CN102140158B - Polyurethane material based on carbon dioxide copolymer polyalcohol and application thereof - Google Patents
Polyurethane material based on carbon dioxide copolymer polyalcohol and application thereof Download PDFInfo
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- CN102140158B CN102140158B CN 201010614201 CN201010614201A CN102140158B CN 102140158 B CN102140158 B CN 102140158B CN 201010614201 CN201010614201 CN 201010614201 CN 201010614201 A CN201010614201 A CN 201010614201A CN 102140158 B CN102140158 B CN 102140158B
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- polyvalent alcohol
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- CURLTUGMZLYLDI-UHFFFAOYSA-N carbon dioxide Natural products O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 56
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 56
- 229920001577 copolymer Polymers 0.000 title claims abstract description 53
- 239000000463 material Substances 0.000 title claims abstract description 45
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 41
- 239000004814 polyurethane Substances 0.000 title claims abstract description 41
- 150000005846 sugar alcohols Polymers 0.000 title abstract 7
- 239000004970 Chain extender Substances 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000012948 isocyanate Substances 0.000 claims abstract description 13
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000003381 stabilizer Substances 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 62
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 36
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 claims description 21
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 235000011089 carbon dioxide Nutrition 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 125000004185 ester group Chemical group 0.000 claims description 7
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 claims description 6
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 6
- 239000013543 active substance Substances 0.000 claims description 6
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 claims description 6
- 229920001971 elastomer Polymers 0.000 claims description 5
- 239000000806 elastomer Substances 0.000 claims description 5
- 229920005862 polyol Polymers 0.000 claims description 5
- 150000003077 polyols Chemical class 0.000 claims description 5
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- 238000007334 copolymerization reaction Methods 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- AKABKVXLWWIVIW-UHFFFAOYSA-N 1,1-diisocyanatohexane Chemical compound CCCCCC(N=C=O)N=C=O AKABKVXLWWIVIW-UHFFFAOYSA-N 0.000 claims description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-O N-dimethylethanolamine Chemical compound C[NH+](C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-O 0.000 claims description 3
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical group 0.000 claims description 3
- 150000001718 carbodiimides Chemical class 0.000 claims description 3
- 150000004985 diamines Chemical class 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 3
- 239000003063 flame retardant Substances 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims description 3
- 229960003511 macrogol Drugs 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 239000012745 toughening agent Substances 0.000 claims description 3
- 229960004418 trolamine Drugs 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 abstract description 10
- 229920000570 polyether Polymers 0.000 abstract description 9
- 239000004721 Polyphenylene oxide Substances 0.000 abstract description 7
- 230000007062 hydrolysis Effects 0.000 abstract description 5
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 5
- 229920000642 polymer Polymers 0.000 abstract description 5
- 239000006260 foam Substances 0.000 abstract description 3
- 238000005299 abrasion Methods 0.000 abstract 1
- 239000004088 foaming agent Substances 0.000 abstract 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
- 238000005266 casting Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 229920003225 polyurethane elastomer Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- -1 small molecules diol Chemical group 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000005587 carbonate group Chemical group 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010795 gaseous waste Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a polyurethane material based on carbon dioxide copolymer polyalcohol, belonging to the field of polyurethane sole materials. A polyalcohol component A and an isocyanate component B are fully mixed, poured, foamed and demolded to prepare polyurethane micropore elastic body sole, wherein the polyalcohol component is formed by the mixing of carbon dioxide polymer polyalcohol, a foaming agent, a foam stabilizer, a catalyst, a chain extender according to a definite proportion, the isocyanate component is prepared by the reaction of carbon dioxide polymer polyalcohol, a chain extender and isocyanate according to a certain proportion under controlled conditions. Compared with polyether and polyester type sole material, the polyurethane sole material has excellent hydrolysis resistance performance of polyether type polyurethane sole and wear-resistance and high strength of polyester type polyurethane sole, can solve the problems of low polyether strength, no abrasion resistance and no hydrolysis resistance of polyester. In addition, the carbon dioxide polymer polyalcohol adopted by the polyurethane material is synthesized by taking carbon dioxide as the main raw material; the raw material has low cost; and therefore, the polyurethane material has wide market application space.
Description
Technical field
The present invention relates to a kind of polyurethane material material, particularly relate to a kind of carbon dioxide copolymer polyvalent alcohol, belong to the polyurethane sole materials field for basic polyurethane material and uses thereof.
