CN108250418A - Terminal hydroxy liquid rubber modified aromatic polyester polyol and its preparation method and application - Google Patents
Terminal hydroxy liquid rubber modified aromatic polyester polyol and its preparation method and application Download PDFInfo
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- CN108250418A CN108250418A CN201711500643.2A CN201711500643A CN108250418A CN 108250418 A CN108250418 A CN 108250418A CN 201711500643 A CN201711500643 A CN 201711500643A CN 108250418 A CN108250418 A CN 108250418A
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
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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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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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
- C08G18/42—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
- C08G18/65—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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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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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- 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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- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/916—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- 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
- C08J9/12—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 physical blowing agent
- C08J9/14—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 physical blowing agent organic
- C08J9/143—Halogen containing compounds
- C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
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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
- C08J9/12—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 physical blowing agent
- C08J9/14—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 physical blowing agent organic
- C08J9/143—Halogen containing compounds
- C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
- C08J9/146—Halogen containing compounds containing carbon, halogen and hydrogen only only fluorine as halogen atoms
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- 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
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
- C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
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- Polymers & Plastics (AREA)
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- General Chemical & Material Sciences (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a kind of terminal hydroxy liquid rubber modified aromatic polyester polyol and its preparation method and application, the terminal hydroxy liquid rubber modified aromatic polyester polyol is terminal hydroxy liquid rubber, the esterification of small molecule dihydric alcohol and aromatic acid, polycondensation product；The hydroxyl value of the terminal hydroxy liquid rubber modified aromatic polyester polyol is (28.0~112.0) mgKOH/g.Terminal hydroxy liquid rubber modified aromatic polyester polyol is used for the preparation of polyurethane elastomer stoste, improves low temperature folding resistance and wearability of High Hardness Polyurethane Elastomer etc., and hardness rises less at low ambient temperatures.
Description
Technical field
The present invention relates to a kind of modified aromatic polyester polyol and its preparation method and application.
Background technology
Microporous polyurethane elastomer refers to density between 0.25~0.9g/cm3Fretting map polyurethane material, processing letter
Single, it is various to have the advantages that light, elasticity is good, wear-resisting, folding, oil resistivity are good etc., can as shoes parts, material for sole of shoe, hold
The uses such as roller tire and automatic buffer material play a significant role in national economy life.But polyurethane elastomer is simultaneously
It is inperfect in every way, it often needs to add auxiliary agent or modified material to improve certain aspect performance, expanded application field.Application number
201510481696.9 Chinese patent application to substitute polyester polyol or polyether polyol with end hydroxy butadiene be poly-
Urethane strand soft segment improves the cryogenic property and elasticity of polyurethane elastomer.Application No. is 201510083380.4 China specially
The end hydroxy butadiene that part is added in profit application in composite polyurethane elastic composition improves the low of polyurethane elastomer
Temperature characteristics.End hydroxy butadiene is added directly into polyurethane system by these patent application documents, and there are Miscibilities
The problem of difference and production operation difficulty are big.Chinese patent application application No. is 201210250546.3 is by poly- sebacic acid-poly- fourth
Diene binary alcohol esters polyalcohol and polyethylene glycol-Isosorbide-5-Nitrae butanediol adipate ester polyhydric alcohol conjugate are more as polyurethane sole materials
Polyester polyol in first alkoxide component improves the resistance to low temperature of polyurethane shoe-sole.But polybutadiene dihydric alcohol is different from common
Small molecule polyol, primary hydroxyl is less high, and the difficulty that single polybutadiene dihydric alcohol is reacted with binary acid is larger, raw simultaneously
The proportion of primary OH groups of poly- sebacic acid-polybutadiene binary alcohol esters polyalcohol of production is not high, causes subsequent reactions activity low, Er Qieju
The intermiscibility of sebacic acid-polybutadiene binary alcohol esters polyalcohol and polyethylene glycol-Isosorbide-5-Nitrae butanediol adipate ester polyalcohol is not yet
Good, the polyurethane shoe-sole of subsequent production is susceptible to decortication phenomenon.
