CN104086740A - Method for preparing organic silicon graft modified polyurethane resin for synthetic leather - Google Patents
Method for preparing organic silicon graft modified polyurethane resin for synthetic leather Download PDFInfo
- Publication number
- CN104086740A CN104086740A CN201410324844.1A CN201410324844A CN104086740A CN 104086740 A CN104086740 A CN 104086740A CN 201410324844 A CN201410324844 A CN 201410324844A CN 104086740 A CN104086740 A CN 104086740A
- Authority
- CN
- China
- Prior art keywords
- synthetic leather
- organosilicon
- urethane resin
- organic silicon
- modified urethane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002649 leather substitute Substances 0.000 title claims abstract description 27
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title abstract description 12
- 238000000034 method Methods 0.000 title abstract description 11
- 229910052710 silicon Inorganic materials 0.000 title abstract description 10
- 239000010703 silicon Substances 0.000 title abstract description 10
- 229920005749 polyurethane resin Polymers 0.000 title abstract description 5
- 229920000642 polymer Polymers 0.000 claims abstract description 11
- 239000004970 Chain extender Substances 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 24
- 150000003673 urethanes Chemical class 0.000 claims description 23
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 9
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 8
- 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 8
- 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 7
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000003863 metallic catalyst Substances 0.000 claims description 6
- 125000002524 organometallic group Chemical group 0.000 claims description 6
- 150000003384 small molecules Chemical class 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- -1 cyclohexyl dimethanol Chemical compound 0.000 claims description 4
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 claims description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 3
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 3
- 229940043232 butyl acetate Drugs 0.000 claims description 3
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 3
- 239000012467 final product Substances 0.000 claims description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 3
- 229940100573 methylpropanediol Drugs 0.000 claims description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229920005906 polyester polyol Polymers 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 229920005862 polyol Polymers 0.000 claims description 3
- 150000003077 polyols Chemical class 0.000 claims description 3
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 abstract description 13
- 239000004814 polyurethane Substances 0.000 abstract description 13
- 239000011248 coating agent Substances 0.000 abstract description 10
- 238000000576 coating method Methods 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 8
- 229920005989 resin Polymers 0.000 abstract description 7
- 239000011347 resin Substances 0.000 abstract description 7
- 238000005406 washing Methods 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 230000005923 long-lasting effect Effects 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 2
- 150000005846 sugar alcohols Polymers 0.000 abstract 2
- 125000005442 diisocyanate group Chemical group 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 238000004381 surface treatment Methods 0.000 abstract 1
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 10
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 5
- 239000005051 trimethylchlorosilane Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000002352 surface water Substances 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000004375 physisorption Methods 0.000 description 2
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
-
- 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
-
- 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
- C08G18/61—Polysiloxanes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
- D06M15/572—Reaction products of isocyanates with polyesters or polyesteramides
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention discloses a method for preparing an organic silicon graft modified polyurethane resin for synthetic leather. The method comprises the following step: polymerizing a chain extender, diisocyanate, a polymer polyhydric alcohol, micromolecule polyhydric alcohol and an organic metal catalyst in an organic solvent at 50-100 DEG C, wherein organic silicon of which one end contains two hydroxide radicals and the other end contains no active hydroxide radical is adopted as the chain extender. In the process that the grafted organic silicon modified resin is filmed, organic silicon chain segments are connected with a polyurethane structure through covalent bonds, the organic silicon chain segments are enriched on the surface of a coating, the water contact angle of the surface of the obtained coating is improved, the surface of the coating is smooth in hand feeling and bright in gloss, the properties of the surface of the coating are long-lasting and are hard to damage by mechanical and washing action, and thus the resin is an excellent and long-lasting synthetic leather surface treatment material.
Description
Technical field
The present invention relates to New Chemical Material field, specifically the preparation method of the organosilicon grafted and modified urethane resin of a kind of use for synthetic leather.
Background technology
Organosilicon has lower surface energy, and organosilicon material is attached to the feel that synthetic leather coatingsurface can improve coatingsurface, improves coating waterproof, antifouling ability.But simple organosilicon material is during as surface modifier, and organosilicon is only attached to coatingsurface by weak physisorption, be vulnerable to mechanical effect or washing and destroy, along with coated material extends duration of service, coatingsurface performance is progressively lost.In order to increase the long-lasting of organosilicon surface, normally organosilicon structure is accessed by chemical bond in the molecular structure of coating urethane resin, obtain organic silicon modified polyurethane resin.When adopting this organic silicon modified polyurethane resin as synthetic leather coated material, introduce the organosilicon segment of resin structure due to its low surface energy effect, in resin film process, in coatingsurface enrichment, provide coating excellent surface properties, organosilicon segment in coatingsurface enrichment is to be connected in resinous molecular structure by chemical bond-linking, can not destroyed by mechanical effect or washing.
