurethane resin B2 components.
It is 45 by polyurethane resin component A, the polyurethane resin B1 components that temperature is 45 DEG C and temperature that temperature is 45 DEG C
DEG C polyurethane resin B2 components, after mixing in the casting machine, 3min shapings, the demoulding, natural ring are reacted in 45 DEG C of casees bubbles of injection
Curing in 2 days is placed under border and obtains final product pu tire.
Embodiment 6
The polyethylene glycol oxide of 200.0kg-propylene oxide trihydroxylic alcohol (number-average molecular weight is 8000), the styrene of 160.0kg
Graft copolymerization ethylene oxide-propylene oxide trihydroxylic alcohol (number-average molecular weight is 8000), 36.0kg1,4- butanediol, the three of 1.08kg
The ethylene glycol solution of ethylene diamine, double (dimethylaminoethyl) ethers of the 70wt% of 2.16kg are matched somebody with somebody with 30wt% dipropylene glycols
Into solution, after 4.32kg water and 4.68kg organosilicons foam stabilizer react 2.5h at 50 DEG C, be cooled to 40 DEG C, mix 1.5h,
Obtain polyurethane resin component A.
By the methyl diphenylene diisocyanate of 172.5kg, the polyethylene glycol adipate glycol of 10.05kg (divide equally by number
Son amount reacts 2h for the phosphoric acid 2000) with 0.010kg at 75 DEG C, obtains final product polyurethane resin B component.
By the methyl diphenylene diisocyanate of 20.3kg, the isocyanide of Carbodiimide-Modified diphenyl methane two of 14.2kg
Acid esters, the poly terephthalic acid diethylene glycol esterdiol (number-average molecular weight is 2000) of 26.4kg and the phosphoric acid of 0.005kg are 75
DEG C reaction 2h, obtain final product polyurethane resin B2 components.
It is 35 by polyurethane resin component A, the polyurethane resin B1 components that temperature is 35 DEG C and temperature that temperature is 35 DEG C
DEG C polyurethane resin B2 components, after mixing in the casting machine, 5min shapings, the demoulding, natural ring are reacted in 35 DEG C of casees bubbles of injection
Curing in 2 days is placed under border and obtains final product pu tire.
Comparative example 1
The polyethylene glycol oxide of 221.7kg-propylene oxide trihydroxylic alcohol (number-average molecular weight is 6000), the styrene of 55.4kg connects
Branch copolymerization ethylene oxide-propylene oxide trihydroxylic alcohol (number-average molecular weight is 6000), 1.39kg ethylene glycol, the triethylene two of 0.22kg
The ethylene glycol solution of amine, double (dimethylaminoethyl) ethers of the 70wt% of 0.89kg are molten with what 30wt% dipropylene glycols were made into
After liquid, 2.77kg water and 0.28kg organosilicons foam stabilizer react 2.5h at 50 DEG C, 40 DEG C are cooled to, mix 1.5h, gathered
Urethane Resin A component.
By the methyl diphenylene diisocyanate of 49.94kg, the Carbodiimide-Modified diphenyl methane two of 15.1kg is different
Cyanate, the polyadipate ethylene glycol butyl glycol ester diol (number-average molecular weight is 1000) of 0.76kg, 2.28kg's is poly- to benzene two
The phosphoric acid of formic acid glycol ester glycol (number-average molecular weight is 1000) and 0.0017kg reacts 3h at 65 DEG C, obtains final product polyurethane resin
B component.
By the polyurethane resin component A that temperature is 35 DEG C and the polyurethane resin B component that temperature is 35 DEG C, in casting machine
After mixing, 5min shapings are reacted in 35 DEG C of case bubbles of injection, the demoulding is placed curing in 2 days and obtains final product pu tire under natural environment.It is right
Ratio 2
The polyethylene glycol oxide of 101.0kg-propylene oxide trihydroxylic alcohol (number-average molecular weight is 10000), the acrylonitrile of 101.0kg
Graft copolymerization ethylene oxide-propylene oxide trihydroxylic alcohol (number-average molecular weight is 10000), 2.02kg ethylene glycol, three second of 1.01kg
The ethylene glycol solution of alkene diamines, double (dimethylaminoethyl) ethers of the 70wt% of 1.01kg are made into 30wt% dipropylene glycols
Solution, after 3.03kg water and 4.04kg organosilicons foam stabilizer react 1.5h at 60 DEG C, be cooled to 45 DEG C, mix 1.0h, obtain
To described polyurethane resin component A.
