CN106336498B - Hydrolysis resistance agent for fluorine-silicon modified polyurethane artificial leather and preparation method thereof - Google Patents
Hydrolysis resistance agent for fluorine-silicon modified polyurethane artificial leather and preparation method thereof Download PDFInfo
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- CN106336498B CN106336498B CN201610792922.XA CN201610792922A CN106336498B CN 106336498 B CN106336498 B CN 106336498B CN 201610792922 A CN201610792922 A CN 201610792922A CN 106336498 B CN106336498 B CN 106336498B
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- modified polyurethane
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- 230000007062 hydrolysis Effects 0.000 title claims abstract description 76
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 76
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 60
- 239000004814 polyurethane Substances 0.000 title claims abstract description 60
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 44
- 239000002649 leather substitute Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000003756 stirring Methods 0.000 claims abstract description 29
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 21
- 229920000570 polyether Polymers 0.000 claims abstract description 21
- 239000003921 oil Substances 0.000 claims abstract description 17
- 239000010702 perfluoropolyether Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 16
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 claims description 16
- 229920002545 silicone oil Polymers 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000012948 isocyanate Substances 0.000 claims description 14
- 238000004321 preservation Methods 0.000 claims description 10
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 229940008841 1,6-hexamethylene diisocyanate Drugs 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
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 6
- KCZQSKKNAGZQSZ-UHFFFAOYSA-N 1,3,5-tris(6-isocyanatohexyl)-1,3,5-triazin-2,4,6-trione Chemical compound O=C=NCCCCCCN1C(=O)N(CCCCCCN=C=O)C(=O)N(CCCCCCN=C=O)C1=O KCZQSKKNAGZQSZ-UHFFFAOYSA-N 0.000 claims description 4
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- 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 4
- 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 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- GPAMBYNRXCUNML-UHFFFAOYSA-N 1,1,1,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctan-2-ol Chemical compound FC(F)(F)C(F)(O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F GPAMBYNRXCUNML-UHFFFAOYSA-N 0.000 claims description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 2
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 claims description 2
- 229920005749 polyurethane resin Polymers 0.000 abstract description 32
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 24
- 229910052731 fluorine Inorganic materials 0.000 abstract description 24
- 239000011737 fluorine Substances 0.000 abstract description 24
- 239000002904 solvent Substances 0.000 abstract description 17
- 239000004094 surface-active agent Substances 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 11
- 150000001875 compounds Chemical class 0.000 abstract description 10
- 229920000728 polyester Polymers 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 7
- WZELXJBMMZFDDU-UHFFFAOYSA-N Imidazol-2-one Chemical group O=C1N=CC=N1 WZELXJBMMZFDDU-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003513 alkali Substances 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
- 239000000203 mixture Chemical group 0.000 abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 22
- 125000004432 carbon atom Chemical group C* 0.000 description 16
- 150000002513 isocyanates Chemical class 0.000 description 10
- 125000000217 alkyl group Chemical group 0.000 description 8
- 125000005442 diisocyanate group Chemical group 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 239000004135 Bone phosphate Substances 0.000 description 6
- AQYSYJUIMQTRMV-UHFFFAOYSA-N hypofluorous acid Chemical compound FO AQYSYJUIMQTRMV-UHFFFAOYSA-N 0.000 description 6
- -1 siloxane structure Chemical group 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 5
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 4
- 239000010985 leather Substances 0.000 description 4
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000002791 soaking Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 125000003158 alcohol group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 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
-
- 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
- C08G18/08—Processes
- C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
- C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
- C08G18/0847—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers
- C08G18/0852—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers the solvents being organic
-
- 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
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
- C08G18/2885—Compounds containing at least one heteroatom other than oxygen or nitrogen containing halogen atoms
-
- 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
- C08G18/48—Polyethers
- C08G18/4829—Polyethers containing at least three hydroxy groups
-
- 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
-
- 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
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention discloses a novel hydrolysis-resistant agent for fluorine-silicon modified polyurethane artificial leather, which comprises a reactive fluorine-silicon modified polyurethane compound solution, wherein the solution consists of a reactive fluorine-silicon modified polyurethane resin A, a solvent B and a fluorine-containing surfactant C; the solvent B is 2-imidazolone or a mixture of 2-imidazolone and N, N-dimethylformamide; the fluorosurfactant C is a perfluoropolyether oil. The preparation method comprises the following preparation steps: 1) preparing reactive fluorine-silicon modified polyurethane; 2) and (3) preparing reactive fluorine-silicon modified polyurethane. The hydrolysis resistance agent provided by the invention is simultaneously suitable for polyester type polyurethane resin and polyether type polyurethane resin, has excellent hydrolysis resistance effect, and also has good hydrolysis resistance under the condition of high-temperature high-concentration alkali liquor; meanwhile, the preparation method provided by the invention has the advantages of simple process, convenient operation and applicability and convenience for hydrolysis resistance agent, and can exert hydrolysis resistance effect by directly adding the hydrolysis resistance agent into polyurethane resin and uniformly stirring.
