CN109608606A - A kind of preparation method for automobile-used polyurethane solid tyre of digging up mine - Google Patents
A kind of preparation method for automobile-used polyurethane solid tyre of digging up mine Download PDFInfo
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- CN109608606A CN109608606A CN201811295725.2A CN201811295725A CN109608606A CN 109608606 A CN109608606 A CN 109608606A CN 201811295725 A CN201811295725 A CN 201811295725A CN 109608606 A CN109608606 A CN 109608606A
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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
- C08G18/67—Unsaturated compounds having active hydrogen
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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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
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- C08G18/3206—Polyhydroxy compounds aliphatic
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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
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3802—Low-molecular-weight compounds having heteroatoms other than oxygen having halogens
- C08G18/3814—Polyamines
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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
- C08G18/4018—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
- C08G18/42—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
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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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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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
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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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
- C08G18/65—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
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6607—Compounds of groups C08G18/42, 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6614—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6618—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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Abstract
A kind of preparation method for automobile-used polyurethane solid tyre of digging up mine, step are as follows: (1) by binary acid and polyol reaction, polyester polyol is made；(2) polyester polyol that step (1) is prepared and chain extender, paraphenylene diisocyanate carry out prepolymerization reaction and are made with hydroxy-end capped oligomer a, again with terminal hydroxy liquid rubber, organosilicon foam stabilizer, catalyst, foaming agent mixing, component A is obtained；(3) polycarbonate polyol, polytetrahydrofuran polyol and paraphenylene diisocyanate are subjected to prepolymerization reaction, are made with hydroxy-end capped oligomer b, then reacted with Isocyanate prepolymers, obtain B component；(4) two component of A, B is mixed, is poured into after solidifying in tire-mold and obtains product；The tearing strength and wear-resisting property for improving pu tire, overcome the disadvantage of pu tire non-skid property difference, rigidity reinforced, reduce the load deformation amount of tire, enhancing compression recovery performance, hydrolytic resistance and ageing-resistant.
Description
Technical field
The present invention relates to polyurethane material fields, and in particular to a kind of preparation side of automobile-used polyurethane solid tyre of digging up mine
Method.
Background technique
Polyurethane solid tyre using more and more extensive, is mainly used in slow-moving vehicle in sphere of life, such as wheelchair,
Shared bicycle, toy car, trolley etc., using less in large-scale industrial vehicle and machinery.Domestic mining vehicle is basic at present
On all use inflated rubber tire, due to working environment complexity, inflated rubber tire is prone to wear puncture, generally all can mining vehicle
One layer of metal coating chain is tied up on pneumatic tire, using trouble, tire wear is fast, and risk is high, and pneumatic tire is gone back at present
There is no good method to solve problems.Pneumatic tire is replaced with solid rubber tyre, can be to avoid the above problem, but rubber
Glue solid tyre very dense, resilience performance is poor, and wear-resisting and tearing strength is also short of a bit, and it is extremely multiple not to be suitable for working environment
Miscellaneous place.Automobile-used polyurethane solid tyre of digging up mine has not been reported yet.Under automobile-used polyurethane solid tyre of digging up mine should meet
The requirement of face several points: (1) greatly, tire needs compression resilience good, and load deformation amount is small, good operation stability for mining vehicle weight bearing；(2)
Wearability is good, and tearing strength is high；(3) hydrolytic resistance, solvent resistance and resistance to ag(e)ing are good, and mining environment is special, damp and hot, oiliness,
The various substances such as corrosivity can all contact；(4) non-skid property of tire reaches requirement, and non-skid property difference is polyurethane material maximum
The shortcomings that.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of automobile-used polyurethane solid tyre of digging up mine, and reach mining vehicle tire
Application requirement.