Invention content
The object of the present invention is to provide aromatic modified polyester polyol of terminal hydroxy liquid rubber and its preparation method and application,
It is of the existing technology to solve the problems, such as.
Terminal hydroxy liquid rubber modified aromatic polyester polyol of the present invention is terminal hydroxy liquid rubber, small molecule binary
The esterification of alcohol and aromatic acid, polycondensation product；
The hydroxyl value of the terminal hydroxy liquid rubber modified aromatic polyester polyol is (28.0~112.0) mgKOH/g；
Preferably,
The hydroxyl value of the terminal hydroxy liquid rubber modified aromatic polyester polyol is (56.0~112.0) mgKOH/g；
The acid value of the terminal hydroxy liquid rubber modified aromatic polyester polyol is (0.1~0.6) mgKOH/g；
The molar ratio of the carboxyl in hydroxyl and aromatic acid in the terminal hydroxy liquid rubber and small molecule dihydric alcohol is
(1.2~1.6): 1.
The mass ratio of the terminal hydroxy liquid rubber and small molecule dihydric alcohol is 2: 1~1: 3.
The terminal hydroxy liquid rubber is the poly- butyronitrile liquid rubber of terminal hydroxy group, terminal hydroxyl polybutadiene liquid rubber, end hydroxyl
One or more in base butylbenzene liquid rubber, hydroxyl terminated polyisoprene liquid rubber；
The degree of functionality of terminal hydroxy liquid rubber is 1.9~2.4, and number-average molecular weight is 250~500；
The small molecule dihydric alcohol is ethylene glycol, diethylene glycol, 1,4-butanediol, 1,6- hexylene glycols, neopentyl glycol, 1,3-
One or more in propylene glycol；
The aromatic acid is terephthalic acid (TPA), the one or more in phthalic acid, M-phthalic acid, phthalic anhydride；
The preparation method of the terminal hydroxy liquid rubber modified aromatic polyester polyol, small point is sequentially added into reaction kettle
Sub- dihydric alcohol, terminal hydroxy liquid rubber, aromatic acid and (40~160) ppm titanium class catalyst, open stirring, start to warm up to
Constant temperature (1~2) h when (150~170) DEG C stablizes dewatering speed (by rectifying column, keeping 90~105 DEG C of tower top temperature) and treats reality
Border water yield reaches theoretical 80% or so subsequent temperature of continuing rising of water yield, is warming up to (180~200) DEG C or so, opens vacuum pump, control
Vacuum degree processed slowly gradually increases.Treat that being warming up to (225~255) DEG C after theoretical water outlet again carries out ester exchange reaction,
And be passed through nitrogen and take away superfluous polyalcohol and small molecular alcohol, take control point in a sample after timing 5h per 2h since vacuumizing
Analysis restores normal pressure, is down to room temperature, discharging preserves to final acid value and hydroxyl value.
The titanium class catalyst is tetraisopropyl titanate, one kind of tetrabutyl titanate or mixture.
The terminal hydroxy liquid rubber modified aromatic polyester polyol is used to prepare Low temperature-resistanpolyurethane polyurethane elastomer stoste, subtracts
The defects of hardness of little tradition High Hardness Polyurethane Elastomer varies with temperature greatly, and low temperature folding resistance is poor.
The Low temperature-resistanpolyurethane polyurethane elastomer stoste includes polyurethane stock solution component A and polyurethane stock solution B component；
The polyurethane stock solution component A is made of the raw material of following parts by weight：
The chain extender is ethylene glycol, 1,4-butanediol, diglycol, 1,2-PD, neopentyl glycol, methyl-prop
One or more in glycol, 1,6- hexylene glycols, 1,3-PD, glycerine, trimethylolpropane, trimethylolethane；
The foam stabilizer is organic silicon modified by polyether class surfactant；
The physical blowing agent is pentafluoropropane, dichloro one fluoroethane, one or more in 3-pentafluorobutane；
The catalyst is triethylene diamine, 70% bis- (dimethylaminoethyl) ethereal solutions, dimethyl cyclohexyl amine, N- methyl
One or more in dicyclohexyl amine；
The polyurethane stock solution B component is made of the raw material of following parts by weight：
50~70 parts of isocyanates；
30~50 parts of terminal hydroxy liquid rubber modified aromatic polyester polyol；
0.002~0.01 part of phosphoric acid.