The patent of existing a large amount of organic silicon modified polyurethane synthetic leather resins is announced both at home and abroad, but nearly all patent all adopts the organic-silicon-modified method of main chain, as CN102604026 adopts the polyether-polysiloxane copolymers that two ends are hydroxyl, reacts with base polyurethane prepolymer for use as.
Adopting this two ends is that the polyether-polysiloxane copolymers of hydroxyl reacts with base polyurethane prepolymer for use as, and organosilicon segment is connected in polyurethane backbone.
In theory, this organosilicon segment being connected in polyurethane backbone is subject to the coatingsurface that is difficult to obtain in film coated surface enrichment low surface energy in film process that is pinned in of polymer segment.
Reasonable manner be by organosilicon inarch on urethane side chain, obtain side chain organic silicon modified polyurethane.
This grafted-organosilicon modified urethane resin, the less main polymer chain that is subject to of its side chain pins down, and in film process, organosilicon segment is more gives in coatingsurface enrichment the surface property that coating is better.
Yet the synthetic very difficulty of grafted-organosilicon modified urethane, up to the present also there is no real grafted-organosilicon modified urethane research and patent to announce, Chinese patent CN103483526 has announced a kind of organosilicon grafted and modified PAUR performed polymer and preparation and application, it adopts the organosilicon that two ends are hydroxyl to react with trimethylchlorosilane, attempt to seal the organosilyl terminal hydroxy group acquisition one-ended hydroxy organosilicon that two ends are hydroxyl, then one-ended hydroxy organosilicon is introduced to urethane as graft side chain.There is serious theoretical defects in this patent, 1mol two ends are that organosilicon and the 1mol trimethylchlorosilane of hydroxyl reacts completely and react for a kind of probability selection, organosilyl two terminal hydroxy group that 25% two ends are hydroxyl in theory all can react with trimethylchlorosilane and form organic hydroxy silicate for no reason, and this part product can not react and be connected to polyurethane structural with base polyurethane prepolymer for use as; 50% two ends are that an organosilyl terminal hydroxy group of hydroxyl reacts and forms one-ended hydroxy organosilicon with trimethylchlorosilane, and one-ended hydroxy organosilicon reacts with base polyurethane prepolymer for use as and can only become the end of polyurethane structural chain and can not become graft side chain; 25% two ends are that organosilyl two terminal hydroxy group of hydroxyl all do not react with trimethylchlorosilane, and this part organosilicon reacts with base polyurethane prepolymer for use as becomes polyurethane structural main chain.Therefore can say that Chinese patent CN103483526 does not synthesize organosilicon grafted and modified urethane, in the organosilicon in its reaction raw materials, 25% is blended in urethane resin with free form, and 25% becomes polyurethane backbone, and 50% becomes urethane end chain.
Summary of the invention
The object of the present invention is to provide the preparation method of the organosilicon grafted and modified urethane resin of use for synthetic leather that a kind of coatingsurface consistency of performance keeps, feel is smooth.
For achieving the above object, the invention provides following technical scheme:
A preparation method for the organosilicon grafted and modified urethane resin of use for synthetic leather, by chainextender and vulcabond, polymer polyatomic alcohol, small molecules polyvalent alcohol, organo-metallic catalyst in organic solvent, polymerization and get final product under the condition of 50-100 ℃; Described chainextender adopts a kind of one end to contain two hydroxyls, and the other end is not containing the organosilicon of active hydrogen group, and its general structure is:
Wherein: R is CH
3-or CH
3cH
2-, R
1for-CH
2cH
2cH
2-, R
2for-CH
2cH
2-or-CH
2cH (CH
3)-, n=6～1300, m=4～50.
As the further scheme of the present invention: a kind of or its arbitrary combination that described vulcabond is following compound: tolylene diisocyanate (TDI), hexamethylene-diisocyanate (HDI), isophorone diisocyanate (IPDI), diphenylmethanediisocyanate (MDI), dicyclohexyl methane diisocyanate (HMDI).
As the further scheme of the present invention: described polymer polyatomic alcohol is selected from average functionality, and to be equal to or greater than 2 molecular-weight average be 400～4000 polyether glycol, a kind of or its arbitrary combination of polyester polyol or polycarbonate polyol.
As the further scheme of the present invention: a kind of or its arbitrary combination that described small molecules polyvalent alcohol is following compound: ethylene glycol, 1, ammediol, BDO, methyl propanediol, Diethylene Glycol, neopentyl glycol, TriMethylolPropane(TMP), cyclohexyl dimethanol.