Its step are as follows for the preparation method of this automobile-used polyurethane solid tyre of mining:
(1) it prepares polyester polyol: binary acid and polyalcohol is mixed with the ratio that mass ratio is 100 ︰ (65~80),
Polyesterification reaction is carried out under the action of catalyst A, polyester polyol is made, wherein the binary acid is decanedioic acid and adipic acid
It take mass ratio as the mixture of 100 ︰ (0~100), the polyalcohol is 1,6- hexylene glycol, neopentyl glycol and trihydroxy methyl third
Alkane is with 100 ︰ of the mass ratio (mixture of 10~50) ︰ (0~0.5)；
(2) preparation of component A: polyester polyol that step (1) is prepared and chain extender, paraphenylene diisocyanate with
100 ︰ of mass ratio (ratio of 12~20) ︰ (8~14) mixes, and carries out prepolymerization reaction, is made with hydroxy-end capped oligomer a, then
By oligomer a and terminal hydroxy liquid rubber, organosilicon foam stabilizer, catalyst B, foaming agent with 100 ︰ of mass ratio (20~50) ︰
The ratio of (0.4~1) ︰ (1.8~3.5) ︰ (0.2~2) mixes, and obtains component A, wherein the chain extender is that 3,3'- bis- is chloro-
4,4'- diaminodiphenyl-methane and ethylene glycol take mass ratio as the mixture of 100 ︰ (25~40)；
(3) preparation of B component: by polycarbonate polyol, polytetrahydrofuran polyol and paraphenylene diisocyanate with matter
Than 100 ︰, (ratio of 100~130) ︰ (12~21) carries out prepolymerization reaction to amount, is made with hydroxy-end capped oligomer b, this is low
Polymers b and isocyanates b is mixed with the ratio of 100 ︰ of mass ratio (160~180), carries out prepolymerization reaction, obtains B component, wherein
The isocyanates b is 4,4 '-methyl diphenylene diisocyanates, two isocyanide of Carbodiimide-Modified 4,4 '-diphenyl methane
Acid esters is the mixture of 100 ︰ (24~45) with mass ratio；
(4) production of pu tire: two component of A, B is sufficiently mixed with certain mass ratio, is poured into tire-mold
Product is obtained after solidification, wherein the dosage of component A and B component is mole of the active hydrogen molal quantity of component A and the-NCO of B component
The ratio between number is 100 ︰ (90~110).
The preparation method of this automobile-used polyurethane solid tyre of mining has the advantage that (a) originally compared with prior art
The component A and B component of polyurethane resin are made up of two-step method for invention, increase segment, and paraphenylene diisocyanate is mentioned
Before be reacted in polyalcohol, improve the tearing strength and wear-resisting property of pu tire.(b) present invention is added in component A
Terminal hydroxy liquid rubber, overcomes the disadvantage of pu tire non-skid property difference.(c) present invention is with the chloro- 4,4'- of 3,3'- bis-
The mixture of diaminodiphenyl-methane and ethylene glycol makees chain extender, makes the rigidity reinforced of polyurethane material, reduces the negative of tire
Lotus deformation quantity enhances compression recovery performance.(d) all polyalcohols selected by the present invention all have good hydrolytic resistance and resistance to
Aging.
