CN108285524A - On-slip type polyurethane elastomer stoste and its preparation method and application - Google Patents
On-slip type polyurethane elastomer stoste and its preparation method and application Download PDFInfo
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- CN108285524A CN108285524A CN201711500957.2A CN201711500957A CN108285524A CN 108285524 A CN108285524 A CN 108285524A CN 201711500957 A CN201711500957 A CN 201711500957A CN 108285524 A CN108285524 A CN 108285524A
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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
- C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
- C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
- C08G18/4252—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids derived from polyols containing polyether groups and polycarboxylic acids
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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
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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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
- 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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- 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
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6204—Polymers of olefins
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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
- C08G18/65—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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- 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
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
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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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- 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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- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a kind of on-slip type polyurethane elastomer stoste and its preparation method and application, the on-slip type polyurethane elastomer stoste includes polyurethane stock solution component A and polyurethane stock solution B component；The polyurethane stock solution component A contains polyether ester dihydric alcohol, polyester polyol；The polyurethane stock solution B component contains terminal hydroxy liquid modified rubber polyester polyol.On-slip type polyurethane elastomer stoste can be applied to security protection sole, non-slip mat etc., improve security protection effect.
Description
Technical field
The present invention relates to a kind of polyurethane elastomer stostes and its preparation method and application.
Background technology
Polyurethane is a kind of with carbamate segment repetitive structure list made of isocyanates and polyol reaction
The polymer of member.For polyurethane shoe-sole compared with General Purpose Rubber sole, it has the characteristics that light weight, wear-resisting property are good.Polyurethane
Sole using polyurethane stock solution as primary raw material, solve the problems such as current Plastics in China bottom and reclaimed rubber bottom are easy disconnected bottom and
Rubber-sole is easy the problem of coming unglued.By increasing various additives, makes polyurethane shoe-sole in wear-resisting, oil resistivity, electrical isolation, prevents
It is greatly improved in terms of electrostatic and acid-proof alkaline.But due to the characteristic of polyurethane material, non-skid property is always to hinder
Polyurethane is hindered to go deep into the barrier that wide model uses in sole field.The antiskid property of sole directly affects comfortable when shoes are worn
Property and safety.Antiskid property is poor, on foot when be easy skid wrestling, especially wet, light, cunning road surface on.As the whole world is built
The construction of the development of industry, especially public place, building ground is more and more high-grade, magnificent beautiful, splendid, but mostly neglects
The anti-skidding problem in ground has been omited, the sliding accident for falling tumble injury is caused to often occur.
At this stage, the main material of production on-slip type sole or rubber, based on the materials such as TPR, not only production cost is high,
Production technology is complicated, but also sole is heavy, reduces wearing comfort.And there is also certain dirts to environment for such material
Dye, is unfavorable for the sustainable development of environment.Therefore a kind of on-slip type polyurethane elastomer stoste is developed to accord with the demands of the market, it should
Polyurethane elastomer stoste is green product, and the product produced using the polyurethane elastomer stoste has preferable stop
Slip energy, and processing and forming technology is simple, production cost is low, and wearing comfort is high.
Invention content
The object of the present invention is to provide a kind of on-slip type polyurethane elastomer stostes and its preparation method and application, to solve
Problem of the existing technology.
The on-slip type 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 polyether ester dihydric alcohol is the polytetrahydrofuran ether dihydric alcohol and small molecule binary of number-average molecular weight 100~800
The esterification of alcohol and adipic acid, polycondensation product；
The number-average molecular weight of the polyether ester dihydric alcohol is 3000~6000；
The parts by weight of each raw material are in the polyether ester dihydric alcohol：
20~40 parts of polytetrahydrofuran ether dihydric alcohol；
10~30 parts of small molecule dihydric alcohol；
40~85 parts of adipic acid；
The molar ratio of hydroxyl and carboxyl in adipic acid is in the polytetrahydrofuran ether dihydric alcohol and small molecule dihydric alcohol
(1.2~1.3): 1.
The small molecule dihydric alcohol is ethylene glycol, diethylene glycol, 1,4-butanediol, 1,6- hexylene glycols, 1,3-PD, new
One or more in pentanediol.
The preparation method of the polyether ester dihydric alcohol, sequentially added into reaction kettle polytetrahydrofuran ether dihydric alcohol, small point
Sub- dihydric alcohol and adipic acid are opened stirring, are started to warm up, until constant temperature (1~2) h when (120~150) DEG C, stablizes dewatering speed
(by destilling tower, tower top temperature keeps (90~100) DEG C), subsequent temperature of continuing rising, nitrogen switches when being warming up to (160~190) DEG C
It is passed through from lower part, and is gradually increased nitrogen amount dehydration.It is warming up to (210~240) DEG C, (40-160) is added after constant temperature (1~2) h
Ppm titanium class catalyst, and open and vacuumize, transesterification is carried out, (4~6) h is controlled in taking a sample to carry out per 2h from vacuumizing
Analysis restores normal pressure until acid value is less than or equal to 0.5, hydroxyl value (18~36) mgKOH/g, and nitrogen switching top is passed through, starts
Cooling is cooled to (100~120) DEG C and starts sampling and do final analysis and blowing, preserves.