As the further scheme of the present invention: described organo-metallic catalyst is organotin, organo-bismuth.
As the further scheme of the present invention: a kind of or its arbitrary combination that described organic solvent is following compound: butanone, pimelinketone, toluene, dimethylbenzene, dimethyl formamide, ethyl acetate, butylacetate.
Compared with prior art, the invention has the beneficial effects as follows: using organosilicon as side chain graft in polyurethane structural with the resin comparison of organosilicon as main chain, grafted-organosilicon modified resin organosilicon segment in film process is connected on polyurethane structural by covalent linkage, in the higher enrichment of coatingsurface, the coatingsurface water contact angle obtaining improves, and coatingsurface feel is more smooth, and gloss is higher, coatingsurface consistency of performance keeps, and is difficult to be destroyed by machinery and cleaning function.The present invention is a kind of good, long-acting synthetic leather finish materials.
Embodiment
Below in conjunction with the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is only the present invention's part embodiment, rather than whole embodiment.Embodiment based in the present invention, those of ordinary skills, not making the every other embodiment obtaining under creative work prerequisite, belong to the scope of protection of the invention.
In the embodiment of the present invention, the preparation method of the organosilicon grafted and modified urethane resin of a kind of use for synthetic leather, by chainextender and vulcabond, polymer polyatomic alcohol, small molecules polyvalent alcohol, organo-metallic catalyst in organic solvent, polymerization and get final product under the condition of 50-100 ℃; Described chainextender adopts a kind of one end to contain two hydroxyls, and the other end is not containing the organosilicon of active hydrogen group, and its general structure is:
Wherein: R is CH
3-or CH
3cH
2-, R
1for-CH
2cH
2cH
2-, R
2for-CH
2cH
2-or-CH
2cH (CH
3)-, n=6～1300, m=4～50; Described vulcabond is a kind of of following compound or its arbitrary combination: tolylene diisocyanate (TDI), hexamethylene-diisocyanate (HDI), isophorone diisocyanate (IPDI), diphenylmethanediisocyanate (MDI), dicyclohexyl methane diisocyanate (HMDI); Described polymer polyatomic alcohol is selected from average functionality, and to be equal to or greater than 2 molecular-weight average be 400～4000 polyether glycol, a kind of or its arbitrary combination of polyester polyol or polycarbonate polyol; A kind of or its arbitrary combination that described small molecules polyvalent alcohol is following compound: ethylene glycol, 1,3-PD, BDO, methyl propanediol, Diethylene Glycol, neopentyl glycol, TriMethylolPropane(TMP), cyclohexyl dimethanol; Described organo-metallic catalyst is organotin, organo-bismuth; Described organic solvent is a kind of of following compound or its arbitrary combination: butanone, pimelinketone, toluene, dimethylbenzene, dimethyl formamide, ethyl acetate, butylacetate.
Embodiment 1
By 140 parts of polyester glycols, its molecular weight is 2000, is warmed up to 110 ° of C, vacuum hydro-extraction 1 hour, cool to 50 ° of C, in reactor, add 400 parts of dimethyl formamides, two hydroxyls are contained in 30 parts of one end, and the other end does not contain active hydrogen group from preparing high-purity organosilicon, its molecular weight 50000,8 parts of BDOs, 10 parts of ethylene glycol stir; Add 25 parts of TDI, 35 parts of MDI, 0.5 part of organic bismuth catalyst, stirring is warming up to 75 ° of C, reacts 3.5 hours, adds 250 parts of toluene, keep 75 ° of C of temperature, with 8.8 parts of MDI tackifies, every 45min, feed intake once, each 0.5～3 part, after reaching preset value, viscosity cools to 60 ° of C, add 100 parts of butanone and stir, be cooled to 30 ° of C dischargings, obtaining solid content is 25% organosilicon grafted and modified urethane resin.
Comparative example 2
Synthesis technique is identical with embodiment 1, two hydroxyls are contained in 30 parts of one end in embodiment 1, the other end does not replace with from preparing high-purity organosilicon the polyether-polysiloxane copolymers that 30 parts of two ends are hydroxyl containing active hydrogen group, the molecular weight 50000 of described polyether-polysiloxane copolymers, obtaining solid content is 25% organosilicon backbone modification urethane resin.
