CN100570049C - A kind of preparation method of synthetic leather dry process PU slurry - Google Patents
A kind of preparation method of synthetic leather dry process PU slurry Download PDFInfo
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- CN100570049C CN100570049C CNB2007100469940A CN200710046994A CN100570049C CN 100570049 C CN100570049 C CN 100570049C CN B2007100469940 A CNB2007100469940 A CN B2007100469940A CN 200710046994 A CN200710046994 A CN 200710046994A CN 100570049 C CN100570049 C CN 100570049C
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- synthetic leather
- dry process
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- leather dry
- preparation
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- 239000002649 leather substitute Substances 0.000 title claims abstract description 36
- 239000002002 slurry Substances 0.000 title claims abstract description 33
- 238000001035 drying Methods 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000004814 polyurethane Substances 0.000 claims abstract description 59
- 229920002635 polyurethane Polymers 0.000 claims abstract description 47
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229920000642 polymer Polymers 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 230000003750 conditioning effect Effects 0.000 claims abstract description 9
- 238000005260 corrosion Methods 0.000 claims abstract description 9
- 230000007797 corrosion Effects 0.000 claims abstract description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 23
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 14
- 239000004970 Chain extender Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- 230000018044 dehydration Effects 0.000 claims description 5
- 238000006297 dehydration reaction Methods 0.000 claims description 5
- 125000005474 octanoate group Chemical group 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 150000002009 diols Chemical class 0.000 claims description 4
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 229940043237 diethanolamine Drugs 0.000 claims description 2
- 150000002222 fluorine compounds Chemical class 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 11
- 238000011084 recovery Methods 0.000 abstract description 4
- 238000007599 discharging Methods 0.000 abstract description 3
- 239000007789 gas Substances 0.000 abstract description 3
- 239000002912 waste gas Substances 0.000 abstract description 3
- 238000007613 slurry method Methods 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 8
- 208000005156 Dehydration Diseases 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 210000000981 epithelium Anatomy 0.000 description 3
- 230000001815 facial effect Effects 0.000 description 3
- 238000007581 slurry coating method Methods 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000006353 oxyethylene group Chemical group 0.000 description 2
- -1 poly-adipate glycol propylene glycol ester Chemical class 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical class OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical group [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
Abstract
The present invention relates to a kind of synthetic leather dry process PU slurry and preparation method thereof, described synthetic leather dry process PU slurry is filled a prescription as follows by weight: amorphous polyurethane polymer 20-35 part, surface energy conditioning agent 0.1-2 part, corrosion inhibiter 0.1-3 part, dimethyl formamide 60-80 part.In the amorphous polyurethane polymer solution of 20-35%, make described synthetic leather dry process PU slurry by described recipe ratio adding surface energy conditioning agent and corrosion inhibiter stirring.This synthetic leather dry process PU slurry can be realized whole recovery of dry method waste gas, effectively solves the problem that the dry method exhaust gas discharging pollutes environment.
Description
Technical field
The invention belongs to the synthetic leather field.
Background technology
In the present domestic synthetic leather production process, the used dry process PU slurry of preparation synthetic leather is made up of polyurethane (PU) resin and poisonous and hazardous organic solvent.More common dry method slurry basic composition is toluene, butanone, dimethyl formamide (DMF), polyurethane resin.In order to alleviate problem of environmental pollution, a large amount of research all is devoted to develop the recovery technology of toluene, butanone and DMF.At present, the technology that the DMF in the dry method PU waste gas recycles is successfully developed in existing research, but to the recovery of toluene, butanone because technical difficulty height, process route are long, equipment investment is big, up to the present still is in conceptual phase.Problem of environmental pollution is still quite serious in the synthetic leather industry.
Summary of the invention
Technical problem to be solved by this invention provides a kind of synthetic leather dry process PU slurry, and this synthetic leather dry process PU dyestuff can be realized whole recovery of dry method waste gas, thereby can effectively solve the problem that the dry method exhaust gas discharging pollutes environment.The present invention also will provide a kind of preparation method of this synthetic leather dry process PU slurry.
For achieving the above object, the technical solution used in the present invention is:
A kind of use for synthetic leather environment-friendly type dry method PU slurry, its raw material is filled a prescription as follows by weight: amorphous polyurethane polymer 20-35 part, dimethyl formamide 60-80 part, surface energy conditioning agent 0.1-2 part, corrosion inhibiter 0.1-3 part.
Described surface energy conditioning agent comprises one or more in following: Nonyl pheno base ether, aliphatic alcohol polyethenoxy base ether, organosilicon derivates, Organic fluoride derivative.Described corrosion inhibiter comprises one or more in following: ethanol, ethylene glycol, propylene glycol, glycerol, isopropyl alcohol, monoethanolamine, diethanol amine, triethanolamine, water.The material system of described amorphous urethane polymers is filled a prescription as follows by weight: polyester diol 10-30 part, vulcabond 5-20 part, dihydroxy chain extender 1-10 part, three hydroxyl chain extender 1-6 parts, catalyst 0.1-3 part.