The isocyanates is methyl diphenylene diisocyanate, Carbodiimide-Modified diisocyanate, toluene two are different
Cyanate, isoflurane chalcone diisocyanate, hexamethylene diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl two are different
One or more in cyanate.
The preparation method of the polyurethane stock solution component A：By terminal hydroxy liquid rubber modified aromatic polyester polyol, chain extension
Agent, foam stabilizer, water, physical blowing agent and catalyst are placed in reaction kettle, are gone out after being sufficiently mixed (2~4) h at (30~50) DEG C
Material, is sealed.
The preparation method of the polyurethane stock solution B component：Isocyanates, terminal hydroxy liquid rubber modified aromatic polyester is more
First alcohol, phosphoric acid are placed in reaction kettle, and (2~3) h is reacted under the conditions of (60~80) DEG C, is cooled to (30~40) DEG C, control-NCO
Content is (17~19) wt% relative to the total weight of B component, and discharging is sealed.
The application process of the Low temperature-resistanpolyurethane polyurethane elastomer stoste, it is (45~50) to control the temperature of component A and B component
℃；The ratio of the two is adjusted, it is 1: 1 to make the ratio between the molal quantity of active hydrogen and the-NCO molal quantitys of B component in component A；By two groups
It point is injected into the mold of (40~60) DEG C after (4~6) min and taken off with after the speed of (4000~8000) r/min quickly mixing
Mould, (20~28) h curings, obtains out Low temperature-resistanpolyurethane polyurethane elastomer.
Compared with prior art, the present invention has the following advantages：
(1) the small molecule dihydric alcohol of part is substituted using terminal hydroxy liquid rubber, production terminal hydroxy group liquid is reacted with aromatic acid
Body rubber modified aromatic polyester polyol, is used to prepare polyurethane elastomer stoste, improves the resistance to of High Hardness Polyurethane Elastomer
Cryogenic property improves low temperature folding resistance, reduce hardness increase rate under low temperature environment, and the hardness of elastomer at low ambient temperatures
Rise less, be more suitable for use in winter；
(2) terminal hydroxy liquid rubber modified aromatic polyester polyol of the invention and the other raw materials of polyurethane stock solution system
Compatibility is good；
(3) lower temperature resistance of polyurethane elastomer of the invention is excellent, and wearability is strong.
Specific embodiment
Below by specific embodiment, the present invention is further elaborated, it should be understood that the reality of the present invention
The specific material proportion described in example is applied, process conditions and result are merely to illustrate the present invention, this can not be limited with this
The protection domain of invention, the equivalent change or modification that every Spirit Essence according to the present invention is done, should all cover in this hair
In bright protection domain.
Embodiment 1
The ethylene glycol of 5.8kg, the 1,4-butanediol of 5.8kg, the poly- fourth of terminal hydroxy group of 23.1kg are sequentially added into reaction kettle
Diene liquid rubber (molecular weight 250, degree of functionality 1.9), the terephthalic acid (TPA) of 25.4kg and 2.4g titanium class catalyst are opened
Stirring is started to warm up to constant temperature 2h at 150 DEG C, stablizes dewatering speed (by rectifying column, tower top temperature is kept for 90 DEG C), after of continuing rising
Temperature to 180 DEG C of opening vacuum pumps, control vacuum degree slowly gradually increases.225 DEG C of progress ester exchange reactions are warming up to, and are passed through nitrogen
Gas takes away superfluous polyalcohol and small molecular alcohol, and often 2h takes a sample middle control analysis to final after timing 5h since vacuumize ing
Acid value is (0.1~0.6) mgKOH/g or so, hydroxyl value 112.0mgKOH/g, restores normal pressure, is down to room temperature, and discharging is preserved, obtained
To terminal hydroxy liquid rubber modified aromatic polyester polyol P1.