By the methyl diphenylene diisocyanate of 52.64kg, the Carbodiimide-Modified diphenyl methane two of 12.1kg is different
Cyanate, the polyadipate ethylene glycol butyl glycol ester diol (number-average molecular weight is 2000) of 12.1kg, the polyadipate of 4.34kg
The phosphoric acid of diethylene glycol esterdiol (number-average molecular weight is 2000) and 0.0022kg reacts 2h at 75 DEG C, obtains final product polyurethane resin B
Component.
By the polyurethane resin component A that temperature is 45 DEG C and the polyurethane resin B component that temperature is 45 DEG C, in casting machine
After mixing, 3min shapings are reacted in 45 DEG C of case bubbles of injection, the demoulding is placed curing in 2 days and obtains final product pu tire under natural environment.
The properties test of the pu tire obtained by embodiment 1~4 and comparative example 1~2 is as follows：
Table I
By embodiment 1 and embodiment 2, embodiment 3 and embodiment 4 understand, in the premise that polyurethane resin component A is constant
Under, the ratio of the simple adjustment component of resin B 1 and B2 components can be obtained different hardness, different physical property and different compression deformation rates
Pu tire, improves production efficiency, while energy saving is consumed, saves production cost.Comparative example 1 and comparative example 1,
Embodiment 3 and comparative example 2 are understood, are more easy to that hardness higher compression deformation rate is obtained more using tire polyurethane resin of the present invention
It is low, or the also lower pu tire of the relatively low compression deformation rate of hardness.
Although above-described embodiment is described in detail to technical scheme, technical side of the invention
Case is not limited to above example, in the case of thought of the invention and objective is not departed from, to scope of the present invention patent
The equivalent change or modification that content is made, all should be technology category of the invention.
Claims (10)
1. tire polyurethane resin, it is characterised in that comprising Resin A component, the component of resin B 1 and the component of resin B 2；The tree
Fat component A is made up of following component：Polyvalent alcohol A, crosslinking agent, catalyst, foaming agent and foam stabilizer；
The component of the resin B 1 contains by the component of following parts by weight：
100 parts of isocyanates B1；
10~40 parts of polyvalent alcohol B1；
0.002~0.010 part of side reaction inhibitor；
The component of the resin B 2 is made up of the component of following parts by weight：
100 parts of isocyanates B2；
50~100 parts of polyvalent alcohol B2；
0.002~0.010 part of side reaction inhibitor；
Described isocyanates B1 is selected from methyl diphenylene diisocyanate, Carbodiimide-Modified diphenylmethane diisocyanate
One or more in ester, toluene di-isocyanate(TDI) or naphthalene diisocyanate；
The polyvalent alcohol B1 is polyadipate system polyester diol；
The isocyanates B2 be methyl diphenylene diisocyanate, carbodiimide modified diphenylmethane diisocyanate,
One or more in toluene di-isocyanate(TDI) or naphthalene diisocyanate；
The polyvalent alcohol B2 is polyadipate system PEPA or poly terephthalic acid system PEPA.
2. tire polyurethane resin according to claim 1, it is characterised in that the Resin A component is by following component
Composition：
3. tire polyurethane resin according to claim 2, it is characterised in that the Resin A component is by following component
Composition：
The Resin A component is made up of the component of following parts by weight：
4. tire polyurethane resin according to claim 1, it is characterised in that the component of the resin B 1 is by following weight
The component composition of number：
100 parts of isocyanates B1；
12~20 parts of polyvalent alcohol B1；
0.002~0.010 part of side reaction inhibitor；
The component of the resin B 2 is made up of the component of following parts by weight：
100 parts of isocyanates B2；
50~90 parts of polyvalent alcohol B2；
0.002~0.010 part of side reaction inhibitor；
Described isocyanates B1 is selected from methyl diphenylene diisocyanate, Carbodiimide-Modified diphenylmethane diisocyanate
One or more in ester, toluene di-isocyanate(TDI) or naphthalene diisocyanate；
The polyvalent alcohol B1 is that one or more mixtures and adipic acid in ethylene glycol, diethylene glycol, BDO are logical
Cross condensation copolymerization to form, number-average molecular weight is 1000~3000；
The isocyanates B2 be methyl diphenylene diisocyanate, carbodiimide modified diphenylmethane diisocyanate,
One or more in toluene di-isocyanate(TDI) or naphthalene diisocyanate；
The polyvalent alcohol B2 be ethylene glycol, diethylene glycol, BDO in one or more mixtures and adipic acid or
Terephthalic acid (TPA) is formed by condensation copolymerization, and number-average molecular weight is 1000~3000；
The side reaction inhibitor is phosphoric acid.