Above-mentioned polyester diol is polyethylene glycol adipate, PPA or poly-adipate glycol propylene glycol ester.Described dihydroxy chain extender is ethylene glycol, propylene glycol or butanediol.Described three hydroxyl chain extenders are glycerol or trimethylolpropane.Described catalyst is stannous octoate or dibutyl tin laurate.
A kind of preparation method of described synthetic leather dry process PU slurry, at first in polymeric kettle, PPA is cooled to 70-85 ℃ 90-105 ℃ of following vacuum dehydration after 1 hour, add methyl diphenylene diisocyanate, DMF, 80 ℃ of following stirring reactions 2 hours, add the dihydroxy chain extender by recipe ratio then, three hydroxyl chain extenders, the inferior tin reaction of octoate catalyst makes the amorphous polyurethane polymer solution of 20-35%, obtains described synthetic leather dry process PU slurry by described recipe ratio adding surface energy conditioning agent and corrosion inhibiter stirring at last in the amorphous polyurethane polymer solution of gained.
Because the technique scheme utilization, the present invention compared with prior art has following advantage:
Synthetic leather dry process PU slurry is single component solvent with DMF, avoided the use of the mixed solvent of DMF, toluene, butanone.Because DMF has extremely strong water-soluble, therefore adopt the DMF reclaimer of present domestic maturation, can finish the recycling of whole solvents, solved the problem that the dry method exhaust gas discharging pollutes environment effectively.
By adding chain extender polyether polyols with reduced unsaturation is advanced the solution that the shape chain extending reaction obtains amorphous polyurethane polymer, the surface energy conditioning agent and the corrosion inhibiter that directly add recipe ratio then in this solution prepare described synthetic leather dry process PU slurry, and the preparation method is simple, production cost is low.
The specific embodiment
Below the specific embodiment of the present invention is described:
Embodiment 1:
A kind of synthetic leather dry process PU slurry, its raw material is filled a prescription as follows by weight: 25 parts of amorphous polyurethane polymers, 75 parts of dimethyl formamides, 1 part in Nonyl pheno base ether, 3 parts of ethanol.
The preparation method of described synthetic leather dry process PU slurry:
At first in polymeric kettle, 26 parts of polyethylene glycol adipates are cooled to 80 ℃ 100 ℃ of following vacuum dehydrations after 1 hour, at 80 ℃ of following stirring reactions after 2 hours, add 30 parts of methyl diphenylene diisocyanates, DMF700 part, and then add 4 parts of ethylene glycol and 3 parts of glycerol, 1.2 parts of reactions of the inferior tin of octoate catalyst make 25% amorphous polyurethane polymer solution.
1 part in adding Nonyl pheno base ether, 3 parts of stirrings of ethanol obtain described synthetic leather dry process PU slurry in the amorphous polyurethane polymer solution of 100 parts of gained.
After testing, the synthetic leather dry process PU slurry of gained contains solid content 24.5%, and viscosity is 86Pa.S, and the PU epithelium transparency is good, and PU slurry coating is good, and does not have facial mask corrosivity.
Embodiment 2:
A kind of synthetic leather dry process PU slurry, its raw material is filled a prescription as follows by weight: 35 parts of amorphous polyurethane polymers, 65 parts of dimethyl formamides, 1 part in fatty alcohol oxyethylene group ether, 3 parts of ethanol.
At first in polymeric kettle, will gather 26 parts of adipate glycol propylene glycol esters and be cooled to 80 ℃ after 1 hour 100 ℃ of following vacuum dehydrations, at 80 ℃ of following stirring reactions after 2 hours, add 30 parts of methyl diphenylene diisocyanates, DMF500 part, and then add 6 parts of ethylene glycol and 3 parts of glycerol, the inferior tin of octoate catalyst make 35% amorphous polyurethane polymer for 1.2 parts.Entire reaction is carried out under protection of nitrogen gas.
1 part in adding fatty alcohol oxyethylene group ether, 3 parts of stirrings of ethanol obtain described use for synthetic leather environment-friendly type dry method PU slurry in the amorphous polyurethane polymer of 100 parts of gained.
After testing, the synthetic leather dry process PU slurry of gained contains solid content 29.5%, and viscosity is 89Pa.S, and the PU epithelium transparency is good, and PU slurry coating is good, and does not have facial mask corrosivity.
Embodiment 3:
A kind of synthetic leather dry process PU slurry, its raw material is filled a prescription as follows by weight: 20 parts of amorphous polyurethane polymers, 80 parts of dimethyl formamides, 1.5 parts of organosilicon derivates, 3 parts of ethanol.
The preparation method of described synthetic leather dry process PU slurry: at first in polymeric kettle, 26 parts of PPA are cooled to 80 ℃ 100 ℃ of following vacuum dehydrations after 1 hour, add 30 parts of methyl diphenylene diisocyanates, 850 parts of DMF, 80 ℃ of following stirring reactions 2 hours, and then add 4 parts of ethylene glycol, 3 parts of glycerol, 1.2 parts of reactions of the inferior tin of octoate catalyst and make described 20% amorphous polyurethane polymer solution.