The titanium class catalyst is tetraisopropyl titanate, one kind of tetrabutyl titanate or mixture.
The polyester polyol be polyadipate system polyester polyol, degree of functionality be 2~4, number-average molecular weight be 1000~
5000。
The chain extender is ethylene glycol, 1,2-PD, 1,3-PD, 1,4-butanediol, diglycol, a contracting
One or more in dipropylene glycol, neopentyl glycol, 1,6- hexylene glycols, cyclohexanedimethanol；
The on-slip agent contains rosin, liquid rubber, zinc oxide and plasticizer；
The parts by weight of each raw material are in the on-slip agent：
The rosin is one or both of natural rosin and rosin resin；
The liquid rubber is the poly- butyronitrile liquid rubber of terminal hydroxy group, terminal hydroxyl polybutadiene liquid rubber, terminal hydroxy group polychlorostyrene
The poly- butyronitrile liquid of butadiene liquid rubber, liquid end hydroxy styrene-butadiene rubber, hydroxyl terminated polyisoprene liquid rubber, end carboxyl
One or more in rubber, carboxyl-terminated polybutadiene liquid rubber, end carboxyl polyisoprene liquid rubber, function
Degree is 1.9~2.4, and number-average molecular weight is 250~500；
The oxidant is nano zine oxide, and grain size is between (1~100) nm；
The plasticizer be butyrolactone, acylated citrate tributyl, mixed dibasic acid dimethyl ester, propene carbonate, oneself two
One or more in sour di-isooctyl；
The preparation method of the on-slip agent includes the following steps：
(1) 1~10 part of zinc oxide is added in 5~10 parts of plasticizer, is put into ball mill grinding (240~300) min,
Obtain zinc oxide slurry；
(2) zinc oxide slurry, 40~50 parts of rosin and 0~10 part of liquid rubber that step (1) obtains are added to 35~
It in 40 parts of plasticizer, is put into after placing (1~3) h in (80~100) DEG C baking oven, takes out and stir (20~40) using blender
Min is to get on-slip agent.
The catalyst is tertiary amine catalyst or organic tin catalyst；
The tertiary amine catalyst is in triethylene diamine, tetramethyl diethylenetriamines, dibutyl tin laurate
It is a kind of.
The polyurethane stock solution B component is made of the raw material of following parts by weight：
20~60 parts of terminal hydroxy liquid modified rubber polyester polyol；
50~75 parts of diisocyanate.
NCO content is 15~18wt% in the polyurethane stock solution B component.
The diisocyanate is methyl diphenylene diisocyanate, Carbodiimide-Modified diphenylmethane diisocyanate
In ester, toluene di-isocyanate(TDI), isophorone diisocyanate, polymethylene polyphenyl diisocyanate, naphthalene diisocyanate
One or more；
The terminal hydroxy liquid modified rubber polyester polyol is terminal hydroxy liquid rubber, small molecule dihydric alcohol and adipic acid
Esterification, polycondensation product；
The hydroxyl value of the liquid rubber modified polyester polyol be (28.0~112.0) mgKOH/g, acid value be (0.1~
0.6) mgKOH/g；
The terminal hydroxy liquid rubber is the poly- butyronitrile liquid rubber of terminal hydroxy group, terminal hydroxyl polybutadiene liquid rubber, end hydroxyl
Base polychlorobutadiene liquid rubber, liquid end hydroxy styrene-butadiene rubber, one kind in hydroxyl terminated polyisoprene liquid rubber or one
Kind or more；
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, 1,3-PD, new
One or more in pentanediol；
The mass ratio of the terminal hydroxy liquid rubber and small molecule dihydric alcohol is 2: 1~1: 3；
The molar ratio of the carboxyl in hydroxyl and adipic acid in the terminal hydroxy liquid rubber and small molecule dihydric alcohol is
(1.2~1.6): 1.
The preparation method of the liquid rubber modified polyester polyol, sequentially added into reaction kettle small molecule dihydric alcohol and
Terminal hydroxy liquid rubber, titanium class 40~160ppm of catalyst open stirring, start to warm up to constant temperature (1 when (140~160) DEG C
~2) h stablizes dewatering speed (by rectifying column, keeping tower top temperature (90~105) DEG C), is warming up to (170~190) DEG C and beats
Vacuum pump is opened, control vacuum degree slowly gradually increases, and is warming up to (215~235) DEG C and carries out ester exchange reaction, and is passed through nitrogen
Superfluous polyalcohol and small molecular alcohol are taken away, often 2h takes a sample middle control analysis to final after timing 5h since vacuumize ing
Acid value and hydroxyl value restore normal pressure, are down to room temperature, and discharging preserves.