Specific embodiment
The step of preparation method of this automobile-used polyurethane solid tyre of mining, is as follows:
(1) it prepares polyester polyol: binary acid and polyalcohol is mixed with the ratio that mass ratio is 100 ︰ (65~80),
Carry out polyesterification reaction under the action of catalyst A, polyester polyol be made, wherein the binary acid be decanedioic acid and adipic acid with
Mass ratio is the mixture of 100 ︰ (0~100), and the polyalcohol is 1,6- hexylene glycol, neopentyl glycol and trimethylolpropane
With 100 ︰ of the mass ratio (mixture of 10~50) ︰ (0~0.5)；
(2) preparation of component A: polyester polyol that step (1) is prepared and chain extender, paraphenylene diisocyanate with
100 ︰ of mass ratio (ratio of 12~20) ︰ (8~14) mixes, and carries out prepolymerization reaction, is made with hydroxy-end capped oligomer a, then
By oligomer a and terminal hydroxy liquid rubber, organosilicon foam stabilizer, catalyst B, foaming agent with 100 ︰ of mass ratio (20~50) ︰
The ratio of (0.4~1) ︰ (1.8~3.5) ︰ (0.2~2) mixes, and obtains component A, wherein the chain extender is that 3,3'- bis- is chloro-
4,4'- diaminodiphenyl-methane and ethylene glycol take mass ratio as the mixture of 100 ︰ (25~40)；
(3) preparation of B component: by polycarbonate polyol, polytetrahydrofuran polyol and paraphenylene diisocyanate with matter
Than 100 ︰, (ratio of 100~130) ︰ (12~21) carries out prepolymerization reaction to amount, is made with hydroxy-end capped oligomer b, this is low
Polymers b and isocyanates b is mixed with the ratio of 100 ︰ of mass ratio (160~180), carries out prepolymerization reaction, obtains B component, wherein
The isocyanates b is 4,4 '-methyl diphenylene diisocyanates, two isocyanide of Carbodiimide-Modified 4,4 '-diphenyl methane
Acid esters is the mixture of 100 ︰ (24~45) with mass ratio；
(4) production of pu tire: two component of A, B is sufficiently mixed, and is poured into after solidifying in tire-mold and is produced
Product, it is 100 ︰ that wherein the dosage of component A and B component, which is the ratio between active hydrogen molal quantity and molal quantity of-NCO of B component of component A,
(90~110).
Catalyst A in the preparation method of this automobile-used polyurethane solid tyre of mining can be tetraisopropyl titanate or two
The mixture of one or both of butyl tin oxide.
The number-average molecular weight of polytetrahydrofuran polyol in the preparation method of this automobile-used polyurethane solid tyre of mining
It can be 1000~2000, the number-average molecular weight of polycarbonate polyol can be 1000.
Catalyst B in the preparation method of this automobile-used polyurethane solid tyre of mining can be di lauric dibutyl
One of tin, triethylene diamine, tetramethyl diethylenetriamines or two or more mixtures.
Terminal hydroxy liquid rubber in the preparation method of this automobile-used polyurethane solid tyre of mining can be poly- for terminal hydroxy group
The mixture of one or both of butadiene acrylonitrile, terminal hydroxy group hydrogenated butadiene polymer.
Organosilicon foam stabilizer in the preparation method of this automobile-used polyurethane solid tyre of mining can be DC-193, DC-
The mixture of one or more of 3042 and DC-3043.
Foaming agent in the preparation method of this automobile-used polyurethane solid tyre of mining can be one of water, chlorofluorocarbons
Or two kinds of mixture.
The tyre surface hardness of tire made of preparation method with this automobile-used polyurethane solid tyre of mining is 70~95 Shaos
Family name A, sidewall hardness are 65~90 shore A, and compact density is 0.85~0.9g/cm3, tearing toughness is more than 85KN/m, DIN roller
Cylinder abrasion are less than 50mm3, more than 72 hours, weatherability was more than 5 years (clumps for hydrolysis test (impregnating in 10% sodium hydroxide solution)
Woods is tested 5 weeks), performance indexes all increases, and reaches the application requirement of mining vehicle tire.
The specific operation process of the preparation of this automobile-used polyurethane solid tyre of mining is as follows:
(1) binary acid and polyalcohol are under the action of catalyst A, under nitrogen protection in 230 DEG C~240 DEG C progress polyester
Change reaction, reaction is reduced to 1mgKOH/g hereinafter, stopping reaction when hydroxyl value is 74~114mgKOH/g to acid value, polyester polyols are made
Alcohol.