Background technology
Polyurethane material is the Multifunction macromolecular material of one type of excellent property, in material industry, occupies crucial status, is one of the world's six big synthetic materialss.Microporous polyurethane elastomer is owing to have excellent abrasive, resistance to tearing, shock-resistance, fabulous rebound resilience and characteristics such as light, comfortable and easy to wear; More and more widely be applied to material for sole of shoe; At present; Polyurethane material has accounted in the whole world footwear industry greatly, and the domestic market demand amount is also very huge, reaches the MT level.
Usually there are two types at the bottom of the polyurethane shoe: polyester type and polyether-type.Polyester type is to be main raw material(s) with the polyester polyol; Through preparing with isocyanate reaction; Have good mechanical property at the bottom of the polyester type shoes, like HS, excellent wear, solvent-resisting etc., but hydrolysis takes place in very easily; Make that flexural property variation, sole chap, come unstuck etc., the work-ing life and the Application Areas of product are restricted.Polyether-type is to be main raw material(s) with the polyether glycol; Through preparing with isocyanate reaction; Overcome the not shortcoming of hydrolysis of polyester type at the bottom of the polyether type polyurethane shoes, hydrolysis does not take place basically, weather resistance is good; Yet intensity is low at the bottom of the polyether type polyurethane shoes, wear resisting property is poor, can only be used for the lower place of wear resisting property requirement.Develop a kind of new polyurethane sole that has excellent wear and anti-hydrolytic performance simultaneously and have crucial meaning.
Under the initiation of small molecules polyvalent alcohol; Carbonic acid gas and propylene oxide can pass through copolymerization carbon dioxide copolymer polyvalent alcohol; Resulting polyvalent alcohol belongs to aliphatic polycarbonate polybasic alcohol; With it is that the urethane of feedstock production not only has good mechanical property and wear resisting property, and anti-hydrolytic performance is also very good, is a kind of novel polyols that gathers ester and polyethers advantage.ZL9909459, CN101633731, CN101024685A, CN101029128A etc. have reported the compound method of such carbon dioxide copolymer polyvalent alcohol respectively; CN1400229A has then reported synthetic based on the urethane foam of this polyvalent alcohol, and what obtain high carbon acid ester group content can be used in packing, sound damping polyurethane semihard foam.CN1865311 has reported the synthetic of a kind of polyurethane elastomer based on the carbonic acid gas ethylene oxide copolymer.The research report of at present relevant said material mainly concentrates on aspects such as coating, tackiness agent, porous plastics, does not see the research report that is used for micro-pore elastomer sole aspect.
Summary of the invention
First purpose of the present invention provides the polyurethane material of a kind of carbon dioxide copolymer polyvalent alcohol for the basis.
Another object of the present invention provides a kind of purposes of above-mentioned polyurethane material.
First purpose of the present invention is achieved through following technical scheme:
A kind of carbon dioxide copolymer polyvalent alcohol is the polyurethane material on basis, and it is characterized in that: it comprises polyvalent alcohol component A and isocyanic acid component B;
Polyol component A squeezes into the carbon dioxide copolymer polyvalent alcohol to mix batch can with chainextender, water, suds-stabilizing agent, catalyst by proportion; Be warmed up to 40～60 ℃; And under this temperature, mixed 0.2～1 hour; Remove bubble and make, wherein the ratio of each component is according to weight ratio carbon dioxide copolymer polyvalent alcohol: chainextender: water: suds-stabilizing agent: catalyzer=100: 1～15: 0.1～2: 0.1～2: 0.1～2;
The isocyanic acid B component is to adopt carbon dioxide copolymer polyvalent alcohol and chainextender, vulcabond according to certain ratio; Drop in the reaction kettle; Under agitation, 0～120 ℃ of reaction prepared in 0.1～10 hour; The ratio of each component is according to weight ratio carbon dioxide copolymer polyvalent alcohol: vulcabond: chainextender=100: 120～250: 2～30; Viscosity 0～120 ℃ of following isocyanic acid B component is 200～800mPa.s, and the weight percentage of isocyano NCO that guarantees the isocyanic acid B component simultaneously is 17～24%.