The titanium class catalyst is tetraisopropyl titanate, one kind of tetrabutyl titanate or mixture.
The preparation method of the on-slip type polyurethane elastomer stoste component A, by polyether ester dihydric alcohol, polyester polyol,
Chain extender, plasticizer are added in the reaction kettle with temperature control and agitating device, controlled at mixing (2.5 at (45~55) DEG C
~3.5) it after h, (25~35) DEG C is cooled to adds water, catalyst and on-slip agent and be sufficiently stirred (2~3) h, be uniformly mixed, go out
Material, is sealed.
The preparation method of the on-slip type polyurethane elastomer stoste B component, by liquid rubber modified polyester polyol and
Hybrid reaction in the reaction kettle with temperature control and agitating device is added in diisocyanate, and reaction temperature is (55~65) DEG C, reaction
Time is (2~3) h, and cooling discharge is sealed.
The on-slip type polyurethane stoste can be used for preparing on-slip polyurethane elastomer, and preparation method includes the following steps：
By the polyurethane stock solution B groups that polyurethane stock solution component A and temperature that temperature is (48~52) DEG C are (43~47) DEG C
Point, after being mixed in two-component casting machine, the ratio between component A reactive hydrogen molal quantity and B component isocyanate groups molal quantity are 1:
1, it injects reaction (5~7) min moldings, demoulding in (45~50) DEG C mold and cures (22~24) in (60~70) DEG C baking oven
To get the on-slip polyurethane elastomer after h.
Compared with prior art, the present invention has the following advantages：
(1) rosin, zinc oxide, liquid rubber and plasticizer are mixed with on-slip agent, are added to polyurethane elastomer original
In liquid, the anti-slip effect of polyurethane elastomer is improved；
(2) terminal hydroxy liquid modified rubber polyester polyol is utilized to improve the resistance to low temperature of polyurethane elastomer, low
Under warm environment, polyurethane elastomer hardness goes up few, antiskid property and is risen using comfort；
(3) on-slip type polyurethane elastomer stoste of the present invention can be applied to security protection sole, non-slip mat etc., improve safety
Protection effect.
Specific implementation mode
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.
The preparation of polyether ester dihydric alcohol
Embodiment 1
16.4kg polytetrahydrofuran ether dihydric alcohol (number-average molecular weight 100), the second of 8.2kg are sequentially added into reaction kettle
The adipic acid of glycol and 35.4kg is opened stirring, is started to warm up, until constant temperature 2h at 120 DEG C, stablizes dewatering speed and (pass through distillation
Tower, tower top temperature are kept for 90 DEG C), subsequent temperature of continuing rising, nitrogen switching is passed through from lower part when being warming up to 160 DEG C, and is gradually increased nitrogen
Tolerance is dehydrated.210 DEG C are warming up to, the tetraisopropyl titanate of 2.4g is added after constant temperature 2h, and start to vacuumize, carries out transesterification,
A sample is taken to carry out middle control analysis per 2h in 4h since vacuumizing, until acid value is less than or equal to 0.5mgKOH/g, hydroxyl value
37.4 mgKOH/g, restore normal pressure, nitrogen switching top be passed through, start to cool down, be cooled to 100 DEG C start sampling do final analysis
And blowing, it preserves, obtains polyether ester dihydric alcohol 1.
Embodiment 2
11.5kg polytetrahydrofuran ether dihydric alcohol (number-average molecular weight 400), 15.3kg are sequentially added into reaction kettle
The adipic acid of ethylene glycol and 33.2kg is opened stirring, is started to warm up, until constant temperature 1h at 150 DEG C, stablizes dewatering speed and (pass through steaming
Tower is evaporated, tower top temperature is kept for 100 DEG C), subsequent temperature of continuing rising, nitrogen switching is passed through from lower part when being warming up to 190 DEG C, and is gradually added
Big nitrogen amount dehydration.240 DEG C are warming up to, the tetraisopropyl titanate of 5.4g is added after constant temperature 1h, and start to vacuumize, carries out ester
It exchanges, takes a sample to carry out middle control analysis per 2h in the 4h since vacuumizing, until acid value is less than or equal to 0.5mgKOH/g,
Hydroxyl value 28.0mgKOH/g restores normal pressure, and nitrogen switching top is passed through, starts to cool down, be cooled to 120 DEG C start sampling do it is final
Analysis and blowing preserve, obtain polyether ester dihydric alcohol 2.