Description
Technical Field
The invention relates to a fluorine-silicon modified polyurethane artificial leather hydrolysis-resistant agent and a preparation method thereof.
Background
Polyurethane artificial leather has been widely used in various aspects of daily life, but polyurethane contains a large amount of easily hydrolyzable groups, which affects the service life of polyurethane artificial leather and gradually fails to meet the market requirements. In order to improve the service performance of polyurethane artificial leather, a hydrolysis resisting agent is introduced in the market, and the polyether polyester polyurethane artificial leather has good resistance to 10% sodium hydroxide solution at normal temperature, but has poor resistance to high-temperature high-concentration alkali liquor; for pure polyester polyurethane artificial leather, the improvement of hydrolysis resistance under normal temperature is not ideal.
The fluorine-containing material has aging resistance, solvent resistance, excellent thermal stability and water and oil repellent performance. The urethane group in the fluorine-containing polyurethane has better compatibility with the polyurethane resin body, and can be uniformly dispersed in the polyurethane resin body. Meanwhile, because the fluorine-containing polyurethane compound has extremely low surface energy, a small amount of the fluorine-containing polyurethane compound is added into polyurethane resin, and the fluorine-containing polyurethane compound can be enriched on the surface of a polyurethane product, so that the polyurethane product is endowed with water and oil resistance, and the hydrolysis resistance and weather resistance are improved.
Fluorine-containing polyurethanes have been disclosed in patents such as Chinese patent ZL200710134368.7, U.S. patent US3547894, Japanese patent WO98/51726 and the like, but these fluorine-containing polyurethanes do not have sufficient hydrolysis resistance. The water drawing agent prepared by the Chinese patent ZL201010287377.1 has better hydrolysis resistance to polyether polyurethane artificial leather under the normal temperature condition, but has poorer hydrolysis resistance under the high-temperature and high-concentration alkali liquor condition; the hydrolysis resistance of the pure polyester type polyurethane artificial leather is improved to a limited extent, and the preparation process is relatively complex.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a fluorine-silicon modified polyurethane artificial leather hydrolysis resistance agent with excellent hydrolysis resistance in high-temperature and high-concentration alkali liquor and a preparation method thereof, so as to solve the problem of the performance deficiency of the existing hydrolysis resistance agent. The hydrolysis resistance agent provided by the invention is simultaneously suitable for polyester type polyurethane resin and polyether type polyurethane resin, has excellent hydrolysis resistance effect, and also has good hydrolysis resistance under the condition of high-temperature high-concentration alkali liquor; meanwhile, the preparation method provided by the invention has the advantages of simple process, convenient operation and convenient use of the hydrolysis resistance agent, can exert the hydrolysis resistance effect by directly adding the hydrolysis resistance agent into the polyurethane resin and uniformly stirring, and can be industrially popularized and applied.
