CN108276896B - Moisture-cured leather finishing agent and preparation method thereof - Google Patents
Moisture-cured leather finishing agent and preparation method thereof Download PDFInfo
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- CN108276896B CN108276896B CN201810167065.3A CN201810167065A CN108276896B CN 108276896 B CN108276896 B CN 108276896B CN 201810167065 A CN201810167065 A CN 201810167065A CN 108276896 B CN108276896 B CN 108276896B
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- antioxidant
- coating agent
- diisocyanate
- polyol
- silicone oil
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- 239000010985 leather Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000011248 coating agent Substances 0.000 claims abstract description 39
- 229920002545 silicone oil Polymers 0.000 claims abstract description 33
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 25
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 25
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000003960 organic solvent Substances 0.000 claims abstract description 19
- 229920005862 polyol Polymers 0.000 claims abstract description 19
- 150000003077 polyols Chemical class 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 238000013008 moisture curing Methods 0.000 claims abstract description 11
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 10
- 239000004970 Chain extender Substances 0.000 claims abstract description 7
- 239000000565 sealant Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 39
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 20
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 10
- 229920000570 polyether Polymers 0.000 claims description 10
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical group CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 10
- 239000008096 xylene Substances 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 8
- 238000000034 method Methods 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 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 5
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 4
- 229920005906 polyester polyol Polymers 0.000 claims description 4
- 239000002981 blocking agent Substances 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 claims description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 8
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 description 8
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 229920002635 polyurethane Polymers 0.000 description 5
- 239000004814 polyurethane Substances 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 3
- 229920000909 polytetrahydrofuran Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- AKQZPPKQVZVYCC-UHFFFAOYSA-N 4,4,4-trichlorobut-1-ene Chemical compound ClC(Cl)(Cl)CC=C AKQZPPKQVZVYCC-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229920002396 Polyurea Polymers 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
-
- 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
- C08G18/65—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
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 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
- C08G18/65—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
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/8083—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with compounds containing at least one heteroatom other than oxygen or nitrogen
- C08G18/809—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/06—Polyurethanes from polyesters
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a moisture curing leather finishing agent and a preparation method thereof, wherein the finishing agent is prepared from the following raw materials in percentage by weight: 10 to 20 percent of diisocyanate, 30 to 50 percent of polyol, 35 to 65 percent of organic solvent, 0.10 to 0.60 percent of chain extender, 0.20 to 0.80 percent of sealant, 0.15 percent of antioxidant and 0.20 percent of silicone oil. Free isocyanate groups in the coating agent are sealed, the coating agent is stored for 96 hours at the temperature of 60 ℃, the viscosity of the coating agent is increased to be within 0.12 time of the original viscosity, the shelf life of the coating agent is effectively prolonged, and the application prospect is good.
Description
Technical Field
The invention belongs to the field of leather finishing agents, and particularly relates to a moisture-curing leather finishing agent and a preparation method thereof.
Background
The moisture curing finishing agent can produce bright synthetic leather and is widely applied to cases, clothes and shoe materials. The moisture curing leather finishing agent mainly comprises polyurethane prepolymer, solvent, auxiliary agent and the like. After the moisture curing coating agent is coated on Base leather, the Base leather is directly placed in the air without being dried. The prepolymer of the polyurethane absorbs moisture in the air to react; after 2 hours the Base surface was dry and after 10 hours the polyurethane coating was completely cured. The polyurethane prepolymer in the moisture-curable finishing agent reacts with water molecules in the air at normal temperature to form a high-strength polyurea structure. The molecular structure of the polyurethane coated leather has special luster and brightness, is favored by the leather industry market, and becomes a hotspot of the resin processing post-treatment.