(2) preparation of component A: reaction kettle is added in polyester polyol made from step (1), 90~95 DEG C is heated to, adds
Enter chain extender, be uniformly mixed, after chain extender is completely dissolved, paraphenylene diisocyanate is added, is uniformly mixed, to two isocyanide of benzene
After acid esters is completely dissolved, cooled down with water-bath, be rapidly decreased to 65~70 degrees Celsius, reacted a hour, terminal hydroxy liquid rubber is added
Glue, organosilicon foam stabilizer, catalyst B, foaming agent are uniformly mixed, and obtain component A.
(3) preparation of B component: reaction kettle is added in polycarbonate polyol and polytetrahydrofuran polyol, is heated to 90
~95 DEG C, paraphenylene diisocyanate is added, is uniformly mixed, after paraphenylene diisocyanate is completely dissolved, is cooled down with water-bath, rapidly
65~70 degrees Celsius are down to, a hour is reacted, the isocyanates b of melting is added, is reacted a hour, B component is obtained.
(4) preparation of pu tire: tire-mold is heated to 50~55 DEG C, is placed on motor with 400~600r/min
Speed rotation, the temperature for controlling component A and B component is 60~70 DEG C, adjusts the dosage of component A and B component, makes component A
The ratio between active hydrogen molal quantity and the molal quantity of-NCO of B component are 100 ︰ (90~110), and two components are sufficiently mixed in injection molding machine
Close, be poured into tire-mold, mold stops rotating after five minutes, place 30~after sixty minutes open mold can obtain polyurethane
Solid tyre.
The present invention will be further explained below with reference to examples.
Embodiment 1
(1) by 113kg decanedioic acid, 67.8kg1,6- hexylene glycol, 7.1kg neopentyl glycol, 0.33kg trimethylolpropane,
0.8kg tetraisopropyl titanate mixes, and 230 DEG C of progress polyesterification reactions are heated under nitrogen protection, and reaction to acid value is
0.8mgKOH/g, hydroxyl value stop reaction when being 112mgKOH/g, and polyester polyol is made.
(2) preparation of component A: by the polyester polyol investment reaction kettle of 150kg step (1) preparation, being heated to 95 DEG C,
14.4kg3, chloro- 4, the 4'- diaminodiphenyl-methane of 3'- bis- is added, 3.6kg ethylene glycol is uniformly mixed, completely molten to chain extender
12kg paraphenylene diisocyanate is added in Xie Hou, is uniformly mixed, after paraphenylene diisocyanate is completely dissolved, is cooled down with water-bath, fast
Prompt drop reacts a hour to 70 DEG C, and 85kg hydroxyl terminated butadiene acrylonitrile copolymer, 0.68kgDC-3042,3.1kg catalysis is added
Agent triethylene diamine, 0.34kg water are uniformly mixed, and obtain component A.
(3) preparation of B component: by 10kg polycarbonate glycol (number-average molecular weight 1000), 10kg polytetrahydrofuran two
Alcohol (number-average molecular weight 2000) is put into reaction kettle, is heated to 95 DEG C, and 1.4kg paraphenylene diisocyanate is added, and is uniformly mixed,
After paraphenylene diisocyanate is completely dissolved, cooled down with water-bath, be rapidly decreased to 70 degrees Celsius, reacted a hour, is added
The 4,4 '-methyl diphenylene diisocyanates and 6.6kg Carbodiimide-Modified 4,4 '-diphenyl methane two of 27.4kg melting are different
Cyanate reacts a hour, obtains B component.
(4) preparation of pu tire: tire-mold is heated to 55 DEG C, is placed on motor and is revolved with the speed of 400r/min
Turning, the temperature for controlling component A and B component is 65 DEG C, 145.2kgA material and 54.8kgB material is placed in injection molding machine and is sufficiently mixed,
It is poured into tire-mold, mold stops rotating after five minutes, places opening mold after sixty minutes and obtains polyurethane solid tyre.