Again polyvalent alcohol component A, isocyanic acid B component temperature are controlled at 40～50 ℃; Then two components are mixed, mix the back and guarantee isocyanate index (isocyanate index is meant that the ratio of the consumption of the needed isocyanic ester of all reactive hydrogen complete reactions in isocyanic ester consumption and the mixed system multiply by 100) in 95～105 scope;
Described carbon dioxide copolymer polyvalent alcohol is that carbonic acid gas is a starting raw material; Under initiator, catalyst action, become the carbon dioxide copolymer polyvalent alcohol of high carbon acid ester group with epoxypropane copolymerization; In the described carbon dioxide copolymer polyvalent alcohol, the molar content of high carbon acid ester group is preferably between 0.20～0.45 between 0.25～0.50; Number-average molecular weight is between 1000～8000, preferably between 1500～2500.
Described chainextender is terepthaloyl moietie, Diethylene Glycol, 1,2-Ucar 35,1, ammediol, dipropylene glycol, Diethylene Glycol, 1,4-butyleneglycol, pentanediol, 1, the mixture of one or more in the 6-pinakon.
Described catalyzer is an amines catalyst, comprises N, N-dimethylcyclohexylamine, triethyl diamines, triethylamine, N, the mixture of one or more in N-dimethylethanolamine, trolamine and the triethylene diamino salt.
Said initiator is terepthaloyl moietie, Diethylene Glycol, 1,2-Ucar 35,1, ammediol, dipropylene glycol, Diethylene Glycol, 1; 4-butyleneglycol, pentanediol, 1,6-pinakon, Macrogol 200; PEG 400, W 166 400, the mixture of one or more in the W 166 700.
Described vulcabond is a tolylene diisocyanate (TDI), 1; 6-hexylidene diisocyanate (HDI), diphenylmethanediisocyanate (MDI), carbodiimide modification vulcabond (MDI), 1, the mixture of one or more in the 5-naphthalene diisocyanate (NDI).
Also can add tensio-active agent according to its concrete application, described tensio-active agent is silicone surfactant such as Dabco DC3043 and Dabco DC193
Also can add a certain amount of other auxiliary agents, like fire retardant, toughener, filler, oxidation inhibitor, photostabilizer etc. according to its concrete application requiring.
A kind of polyurethane material that is the basis with the carbon dioxide copolymer polyvalent alcohol of the present invention can be used as material for sole of shoe and is used to produce the micro-pore elastomer sole.
Contain a large amount of ehter bonds in the many alcohol resins of aliphatic polycarbonate that the present invention adopts, the existence of diether linkage structure makes polymkeric substance have the submissive performance of good low temperature.Simultaneously, these many alcohol also contain a large amount of ester bonds, and the existence of ester bond makes polymkeric substance have good wear resistance, can replace polyethers and polyester, satisfies the shoe sole production actual demand.Compare the polyurethane material of a kind of carbon dioxide copolymer polyvalent alcohol of the present invention with general microporous polyether-type polyurethane elastomer material for sole of shoe, have higher intensity and wear resistance for the basis; Compare with the polyester type polyurethane micropore elastomer material for sole of shoe, then have stronger anti-hydrolytic performance, can be used as material for sole of shoe, be used to prepare sports shoes at the bottom of, leather shoes, playshoes, labour protection sole, military sole etc.Simultaneously because the carbon dioxide copolymer polyvalent alcohol is an industrial gaseous waste carbonic acid gas with cheapness prepares as main raw material(s); Cost is lower than polyester and polyether glycol; The present invention not only can provide a kind of cheapness, high performance new polyurethane micro-pore elastomer sole for society; And consumed environmentally harmful carbonic acid gas indirectly, have crucial environment protection and utilization of resources meaning.
Embodiment
Below in conjunction with specific embodiment the present invention is further described.
Embodiment 1
A kind of carbon dioxide copolymer polyvalent alcohol is the polyurethane material on basis, and it is characterized in that: it comprises polyvalent alcohol component component A and isocyanic acid component B;
Polyol component A squeezes into the carbon dioxide copolymer polyvalent alcohol with chainextender, water, suds-stabilizing agent, catalyzer etc. to mix batch can in proportion; Be warmed up to 40～60 ℃; And under this temperature, mixed 0.2～1 hour; Remove bubble and make, wherein the ratio of each component is according to weight ratio carbon dioxide copolymer polyvalent alcohol: chainextender: water: suds-stabilizing agent: catalyzer=100: 1～15: 0.1～2: 0.1～2: 0.1～2;
The isocyanic acid B component is to adopt carbon dioxide copolymer polyvalent alcohol and small molecules diol chain-extension agent, vulcabond according to certain ratio; Drop in the reaction kettle; Under agitation, 0～120 ℃ of reaction prepared in 0.1～10 hour; The ratio of each component is according to weight ratio carbon dioxide copolymer polyvalent alcohol: vulcabond: chainextender=100: 120～250: 2～30; Viscosity 0～120 ℃ of following isocyanic acid B component is 200～800mPa.s, and the weight percentage of isocyano NCO that guarantees the isocyanic acid B component simultaneously is 17～24%.