In order to solve the technical problems, the following technical scheme is adopted:
the hydrolysis resistance agent for the fluorine-silicon modified polyurethane artificial leather comprises a reactive fluorine-silicon modified polyurethane compound solution, wherein the solution consists of a reactive fluorine-silicon modified polyurethane resin A, a solvent B and a fluorine-containing surfactant C, and the reactive fluorine-silicon modified polyurethane resin A accounts for 20-80 wt% of the hydrolysis resistance agent; the solvent B is 2-imidazolone or a mixture of 2-imidazolone and N, N-dimethylformamide, and accounts for 20-80 wt% of the hydrolysis resistant agent; the fluorine-containing surfactant C is perfluoropolyether oil, and accounts for 0.1-5 wt% of the hydrolysis resistant agent.
Further, the general formula of the reactive fluorine-silicon modified polyurethane resin A is as follows: (PF) x (FPU) (S) z, wherein PF is a fluorine-containing monohydric alcohol with 1-9 carbon atoms or a fluorine-containing polyether monohydric alcohol with 1-30 carbon atoms, and x represents an integer of 1-3; FPU is a body formed by diisocyanate and triisocyanate containing partial single active groups and fluorinated hydroxyl silicone oil or a body formed by diisocyanate containing partial single active groups, fluorinated hydroxyl silicone oil and polyol; wherein S is a compound with a terminal group containing a reactive group, and z is an integer of 0-3.
Further, the fluorine-containing monohydric alcohol is a fluorine-containing monohydric alcohol having 1 to 9 carbon atoms, and the general formula is CF3(CF2)nCH2CH2OH or CF3(CF2)nSO2N(R1)(CH2)mOH, n is an integer of 0 to 6, m is an integer of 0 to 6, R1Alkyl or hydrogen, the fluorine-containing polyether monohydric alcohol with 1-30 carbon atoms has the general formula of CF3(CF2)pO(CFRCF2O)q(CH2)aOH, wherein p represents an integer of 0 to 2, q is an integer of 0 to 15, a is an integer of 1 to 5, R is-F or-CF3。
Further, the diisocyanate is one or a combination of two or more of toluene diisocyanate, diphenylmethane diisocyanate, and isophorone diisocyanate.
Furthermore, the FPU contains 0.5-5% of tribasic isocyanate or tribasic alcohol, the tribasic isocyanate is 1, 6-hexamethylene diisocyanate trimer, the tribasic alcohol is propylene oxide polyether tribasic alcohol, and the molecular weight of the propylene oxide polyether tribasic alcohol is 200-600.
Further, the general formula of the fluorinated hydroxyl silicone oil is HO (CH)3SiR2O)bOH, wherein R2Is alkyl or perfluoroalkyl of 1-9 carbon atoms or fluoropolyether alkyl of 1-30 carbon atoms, and the general formula of the perfluoroalkyl of 1-9 carbon atoms is CF3(CF2)nCH2CH2Or CF3(CF2)nSO2N(R1)(CH2)mCH2CH2N is an integer of 0 to 6, m is an integer of 0 to 6, R1 is an alkyl group or hydrogen, and the fluorine-containing polyether alkyl group having 1 to 30 carbon atoms has a general formula of CF3(CF2)pO(CFRCF2O)q(CH2)aCH2CH2Wherein p represents an integer of 0 to 2, q is an integer of 0 to 15, a is an integer of 1 to 5, R is-F or-CF3。
Further, the compound with the terminal group containing the reactive group is monoisocyanate containing a siloxane structure or alcohol containing an epoxy group, and the general formula of the monoisocyanate containing the siloxane structure is OCNCH2(CH2)dSi(OR3)3Wherein d is an integer of 1 to 20, R3The alcohol group being a methyl or ethyl group and the epoxy group being of the general formula HO (CH)2)eCHOCH2Wherein e is an integer of 1-20.
Further, the solvent is 2-imidazolidinone or a combination of 2-imidazolidinone and N, N-dimethylformamide.