Embodiment 2
The ethylene glycol of 12.8kg, the poly- butyronitrile alkene liquid rubber (molecule of terminal hydroxy group of 12.8kg are sequentially added into reaction kettle
It is 500 to measure, degree of functionality 2.4), the terephthalic acid (TPA) of 24.2kg, the phthalic acid of 10.1kg and 5.6g titanium class catalyst are beaten
Stirring is opened, is started to warm up to constant temperature 2h at 170 DEG C, stablizes dewatering speed (by rectifying column, tower top temperature is kept for 105 DEG C), after
Continuous to be warming up to 200 DEG C of opening vacuum pumps, control vacuum degree slowly gradually increases.255 DEG C of progress ester exchange reactions are warming up to, and are led to
Enter nitrogen and take away superfluous polyalcohol and small molecular alcohol, since vacuumize ing after timing 5h often 2h take a sample middle control analysis to
Final acid value is (0.1~0.6) mgKOH/g, hydroxyl value 56.0mgKOH/g, restores normal pressure, is down to room temperature, and discharging is preserved, obtained
Terminal hydroxy liquid rubber modified aromatic polyester polyol P2.
Embodiment 3
Sequentially added into reaction kettle the ethylene glycol of 7.0kg, 7.0kg 1,4-butanediol, 14.0kg the poly- butyronitrile of terminal hydroxy group
Alkene liquid rubber (molecular weight 500, degree of functionality 2.4), the M-phthalic acid and 6.6g titanium class catalyst, opening of 32.0kg stir
It mixes, starts to warm up to constant temperature 2h at 170 DEG C, stablize dewatering speed (by rectifying column, tower top temperature is kept for 105 DEG C), after of continuing rising
Temperature to 200 DEG C of opening vacuum pumps, control vacuum degree slowly gradually increases.255 DEG C of progress ester exchange reactions are warming up to, and are passed through nitrogen
Gas takes away superfluous polyalcohol and small molecular alcohol, and often 2h takes a sample middle control analysis to final after timing 5h since vacuumize ing
Acid value is (0.1~0.6) mgKOH/g, hydroxyl value 56.0mgKOH/g, restores normal pressure, is down to room temperature, and discharging preserves, and obtains end hydroxyl
Base fluid body rubber modified aromatic polyester polyol P3.
Embodiment 4
The ethylene glycol of 6.1kg, the 1,4-butanediol of 12.2kg, the poly- fourth of terminal hydroxy group of 6.1kg are sequentially added into reaction kettle
Diene liquid rubber (molecular weight 500, degree of functionality 2.4), the terephthalic acid (TPA) of 35.6kg and 9.6g titanium class catalyst are opened
Stirring is started to warm up to constant temperature 2h at 160 DEG C, is stablized dewatering speed (by rectifying column, tower top temperature is kept for 105 DEG C), is continued
190 DEG C of opening vacuum pumps are warming up to, control vacuum degree slowly gradually increases.230 DEG C of progress ester exchange reactions are warming up to, and are passed through
Nitrogen takes away superfluous polyalcohol and small molecular alcohol, and a sample middle control analysis is taken to most per 2h after timing 5h since vacuumizing
Whole acid value is (0.1~0.6) mgKOH/g, hydroxyl value 28.0mgKOH/g, restores normal pressure, is down to room temperature, and discharging is preserved, held
Liquid hydroxyl rubber modified aromatic polyester polyol P4.
Embodiment 5
By the ethylene glycol of terminal hydroxy liquid rubber modified aromatic polyester polyol P1,2.80kg of 50.00kg, 0.70kg
Trimethylolpropane, the organic silicon modified by polyether class surfactant of 0.05kg, the water of 0.025kg, 0.50 pentafluoropropane and
The triethylene diamine of 0.40kg is placed in reaction kettle, is discharged, is sealed after 4h is sufficiently mixed at 30 DEG C, obtains polyurethane original
Liquid component A.
The terminal hydroxy liquid rubber modified aromatic polyester of the methyl diphenylene diisocyanate of 25.00kg, 15.00kg is more
The phosphoric acid of first alcohol P1,1.00g are placed in reaction kettle, react 3h under the conditions of 60 DEG C, are cooled to 30 DEG C, control-NCO content is opposite
It is 18wt% in the total weight of B component, discharging is sealed, obtains polyurethane stock solution B component.