Again polyvalent alcohol component A, isocyanic acid B component temperature are controlled at 40～50 ℃; Then two components are mixed, mix the back and guarantee isocyanate index (isocyanate index is meant that the ratio of the consumption of the needed isocyanic ester of all reactive hydrogen complete reactions in isocyanic ester consumption and the mixed system multiply by 100) in the scope of 95-105;
Described carbon dioxide copolymer polyvalent alcohol is that carbonic acid gas is a starting raw material; Under initiator, catalyst action, become the carbon dioxide copolymer polyvalent alcohol of high carbon acid ester group with epoxypropane copolymerization; In the described carbon dioxide copolymer polyvalent alcohol, the molar content of high carbon acid ester group is preferably between 0.20～0.45 between 0.25～0.50; Number-average molecular weight is between 1000～8000, preferably between 1500～2500.
Described chainextender is terepthaloyl moietie, Diethylene Glycol, 1,2-Ucar 35,1, ammediol, dipropylene glycol, Diethylene Glycol, 1,4-butyleneglycol, pentanediol, 1, the mixture of one or more in the 6-pinakon.
Described catalyzer is an amines catalyst, comprises N, N-dimethylcyclohexylamine, triethyl diamines, triethylamine, N, the mixture of one or more in N-dimethylethanolamine, trolamine and the triethylene diamino salt.
Said initiator is terepthaloyl moietie, Diethylene Glycol, 1,2-Ucar 35,1, ammediol, dipropylene glycol, Diethylene Glycol, 1; 4-butyleneglycol, pentanediol, 1,6-pinakon, Macrogol 200; PEG 400, W 166 400, the mixture of one or more in the W 166 700.
Described vulcabond is a tolylene diisocyanate (TDI), 1; 6-hexylidene diisocyanate (HDI), diphenylmethanediisocyanate (MDI), carbodiimide modification vulcabond (MDI), 1, the mixture of one or more in the 5-naphthalene diisocyanate (NDI).
Also can add tensio-active agent according to its concrete application, described tensio-active agent is silicone surfactant such as DabcoDC3043 and Dabco DC193
Also can add a certain amount of other auxiliary agents, like fire retardant, toughener, filler, oxidation inhibitor, photostabilizer etc. according to its concrete application requiring.
Embodiment 2
200 gram glycol ethers, 5 liters of propylene oxide, 100 gram DMC catalysts are added in 10 liters of reaction kettles, add carbonic acid gas to system pressure and rise to 2Mpa.Open to stir and heating unit, system is warming up to 60 ℃, replenish and add carbonic acid gas, reach behind the 6.0Mpa in 60 ℃ of reactions 10 hours down to pressure, be cooled to room temperature, agitation condition decompression down takes off discharging behind the residual epoxy propane.Obtain the faint yellow thickness resin of 5890g, test shows, the carbonate group mass contg is 0.37 in the product, hydroxyl value is 45.
Embodiment 3
Get 2kg according to the carbon dioxide copolymer polyvalent alcohol of embodiment 2 methods preparations and terepthaloyl moietie, water, Dabco DC193, triethylene diamine according to 100: 15: 0.5: 0.5: 0.5 ratio is squeezed into and is mixed batch can; Be warming up to 45 ℃; Mixed 1 hour, and added the A batch can of sole casting molding machine; Get a certain amount of carbon dioxide copolymer polyvalent alcohol, diphenylmethanediisocyanate (MDI), the terepthaloyl moietie for preparing according to the method for embodiment 2 and add retort B according to 100: 250: 15 ratio; 60 ℃ of down reactions 5 hours, obtain isocyano-content in 18.8% isocyanic acid B component; With the B batch can of isocyanic acid B component adding sole casting molding machine, regulate the material temperature to 45 ℃.Regulate polyvalent alcohol component A, isocyanic acid B component proportioning near central point through regulating the metering revolution speed; Guarantee that isocyanate index is in 95～105 scopes; On die for shoe-sole, coat releasing agent, dry up, cast, matched moulds, insulation 7 minutes; The demoulding then obtains smooth surface, and the edge is not easy the sole that subsides.A kind of polyurethane material physicals that is the basis with the carbon dioxide copolymer polyvalent alcohol of present embodiment is seen table 1.