Embodiment 3
14.6kg polytetrahydrofuran ether dihydric alcohol (number-average molecular weight 800), 14.6kg are sequentially added into reaction kettle
The adipic acid of ethylene glycol and 30.8kg is opened stirring, is started to warm up, until constant temperature 1h at 150 DEG C, stablizes dewatering speed and (pass through steaming
Tower is evaporated, tower top temperature is kept for 100 DEG C), subsequent temperature of continuing rising, nitrogen switching is passed through from lower part when being warming up to 180 DEG C, and is gradually added
Big nitrogen amount dehydration.230 DEG C are warming up to, the tetraisopropyl titanate of 9.6g is added after constant temperature 1h, and start to vacuumize, carries out ester
It exchanges, takes a sample to carry out middle control analysis per 2h in the 4h since vacuumizing, until acid value is less than or equal to 0.5mgKOH/g,
Hydroxyl value 18.7mgKOH/g restores normal pressure, and nitrogen switching top is passed through, starts to cool down, be cooled to 120 DEG C start sampling do it is final
Analysis and blowing preserve, obtain polyether ester dihydric alcohol 3.
The preparation of on-slip agent
Embodiment 4
(1) nano zine oxide of 100g is added in the butyrolactone of 500g, is put into ball mill grinding 300min, obtains oxygen
Change zinc slurry；
(2) natural rosin of zinc oxide slurry, 4000g that step (1) obtains is added in the butyrolactone of 3500g, is put
Enter after placing 3h in 80 DEG C of baking ovens, takes out and stir 40min using blender to get on-slip agent 1.
Embodiment 5
(1) nano zine oxide of 100g is added in the butyrolactone of 100g, is put into ball mill grinding 240min, obtains oxygen
Change zinc slurry；
(2) natural rosin of the zinc oxide slurry, 5000g that obtain step (1), the terminated polybutadiene liquid rubber of 100g add
Enter into the butyrolactone of 4000g, be put into after placing 1h in 100 DEG C of baking ovens, takes out and stir 20min using blender to get on-slip
Agent 2.
Embodiment 6
(1) nano zine oxide of 100g is added in the butyrolactone of 80g, is put into ball mill grinding 260min, obtains oxygen
Change zinc slurry；
(2) natural rosin of the zinc oxide slurry, 5000g that obtain step (1), the terminated polybutadiene liquid rubber of 50g add
Enter into the butyrolactone of 4000g, be put into after placing 1h in 100 DEG C of baking ovens, takes out and stir 30min using blender to get on-slip
Agent 3.
The preparation of terminal hydroxy liquid modified rubber polyester polyol
Embodiment 7
The ethylene glycol of 6.0kg, the 1,4-butanediol of 6.0kg, the poly- fourth of terminal hydroxy group of 24.0kg are sequentially added into reaction kettle
Diene liquid rubber (molecular weight 250, degree of functionality 1.9), the adipic acid and 2.4g titanium class catalyst, opening of 24.0kg stir
It mixes, starts to warm up to constant temperature 2h at 140 DEG C, stablize dewatering speed (by rectifying column, tower top temperature is kept for 90 DEG C), after of continuing rising
Temperature to 170 DEG C of opening vacuum pumps, control vacuum degree slowly gradually increases.215 DEG C of progress ester exchange reactions are warming up to, and are passed through
Nitrogen takes 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 or so, hydroxyl value 112.0mgKOH/g, restores normal pressure, is down to room temperature, and discharging is protected
It deposits, obtains liquid rubber modified polyester polyol 1.
Embodiment 8
The poly- butyronitrile alkene liquid rubber (molecule of terminal hydroxy group of ethylene glycol, 13.8kg that 13.8kg is sequentially added into reaction kettle
Amount is 500, degree of functionality 2.4), the adipic acid and 5.6g titanium class catalyst of 32.4kg are opened stirring, are started to warm up to 160 DEG C
Shi Hengwen 2h stablize dewatering speed (by rectifying column, tower top temperature is kept for 105 DEG C), are continuously heating to 190 DEG C of opening vacuum
Pump, control vacuum degree slowly gradually increase.235 DEG C of progress ester exchange reactions are warming up to, and is passed through nitrogen and takes away the polynary of surplus
Alcohol and small molecular alcohol, since vacuumizing after timing 5h per 2h take a sample middle control analysis to final acid value be (0.1~
0.6) mgKOH/g, hydroxyl value 56.0mgKOH/g restore normal pressure, are down to room temperature, and discharging preserves, and obtain liquid rubber modified poly-
Ester polyol 2.
Embodiment 9
The ethylene glycol of 6.5kg, the 1,4-butanediol of 13.0kg, the poly- fourth of terminal hydroxy group of 6.5kg are sequentially added into reaction kettle
Diene liquid rubber (molecular weight 500, degree of functionality 2.4), the adipic acid and 9.6g titanium class catalyst, opening of 34.0kg stir
It mixes, starts to warm up to constant temperature 2h at 160 DEG C, stablize dewatering speed (by rectifying column, tower top temperature is kept for 105 DEG C), after of continuing rising
Temperature to 190 DEG C of opening vacuum pumps, 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, 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 28.0mgKOH/g, restores normal pressure, is down to room temperature, and discharging is preserved, obtained
To liquid rubber modified polyester polyol 3.