It is 45 DEG C to control the temperature of component A and B component；The mass ratio for adjusting component A and B component is 0.80: 1；By two groups
Divide after the speed of 4000r/min quickly mixing, to be injected into 40 DEG C of mold and be demoulded after 6min, cure 28h, obtain low temperature resistant
Polyurethane elastomer.
Embodiment 6
By the ethylene glycol of terminal hydroxy liquid rubber modified aromatic polyester polyol P3,3.00kg of 50.00kg, 3.00kg
1,4-butanediol, the organic silicon modified by polyether class surfactant of 0.20kg, the water of 0.15kg, 1.50kg dichloro one fluoroethane
It is placed in reaction kettle with 70% bis- (dimethylaminoethyl) ethereal solutions of 0.60kg, discharges after 2h is sufficiently mixed at 50 DEG C, it is close
Envelope preserves, and obtains polyurethane stock solution component A.
The Carbodiimide-Modified diphenyl methane two of the methyl diphenylene diisocyanate of 18.00kg, 12.00kg is different
Cyanate, 25.00kg the phosphoric acid of terminal hydroxy liquid rubber modified aromatic polyester polyol P2,3.00g be placed in reaction kettle,
2h is reacted under the conditions of 80 DEG C, is cooled to 40 DEG C, control-NCO content is 17wt% relative to the total weight of B component, is discharged, sealing
It preserves, obtains polyurethane stock solution B component.
It is 50 DEG C to control the temperature of component A and B component；The mass ratio for adjusting component A and B component is 0.85: 1；By two groups
Divide after the speed of 8000r/min quickly mixing, to be injected into 60 DEG C of mold and be demoulded after 4min, cure 20h, obtain low temperature resistant
Polyurethane elastomer.
Embodiment 7
By the ethylene glycol of terminal hydroxy liquid rubber modified aromatic polyester polyol P4,5.00kg of 50.00kg, 2.50kg
1,4-butanediol, the organic silicon modified by polyether class surfactant of 0.30kg, the water of 0.30kg, 2.00kg 3-pentafluorobutane and
The triethylene diamine of 0.85kg is placed in reaction kettle, is discharged, is sealed after 4h is sufficiently mixed at 30 DEG C, obtains polyurethane original
Liquid component A.
The terminal hydroxy liquid rubber modified aromatic polyester of the methyl diphenylene diisocyanate of 35.00kg, 25.00kg is more
The phosphoric acid of first alcohol P1,9.60g are placed in reaction kettle, react 3h under the conditions of 60 DEG C, are cooled to 30 DEG C, control-NCO content is opposite
It is 19wt% in the total weight of B component, discharging is sealed, obtains polyurethane stock solution B component.
It is 45 DEG C to control the temperature of component A and B component；The mass ratio for adjusting component A and B component is 0.96: 1；By two groups
Divide after the speed of 6000r/min quickly mixing, to be injected into 40 DEG C of mold and be demoulded after 6min, cure 28h, obtain low temperature resistant
Polyurethane elastomer.
Comparative example 1
By the polyethylene terephthalate of 50.00kg -1,4-butanediol esterdiol (hydroxyl value 112.0mgKOH/g),
The ethylene glycol of 2.80kg, the trimethylolpropane of 0.70kg, the organic silicon modified by polyether class surfactant of 0.05kg,
The triethylene diamine of the water of 0.025kg, 0.50 pentafluoropropane and 0.40kg is placed in reaction kettle, after being sufficiently mixed 4h at 30 DEG C
Discharging, is sealed, obtains polyurethane stock solution component A.
By polyethylene terephthalate-Isosorbide-5-Nitrae-fourth two of the methyl diphenylene diisocyanate of 25.00kg, 15.00kg
Alcohol esterdiol (hydroxyl value 112.0mgKOH/g), 1.00g phosphoric acid be placed in reaction kettle, 3h is reacted under the conditions of 60 DEG C, cool down
To 30 DEG C, control-NCO content is 18wt% relative to the total weight of B component, and discharging is sealed, obtains polyurethane stock solution B
Component.
