CN106832218A - Recovery sponge polyurethane resin high and preparation method and application - Google Patents
Recovery sponge polyurethane resin high and preparation method and application Download PDFInfo
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- CN106832218A CN106832218A CN201611272194.6A CN201611272194A CN106832218A CN 106832218 A CN106832218 A CN 106832218A CN 201611272194 A CN201611272194 A CN 201611272194A CN 106832218 A CN106832218 A CN 106832218A
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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
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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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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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
- C08G18/4072—Mixtures of compounds of group C08G18/63 with other macromolecular compounds
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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
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
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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
- C08G18/63—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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- C08G18/00—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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- 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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- 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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- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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Abstract
The invention discloses a kind of recovery sponge polyurethane high and preparation method and application, 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, 5~40 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 polyether-tribasic alcohol, isocyanates B2 is methyl diphenylene diisocyanate, carbodiimide modified diphenylmethane diisocyanate, toluene di-isocyanate(TDI) or naphthalene diisocyanate, polyvalent alcohol B2 is PPG.The present invention can be obtained the excellent polyurethane sponge of different hardness resilience, low cost.
Description
Technical field
The present invention relates to a kind of sponge polyurethane resin and preparation method and application.
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.It is poly-
The features such as urethane sponge has light weight, resilience good.
Resin generally double-component raw material for producing polyurethane sponge --- polyol blends and prepolymer are (referred to as
AB material/AB components or black and white material).
The polyurethane sponge of different performance requirement needs different types of AB material to use cooperatively.Produced for polyurethane sponge
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 sponge 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 recovery sponge polyurethane resin high and preparation method and application, to overcome
The defect that prior art is present.
Recovery sponge polyurethane resin high of the present invention, comprising Resin A component, 2 groups of the component of resin B 1 and resin B
Point；
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；
5~40 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；
Polyvalent alcohol B1 is polyether-tribasic alcohol in the component of the resin B 1, preferred number average molecular weight 6000~10000 it is poly-
Ethylene oxide-propylene oxide trihydroxylic alcohol；
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 PPG, the polyoxy of preferred number average molecular weight 3000~7000 in the component of the resin B 2
Change ethylene oxide-propylene oxide dihydroxylic alcohols；
Side reaction inhibitor is phosphoric acid in the component of the resin B 2.
The preparation method of described polyurethane sponge 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 recovery sponge polyurethane resin high, for preparing high-rebound polyurethane sponge, preparation method includes as follows
Step：
By polyurethane resin component A that temperature is 20~25 DEG C, the polyurethane resin B1 components that temperature is 20~25 DEG C and
Temperature is 20~25 DEG C of polyurethane resin B2 components, after mixing in the casting machine, reaction 5 in 25~30 DEG C of casees bubbles of injection~
10min is molded, the demoulding, and section obtains final product described polyurethane sponge.
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：
Present invention recovery sponge high includes Resin A component, B1 components and B2 components with polyurethane resin, by adjusting B1 groups
Divide the mass ratio with B2 components, the polyurethane sponge of different performance can be obtained.Compared to common dual-component polyurethane resin, this
Invention product manufacturer during polyurethane sponge is produced need not configure various different materials, and production is different to require sponge
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 polyurethane sponge performance is more preferably.Polyurethane sponge hardness adjustable extent using production of the present invention is wide, resilience
Property it is high, abscess it is fine and closely woven it is uniform, be more suitable for continuous production operation, 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 45.1kg, the isocyanide of Carbodiimide-Modified diphenyl methane two of 15.0kg
Acid esters, the polyethylene glycol oxide-propylene oxide trihydroxylic alcohol (number-average molecular weight is 6000) of 0.75kg 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 4.51kg, (number is equal for the polyethylene glycol oxide-propylene oxide dihydroxylic alcohols of 2.26kg
Molecular weight is that the phosphoric acid 3000) with 0.0002kg reacts 3h at 65 DEG C, obtains final product polyurethane resin B2 components.
It is 20 by polyurethane resin component A, the polyurethane resin B1 components that temperature is 20 DEG C and temperature that temperature is 20 DEG C
DEG C polyurethane resin B2 components, after mixing in the casting machine, 10min shapings, the demoulding are reacted in 25 DEG C of casees bubbles of injection, section is
Obtain polyurethane sponge.
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 6.91kg, the isocyanide of Carbodiimide-Modified diphenyl methane two of 2.30kg
Acid esters, the polyethylene glycol oxide-propylene oxide trihydroxylic alcohol (number-average molecular weight is 6000) of 0.11kg and the phosphoric acid of 0.00032kg are 65
DEG C reaction 3h, obtain final product polyurethane resin B1 components.
By the methyl diphenylene diisocyanate of 55.9kg, (number is equal for the polyethylene glycol oxide-propylene oxide dihydroxylic alcohols of 28.0kg
Molecular weight is that the phosphoric acid 3000) with 0.002kg reacts 3h at 65 DEG C, obtains final product polyurethane resin B2 components.