Embodiment 10
By the polyethylene glycol adipate dihydric alcohol of the polyether ester dihydric alcohol 1 of 6.0kg, 0.30kg, (number-average molecular weight is
4000), the ethylene glycol of 0.30kg, 0.20kg butyrolactone be added in the reaction kettle with temperature control and agitating device, control temperature
It is to be cooled to triethylene diamine catalyst that 25 DEG C add 0.14kg after mixing 3.5h at 45 DEG C and 0.50kg on-slip agent 1 is filled
Divide stirring 3h, is uniformly mixed to get polyurethane stock solution component A.
By the liquid rubber modified polyester polyol 1 of 2.0kg, the Carbodiimide-Modified MDI of the MDI and 0.1kg of 3.0kg
Hybrid reaction in the reaction kettle with temperature control and agitating device is added, reaction temperature is 55 DEG C, and the reaction time is 3h to get poly- ammonia
Ester stoste B component.
The polyurethane stock solution B component for being 43 DEG C by polyurethane stock solution component A and temperature that temperature is 48 DEG C, is poured in two-component
In note machine after in mass ratio 1.8: 1 mixing, injects reaction 7min moldings, demoulding in 45 DEG C of molds and cured in 60 DEG C of baking ovens
To get the on-slip polyurethane elastomer after for 24 hours.
Embodiment 11
By the polyethylene glycol adipate trihydroxylic alcohol of the polyether ester dihydric alcohol 2 of 9.0kg, 1.0kg, (number-average molecular weight is
3000), the ethylene glycol of 1.0kg, 1.0kg butyrolactone be added in the reaction kettle with temperature control and agitating device, controlled at
After mixing 2.5h at 55 DEG C, it is cooled to 35 DEG C and adds 0.020kg water, the triethylene diamine catalyst of 0.25kg and 1.5kg
On-slip agent 2 is sufficiently stirred 2h, is uniformly mixed to get polyurethane stock solution component A.
By the liquid rubber modified polyester polyol 2 of 6.0kg, the Carbodiimide-Modified MDI of the MDI and 0.5kg of 7.0kg
Hybrid reaction in the reaction kettle with temperature control and agitating device is added, reaction temperature is 65 DEG C, and the reaction time is 2h to get poly- ammonia
Ester stoste B component.
The polyurethane stock solution B component for being 47 DEG C by polyurethane stock solution component A and temperature that temperature is 52 DEG C, is poured in two-component
In note machine after in mass ratio 1.2: 1 mixing, injects reaction 5min moldings, demoulding in 50 DEG C of molds and cured in 70 DEG C of baking ovens
To get the on-slip polyurethane elastomer after 22h.
Embodiment 12
By the polyethylene glycol adipate tetrahydroxylic alcohol of the polyether ester dihydric alcohol 3 of 8.0kg, 0.80kg, (number-average molecular weight is
5000), the ethylene glycol of 0.40kg, 0.60kg butyrolactone be added in the reaction kettle with temperature control and agitating device, control temperature
It is after mixing 3h at 50 DEG C, to be cooled to 30 DEG C of triethylene diamine catalyst and 1.0kg for adding the water of 0.010kg, 0.20kg
On-slip agent 3 be sufficiently stirred 2h, be uniformly mixed to get polyurethane stock solution component A.
By the liquid rubber modified polyester polyol 3 of 5.5kg, the Carbodiimide-Modified MDI of the MDI and 0.3kg of 6.0kg
Hybrid reaction in the reaction kettle with temperature control and agitating device is added, reaction temperature is 60 DEG C, and the reaction time is 3h to get poly- ammonia
Ester stoste B component.
The poly- nitrogen ester stoste B component for being 45 DEG C by polyurethane stock solution component A and temperature that temperature is 50 DEG C, is poured in two-component
In note machine after in mass ratio 2.1: 1 mixing, injects reaction 5min moldings, demoulding in 50 DEG C of molds and cured in 60 DEG C of baking ovens
To get the on-slip polyurethane elastomer after for 24 hours.
Comparative example 1
By the polyethylene glycol adipate dihydric alcohol of the polyether ester dihydric alcohol 1 of 6.0kg, 0.30kg, (number-average molecular weight is
4000), the ethylene glycol of 0.30kg, 0.20kg butyrolactone be added in the reaction kettle with temperature control and agitating device, control temperature
Be after mixing 3.5h at 45 DEG C, to be cooled to 25 DEG C of triethylene diamine catalyst for adding 0.14kg, the zinc oxide of 6.2g and
0.25kg natural rosins are sufficiently stirred 3h, are uniformly mixed to get polyurethane stock solution component A.
By the liquid rubber modified polyester polyol 1 of 2.0kg, the Carbodiimide-Modified MDI of the MDI and 0.1kg of 5.0kg
Hybrid reaction in the reaction kettle with temperature control and agitating device is added, reaction temperature is 55 DEG C, and the reaction time is 3h to get poly- ammonia
Ester stoste B component.