Embodiment 2
(1) by 79.7kg decanedioic acid, 33.3kg adipic acid, 63.3kg1,6- hexylene glycol, 15.8kg neopentyl glycol, 0.19kg
Trimethylolpropane, 0.8kg tetraisopropyl titanate mix, and 233 DEG C of progress polyesterification reactions are heated under nitrogen protection, reaction is extremely
Stop reaction when acid value is 0.8mgKOH/g, hydroxyl value is 86mgKOH/g, polyester polyol is made.
(2) preparation of component A: by the polyester polyol investment reaction kettle of 150kg step (1) preparation, being heated to 95 DEG C,
16.2kg3, chloro- 4, the 4'- diaminodiphenyl-methane of 3'- bis- is added, 4.8kg ethylene glycol is uniformly mixed, completely molten to chain extender
15kg paraphenylene diisocyanate is added in Xie Hou, is uniformly mixed, after paraphenylene diisocyanate is completely dissolved, is cooled down with water-bath, fast
Prompt drop reacts a hour to 70 DEG C, and 75.6kg terminal hydroxy group hydrogenated butadiene polymer, 0.9kgDC-3042,4.2kg catalyst is added
Triethylene diamine, 0.34kg water are uniformly mixed, and obtain component A.
(3) preparation of B component: by 10kg polycarbonate glycol (number-average molecular weight 1000), 11kg polytetrahydrofuran two
Alcohol (number-average molecular weight 1500) is put into reaction kettle, is heated to 95 DEG C, and 1.5kg paraphenylene diisocyanate is added, and is uniformly mixed,
After paraphenylene diisocyanate is completely dissolved, cooled down with water-bath, be rapidly decreased to 70 degrees Celsius, reacted a hour, is added
The 4,4 '-methyl diphenylene diisocyanates and 9.3kg Carbodiimide-Modified 4,4 '-diphenyl methane two of 27.7kg melting are different
Cyanate reacts a hour, obtains B component.
(4) preparation of pu tire: tire-mold is heated to 55 DEG C, is placed on motor and is revolved with the speed of 600r/min
Turning, the temperature for controlling component A and B component is 65 DEG C, 149.9kgA material and 50.1kgB material is placed in injection molding machine and is sufficiently mixed,
It is poured into tire-mold, mold stops rotating after five minutes, opens mold after placing 50 minutes and obtains polyurethane solid tyre.
Embodiment 3
(1) by 63.8kg decanedioic acid, 49.2kg adipic acid, 62.7kg1,6- hexylene glycol, 21.9kg neopentyl glycol, 0.06kg
Trimethylolpropane, 0.8kg Dibutyltin oxide mix, and 235 DEG C of progress polyesterification reactions are heated under nitrogen protection, reaction is extremely
Stop reaction when acid value is 0.8mgKOH/g, hydroxyl value is 79mgKOH/g, polyester polyol is made.
(2) preparation of component A: by the polyester polyol investment reaction kettle of 150kg step (1) preparation, being heated to 95 DEG C,
17.8kg3, chloro- 4, the 4'- diaminodiphenyl-methane of 3'- bis- is added, 6.2kg ethylene glycol is uniformly mixed, completely molten to chain extender
18kg paraphenylene diisocyanate is added in Xie Hou, is uniformly mixed, after paraphenylene diisocyanate is completely dissolved, is cooled down with water-bath, fast
Prompt drop reacts a hour to 70 DEG C, and 59.4kg hydroxyl terminated butadiene acrylonitrile copolymer, 1.5kgDC-3042,5.9kg catalysis is added
Agent tetramethyl diethylenetriamines, 3.7kg Propellent 14 1b are uniformly mixed, and obtain component A.
(3) preparation of B component: by 10kg polycarbonate glycol (number-average molecular weight 1000), 12kg polytetrahydrofuran two
Alcohol (number-average molecular weight 1000) is put into reaction kettle, is heated to 95 DEG C, and 1.8kg paraphenylene diisocyanate is added, and is uniformly mixed,
After paraphenylene diisocyanate is completely dissolved, cooled down with water-bath, be rapidly decreased to 70 degrees Celsius, reacted a hour, is added
The 4,4 '-methyl diphenylene diisocyanates and 4,4 '-diphenyl methane of 11.1kg Carbodiimide-Modified two of 29.2kg melting
Isocyanates reacts a hour, obtains B component.