Further, the surfactant is perfluoropolyether oil surfactant, and the perfluoropolyether oil surfactant is CF3CF2O(CF2CF2O)2CH2CH2OH。
The preparation method of the hydrolysis resistance agent for the fluorine-silicon modified polyurethane artificial leather comprises the following preparation steps:
1) preparing reactive fluorine-silicon modified polyurethane:
(a) preparation of monofluoroalcohol terminated isocyanate: diisocyanate and a solvent are added into a reactor and heated, and then monohydric fluoroalcohol and a part of solvent are added into the reactor in batches after being uniformly mixed for carrying out end capping reaction, so as to prepare the monohydric fluoroalcohol end capped isocyanate.
(b) Synthesis of fluorosilicone polyurethane resin: firstly, adding 1, 6-hexamethylene diisocyanate tripolymer or propylene oxide polyether trihydric alcohol into the prepared monofluorol end-capped isocyanate reaction liquid, and adding fluorinated hydroxyl silicone oil and partial solvent mixed liquid in batches to synthesize the fluorosilicone polyurethane resin.
(c) Synthesizing reactive fluorine-silicon modified polyurethane resin: firstly, adding isocyanate siloxane or monohydroxy alkylene oxide into the synthesized fluorine-silicon polyurethane resin reaction liquid, and reaching a reaction end point when no NCO group exists, thereby obtaining the reactive fluorine-silicon modified polyurethane.
2) Preparing reactive fluorine-silicon modified polyurethane: and (c) adding the solvent and the surfactant into the prepared synthetic fluorine-silicon polyurethane resin (b) or the prepared reactive fluorine-silicon modified polyurethane (c), and uniformly stirring to obtain the hydrolysis resisting agent for fluorine-silicon modified polyurethane artificial leather.
Due to the adoption of the technical scheme, the method has the following beneficial effects:
(1) the fluorine-silicon modified polyurethane hydrolysis-resistant agent provided by the invention is simultaneously suitable for polyester polyurethane resin and polyether polyurethane resin, has an excellent hydrolysis-resistant effect, and also has good hydrolysis resistance under the condition of high-temperature and high-concentration alkali liquor;
(2) the fluorine-silicon modified polyurethane hydrolysis-resistant agent provided by the invention has a body structure, and the hydrolysis resistance under a high-temperature condition is effectively improved;
(3) the fluorine-silicon modified polyurethane hydrolysis-resistant agent provided by the invention can also introduce a cross-linking group with reaction activity, so that a firm hydrolysis-resistant molecular layer can be formed on the surface of artificial leather;
(4) the preparation method of the fluorine-silicon modified polyurethane hydrolysis-resistant agent provided by the invention is simple in process, convenient to operate and convenient to use, and the hydrolysis-resistant agent is directly added into polyurethane resin and uniformly stirred to exert hydrolysis-resistant effect, so that the fluorine-silicon modified polyurethane hydrolysis-resistant agent can be industrially popularized and applied.
Detailed Description
The hydrolysis resistance agent for the fluorine-silicon modified polyurethane artificial leather comprises a reactive fluorine-silicon modified polyurethane compound solution, wherein the solution consists of a reactive fluorine-silicon modified polyurethane resin A, a solvent B and a fluorine-containing surfactant C, and the reactive fluorine-silicon modified polyurethane resin A accounts for 20-80 wt% of the hydrolysis resistance agent; the solvent B is 2-imidazolone or a mixture of 2-imidazolone and N, N-dimethylformamide, and accounts for 20-80 wt% of the hydrolysis resistant agent; the fluorine-containing surfactant C is perfluoropolyether oil, and accounts for 0.1-5 wt% of the hydrolysis resistant agent.
The general formula of the reactive fluorine-silicon modified polyurethane resin A is as follows: (PF) x (FPU) (S) z, wherein PF is a fluorine-containing monohydric alcohol with 1-9 carbon atoms or a fluorine-containing polyether monohydric alcohol with 1-30 carbon atoms, and x represents an integer of 1-3; FPU is a body formed by diisocyanate and triisocyanate containing partial single active groups and fluorinated hydroxyl silicone oil or a body formed by diisocyanate containing partial single active groups, fluorinated hydroxyl silicone oil and polyol; wherein S is a compound with a terminal group containing a reactive group, and z is an integer of 0-3.