It is 45 DEG C to control the temperature of component A and B component；The mass ratio for adjusting component A and B component is 0.80: 1；By two groups
Divide after the speed of 4000r/min quickly mixing, to be injected into 40 DEG C of mold and be demoulded after 6min, cure 28h, obtain low temperature resistant
Polyurethane elastomer.
Comparative example 2
By the poly- M-phthalic acid of terminal hydroxy liquid rubber modified aromatic polyester polyol P2,30.00kg of 20.00kg-
Ethylene glycol -1,4-butanediol esterdiol (hydroxyl value 56.0mgKOH/g), the ethylene glycol of 3.00kg, 3.00kg 1,4-butanediol,
The organic silicon modified by polyether class surfactant of 0.20kg, the water of 0.15kg, the dichloro one fluoroethane of 1.50kg and 0.60kg
70% bis- (dimethylaminoethyl) ethereal solutions are placed in reaction kettle, are discharged, are sealed after 2h is sufficiently mixed at 50 DEG C, obtain
Polyurethane stock solution component A.
The Carbodiimide-Modified diphenyl methane two of the methyl diphenylene diisocyanate of 18.00kg, 12.00kg is different
Cyanate, 25.00kg the phosphoric acid of terminal hydroxy liquid rubber modified aromatic polyester polyol P2,3.00g be placed in reaction kettle,
2h is reacted under the conditions of 80 DEG C, is cooled to 40 DEG C, control-NCO content is 17wt% relative to the total weight of B component, is discharged, sealing
It preserves, obtains polyurethane stock solution B component.
It is 50 DEG C to control the temperature of component A and B component；The mass ratio for adjusting component A and B component is 0.85: 1；By two groups
Divide after the speed of 8000r/min quickly mixing, to be injected into 60 DEG C of mold and be demoulded after 4min, cure 20h, obtain low temperature resistant
Polyurethane elastomer.
Comparative example 3
By the terminal hydroxyl polybutadiene liquid rubber (hydroxyl value 28.0mgKOH/g) of 25.00kg, 25.00kg it is poly- to benzene
Dioctyl phthalate-ethylene glycol -1,4-butanediol esterdiol (hydroxyl value 28.0mgKOH/g), the ethylene glycol of 5.00kg, 2.50kg Isosorbide-5-Nitrae -
Butanediol, the organic silicon modified by polyether class surfactant of 0.30kg, the water of 0.30kg, 2.00kg 3-pentafluorobutane and 0.85kg
Triethylene diamine be placed in reaction kettle, discharge, be sealed after 4h is sufficiently mixed at 30 DEG C, obtain polyurethane stock solution A groups
Point.
By the terminal hydroxyl polybutadiene liquid rubber (hydroxyl value of the methyl diphenylene diisocyanate of 35.00kg, 15.00kg
For 28.0mgKOH/g), poly terephthalic acid-ethylene glycol -1,4-butanediol esterdiol (hydroxyl value 28.0mgKOH/ of 10.00kg
G), the phosphoric acid of 9.60g is placed in reaction kettle, reacts 3h under the conditions of 60 DEG C, is cooled to 30 DEG C, control-NCO content is relative to B
The total weight of component is 19wt%, and discharging is sealed, obtains polyurethane stock solution B component.
It is 45 DEG C to control the temperature of component A and B component；The mass ratio for adjusting component A and B component is 0.96: 1；By two groups
Divide after the speed of 6000r/min quickly mixing, to be injected into 40 DEG C of mold and be demoulded after 6min, cure 28h, obtain low temperature resistant
Polyurethane elastomer.
Every physical property measurement result of polyurethane elastomer obtained by Application Example 5~7 and comparative example 1~3 is listed in
Table 1.
Table 1
To sum up, the present invention is reacted with terminal hydroxy liquid rubber with small molecule dihydric alcohol, phthalic acid prepares terminal hydroxy group liquid
Body rubber modified aromatic polyester polyol, then polyurethane stock solution component A is mixed with itself and chain extender, foaming agent etc., it is and different
Polyisocyanate reactant prepares polyurethane stock solution B component, and Low temperature-resistanpolyurethane polyurethane elastomer, wherein polyurethane is made in the mixing cast of AB components
Each materials compatibility is good in stoste, and without other polyester polyol is coordinated to use again in raw material, the polyurethane of moulding by casting
Elastomer formation effect is good, and hardness is high, and low temperature folding is strong, and hardness rises less at low ambient temperatures, is more suitable for using in winter.