The polyurethane stock solution B component for being 43 DEG C by polyurethane stock solution component A and temperature that temperature is 48 DEG C, is poured in two-component
In note machine after in mass ratio 2.3: 1 mixing, injects reaction 7min moldings, demoulding in 45 DEG C of molds and cured in 60 DEG C of baking ovens
To get the on-slip polyurethane elastomer after for 24 hours.
Comparative example 2
By the PolyTHF dihydric alcohol (number-average molecular weight 4000) of 9.0kg, the polyethylene glycol adipate three of 1.0kg
First alcohol (number-average molecular weight 3000), the ethylene glycol of 1.0kg, 1.0kg butyrolactone be added it is anti-with temperature control and agitating device
It answers in kettle, after mixing 2.5h at 55 DEG C, is cooled to 35 DEG C of triethylenes two for adding 0.020kg water, 0.25kg
The on-slip agent 2 of amine catalyst and 1.5kg is sufficiently stirred 2h, is uniformly mixed to get polyurethane stock solution component A.
By the liquid rubber modified polyester polyol 2 of 4.0kg, the Carbodiimide-Modified MDI of the MDI and 0.5kg of 7.0kg
Hybrid reaction in the reaction kettle with temperature control and agitating device is added, reaction temperature is 65 DEG C, and the reaction time is 2h to get poly- ammonia
Ester stoste B component.
The polyurethane stock solution B component for being 47 DEG C by polyurethane stock solution component A and temperature that temperature is 52 DEG C, is poured in two-component
In note machine after in mass ratio 1.1: 1 mixing, injects reaction 5min moldings, demoulding in 50 DEG C of molds and cured in 70 DEG C of baking ovens
To get the on-slip polyurethane elastomer after 22h.
Comparative example 3
By the polyadipate second two of the polyethylene glycol adipate dihydric alcohol (number-average molecular weight 4000) of 9.0kg, 1.0kg
The butyrolactone addition of alcohol ester trihydroxylic alcohol (number-average molecular weight 3000), the ethylene glycol of 1.0kg, 1.0kg is with temperature control and stirring dress
In the reaction kettle set, after mixing 2.5h at 55 DEG C, be cooled to 35 DEG C add 0.020kg water, 0.25kg three
The on-slip agent 2 of ethylene diamine catalyst and 1.5kg is sufficiently stirred 2h, is uniformly mixed to get polyurethane stock solution component A.
By the liquid rubber modified polyester polyol 2 of 4.0kg, the Carbodiimide-Modified MDI of the MDI and 0.5kg of 7.0kg
Hybrid reaction in the reaction kettle with temperature control and agitating device is added, reaction temperature is 65 DEG C, and the reaction time is 2h to get poly- ammonia
Ester stoste B component.
The polyurethane stock solution B component for being 47 DEG C by polyurethane stock solution component A and temperature that temperature is 52 DEG C, is poured in two-component
In note machine after in mass ratio 1.1: 1 mixing, injects reaction 5min moldings, demoulding in 50 DEG C of molds and cured in 70 DEG C of baking ovens
To get the on-slip polyurethane elastomer after 22h.
Comparative example 4
By the polyethylene glycol adipate tetrahydroxylic alcohol of the polyether ester dihydric alcohol 3 of 8.0kg, 0.80kg, (number-average molecular weight is
5000), the ethylene glycol of 0.60kg, 0.60kg butyrolactone be added in the reaction kettle with temperature control and agitating device, control temperature
It is after mixing 3h at 50 DEG C, to be cooled to 30 DEG C of triethylene diamine catalyst and 1.0kg for adding the water of 0.010kg, 0.20kg
On-slip agent 3 be sufficiently stirred 2h, be uniformly mixed to get polyurethane stock solution component A.
By the terminal hydroxyl polybutadiene liquid rubber (number-average molecular weight 4000) of 3.0kg, the MDI and 0.3kg of 6.0kg
Hybrid reaction in the reaction kettle with temperature control and agitating device is added in Carbodiimide-Modified MDI, and reaction temperature is 60 DEG C, instead
It is 3h between seasonable to get polyurethane stock solution B component.
The polyurethane stock solution B component for being 45 DEG C by polyurethane stock solution component A and temperature that temperature is 50 DEG C, is poured in two-component
In note machine after in mass ratio 1.2: 1 mixing, injects reaction 5min moldings, demoulding in 50 DEG C of molds and cured in 60 DEG C of baking ovens
To get the on-slip polyurethane elastomer after for 24 hours.
Every physical property measurement result of polyurethane elastomer obtained by Application Example 10~12 and comparative example 1~3 arranges
In table 1.