The fluorine-containing monohydric alcohol is a fluorine-containing monohydric alcohol with 1-9 carbon atoms, and the general formula is CF3(CF2)nCH2CH2OH or CF3(CF2)nSO2N(R1)(CH2)mOH, n is an integer of 0 to 6, m is an integer of 0 to 6, R1Alkyl or hydrogen, the fluorine-containing polyether monohydric alcohol with 1-30 carbon atoms has the general formula of CF3(CF2)pO(CFRCF2O)q(CH2)aOH, wherein p represents an integer of 0 to 2, q is an integer of 0 to 15, a is an integer of 1 to 5, R is-F or-CF3。
The diisocyanate is one or the combination of more than two of toluene diisocyanate, diphenylmethane diisocyanate and isophorone diisocyanate.
The FPU contains 0.5-5% of trihydric isocyanate or trihydric alcohol, the trihydric isocyanate is 1, 6-hexamethylene diisocyanate trimer, the trihydric alcohol is propylene oxide polyether trihydric alcohol, and the molecular weight of the propylene oxide polyether trihydric alcohol is 200-600.
The general formula of the fluorinated hydroxyl silicone oil is HO (CH)3SiR2O)bOH, wherein R2Is alkyl or perfluoroalkyl of 1-9 carbon atoms or fluoropolyether alkyl of 1-30 carbon atoms, and the general formula of the perfluoroalkyl of 1-9 carbon atoms is CF3(CF2)nCH2CH2Or CF3(CF2)nSO2N(R1)(CH2)mCH2CH2N is an integer of 0 to 6, m is an integer of 0 to 6, R1 is an alkyl group or hydrogen, and the fluorine-containing polyether alkyl group having 1 to 30 carbon atoms has a general formula of CF3(CF2)pO(CFRCF2O)q(CH2)aCH2CH2Wherein p represents an integer of 0 to 2, q is an integer of 0 to 15, a is an integer of 1 to 5, R is-F or-CF3。
The compound with the end group containing the reactive group is monoisocyanate containing a siloxane structure or alcohol containing an epoxy group, and the general formula of the monoisocyanate containing the siloxane structure is OCNCH2(CH2)dSi(OR3)3Wherein d is an integer of 1 to 20, R3The alcohol group being a methyl or ethyl group and the epoxy group being of the general formula HO (CH)2)eCHOCH2Wherein e is an integer of 1-20.
The solvent is 2-imidazolinone or the combination of 2-imidazolinone and N, N-dimethylformamide.
The surfactant is perfluoropolyether oil surfactant, and the perfluoropolyether oil surfactant is CF3CF2O(CF2CF2O)2CH2CH2OH。
A preparation method of a fluorine-silicon modified polyurethane artificial leather hydrolysis-resistant agent comprises the following preparation steps:
1) preparing reactive fluorine-silicon modified polyurethane:
(a) preparation of monofluoroalcohol terminated isocyanate: diisocyanate and a solvent are added into a reactor and heated, and then monohydric fluoroalcohol and a part of solvent are added into the reactor in batches after being uniformly mixed for carrying out end capping reaction, so as to prepare the monohydric fluoroalcohol end capped isocyanate.
(b) Synthesis of fluorosilicone polyurethane resin: firstly, adding 1, 6-hexamethylene diisocyanate tripolymer or propylene oxide polyether trihydric alcohol into the prepared monofluorol end-capped isocyanate reaction liquid, and adding fluorinated hydroxyl silicone oil and partial solvent mixed liquid in batches to synthesize the fluorosilicone polyurethane resin.
(c) Synthesizing reactive fluorine-silicon modified polyurethane resin: firstly, adding isocyanate siloxane or monohydroxy alkylene oxide into the synthesized fluorine-silicon polyurethane resin reaction liquid, and reaching a reaction end point when no NCO group exists, thereby obtaining the reactive fluorine-silicon modified polyurethane.
2) Preparing reactive fluorine-silicon modified polyurethane: adding a solvent and a surfactant into the prepared reactive fluorine-silicon modified polyurethane, and uniformly stirring to obtain the hydrolysis resistance agent for fluorine-silicon modified polyurethane artificial leather.