1.5 parts of organosilicon derivates of adding, 3 parts of stirrings of ethanol obtain described synthetic leather dry process PU slurry in 100 parts of amorphous polyurethane polymer solution.
After testing, the synthetic leather dry process PU slurry of gained contains fixture 19.5%, and viscosity is 83Pa.S, and the PU epithelium transparency is good, and PU slurry coating is good, and does not have facial mask corrosivity.
Claims (5)
1, a kind of preparation method of synthetic leather dry process PU slurry, the raw material of synthetic leather dry process PU slurry is filled a prescription as follows by weight: amorphous polyurethane polymer 20-35 part, dimethyl formamide 60-80 part, surface energy conditioning agent 0.1-2 part, corrosion inhibiter 0.1-3 part, the material system of described amorphous polyurethane polymer is filled a prescription as follows by weight: polyester diol 10-30 part, vulcabond 5-20 part, dihydroxy chain extender 1-10 part, three hydroxyl chain extender 1-6 parts, catalyst 0.1-3 part, it is characterized in that: described polyester diol is a PPA, described vulcabond is a methyl diphenylene diisocyanate, at first in polymeric kettle, PPA is cooled to 70-85 ℃ 90-105 ℃ of following vacuum dehydration after 1 hour, add methyl diphenylene diisocyanate, dimethyl formamide, 80 ℃ of following stirring reactions 2 hours, add the dihydroxy chain extender by recipe ratio then, three hydroxyl chain extenders, the inferior tin reaction of octoate catalyst makes the amorphous polyurethane polymer solution of 20-35%, obtains described synthetic leather dry process PU slurry by described recipe ratio adding surface energy conditioning agent and corrosion inhibiter stirring at last in the amorphous polyurethane polymer solution of gained.
2, the preparation method of synthetic leather dry process PU slurry according to claim 1 is characterized in that: described surface energy conditioning agent comprises one or more the mixture in following: Nonyl pheno base ether, aliphatic alcohol polyethenoxy base ether, organosilicon derivates, Organic fluoride derivative.
3, the preparation method of synthetic leather dry process PU slurry according to claim 1 is characterized in that: described corrosion inhibiter comprises one or more the mixture in following: ethanol, ethylene glycol, propylene glycol, glycerol, isopropyl alcohol, monoethanolamine, diethanol amine, triethanolamine, water.
4, the preparation method of synthetic leather dry process PU slurry according to claim 1 is characterized in that: described dihydroxy chain extender is ethylene glycol, propylene glycol or butanediol.
5, the preparation method of synthetic leather dry process PU slurry according to claim 1 is characterized in that: described three hydroxyl chain extenders are glycerol or trimethylolpropane.
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| CNB2007100469940A CN100570049C (en) | 2007-10-12 | 2007-10-12 | A kind of preparation method of synthetic leather dry process PU slurry |
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| CNB2007100469940A CN100570049C (en) | 2007-10-12 | 2007-10-12 | A kind of preparation method of synthetic leather dry process PU slurry |
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| CN101135114A CN101135114A (en) | 2008-03-05 |
| CN100570049C true CN100570049C (en) | 2009-12-16 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101929076A (en) * | 2010-09-02 | 2010-12-29 | 安庆中大化学科技有限公司 | Aqueous slurry for synthetic leather |
| CN117186647A (en) * | 2018-06-11 | 2023-12-08 | 莫骏杰 | Organic silicon rubber synthetic leather and preparation method and application thereof |
| CN110028776A (en) * | 2019-04-23 | 2019-07-19 | 福建宝利特科技股份有限公司 | A kind of antifouling solvent-free artificial leather |
| CN113186732A (en) * | 2021-04-14 | 2021-07-30 | 浙江合力革业有限公司 | Process for treating dry-process PU synthetic leather for wet-process recycling |
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|---|---|---|---|---|
| US3311527A (en) * | 1964-01-20 | 1967-03-28 | Gen Tire & Rubber Co | Polyurethane coated fabric |
| US6054176A (en) * | 1997-07-22 | 2000-04-25 | Chifa Leather Corp. | Process for making PU air permeable nubuck sheets |
| CN1057340C (en) * | 1997-12-23 | 2000-10-11 | 南开大学 | High-performance water-thinned polyurethane as leather repairing agent |
| JP2001279583A (en) * | 2000-03-27 | 2001-10-10 | Kuraray Co Ltd | Leather like sheet excellent in water repellent, oil repellent and anti-static properties |
| CN1966852A (en) * | 2006-11-03 | 2007-05-23 | 温州大学 | Polyurethane synthetic leather grain surface paste and method for preparing same |
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Effective date of registration: 20231130 Address after: No. 88, Jilongshan Road, He County Economic Development Zone, Ma'anshan City, Anhui Province Patentee after: Ma'anshan Rui High tech Co.,Ltd. Address before: 215428 Jiangsu city in Taicang Province town of deer deer river Jinchang Road No. 39 Patentee before: WARREN SYNTHETIC LEATHER (SUZHOU) Co.,Ltd. |
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