Embodiment 4
Get 2kg according to the carbon dioxide copolymer polyvalent alcohol of embodiment 2 methods preparations and terepthaloyl moietie, water, Dabco DC193, triethylene diamine according to 100: 10: 1.0: 0.5: 0.5 ratio is squeezed into and is mixed batch can; Be warming up to 45 ℃; Mixed 1 hour, and added the A batch can of sole casting molding machine; Get a certain amount of carbon dioxide copolymer polyvalent alcohol, diphenylmethanediisocyanate (MDI), the terepthaloyl moietie for preparing according to the method for embodiment 2 and add retort B according to 100: 270: 12 ratio; 60 ℃ of down reactions 5 hours, obtain isocyano-content at 20.4% isocyanic acid component B; With the B batch can of isocyanic acid component B adding sole casting molding machine, regulate the material temperature to 45 ℃.Regulate polyvalent alcohol component A, isocyanic acid B component proportioning near central point through regulating the metering revolution speed; Guarantee that isocyanate index is in the 95-105 scope; On die for shoe-sole, coat releasing agent, dry up, cast, matched moulds, insulation 7 minutes; The demoulding then obtains smooth surface, and the edge is not easy the sole that subsides.A kind of polyurethane material physicals that is the basis with the carbon dioxide copolymer polyvalent alcohol of present embodiment is seen table 1.
Embodiment 5
Get 2kg according to the carbon dioxide copolymer polyvalent alcohol of embodiment 2 methods preparations and terepthaloyl moietie, water, Dabco DC193, triethylene diamine according to 100: 15: 1.5: 0.5: 0.5 ratio is squeezed into and is mixed batch can; Be warming up to 45 ℃; Mixed 1 hour, and added the A batch can of sole casting molding machine; Get a certain amount of carbon dioxide copolymer polyvalent alcohol, diphenylmethanediisocyanate (MDI), the terepthaloyl moietie for preparing according to the method for embodiment 2 and add retort B according to 100: 270: 12 ratio; 60 ℃ of down reactions 5 hours, obtain isocyano-content at 20.4% performed polymer B; With the B batch can of performed polymer B adding sole casting molding machine, regulate the material temperature to 45 ℃.Regulate A through regulating the metering revolution speed, isocyanic acid B component proportioning guarantees that near central point isocyanate index is in the 95-105 scope; On die for shoe-sole, coat releasing agent, dry up, cast, matched moulds, insulation 7 minutes; The demoulding then obtains smooth surface, and the edge is not easy the sole that subsides.A kind of polyurethane material physicals that is the basis with the carbon dioxide copolymer polyvalent alcohol of present embodiment is seen table 1.
Table 1: a kind of polyurethane material physicals that is the basis with the carbon dioxide copolymer polyvalent alcohol of the present invention
| Project | Moulding density g/cm 3 | Tensile strength N/cm 2 | Elongation at break % |
| Embodiment 3 | 0.42 | 170 | 189 |
| Embodiment 4 | 0.41 | 210 | 155 |
| Embodiment 5 | 0.24 | 126 | 273 |
Claims (9)
1. a carbon dioxide copolymer polyvalent alcohol is basic polyurethane material, and it is characterized in that: it comprises component A and component B;
Polyol component A squeezes into the carbon dioxide copolymer polyvalent alcohol to mix batch can with chainextender, water, suds-stabilizing agent, catalyst by proportion; Be warmed up to 40～60 ℃; And under this temperature, mixed 0.2～1 hour; Remove bubble and make, wherein the ratio of each component is according to weight ratio carbon dioxide copolymer polyvalent alcohol: chainextender: water: suds-stabilizing agent: catalyzer=100: 1～15: 0.1～2: 0.1～2: 0.1～2;
The isocyanic acid B component is to adopt carbon dioxide copolymer polyvalent alcohol and chainextender, vulcabond according to certain ratio; Drop in the reaction kettle; Under agitation, 0～120 ℃ of reaction prepared in 0.1～10 hour; The ratio of each component is according to weight ratio carbon dioxide copolymer polyvalent alcohol: vulcabond: chainextender=100: 120～250: 2～30; Viscosity 0～120 ℃ of following isocyanic acid B component is 200～800mPa.s, and the weight percentage of isocyano NCO that guarantees the isocyanic acid B component simultaneously is 17～24%;
Again polyol component A, isocyanic acid B component temperature are controlled at 40～50 ℃, then two components are mixed, mix the back and guarantee that isocyanate index is in 95～105 scope.