The present invention will be described in detail with reference to the following embodiments in order to make the technical means, novel features and effects of the invention easier to understand.
Example 1
Putting 250g of diphenylmethane diisocyanate and 50g of anhydrous DMF (dimethyl formamide) into a 2.0L reactor, after the reactor is subjected to vacuum/nitrogen replacement for three times, stirring and heating to 75 ℃, slowly dropwise adding 34.6g of perfluorohexylethanol into a reaction bottle, keeping the temperature and reacting after the dropwise adding is finished until the NCO value is close to 23.8%, adding 50.4g of 1, 6-hexamethylene diisocyanate tripolymer, stirring for 30min, adding 561g of 1# fluorinated hydroxyl silicone oil with the molecular weight of 510 in batches, and keeping the temperature and reacting until the weight percentage of NCO is 0. And adding 554g of anhydrous 2-imidazolidinone and 10.2g of perfluoropolyether oil after the reaction is ended, uniformly stirring, cooling and discharging to obtain the fluorosilicone modified polyurethane artificial leather hydrolysis resisting agent I.
Example 2
175g of toluene diisocyanate and 20g of anhydrous DMF were placed in a 2.0L reactor, the reactor was replaced three times with vacuum/nitrogen, the temperature was raised to 85 ℃ with stirring, and 52.8g of CF was slowly added dropwise3CF2O(CF2CF2O)3CH2CH2And OH, performing heat preservation reaction in a reaction bottle after dropwise adding until the NCO value is close to 32.2%, adding 9.2g of propylene oxide polyether triol with the molecular weight of 200, stirring for 30min, adding 485g of No. 2 fluorinated hydroxyl silicone oil with the molecular weight of 646 in batches, and performing heat preservation reaction until the weight percentage of NCO is 0. Adding 2-isocyanate ethyl trimethoxy silane in batches, keeping the temperature until the NCO value is close to 0, adding 480g of anhydrous 2-imidazolidinone and 9.8g of perfluoropolyether oil, uniformly stirring, cooling and discharging to obtain the hydrolysis-resistant II of the fluorine-silicon modified polyurethane artificial leather.
Example 3
223g of isophorone diisocyanate and 20g of anhydrous 2-imidazolidinone are put into a 2.0L reactor, the reactor is subjected to vacuum/nitrogen replacement for three times, the temperature is raised to 90 ℃ by stirring, 39.3g N-methyl perfluorohexyl sulfonamide ethanol is slowly dripped, the reaction is kept warm in a reaction bottle after the dripping is finished until the NCO value is close to 28.3 percent, 50.4g of 1, 6-hexamethylene diisocyanate trimer is added, the stirring is carried out for 30min, 662g of 3# fluorinated hydroxyl silicone oil with the molecular weight of 630 is added in batches, and the heat preservation reaction is carried out until the weight percentage of NCO is 1 percent. Adding 7.4g of glycidol in batches, keeping the temperature to react until the NCO value is close to 0, adding 641g of anhydrous 2-imidazolidinone and 9.8g of perfluoropolyether oil, uniformly stirring, cooling and discharging to obtain the hydrolysis-resistant polyurethane artificial leather III.
Example 4
250g of diphenylmethane diisocyanate and 50g of anhydrous 2-imidazolidinone were placed in a 2.0L reactor, the reactor was replaced with vacuum/nitrogen for three times, the mixture was stirred and heated to 75 ℃ and 78g of CF was slowly added dropwise3CF2O(CF(CF3)CF2O)4CH2CH2OH, in a reaction bottle, after the dripping is finished, the reaction is carried out under the condition that the NCO value is close to 21.1 percent through heat preservation, 50.4g of 1, 6-hexamethylene diisocyanate tripolymer is added, the mixture is stirred for 30min, and 3# fluoride with the molecular weight of 591 is added in batches591g of hydroxyl silicone oil, and reacting at the constant temperature until the weight percentage of NCO is 0.93%. Adding 14.8g of glycidol in batches, keeping the temperature to react until the NCO value is close to 0, adding 617g of anhydrous 2-imidazolidinone and 17g of perfluoropolyether oil, uniformly stirring, cooling and discharging to obtain the hydrolysis-resistant IV-containing fluorosilicone modified polyurethane artificial leather.