In Chinese patents CN101275169A and CN101275053A, lower trihydric alcohol is used, and the former can form a reticular structure in a prepolymer molecule generated by the reaction of diisocyanate and polyalcohol, so that the prepolymer has better mechanical properties; the latter has very good low-temperature flexing resistance; the two materials can achieve high brightness and strong crystal feeling after being coated on leather, and have better visual effect. Both inventions mention that in the prepolymers of polyurethanes, free isocyanate groups are present. It is known that free isocyanate groups are unstable and are capable of absorbing moisture and carbon dioxide in the air in the open air to react rapidly; secondly, the crosslinking reaction can be dispersed between free isocyanate groups. Leading to continuous increase of viscosity of the finishing agent system until finally crosslinking and curing in a short period, and having short shelf life.
While chinese patents CN104292912A and CN102477698A disclose that addition of chloroprene or trichlorobutene as an auxiliary improves film forming properties of a coating agent and improves gloss and low temperature flex resistance of a leather material, no research is made on synthesis of moisture-curable resins. The used trichlorobutene flash point liquid can emit toxic gas during decomposition; chloroprene is colorless and has special pungent odor, and 2B carcinogen. Therefore, in the two inventions, the chloroprene type auxiliary agent is used, which is not in accordance with the development concept of environmental protection and green.
Disclosure of Invention
The invention provides a moisture-cured leather finishing agent and a preparation method thereof, aiming at the defect of short shelf life of the existing moisture-cured finishing agent. Namely, the moisture curing finishing agent has the advantages that the isocyanate groups are blocked, the isocyanate groups are relatively stable, the shelf life is greatly prolonged, the leather after being finished by the finishing agent has strong crystal feeling and bright surface gloss, and the low-temperature resistant and anti-flexing performance of the coating is better.
The invention is realized by the following technical scheme:
a moisture curing leather finishing agent is prepared from the following raw materials in percentage by weight: 10 to 20 percent of diisocyanate, 30 to 50 percent of polyol, 35 to 65 percent of organic solvent, 0.10 to 0.60 percent of chain extender, 0.20 to 0.80 percent of sealant, 0.15 percent of antioxidant and 0.20 percent of silicone oil.
Preferably, the diisocyanate is toluene diisocyanate or diphenylmethane diisocyanate.
Preferably, the polyol is one or more of polyester polyol, polyether polyol and polytetrahydrofuran diol with the number average molecular weight of 1000 or 2000.
Preferably, the chain extender is one or more than two of ethylene glycol, butanediol or trimethylolpropane.
Preferably, the organic solvent is one or more of butyl acetate, dimethylformamide, butanone, xylene and toluene.
Preferably, the sealing agent is hydroxyl-terminated silicone oil with the number-average molecular weight Mn of 500-500,000.
Preferably, the antioxidant is one or more of antioxidant 1010, antioxidant 1076, antioxidant 1098, antioxidant 168, antioxidant DBPE and antioxidant BHT.
The preparation method of the coating agent comprises the following steps:
(1) putting diisocyanate, polyol, an antioxidant and half of an organic solvent into a reaction kettle, heating to 65-85 ℃, stirring for 3-5 hours, and adding a chain extender solution during the reaction process to prepare the isocyanate-terminated prepolymer.
(2) When the mass fraction of the free isocyanate groups is detected to be 1.1-1.5%, adding a sealing agent, keeping the reaction temperature unchanged, and continuing stirring for 30 minutes; stopping heating, adding the rest half of the organic solvent into the reaction kettle, adding silicone oil, continuing stirring, and discharging after the temperature of the materials is reduced to normal temperature.
Preferably, in the step (1), the diisocyanate, the polyol, the antioxidant and half of the organic solvent are put into a reaction kettle and heated to 75 ℃, and the stirring time is 4 hours.
Preferably, the blocking agent is added when the mass concentration of free isocyanate groups detected in step (2) is 1.3%.