2. a kind of carbon dioxide copolymer polyvalent alcohol according to claim 1 is the polyurethane material on basis; It is characterized in that: described carbon dioxide copolymer polyvalent alcohol is that carbonic acid gas is a starting raw material; Under initiator, catalyst action, become the carbon dioxide copolymer polyvalent alcohol of high carbon acid ester group with epoxypropane copolymerization; In the described carbon dioxide copolymer polyvalent alcohol, the molar content of high carbon acid ester group is between 0.25～0.50, and number-average molecular weight is between 1000～8000.
3. a kind of carbon dioxide copolymer polyvalent alcohol according to claim 1 and 2 is the polyurethane material on basis; It is characterized in that: described chainextender is terepthaloyl moietie, Diethylene Glycol, 1; 2-Ucar 35,1; Ammediol, dipropylene glycol, Diethylene Glycol, 1,4-butyleneglycol, pentanediol, 1, the mixture of one or more in the 6-pinakon.
4. a kind of carbon dioxide copolymer polyvalent alcohol according to claim 1 and 2 is the polyurethane material on basis; It is characterized in that: described catalyzer is an amines catalyst; Comprise N; N-dimethylcyclohexylamine, triethyl diamines, triethylamine, N, the mixture of one or more in N-dimethylethanolamine, trolamine and the triethylene diamino salt.
5. a kind of carbon dioxide copolymer polyvalent alcohol according to claim 2 is the polyurethane material on basis, and it is characterized in that: said initiator is terepthaloyl moietie, Diethylene Glycol, 1,2-Ucar 35,1; Ammediol, dipropylene glycol, Diethylene Glycol, 1,4-butyleneglycol, pentanediol, 1,6-pinakon; Macrogol 200; PEG 400, W 166 400, the mixture of one or more in the W 166 700.
6. a kind of carbon dioxide copolymer polyvalent alcohol according to claim 1 and 2 is the polyurethane material on basis; It is characterized in that: described vulcabond is a tolylene diisocyanate, 1; 6-hexylidene diisocyanate, diphenylmethanediisocyanate, carbodiimide modification vulcabond, 1, the mixture of one or more in the 5-naphthalene diisocyanate.
7. a kind of carbon dioxide copolymer polyvalent alcohol according to claim 1 and 2 is the polyurethane material on basis, and it is characterized in that: it also is added with tensio-active agent, and described tensio-active agent is a silicone surfactant.
8. a kind of carbon dioxide copolymer polyvalent alcohol according to claim 1 and 2 is the polyurethane material on basis, it is characterized in that: also can be added with in fire retardant, toughener, filler, oxidation inhibitor, the photostabilizer one or more.
9. one kind is the purposes of the polyurethane material on basis like the described a kind of carbon dioxide copolymer polyvalent alcohol of claim 1～8, and it is characterized in that: it can be used as material for sole of shoe and is used to produce the micro-pore elastomer sole.
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| CN102504179B (en) * | 2011-09-30 | 2015-02-25 | 南京金三力橡塑有限公司 | Preparation method of hydrolysis-resistant cast polyurethane elastomer |
| KR102169208B1 (en) * | 2012-11-07 | 2020-10-22 | 사우디 아람코 테크놀로지스 컴퍼니 | High strength polyurethane foam compositions and methods |
| CN103497297A (en) * | 2013-09-06 | 2014-01-08 | 旭川化学（昆山）有限公司 | Polyurethane material based on polycarbonate 1, 3-propylene glycol polyol |
| CN113493563A (en) * | 2021-07-14 | 2021-10-12 | 扬州工业职业技术学院 | Polyether polyol and preparation method and application thereof |
| CN115181235B (en) * | 2022-06-14 | 2024-04-19 | 苏州贝彩纳米科技有限公司 | PPC-based polyurethane sound insulation and noise reduction material and preparation method thereof |
| CN118667139B (en) * | 2024-07-02 | 2025-04-01 | 广东工业大学 | A method for synthesizing polycarbonate polyol containing carbamate structure in the main chain |
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