Organosilicon grafted and modified urethane resin and organosilicon backbone modification urethane resin performance compare.The organosilicon grafted and modified urethane resin of embodiment 1 and comparative example's 2 organosilicon backbone modification urethane resins are diluted to solid content 20% with dimethyl formamide respectively, be rolled onto dry-method chemical leather surface, after 150 ° of C are dried, adopt the measurement > > standard test synthetic leather surface water contact angle of ISO 15989:2004 < < plastics film and water contact angle degree.The synthetic leather surface water contact angle that the organosilicon grafted and modified urethane resin of embodiment 1 is processed is 97 °, and the synthetic leather surface water contact angle that comparative example's 2 organosilicon backbone modification urethane resins are processed is 84 °; After synthetic leather washing and drying, again measure contact angle, embodiment 1 and comparative example's 2 water contact angles all do not change, and by feel, are touched with naked eyes and are differentiated, and embodiment 1 coating feel is more smooth, and gloss is higher.
In the present invention, organosilicon grafted and modified urethane resin is coated in to synthetic leather surface as synthetic leather surface treatment agent, side chain organosilicon segment is in coatingsurface enrichment, form low surface energy interface, give synthetic leather good hand and water proof anti-soil performance, polyurethane backbone structure is given coating excellent adhesion energy simultaneously.With the comparison of traditional organic block modified polyurethane resin, the organosilicon side chain of organosilicon grafted and modified urethane is less is subject to pining down of polymer segment and more in coatingsurface enrichment; With simple organic silicon hand feeling agent comparison, the organosilicon segment of organic silicon hand feeling agent is only attached to synthetic leather surface by weak physisorption, be vulnerable to mechanical effect and washing and destroy, and the organosilicon segment of organosilicon grafted and modified urethane is connected on polyurethane structural by covalent linkage, be difficult to be destroyed by machinery and cleaning function.Organosilicon grafted and modified urethane resin prepared by the present invention is a kind of good, long-acting synthetic leather finish materials.
To those skilled in the art, obviously the invention is not restricted to the details of above-mentioned one exemplary embodiment, and in the situation that not deviating from spirit of the present invention or essential characteristic, can realize the present invention with other specific form.Therefore, no matter from which point, all should regard embodiment as exemplary, and be nonrestrictive, scope of the present invention is limited by claims rather than above-mentioned explanation, is therefore intended to include in the present invention dropping on the implication that is equal to important document of claim and all changes in scope.
In addition, be to be understood that, although this specification sheets is described according to embodiment, but not each embodiment only comprises an independently technical scheme, this narrating mode of specification sheets is only for clarity sake, those skilled in the art should make specification sheets as a whole, and the technical scheme in each embodiment also can, through appropriately combined, form other embodiments that it will be appreciated by those skilled in the art that.
Claims (6)
1. a preparation method for the organosilicon grafted and modified urethane resin of use for synthetic leather, is characterized in that, by chainextender and vulcabond, polymer polyatomic alcohol, small molecules polyvalent alcohol, organo-metallic catalyst in organic solvent, polymerization and get final product under the condition of 50-100 ℃; Described chainextender adopts a kind of one end to contain two hydroxyls, and the other end is not containing the organosilicon of active hydrogen group, and its general structure is:
Wherein: R is CH
3-or CH
3cH
2-, R
1for-CH
2cH
2cH
2-, R
2for-CH
2cH
2-or-CH
2cH (CH
3)-, n=6～1300, m=4～50.
2. the preparation method of the organosilicon grafted and modified urethane resin of use for synthetic leather according to claim 1, it is characterized in that a kind of or its arbitrary combination that described vulcabond is following compound: tolylene diisocyanate (TDI), hexamethylene-diisocyanate (HDI), isophorone diisocyanate (IPDI), diphenylmethanediisocyanate (MDI), dicyclohexyl methane diisocyanate (HMDI).
3. the preparation method of the organosilicon grafted and modified urethane resin of use for synthetic leather according to claim 1, it is characterized in that, described polymer polyatomic alcohol is selected from average functionality, and to be equal to or greater than 2 molecular-weight average be 400～4000 polyether glycol, a kind of or its arbitrary combination of polyester polyol or polycarbonate polyol.
4. the preparation method of the organosilicon grafted and modified urethane resin of use for synthetic leather according to claim 1, it is characterized in that, a kind of or its arbitrary combination that described small molecules polyvalent alcohol is following compound: ethylene glycol, 1, ammediol, BDO, methyl propanediol, Diethylene Glycol, neopentyl glycol, TriMethylolPropane(TMP), cyclohexyl dimethanol.
5. the preparation method of the organosilicon grafted and modified urethane resin of use for synthetic leather according to claim 1, is characterized in that, described organo-metallic catalyst is organotin, organo-bismuth.
6. the preparation method of the organosilicon grafted and modified urethane resin of use for synthetic leather according to claim 1, it is characterized in that a kind of or its arbitrary combination that described organic solvent is following compound: butanone, pimelinketone, toluene, dimethylbenzene, dimethyl formamide, ethyl acetate, butylacetate.
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