In the preparation process of the polyurethane prepolymer, at the end of the polymerization reaction, micromolecular alcohols or hydroxyl-terminated silicone oil are introduced as a blocking agent to block free active isocyanate groups, so that the storage stability of the coating agent is improved. The prepared latent moisture-curing coating agent is stored for 96 hours at the temperature of 60 ℃, the viscosity of the coating agent is increased from 800mPa.s to 880mPa.s, and the viscosity increase value is 0.10 times of the original viscosity. If the coating agent is not added, the coating agent is directly gelled from 800mPa.s when the coating agent is stored for 24 hours at the temperature of 60 ℃.
After the coating agent prepared by the invention is coated on Base leather, a prepolymer of polyurethane absorbs moisture in the air to generate a series of chemical reactions, and firstly, the polyurethane prepolymer generates closed chemical bond breakage and is decomposed into micromolecules such as micromolecule alcohols or hydroxyl silicone oil and the like and polyurethane prepolymer with active isocyanate groups; the active isocyanate group reacts with water molecules absorbed from the air to generate polyurethane with a polyurea structure; volatilizing the solvent of the coating agent coating, and curing the surface of the coating; as the reaction proceeds further, more water molecules penetrate through the cured layer formed on the surface, diffuse into the coating, and react with the blocked polyurethane prepolymer until the reaction is completed.
Compared with the prior art, the invention has the following advantages and beneficial effects: the stability of the coating agent is improved, the shelf life of the coating agent is prolonged, the prepared coating agent is stored for 96 hours at the temperature of 60 ℃, and the viscosity increase value of the coating agent is within 0.12 time of the original viscosity.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the invention as claimed is not limited to the examples.
Example 1
Weighing the following raw material components in parts by weight: 177g of toluene diisocyanate, 390g of polyether polyol with the number average molecular weight Mn of 1000, 45g of trimethylolpropane, 72g of butyl acetate, 329g of dimethylbenzene, 1.5g of BHT antioxidant, 2g of silicone oil and 2.0g of hydroxyl-terminated silicone oil with the number average molecular weight Mn of 500.
The method comprises the following specific steps:
toluene diisocyanate, polyether polyol, an antioxidant and half of an organic solvent (a mixture of butyl acetate and xylene) are put into a reaction kettle and heated to 75 ℃, the mixture is stirred for 4 hours, during the reaction process, a butyl acetate solution of trihydroxypropane is added to control the viscosity of the system, when the mass fraction of free isocyanate groups is detected to be 1.3%, hydroxyl-terminated silicone oil is added to seal the free isocyanate groups, the reaction temperature is kept at 75 ℃, and the stirring is continued for 30 minutes. Stopping heating, adding the rest half of the organic solvent into the reaction kettle, adding silicone oil, continuing stirring, and discharging after the temperature of the materials is reduced to normal temperature.
The prepared coating agent is stored for 96 hours at the temperature of 60 ℃, the viscosity of the coating agent is increased from 900mPa.s to 980mPa.s, and the viscosity increase value is 0.08 times of the original viscosity.
Example 2
Weighing the following raw material components in parts by weight: 177g of toluene diisocyanate, 390g of polyether polyol with the number average molecular weight Mn of 1000, 25g of ethylene glycol, 72g of butyl acetate, 329g of dimethylbenzene, 1.5g of BHT antioxidant, 2g of silicone oil and 8.0g of hydroxyl-terminated silicone oil with the number average molecular weight Mn of 500,000.
The method comprises the following specific steps:
toluene diisocyanate, polyether polyol, an antioxidant and half of an organic solvent (a mixture of butyl acetate and xylene) are put into a reaction kettle and heated to 75 ℃, the mixture is stirred for 4 hours, and a butyl acetate solution of ethylene glycol is added in the reaction process to control the viscosity of the system. When the mass concentration of the free isocyanate groups is detected to be 1.3%, adding hydroxyl-terminated silicone oil to seal the free isocyanate groups, keeping the reaction temperature at 75 ℃, and continuing to stir for 30 minutes; stopping heating, adding the rest half of the organic solvent into the reaction kettle, adding silicone oil, continuing stirring, and discharging after the temperature of the materials is reduced to normal temperature.