And (3) testing and comparing the hydrolysis resistance of the fluorine-silicon modified polyurethane artificial leather:
hydrolysis resistance using the present invention was compared with that of Korean product SB-62.
Adding a certain amount of hydrolysis resistant agent and other auxiliaries into the prepared polyurethane slurry, uniformly stirring, and forming according to a wet leather making process. The synthetic leather was cut into strips of 3cm by 20 cm. Taking part of the synthetic leather product to be completely immersed in a sodium hydroxide aqueous solution with the temperature of 80 ℃ and the concentration of 50% for 48 hours, taking out, cleaning and drying, bonding two leather strips by using a hot melt double faced adhesive tape, testing the peel strength after drying, comparing the change of the peel strength before and after soaking in an alkaline solution, and expressing the retention rate by using S:
the same batch of samples was tested in parallel for five data, with the maximum and minimum values removed and the remaining three values averaged. The larger the S value is, the better the hydrolysis resistance effect is.
Test example 1
Taking 100g of five parts of the same polyether polyester polyurethane resin, and respectively adding 0.4g of hydrolysis resistance agent I, hydrolysis resistance agent II, hydrolysis resistance agent III, hydrolysis resistance agent IV and Korean SB-62; respectively adding 2g of SD-7, 1g S-8i, 40g of DMF and 1.0g of color paste, stirring uniformly, and molding according to a wet leather making process. The peel strength retention after 48h of 50% sodium hydroxide solution at 80 ℃ was tested and the results are shown in table 1 below.
Test example 2
Taking 100g of five parts of the same pure polyester polyurethane resin, and respectively adding 0.4g of hydrolysis resistance agent I, hydrolysis resistance agent II, hydrolysis resistance agent III, hydrolysis resistance agent IV and Korean SB-62; respectively adding 2g of SD-7, 1g S-8i, 40g of DMF and 1.0g of color paste, stirring uniformly, and molding according to a wet leather making process. The peel strength retention after 48h of 50% sodium hydroxide solution at 80 ℃ was tested and the results are shown in table 2 below.
TABLE 1 Peel Strength Retention ratio of polyester polyether urethane resin synthetic leather after soaking in 80 deg.C/50% sodium hydroxide lye for 48h
TABLE 2 Peel Strength Retention ratio of pure polyester polyurethane resin synthetic leather after soaking in 80 deg.C/50% sodium hydroxide lye for 48h
The hydrolysis resistance agent prepared by the invention is added into polyurethane resin to endow polyurethane artificial leather with excellent hydrolysis resistance performance, and the hydrolysis resistance effect exceeds that of an imported product SB-62.
The above is only a specific embodiment of the present invention, but the technical features of the present invention are not limited thereto. Any simple changes, equivalent substitutions or modifications made on the basis of the present invention to solve the same technical problems and achieve the same technical effects are all covered in the protection scope of the present invention.
Claims (4)
1. A preparation method of a hydrolysis resistance agent for fluorine-silicon modified polyurethane artificial leather is characterized by comprising the following steps: putting 250g of diphenylmethane diisocyanate and 50g of anhydrous DMF (dimethyl formamide) into a 2.0L reactor, after the reactor is subjected to vacuum/nitrogen replacement for three times, stirring and heating to 75 ℃, slowly dropwise adding 34.6g of perfluorohexylethanol into a reaction bottle, keeping the temperature after dropwise adding, reacting until the NCO value is 23.8%, adding 50.4g of 1, 6-hexamethylene diisocyanate tripolymer, stirring for 30min, adding 561g of 1# fluorinated hydroxyl silicone oil with the molecular weight of 510 in batches, keeping the temperature and reacting until the weight percentage of NCO is 0, adding 554g of anhydrous 2-imidazolidinone and 10.2g of perfluoropolyether oil after the reaction is ended, uniformly stirring, cooling and discharging to obtain the fluorosilicone modified polyurethane hydrolysis-resistant agent I.