(4) preparation of pu tire: tire-mold is heated to 55 DEG C, is placed on motor and is revolved with the speed of 600r/min
Turning, the temperature for controlling component A and B component is 65 DEG C, 151.5kgA material and 48.5kgB material is placed in injection molding machine and is sufficiently mixed,
It is poured into tire-mold, mold stops rotating after five minutes, opens mold after placing 45 minutes and obtains polyurethane solid tyre.
Embodiment 4
(1) by 56.5kg decanedioic acid, 56.5kg adipic acid, 60.2kg1,6 hexylene glycol, 30.1kg neopentyl glycol, 0.8kg bis-
Butyl tin oxide mixes, and 230 DEG C of progress polyesterification reactions are heated under nitrogen protection, and reaction to acid value is 0.8mgKOH/g, hydroxyl
Stop reaction when value is 76mgKOH/g, polyester polyol is made, the catalyst is tetrabutyl titanate.
(2) preparation of component A: by the polyester polyol investment reaction kettle of 150kg step (1) preparation, being heated to 95 DEG C,
21.5kg3, chloro- 4, the 4'- diaminodiphenyl-methane of 3'- bis- is added, 8.5kg ethylene glycol is uniformly mixed, completely molten to chain extender
20kg paraphenylene diisocyanate is added in Xie Hou, is uniformly mixed, after paraphenylene diisocyanate is completely dissolved, is cooled down with water-bath, fast
Prompt drop reacts a hour to 70 DEG C, and 39.6kg terminal hydroxy group hydrogenated butadiene polymer, 3.6kgDC-3042,6.9kg catalyst is added
Tetramethyl diethylenetriamines, 2.9kg Propellent 14 1b are uniformly mixed, and obtain component A.
(3) preparation of B component: by 10kg polycarbonate glycol (number-average molecular weight 1000), 13kg polytetrahydrofuran two
Alcohol (number-average molecular weight 1000) is put into reaction kettle, is heated to 95 DEG C, and 2.1kg paraphenylene diisocyanate is added, and is uniformly mixed,
After paraphenylene diisocyanate is completely dissolved, cooled down with water-bath, be rapidly decreased to 70 degrees Celsius, reacted a hour, is added
The 4,4 '-methyl diphenylene diisocyanates and 4,4 '-diphenyl methane of 14.1kg Carbodiimide-Modified two of 30.6kg melting
Isocyanates reacts a hour, obtains B component.
(4) preparation of pu tire: tire-mold is heated to 55 DEG C, is placed on motor and is revolved with the speed of 600r/min
Turning, the temperature for controlling component A and B component is 65 DEG C, 142.8kgA material and 57.2kgB material is placed in injection molding machine and is sufficiently mixed,
It is poured into tire-mold, mold stops rotating after five minutes, opens mold after placing 30 minutes and obtains polyurethane solid tyre.