Although above-described embodiment is described in detail technical scheme of the present invention, the technical side of the present invention
Case is not limited to above example, thought and objective of the invention is not being departed from, to scope of the present invention patent
The equivalent change or modification that content is made all should be the technology scope of the present invention.
Claims (10)
1. terminal hydroxy liquid rubber modified aromatic polyester polyol, which is characterized in that for terminal hydroxy liquid rubber, small molecule binary
The esterification of alcohol and aromatic acid, polycondensation product；The hydroxyl value of the terminal hydroxy liquid rubber modified aromatic polyester polyol is
(28.0~112.0) mgKOH/g.
2. terminal hydroxy liquid rubber modified aromatic polyester polyol according to claim 1, which is characterized in that the end hydroxyl
The hydroxyl value of base fluid body rubber modified aromatic polyester polyol is (56.0~112.0) mgKOH/g, and acid value is (0.1~0.6)
mgKOH/g。
3. terminal hydroxy liquid rubber modified aromatic polyester polyol according to claim 2, which is characterized in that the end hydroxyl
The molar ratio of the carboxyl in hydroxyl and aromatic acid in base fluid body rubber and small molecule dihydric alcohol is (1.2~1.6): 1；
The mass ratio of the terminal hydroxy liquid rubber and small molecule dihydric alcohol is 2: 1~1: 3.
4. terminal hydroxy liquid rubber modified aromatic polyester polyol according to claim 3, which is characterized in that the end hydroxyl
Base fluid body rubber is the poly- butyronitrile liquid rubber of terminal hydroxy group, terminal hydroxyl polybutadiene liquid rubber, terminal hydroxy group polychlorobutadiene liquid
One or more in rubber, liquid end hydroxy styrene-butadiene rubber, hydroxyl terminated polyisoprene liquid rubber；
The degree of functionality of the terminal hydroxy liquid rubber is 1.9~2.4, and number-average molecular weight is 250~500；
The small molecule dihydric alcohol is ethylene glycol, diethylene glycol, 1,4-butanediol, 1,6- hexylene glycols, neopentyl glycol, 1,3- the third two
One or more in alcohol；
The aromatic acid is terephthalic acid (TPA), the one or more in phthalic acid, M-phthalic acid, phthalic anhydride.
5. the preparation method of terminal hydroxy liquid rubber modified aromatic polyester polyol according to claim 4, feature exist
In sequentially adding the metatitanic acid four of small molecule dihydric alcohol, terminal hydroxy liquid rubber, aromatic acid and (40~160) ppm into reaction kettle
Isopropyl ester or tetrabutyl titanate open stirring, start to warm up to constant temperature (1~2) h when (150~170) DEG C, stablize dewatering speed
It is subsequent of continuing rising that (by rectifying column, keeping 90~105 DEG C of tower top temperature) treats that practical water yield reaches theoretical water yield 80% or so
Temperature is warming up to (180~200) DEG C or so, opens vacuum pump, and control vacuum degree slowly gradually increases.After treating theoretical water outlet
It is warming up to (225~255) DEG C again and carries out ester exchange reaction, and is passed through nitrogen and takes away superfluous polyalcohol and small molecular alcohol,
A sample middle control analysis is taken to final acid value and hydroxyl value per 2h after timing 5h since vacuumizing, is restored normal pressure, is down to room temperature,
Discharging preserves.
6. Low temperature-resistanpolyurethane polyurethane elastomer stoste, which is characterized in that comprising polyurethane stock solution component A and polyurethane stock solution B component,
The polyurethane stock solution component A includes any one of the Claims 1 to 5 terminal hydroxy liquid rubber modified aromatic polyester polyols
Alcohol, it is more that the polyurethane stock solution B component includes any one of the Claims 1 to 5 terminal hydroxy liquid rubber modified aromatic polyester
First alcohol.