2. A preparation method of a hydrolysis resistance agent for fluorine-silicon modified polyurethane artificial leather is characterized by comprising the following steps: 175g of toluene diisocyanate and 20g of anhydrous DMF were placed in a 2.0L reactor, the reactor was replaced three times with vacuum/nitrogen, the temperature was raised to 85 ℃ with stirring, and 52.8g of CF was slowly added dropwise3CF2O(CF2CF2O)3CH2CH2OH, in a reaction bottle, after finishing dropwise adding, carrying out heat preservation reaction until the NCO value is 32.2%, adding 9.2g of propylene oxide polyether triol with the molecular weight of 200, stirring for 30min, adding 485g of 2# fluorinated hydroxyl silicone oil with the molecular weight of 646 in batches, carrying out heat preservation reaction until the weight percentage of NCO is 0, adding 19.1g of 2-isocyanate ethyl trimethoxy silane in batches, carrying out heat preservation reaction until the NCO value is 0, adding 480g of anhydrous 2-imidazolidinone and 9.8g of perfluoropolyether oil, uniformly stirring, cooling and discharging to obtain the hydrolysis-resistant II of the fluorosilicone modified polyurethane artificial leather.
3. A preparation method of a hydrolysis resistance agent for fluorine-silicon modified polyurethane artificial leather is characterized by comprising the following steps: putting 223g of isophorone diisocyanate and 20g of anhydrous 2-imidazolidinone into a 2.0L reactor, after the reactor is subjected to vacuum/nitrogen replacement for three times, stirring and heating to 90 ℃, slowly dropwise adding 39.3g N-methyl perfluorohexyl sulfonamide ethanol, keeping the temperature in a reaction bottle after dropwise adding, adding 50.4g of 1, 6-hexamethylene diisocyanate tripolymer, stirring for 30min, adding 662g of No. 3 fluorinated hydroxyl silicone oil with the molecular weight of 630 in batches, keeping the temperature and reacting until the weight percentage of NCO is 1%, adding 7.4g of glycidol in batches, keeping the temperature and reacting to NCO 0, adding 641g of anhydrous 2-imidazolidinone and 9.8g of perfluoropolyether oil, uniformly stirring, cooling and discharging to obtain the fluorosilicone modified polyurethane hydrolysis-resistant artificial leather III.
4. A preparation method of a hydrolysis resistance agent for fluorine-silicon modified polyurethane artificial leather is characterized by comprising the following steps: 250g of diphenylmethane diisocyanate and 50g of anhydrous 2-imidazolidinone were placed in a 2.0L reactor under vacuum/nitrogenAfter three times of replacement, the temperature was raised to 75 ℃ with stirring, and 78g of CF was slowly added dropwise3CF2O(CF(CF3)CF2O)4CH2CH2OH, in a reaction bottle, after dropwise adding, carrying out heat preservation reaction until the NCO value is 21.1%, adding 50.4g of 1, 6-hexamethylene diisocyanate trimer, stirring for 30min, adding 591g of 3# fluorinated hydroxyl silicone oil with the molecular weight of 591 in batches, carrying out heat preservation reaction until the weight percentage of NCO is 0.93%, adding 14.8g of glycidol in batches, carrying out heat preservation reaction until the NCO value is 0, adding 617g of anhydrous 2-imidazolidinone and 17g of perfluoropolyether oil, uniformly stirring, cooling and discharging to obtain the hydrolysis-resistant IV-modified fluorosilicone polyurethane artificial leather.
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| CN110423454A (en) * | 2019-07-19 | 2019-11-08 | 广州大学 | A kind of highly elastic and highly transparent antifouling polyurethane film and its preparation method and application |
| CN110982080B (en) * | 2019-12-26 | 2022-02-15 | 江苏美思德化学股份有限公司 | Fluorine-containing polyether modified siloxane, preparation method thereof, composite surfactant, preparation method thereof and polyurethane foam |
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