The prepared coating agent is stored for 96 hours at the temperature of 60 ℃, the viscosity of the coating agent is increased from 1000mPa.s to 1120mPa.s, and the viscosity increase value is 0.12 times of the original viscosity.
Example 3
Weighing the following raw material components in parts by weight: 177g of toluene diisocyanate, 390g of polyether polyol with the number average molecular weight Mn of 1000, 10g of trimethylolpropane, 72g of butyl acetate, 329g of dimethylbenzene, 1.5g of BHT antioxidant, 2g of silicone oil and 3.5g of hydroxyl-terminated silicone oil with the number average molecular weight Mn of 1000.
The method comprises the following specific steps:
toluene diisocyanate, polyether polyol, an antioxidant and half of a solvent (a mixture of butyl acetate and xylene) are put into a reaction kettle and heated to 75 ℃, and stirred for 4 hours. In the reaction process, adding a butyl acetate solution of trihydroxy propane to control the viscosity of the system, adding hydroxyl-terminated silicone oil to seal free isocyanate groups when the mass concentration of the free isocyanate groups is detected to be 1.3%, keeping the reaction temperature at 75 ℃, and continuing to stir for 30 minutes; stopping heating, adding the rest half of the organic solvent into the reaction kettle, adding silicone oil, continuing stirring, and discharging after the temperature of the materials is reduced to normal temperature.
The prepared coating agent is stored for 96 hours at the temperature of 60 ℃, the viscosity of the coating agent is increased from 700mPa.s to 720mPa.s, and the viscosity increase value is 0.03 time of the original viscosity.
Example 4
Weighing the following raw material components in parts by weight: 177g of toluene diisocyanate, 390g of polyester polyol with the number average molecular weight Mn of 1000, 50g of butanediol, 72g of butyl acetate, 329g of xylene, 1.5g of BHT antioxidant, 2g of silicone oil and 4.0g of hydroxyl-terminated silicone oil with the number average molecular weight Mn of 2000.
The method comprises the following specific steps:
toluene diisocyanate, polyester polyol, antioxidant and half of the solvent (a mixture of butyl acetate and xylene) were put into a reaction kettle and heated to 75 ℃ and stirred for 4 hours. In the reaction process, adding butyl acetate solution of butanediol to control the viscosity of the system, when the mass concentration of the free isocyanate group is detected to be 1.3%, adding hydroxyl-terminated silicone oil to seal the free isocyanate group, keeping the reaction temperature at 75 ℃, and continuing to stir for 30 minutes; stopping heating, adding the rest half of the organic solvent into the reaction kettle, adding the silicone oil, and continuing stirring. Discharging after the temperature of the materials is reduced to normal temperature.
The prepared coating agent is stored for 96 hours at the temperature of 60 ℃, the viscosity of the coating agent is increased from 900mPa.s to 990mPa.s, and the viscosity increase value is 0.10 times of the original viscosity.
Example 5
Weighing the following raw material components in parts by weight: 125g of diphenylmethane diisocyanate, 442g of polyether polyol with the number average molecular weight Mn of 2000, 25g of trimethylolpropane, 72g of butyl acetate, 329g of dimethylbenzene, 1.5g of BHT antioxidant, 2.0g of silicone oil and 7.5g of hydroxyl-terminated silicone oil with the number average molecular weight Mn of 200,000.
The method comprises the following specific steps:
putting diphenylmethane diisocyanate, polyether polyol, an antioxidant and half of a solvent (a mixture of butyl acetate and xylene) into a reaction kettle, heating to 75 ℃, and stirring for 4 hours. During the reaction, butyl acetate solution of trihydroxy propane is added to control the viscosity of the system. When the mass concentration of the free isocyanate groups is detected to be 1.3%, adding hydroxyl-terminated silicone oil to seal the free isocyanate groups, keeping the reaction temperature at 75 ℃, and continuing to stir for 30 minutes; stopping heating, adding the rest half of the organic solvent into the reaction kettle, adding the silicone oil, and continuing stirring. Discharging after the temperature of the materials is reduced to normal temperature.