It is 20 by polyurethane resin component A, the polyurethane resin B1 components that temperature is 20 DEG C and temperature that temperature is 20 DEG C
DEG C polyurethane resin B2 components, after mixing in the casting machine, 10min shapings, the demoulding are reacted in 25 DEG C of casees bubbles of injection, section is
Obtain polyurethane sponge.
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 47.2g, the isocyanide of Carbodiimide-Modified diphenyl methane two of 11.8kg
Acid esters, the polyethylene glycol oxide-propylene oxide trihydroxylic alcohol (number-average molecular weight is 10000) of 11.8kg 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 4.24kg, (number is equal for the polyethylene glycol oxide-propylene oxide dihydroxylic alcohols of 3.65kg
Molecular weight is that the phosphoric acid 7000) with 0.0002kg reacts 2h at 75 DEG C, obtains final product polyurethane resin B2 components.
It is 25 by polyurethane resin component A, the polyurethane resin B1 components that temperature is 25 DEG C and temperature that temperature is 25 DEG C
DEG C polyurethane resin B2 components, after mixing in the casting machine, 5min shapings, the demoulding are reacted in 30 DEG C of casees bubbles of injection, section is
Obtain polyurethane sponge.
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 7.44kg, the isocyanide of Carbodiimide-Modified diphenyl methane two of 1.86kg
Acid esters, the polyethylene glycol oxide-propylene oxide trihydroxylic alcohol (number-average molecular weight is 10000) of 1.86kg 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 53.9kg, (number is equal for the polyethylene glycol oxide-propylene oxide dihydroxylic alcohols of 46.5kg
Molecular weight is that the phosphoric acid 7000) with 0.009kg reacts 2h at 75 DEG C, obtains final product polyurethane resin B2 components.
It is 25 by polyurethane resin component A, the polyurethane resin B1 components that temperature is 25 DEG C and temperature that temperature is 25 DEG C
DEG C polyurethane resin B2 components, after mixing in the casting machine, 5min shapings, the demoulding are reacted in 30 DEG C of casees bubbles of injection, section is
Obtain polyurethane sponge.
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 124.8kg, polyethylene glycol oxide-propylene oxide trihydroxylic alcohol (number of 17.1kg
Average molecular weight is that the phosphoric acid 9000) with 0.012kg reacts 3h at 65 DEG C, obtains final product polyurethane resin B1 components.
By the methyl diphenylene diisocyanate of 42.6kg, the isocyanide of Carbodiimide-Modified diphenyl methane two of 35.4kg
Acid esters, the polyethylene glycol oxide-propylene oxide dihydroxylic alcohols (number-average molecular weight is 3000) of 64.2kg and the phosphoric acid of 0.012kg are at 65 DEG C
Reaction 3h, obtains final product polyurethane resin B2 components.
It is 25 by polyurethane resin component A, the polyurethane resin B1 components that temperature is 25 DEG C and temperature that temperature is 25 DEG C
DEG C polyurethane resin B2 components, after mixing in the casting machine, 5min shapings, the demoulding are reacted in 30 DEG C of casees bubbles of injection, section is
Obtain polyurethane sponge.
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), 7.20kg1,4- 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 86.4kg, (number is equal for the polyethylene glycol oxide-propylene oxide trihydroxylic alcohol of 5.03kg
Molecular weight is that the phosphoric acid 8000) with 0.005kg reacts 2h at 75 DEG C, obtains final product polyurethane resin B1 components.
By the methyl diphenylene diisocyanate of 10.2kg, the isocyanide of Carbodiimide-Modified diphenyl methane two of 7.12kg
Acid esters, the polyethylene glycol oxide-propylene oxide dihydroxylic alcohols (number-average molecular weight is 4000) of 13.2kg and the phosphoric acid of 0.002kg are at 75 DEG C
Reaction 2h, obtains final product polyurethane resin B2 components.
It is 20 by polyurethane resin component A, the polyurethane resin B1 components that temperature is 20 DEG C and temperature that temperature is 20 DEG C
DEG C polyurethane resin B2 components, after mixing in the casting machine, 10min shapings, the demoulding are reacted in 25 DEG C of casees bubbles of injection, section is
Obtain polyurethane sponge.
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 49.61kg, the Carbodiimide-Modified diphenyl methane two of 15.0kg is different
Cyanate, the polyethylene glycol oxide-propylene oxide trihydroxylic alcohol (number-average molecular weight is 6000) of 0.75kg, the polyoxyethylene of 2.26kg
The phosphoric acid of alkene-propylene oxide dihydroxylic alcohols (number-average molecular weight is 3000) and 0.0017kg reacts 3h at 65 DEG C, obtains final product polyurethane tree
Fat B component.
By polyurethane resin component A, the polyurethane resin B component that temperature is 20 DEG C that temperature is 20 DEG C, in casting machine
After mixing, 10min shapings are reacted in 25 DEG C of case bubbles of injection, the demoulding, section obtains final product polyurethane sponge.