Table 1
Density measurement method is with reference to GB/T1033, and hardness measuring method is with reference to ASTM D 2240, rebound test method reference
GB/T 1681, hydrolysis is with reference to SATRATM344, and folding test method is with reference to ASTM D1790, DIN wear-resisting test method references
GB/T 9867, on-slip test method is with reference to ISO 13287.
To sum up, although the present invention has been described in detail technical scheme of the present invention with above-described embodiment,
But technical scheme of the present invention is not limited to above example, in the thought and objective for not departing from the present invention, to this hair
Equivalent change or modification made by the content of bright claim all should be the technology scope of the present invention.
Claims (15)
1. on-slip type polyurethane elastomer stoste, which is characterized in that include polyurethane stock solution component A and polyurethane stock solution B component；
The polyurethane stock solution component A contains polyether ester dihydric alcohol, polyester polyol；The polyurethane stock solution B component contains terminal hydroxy group
Liquid rubber modified polyester polyol.
2. on-slip type polyurethane elastomer stoste according to claim 1, which is characterized in that
The polyurethane stock solution component A is 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：
20~60 parts of terminal hydroxy liquid modified rubber polyester polyol；
50~75 parts of diisocyanate.
NCO content is 15~18wt% in the polyurethane stock solution B component.
3. on-slip type polyurethane elastomer stoste according to claim 2, which is characterized in that the polyether ester dihydric alcohol is
The polytetrahydrofuran ether dihydric alcohol of number-average molecular weight 100~800 and esterification, the polycondensation reaction of small molecule dihydric alcohol and adipic acid are produced
Object；
The number-average molecular weight of the polyether ester dihydric alcohol is 3000~6000.
4. on-slip type polyurethane elastomer stoste according to claim 3, which is characterized in that in the polyether ester dihydric alcohol
The parts by weight of each raw material are as follows,
20~40 parts of polytetrahydrofuran ether dihydric alcohol；
10~30 parts of small molecule dihydric alcohol；
40~85 parts of adipic acid；
In the polytetrahydrofuran ether dihydric alcohol and small molecule dihydric alcohol in hydroxyl and adipic acid the molar ratio of carboxyl be (1.2~
1.3)∶1；
The small molecule dihydric alcohol is ethylene glycol, diethylene glycol, 1,4-butanediol, 1,6- hexylene glycols, 1,3-PD, new penta 2
One or more in alcohol.
5. on-slip type polyurethane elastomer stoste according to claim 3 or 4, which is characterized in that the polyether ester binary
The preparation method of alcohol sequentially adds polytetrahydrofuran ether dihydric alcohol, small molecule dihydric alcohol and adipic acid, opening into reaction kettle and stirs
It mixes, starts to warm up, until constant temperature (1~2) h when (120~150) DEG C, stablizing dewatering speed, (by destilling tower, tower top temperature is kept
(90~100) DEG C), subsequent temperature of continuing rising, nitrogen switching is passed through from lower part when being warming up to (160~190) DEG C, and is gradually increased nitrogen
Amount dehydration.It is warming up to (210~240) DEG C, (40-160) ppm tetraisopropyl titanates or the positive fourth of metatitanic acid is added after constant temperature (1~2) h
Ester catalyst, and open and vacuumize, transesterification is carried out, (4~6) h takes a sample to carry out middle control analysis per 2h from vacuumizing, directly
It is less than or equal to 0.5, hydroxyl value (18~36) mgKOH/g to acid value, restores normal pressure, nitrogen switching top is passed through, starts to cool down, cool down
Start sampling to (100~120) DEG C and do final analysis and blowing, preserves.
6. on-slip type polyurethane elastomer stoste according to claim 2, which is characterized in that the polyester polyol is poly-
Adipic acid system polyester polyol, degree of functionality are 2~4, and number-average molecular weight is 1000~5000；
The chain extender is ethylene glycol, 1,2-PD, 1,3-PD, 1,4-butanediol, diglycol, a contracting dipropyl
One or more in glycol, neopentyl glycol, 1,6- hexylene glycols, cyclohexanedimethanol.
7. on-slip type polyurethane elastomer stoste according to claim 2, which is characterized in that the on-slip agent contains pine
Perfume, liquid rubber, zinc oxide and plasticizer；
The parts by weight of each raw material are in the on-slip agent：
The rosin is one or both of natural rosin and rosin resin；
The liquid rubber is the poly- butyronitrile liquid rubber of terminal hydroxy group, terminal hydroxyl polybutadiene liquid rubber, terminal hydroxy group polychlorostyrene fourth two
The poly- butyronitrile liquid rubber of alkene liquid rubber, liquid end hydroxy styrene-butadiene rubber, hydroxyl terminated polyisoprene liquid rubber, end carboxyl,
One or more in carboxyl-terminated polybutadiene liquid rubber, end carboxyl polyisoprene liquid rubber, degree of functionality 1.9
~2.4, number-average molecular weight is 250~500；
The oxidant is nano zine oxide, and grain size is between (1~100) nm；
The plasticizer is butyrolactone, acylated citrate tributyl, mixed dibasic acid dimethyl ester, propene carbonate, adipic acid two
One or more in different monooctyl ester.