The prepared latent moisture-curing coating agent is stored for 96 hours at the temperature of 60 ℃, the viscosity of the coating agent is increased from 800mPa.s to 880mPa.s, and the viscosity increase value is 0.10 times of the original viscosity.
Example 6
Weighing the following raw material components in parts by weight: 115g of diphenylmethane diisocyanate, 452g of polytetrahydrofuran glycol with the number average molecular weight Mn of 2000, 30g of trimethylolpropane, 72g of butyl acetate, 329g of dimethylbenzene, 1.5g of BHT antioxidant, 2.0g of silicone oil and 4.5g of hydroxyl-terminated silicone oil with the number average molecular weight Mn of 10,000.
The method comprises the following specific steps:
diphenylmethane diisocyanate, polytetrahydrofuran diol, an antioxidant and a half of a solvent (a mixture of butyl acetate and xylene) are put into a reaction kettle and heated to 75 ℃, and stirred for 4 hours. In the reaction process, adding a butyl acetate solution of trihydroxy propane to control the viscosity of the system, adding hydroxyl-terminated silicone oil to seal free isocyanate groups when the mass concentration of the free isocyanate groups is detected to be 1.3%, keeping the reaction temperature at 75 ℃, and continuing to stir for 30 minutes; stopping heating, adding the rest half of the organic solvent into the reaction kettle, adding the silicone oil, and continuing stirring. Discharging after the temperature of the materials is reduced to normal temperature.
The prepared latent moisture-curing coating agent is stored for 96 hours at the temperature of 60 ℃, the viscosity of the coating agent is increased from 800mPa.s to 872mPa.s, and the viscosity increase value is 0.09 time of the original viscosity.
Claims (7)
1. The moisture curing leather finishing agent is characterized by comprising the following components in percentage by weight: 10-20% of diisocyanate, 30-50% of polyol, 35-65% of organic solvent, 0.10-0.60% of chain extender, 0.20-0.80% of sealant, 0.15% of antioxidant and 0.20% of silicone oil, wherein the sealant is hydroxyl-terminated silicone oil with the number-average molecular weight Mn of 500-500,000, and the diisocyanate is toluene diisocyanate or diphenylmethane diisocyanate; the polyol is one or more of polyester polyol and polyether polyol with the number average molecular weight of 1000 or 2000.
2. The coating agent according to claim 1, wherein the chain extender is one or more of ethylene glycol, butanediol, and trimethylolpropane.
3. The coating agent according to claim 1 or 2, wherein said organic solvent is one or more selected from the group consisting of butyl acetate, dimethylformamide, methyl ethyl ketone, xylene, and toluene.
4. The coating agent according to claim 3, wherein the antioxidant is one or more of antioxidant 1010, antioxidant 1076, antioxidant 1098, antioxidant 168, antioxidant DBPE and antioxidant BHT.
5. A method for producing a coating agent according to any one of claims 1 to 4, comprising the steps of:
(1) putting diisocyanate, polyol, an antioxidant and half of an organic solvent into a reaction kettle, heating to 65-85 ℃, stirring for 3-5 hours, and adding a chain extender solution in the reaction process to prepare an isocyanate-terminated prepolymer;
(2) when the mass fraction of the free isocyanate groups is detected to be 1.1-1.5%, adding a sealing agent, keeping the reaction temperature unchanged, and continuing stirring for 30 minutes; stopping heating, adding the rest half of the organic solvent into the reaction kettle, adding silicone oil, continuing stirring, and discharging after the temperature of the materials is reduced to normal temperature.
6. The method according to claim 5, wherein the diisocyanate, the polyol, the antioxidant and half of the organic solvent are put into the reaction vessel in the step (1) and heated to 75 ℃ for 4 hours.
7. The process according to claim 5 or 6, wherein the blocking agent is added when the mass concentration of free isocyanate groups detected in step (2) is 1.3%.
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