Comparative example 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 51.44kg, the Carbodiimide-Modified diphenyl methane two of 11.8kg is different
Cyanate, the polyethylene glycol oxide-propylene oxide trihydroxylic alcohol (number-average molecular weight is 10000) of 11.8kg, the polyoxyethylene of 3.65kg
The phosphoric acid of alkene-propylene oxide dihydroxylic alcohols (number-average molecular weight is 7000) and 0.0022kg reacts 2h at 75 DEG C, obtains final product polyurethane tree
Fat B component.
By the polyurethane resin component A that temperature is 25 DEG C and the polyurethane resin B component that temperature is 25 DEG C in casting machine
After mixing, 5min shapings are reacted in 30 DEG C of case bubbles of injection, the demoulding, section obtains final product polyurethane sponge.
The properties test of the polyurethane sponge obtained by embodiment 1~4 and comparative example 1~2 is as follows：
Table I
From embodiment 1 and embodiment 2, embodiment 3 and embodiment 4, in the premise that polyurethane resin component A is constant
Under, it is fine and closely woven uniform that the ratio of the simple adjustment component of resin B 1 and B2 components can be obtained different hardness, different rebound degrees, abscess
Polyurethane sponge, improves production efficiency, while energy saving is consumed, saves production cost.Comparative example 1 and comparative example 1,
Embodiment 3 and comparative example 2 understand that recovery sponge polyurethane resin high of the invention is more easy to be obtained hardness rebound degree higher preferably,
Or hardness is compared with low resilient rate also preferable sponge.
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. recovery sponge polyurethane resin high, it is characterised in that 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 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；
5~40 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 polyether-tribasic alcohol；
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 PPG.
2. recovery sponge polyurethane resin high according to claim 1, it is characterised in that the Resin A component is by such as
The following group is grouped into：
3. recovery sponge polyurethane resin high according to claim 2, it is characterised in that the Resin A component is by such as
The following group is grouped into：
The Resin A component is made up of the component of following parts by weight：
4. recovery sponge polyurethane resin high according to claim 1, it is characterised in that the component of the resin B 1 is by such as
The component composition of lower parts by weight：
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 the polyethylene glycol oxide-propylene oxide trihydroxylic alcohol of number-average molecular weight 6000~10000；
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 the polyethylene glycol oxide-propylene oxide dihydroxylic alcohols of number-average molecular weight 3000~7000；
The side reaction inhibitor is phosphoric acid.
5. recovery sponge polyurethane resin high according to claim 2, it is characterised in that gather in the Resin A component
Polyalcohol A is the mixture of PPG and polymer polyatomic alcohol；The quality of the PPG and polymer polyatomic alcohol
Than being 1: 1~4: 1.
6. recovery sponge polyurethane resin high according to claim 5, it is characterised in that the PPG is number
The polyethylene glycol oxide of average molecular weight 6000~10000-propylene oxide trihydroxylic alcohol；
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 recovery sponge polyurethane resin high according to any one of claim 1~6, it is characterised in that the poly- ammonia
The mass ratio of the component of ester resin B 1 and polyurethane resin B2 components is 1: 9~9: 1；Component A reactive hydrogen molal quantity and B1 components and
The ratio between total isocyanate groups molal quantity of B2 components is 1: 1.
8. the preparation method of the recovery sponge polyurethane resin high according to any one of claim 1~7, its feature exists
In comprising the 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 recovery sponge polyurethane resin high described in any one of claim 1~7, it is characterised in that be used for
Prepare high-rebound polyurethane sponge.
10. application according to claim 9, it is characterised in that application process, comprises the following steps：By temperature be 20~
25 DEG C of polyurethane resin component A, the polyurethane resin B1 components that temperature is 20~25 DEG C and the poly- ammonia that temperature is 20~25 DEG C
The component of ester resin B 2, after mixing in casting machine, 5~10min shapings, the demoulding is reacted in 25~30 DEG C of case bubbles of injection, and section is
Obtain described polyurethane sponge.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108409934A (en) * | 2018-03-09 | 2018-08-17 | 旭川化学（昆山）有限公司 | Height rebound Low temperature-resistanpolyurethane polyurethane sole raw material and preparation method thereof |
| CN117659329A (en) * | 2024-01-26 | 2024-03-08 | 山东球牌化妆用品有限公司 | Polyurethane sponge and preparation method and application thereof |
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| EP0118171A2 (en) * | 1983-03-04 | 1984-09-12 | Arco Chemical Technology, Inc. | Production of polyurethane-forming components having free-isocyanate or hydroxy groups |
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| CN117659329A (en) * | 2024-01-26 | 2024-03-08 | 山东球牌化妆用品有限公司 | Polyurethane sponge and preparation method and application thereof |
| CN117659329B (en) * | 2024-01-26 | 2024-04-30 | 山东球牌化妆用品有限公司 | Polyurethane sponge and preparation method and application thereof |
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