8. on-slip type polyurethane elastomer stoste according to claim 7, which is characterized in that the preparation side of the on-slip agent
Method includes the following steps：
(1) 1~10 part of zinc oxide is added in 5~10 parts of plasticizer, is put into ball mill grinding (240~300) min, obtains
Zinc oxide slurry；
(2) zinc oxide slurry, 40~50 parts of rosin and 0~10 part of liquid rubber that step (1) obtains are added to 35~40 parts
It in plasticizer, is put into after placing (1~3) h in (80~100) DEG C baking oven, takes out and stir (20~40) min using blender, i.e.,
Obtain on-slip agent.
9. on-slip type polyurethane elastomer stoste according to claim 2, which is characterized in that the catalyst is tertiary amines
Catalyst or organic tin catalyst；
The plasticizer is butyrolactone, acylated citrate tributyl, mixed dibasic acid dimethyl ester, propene carbonate, adipic acid two
One or more in different monooctyl ester；
The diisocyanate be methyl diphenylene diisocyanate, carbodiimide modified diphenylmethane diisocyanate,
One in toluene di-isocyanate(TDI), isophorone diisocyanate, polymethylene polyphenyl diisocyanate, naphthalene diisocyanate
Kind or more than one.
10. on-slip type polyurethane elastomer stoste according to claim 2, which is characterized in that the terminal hydroxy liquid rubber
Glue modified poly ester polyalcohol is terminal hydroxy liquid rubber, the esterification of small molecule dihydric alcohol and adipic acid, polycondensation product；
The hydroxyl value of the liquid rubber modified polyester polyol is (28.0~112.0) mgKOH/g, and acid value is (0.1~0.6)
mgKOH/g。
11. on-slip type polyurethane elastomer stoste according to claim 10, which is characterized in that the terminal hydroxy liquid rubber
The degree of functionality of glue 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, 1,3-PD, new penta 2
One or more in alcohol；
The mass ratio of the terminal hydroxy liquid rubber and small molecule dihydric alcohol is 2: 1~1: 3；
The molar ratio of the carboxyl in hydroxyl and adipic acid in the terminal hydroxy liquid rubber and small molecule dihydric alcohol be (1.2~
1.6)∶1。
12. the on-slip type polyurethane elastomer stoste according to claim 10 or 11, which is characterized in that the liquid rubber
The preparation method of modified poly ester polyalcohol sequentially adds small molecule dihydric alcohol, terminal hydroxy liquid rubber, adipic acid into reaction kettle
The tetraisopropyl titanate or n-butyl titanate catalyst of (40~160) ppm is opened stirring, is started to warm up to (140~160)
DEG C when constant temperature (1~2) h, stablize dewatering speed (pass through rectifying column, keep tower top temperature (90~105) DEG C), be warming up to (170~
190) DEG C opening vacuum pump, control vacuum degree slowly gradually increase, and are warming up to (215~235) DEG C and carry out ester exchange reaction, and lead 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 and hydroxyl value, restore normal pressure, are down to room temperature, and discharging preserves.
13. according to Claims 1 to 4, the preparation side of 6,7,9,10,11 any one of them on-slip type polyurethane elastomer stostes
Method, which is characterized in that the preparation method of the on-slip type polyurethane elastomer stoste component A is more by polyether ester dihydric alcohol, polyester
First alcohol, chain extender, plasticizer are added in the reaction kettle with temperature control and agitating device, controlled at being mixed at (45~55) DEG C
It after (2.5~3.5) h, is cooled to (25~35) DEG C and adds water, catalyst and on-slip agent and be sufficiently stirred (2~3) h, mixing is equal
Even, discharging is sealed；
The preparation method of the on-slip type polyurethane elastomer stoste B component, liquid rubber modified polyester polyol and two is different
Hybrid reaction in the reaction kettle with temperature control and agitating device is added in cyanate, and reaction temperature is (55~65) DEG C, reaction time
For (2~3) h, cooling discharge is sealed.
14. according to Claims 1 to 4, the application of 6,7,9,10,11 any one of them on-slip type polyurethane elastomer stostes,
It is characterized in that, being used to prepare on-slip type polyurethane elastomer.
15. the application of on-slip type polyurethane elastomer stoste according to claim 14, which is characterized in that application process,
Include the following steps, polyurethane that polyurethane stock solution component A and temperature that temperature is (48~52) DEG C are (43~47) DEG C is former
Liquid B component, after being mixed in two-component casting machine, the ratio between component A reactive hydrogen molal quantity and B component isocyanate groups molal quantity
It is 1: 1, injects reaction (5~7) min moldings, demoulding in (45~50) DEG C mold, cured in (60~70) DEG C baking oven (22~
24) after h, the on-slip polyurethane elastomer is obtained.
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