Each embodiment the performance test results are as shown in the table:
Claims (7)
1. a kind of preparation method for automobile-used polyurethane solid tyre of digging up mine, it is characterised in that its step are as follows:
(1) it prepares polyester polyol: binary acid and polyalcohol being mixed with the ratio that mass ratio is 100 ︰ (65~80), are being catalyzed
Polyesterification reaction is carried out under the action of agent A, polyester polyol is made, wherein the binary acid is decanedioic acid and adipic acid with quality
Than the mixture for (0~100) 100 ︰, the polyalcohol is 1,6- hexylene glycol, neopentyl glycol and trimethylolpropane with matter
Measure the ratio 100 ︰ (mixture of 10~50) ︰ (0~0.5)；
(2) preparation of component A: the polyester polyol and chain extender, paraphenylene diisocyanate that step (1) is prepared are with quality
Than 100 ︰, (ratio of 12~20) ︰ (8~14) is mixed, and carries out prepolymerization reaction, is made with hydroxy-end capped oligomer a, then will be low
Polymers a and terminal hydroxy liquid rubber, organosilicon foam stabilizer, catalyst B, foaming agent with 100 ︰ of mass ratio (20~50) ︰ (0.4~
1) the ratio mixing of ︰ (1.8~3.5) ︰ (0.2~2), obtains component A, wherein the chain extender is 3,3'- bis- chloro- 4,4'-
Diaminodiphenyl-methane and ethylene glycol take mass ratio as the mixture of 100 ︰ (25~40)；
(3) preparation of B component: by polycarbonate polyol, polytetrahydrofuran polyol and paraphenylene diisocyanate with mass ratio
(ratio of 100~130) ︰ (12~21) carries out prepolymerization reaction to 100 ︰, is made with hydroxy-end capped oligomer b, by this oligomer b
It is mixed with isocyanates b with the ratio of 100 ︰ of mass ratio (160~180), carries out prepolymerization reaction, B component is obtained, wherein described different
Cyanate b be 4,4 '-methyl diphenylene diisocyanates, Carbodiimide-Modified 4,4 '-methyl diphenylene diisocyanate with
Mass ratio is the mixture of 100 ︰ (24~45)；
(4) production of pu tire: two component of A, B is sufficiently mixed, and is poured into after solidifying in tire-mold and is obtained product,
The dosage of middle component A and B component be the ratio between active hydrogen molal quantity and molal quantity of-NCO of B component of component A be 100 ︰ (90~
110)。
2. the preparation method for automobile-used polyurethane solid tyre of digging up mine as described in claim 1, it is characterised in that the catalyst A
For the mixture of one or both of tetraisopropyl titanate or Dibutyltin oxide.
3. the preparation method for automobile-used polyurethane solid tyre of digging up mine as claimed in claim 2, it is characterised in that the poly- tetrahydro
The number-average molecular weight of furan polyols is 1000~2000, and the number-average molecular weight of the polycarbonate polyol is 1000.
4. the preparation method for automobile-used polyurethane solid tyre of digging up mine as claimed in claim 3, the catalyst B is tin dilaurate
One of dibutyl tin, triethylene diamine, tetramethyl diethylenetriamines or two or more mixtures.
5. the preparation method for automobile-used polyurethane solid tyre of digging up mine as claimed in claim 4, it is characterised in that the end hydroxyl
Base fluid body rubber is the mixture of one or both of hydroxyl terminated butadiene acrylonitrile copolymer, terminal hydroxy group hydrogenated butadiene polymer.
6. the preparation method for automobile-used polyurethane solid tyre of digging up mine as claimed in claim 5, it is characterised in that the organosilicon
Foam stabilizer is the mixture of one or more of DC-193, DC-3042 and DC-3043.
7. the preparation method for automobile-used polyurethane solid tyre of digging up mine as claimed in claim 6, it is characterised in that the foaming agent
For the mixture of one or both of water, chlorofluorocarbons.
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| CN110407995A (en) * | 2019-07-24 | 2019-11-05 | 安徽三彩工贸有限责任公司 | A kind of heavy type field vehicle polyurethane solid tyre and its processing technology |
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| CN114276777A (en) * | 2021-12-27 | 2022-04-05 | 烟台德邦科技股份有限公司 | Reactive polyurethane hot melt adhesive and preparation method thereof |
| CN115926101A (en) * | 2023-02-14 | 2023-04-07 | 旭川化学（苏州）有限公司 | Low-temperature-resistant polyurethane sole resin and preparation method and application thereof |
| CN116284644A (en) * | 2023-02-20 | 2023-06-23 | 安徽誉林新材料科技有限公司 | High-wear-resistance polyurethane tire and preparation method thereof |
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