7. Low temperature-resistanpolyurethane polyurethane elastomer stoste according to claim 6, which is characterized in that the polyurethane stock solution A groups
Divide and be made of the raw material of following parts by weight：
The polyurethane stock solution B component is made of the raw material of following parts by weight：
50~70 parts of isocyanates；
30~50 parts of terminal hydroxy liquid rubber modified aromatic polyester polyol；
0.002~0.01 part of phosphoric acid.
8. Low temperature-resistanpolyurethane polyurethane elastomer stoste according to claim 7, which is characterized in that the chain extender is second two
Alcohol, 1,4-butanediol, diglycol, 1,2-PD, neopentyl glycol, methyl propanediol, 1,6- hexylene glycols, 1,3- the third two
One or more in alcohol, glycerine, trimethylolpropane, trimethylolethane；
The chain extender is ethylene glycol, 1,4-butanediol, diglycol, 1,2-PD, neopentyl glycol, methyl-prop two
One or more in alcohol, 1,6- hexylene glycols, 1,3-PD, glycerine, trimethylolpropane, trimethylolethane；
The foam stabilizer is organic silicon modified by polyether class surfactant；
The physical blowing agent is pentafluoropropane, dichloro one fluoroethane, one or more in 3-pentafluorobutane；
The catalyst is triethylene diamine, 70% bis- (dimethylaminoethyl) ethereal solutions, dimethyl cyclohexyl amine, N- methyl bicyclics
One or more in hexylamine；
The isocyanates is methyl diphenylene diisocyanate, Carbodiimide-Modified diisocyanate, toluene diisocynate
Ester, isoflurane chalcone diisocyanate, hexamethylene diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl diisocyanate
One or more in ester.
9. the preparation method of Low temperature-resistanpolyurethane polyurethane elastomer stoste according to claim 8, which is characterized in that including as follows
Step：
(1) by terminal hydroxy liquid rubber modified aromatic polyester polyol, chain extender, foam stabilizer, water, physical blowing agent and catalyst
It is placed in reaction kettle, discharges, be sealed after being sufficiently mixed (2~4) h at (30~50) DEG C, it is former to obtain the polyurethane
Liquid component A；
Isocyanates, terminal hydroxy liquid rubber modified aromatic polyester polyol, phosphoric acid are placed in reaction kettle, in (60~80) DEG C
Under the conditions of react (2~3) h, be cooled to (30~40) DEG C, control-NCO content relative to B component total weight be (17~19)
Wt%, discharging, is sealed to get polyurethane stock solution B component.
10. according to the application of claim 6~8 any one of them Low temperature-resistanpolyurethane polyurethane elastomer stoste, which is characterized in that be used for
Low temperature-resistanpolyurethane polyurethane elastomer is prepared, application process includes the following steps：It is (45~50) to control the temperature of component A and B component
℃；The ratio of the two is adjusted, it is 1: 1 to make the ratio between the molal quantity of active hydrogen and the-NCO molal quantitys of B component in component A；By two groups
After point with the speed of (4000~8000) r/min quickly mixing, it is injected into the mold of (40~60) DEG C and is taken off after (4~6) min
Mould, (20~28) h curings, obtains out Low temperature-resistanpolyurethane polyurethane elastomer.
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| CN109535368A (en) * | 2018-11-29 | 2019-03-29 | 东北师范大学 | A kind of low temperature resistant polyurethane poromerics and preparation method thereof |
| CN110724249A (en) * | 2019-10-11 | 2020-01-24 | 万华化学集团股份有限公司 | Polyester polyol, preparation method and application |
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| CN103570907A (en) * | 2012-07-19 | 2014-02-12 | 旭川化学（昆山）有限公司 | Low temperature resistance polyurethane sole material |
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| CN101781516A (en) * | 2010-02-04 | 2010-07-21 | 广东国望精细化学品有限公司 | Primer coating for extrusion complex of soft package and applications thereof |
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| CN109535368A (en) * | 2018-11-29 | 2019-03-29 | 东北师范大学 | A kind of low temperature resistant polyurethane poromerics and preparation method thereof |
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