5. tire polyurethane resin according to claim 2, it is characterised in that polyvalent alcohol A in the Resin A component
It is PPG and the mixture of polymer polyatomic alcohol；The mass ratio of the PPG and polymer polyatomic alcohol is 1: 1
~4: 1.
6. tire polyurethane resin according to claim 5, it is characterised in that the PPG is the equal molecules of number
Polyethylene glycol oxide-propylene oxide the trihydroxylic alcohol of amount 6000~10000；
The polymer polyatomic alcohol for number-average molecular weight 6000~10000 styrene or acrylonitrile graft copolymer ethylene oxide-
Propylene oxide trihydroxylic alcohol, solid content is 40~50%；
The crosslinking agent is ethylene glycol, BDO, 1,3-PD, one or more in 1,6- butanediol；
The catalyst is the ethylene glycol solution of triethylene diamine and double (dimethylaminoethyl) ethers of 70wt% and 30wt% mono-
The mixture of the solution that contracting DPG is made into, the ethylene glycol solution of the triethylene diamine and double (dimethylaminos of 70wt%
Ethyl) mass ratio of the mixture of solution that is made into of ether and 30wt% dipropylene glycols is 1: 4~1: 1；
The foaming agent is water；
The foam stabilizer is organosilicon foam stabilizer.
7. the tire polyurethane resin according to any one of claim 1~6, it is characterised in that the polyurethane resin
The mass ratio of B1 components and polyurethane resin B2 components is 1: 9~9: 1；Component A reactive hydrogen molal quantity and B1 components and B2 components
The ratio between total isocyanate groups molal quantity is 1: 1.
8. the preparation method of the tire polyurethane resin according to any one of claim 1~7, it is characterised in that including
Following steps：
(1) after polyvalent alcohol A, crosslinking agent, catalyst, foaming agent and foam stabilizer being reacted into 1.5~2.5h at 50~60 DEG C, drop
Temperature mixes 1.0~1.5h to 40~45 DEG C, obtains described polyurethane resin component A；
(2) isocyanates B1, polyvalent alcohol B1 and side reaction inhibitor are reacted into 2~3h at 65~75 DEG C, obtains final product polyurethane tree
Fat B1 components；
(3) isocyanates B2, polyvalent alcohol B2 and side reaction inhibitor are reacted into 2~3h at 65~75 DEG C, obtains final product polyurethane tree
Fat B2 components.
9. according to the application of the tire polyurethane resin described in any one of claim 1~7, it is characterised in that poly- for preparing
Urethane tire.
10. application according to claim 9, it is characterised in that application process, comprises the following steps：By temperature be 35~
45 DEG C of polyurethane resin component A, the polyurethane resin B1 components that temperature is 35~45 DEG C and the poly- ammonia that temperature is 35~45 DEG C
The component of ester resin B 2, after mixing in casting machine, reacts 3~5min shapings, the demoulding, natural environment in 35~45 DEG C of moulds of injection
Lower placement cures the pu tire described in obtaining final product for 2 days.
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| 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 |
| 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 |
| CN111518381A (en) * | 2020-05-29 | 2020-08-11 | 叶正芬 | Two-component polyurethane stock solution for engineering tires and preparation method thereof |
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| CN113292764A (en) * | 2021-05-07 | 2021-08-24 | 湖北祥源新材科技股份有限公司 | Compression-resistant polyurethane foam and preparation method thereof |
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