CN116178671A - Solvent-free polyurethane resin for yellowing-resistant synthetic leather, and preparation method and application thereof - Google Patents

Solvent-free polyurethane resin for yellowing-resistant synthetic leather, and preparation method and application thereof Download PDF

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Publication number
CN116178671A
CN116178671A CN202211711000.3A CN202211711000A CN116178671A CN 116178671 A CN116178671 A CN 116178671A CN 202211711000 A CN202211711000 A CN 202211711000A CN 116178671 A CN116178671 A CN 116178671A
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component
synthetic leather
parts
yellowing
solvent
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Inventor
钱建中
蔡华兵
吴磊
丁小辉
白雪纯
周文
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Shanghai Huide Technology Co ltd
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Shanghai Huide Technology Co ltd
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    • 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
    • C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
    • C08G18/725—Combination of polyisocyanates of C08G18/78 with other polyisocyanates
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • 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
    • C08G18/4081—Mixtures of compounds of group C08G18/64 with other macromolecular compounds
    • 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
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols 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
    • C08G18/28—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
    • C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
    • C08G18/632—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
    • C08G18/6415—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having nitrogen
    • 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
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • 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
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • D06N3/146—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes characterised by the macromolecular diols used
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • D06N3/147—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes characterised by the isocyanates used
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2203/00—Macromolecular materials of the coating layers
    • D06N2203/06—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06N2203/068—Polyurethanes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00—Properties of the materials
    • D06N2209/16—Properties of the materials having other properties
    • D06N2209/1678—Resistive to light or to UV
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear

Abstract

The invention provides solvent-free polyurethane resin for yellowing-resistant synthetic leather, and a preparation method and application thereof, wherein the polyurethane resin comprises A, B and C three solvent-free components; the component A is a hydroxyl component, the component B is an isocyanate component, and the component C is a catalyst component. The invention adopts aliphatic isocyanate (namely HDI trimer) and MDI, H 12 The polyurethane resin for the solvent-free synthetic leather is compounded by MDI, the polyaspartic acid ester is matched with the polyol resin as the component A, and the catalyst is matched, so that the reaction of the hydroxyl component and the NCO component has a higher reaction speed, the reaction of the polyaspartic acid ester and the NCO is slower due to the influence of steric hindrance, the resin has longer operation time which reaches 600-900s, the strength after solidification is high, and the resin system can not only meet the requirement of solvent-free synthetic leather production on the reaction speed, but also effectively improve the yellowing performance of synthetic leather products.

Description

Solvent-free polyurethane resin for yellowing-resistant synthetic leather, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of polyurethane resin, and particularly relates to solvent-free polyurethane resin for yellowing-resistant synthetic leather, and a preparation method and application thereof.
Background
The solvent-free polyurethane synthetic leather is a synthetic leather product prepared by taking solvent-free polyurethane resin as a main raw material and adding no solvent in the production link of the synthetic leather, and the solvent does not participate in the whole process, so that the environmental problem brought by the solvent is naturally solved.
The resin for solvent-free synthetic leather in the current market mostly contains A, B, C components, generally speaking, the component A is a hydroxyl component, the component B is an isocyanate prepolymer, the component C is a catalyst, and when in use, ABC is mixed according to the metering and then coated, and the resin is formed through pre-curing, attaching and curing. The solvent-free synthetic leather polyurethane resin in the current market has fast application growth in the aspects of producing sofa leather, automobile leather, luggage leather, shoe leather and the like, and has become one of the main green production processes in the synthetic leather industry. However, there is a problem in that the solvent-free synthetic leather has poor yellowing resistance in the production of light-colored products because the B component, i.e., the isocyanate prepolymer, is prepared by reacting a polyol with an excessive amount of isocyanate, and the prepolymer contains a large amount of free isocyanate monomer in order to maintain a proper viscosity and isocyanate content. The yellowing resistance can be improved by adding the yellowing resistance auxiliary agent, the yellowing resistance auxiliary agent is usually compounded by an ultraviolet light absorber, an antioxidant and other auxiliary agents, has a certain effect on improving the yellowing resistance, and has similar product application in the market, but the yellowing resistance auxiliary agent cannot provide a long-term yellowing resistance effect, the yellowing resistance performance can be gradually weakened, and meanwhile, the addition amount of the auxiliary agent is larger, and the fact that a certain inhibition exists on the reaction of solvent-free resin in practical application, so that poor curing is caused.
From the above analysis, it is known that the main reason why the yellowing resistance of the solvent-free polyurethane synthetic leather is poor is that the free MDI monomer in the B material is permeable to the surface layer, so if the free MDI monomer in the B material can be reduced, it is theoretically helpful to improve the yellowing problem. However, from the synthetic principle of the material B, namely the isocyanate prepolymer, the free MDI monomer is reduced, from the aspect of formulation design, namely the NCO content of the material B is reduced, namely the molar ratio of MDI to polyol is reduced, which inevitably leads to the increase of the polymerization degree of the prepolymer, the high viscosity, and the difficult uniform mixing during use is unfavorable for the production of solvent-free synthetic leather.
Accordingly, there is a need to provide an improved solution to the above-mentioned deficiencies of the prior art.
Disclosure of Invention
The invention aims to provide solvent-free polyurethane resin for yellowing-resistant synthetic leather, and a preparation method and application thereof, so as to solve the problem of poor yellowing resistance in the production of the existing solvent-free synthetic leather.
In order to achieve the above object, the present invention provides the following technical solutions:
a solvent-free polyurethane resin for yellowing-resistant synthetic leather, which comprises A, B and C three solvent-free components;
the component A is a hydroxyl component, and the preparation raw materials comprise the following components in parts by weight:
30-50 parts of polymer polyol, 350-450 parts of polyether glycol, 100-150 parts of polyether triol, 80-250 parts of polyaspartic acid ester, 10-30 parts of micromolecular glycol and 1-5 parts of flatting agent;
the component B is isocyanate component, and the preparation raw materials comprise the following components in parts by weight:
200-350 parts of polyether glycol, 8-20 parts of micromolecular glycol, 200-300 parts of diphenylmethane diisocyanate, 500-600 parts of hydrogenated diphenylmethane diisocyanate and 150-250 parts of HDI trimer;
the component C is a catalyst component, and the preparation raw materials comprise the following components in parts by weight;
bismuth carboxylate, zinc carboxylate, carboxylate of 1, 8-diazabicyclo [5.4.0] undecene-7.
In the solvent-free polyurethane resin for yellowing-resistant synthetic leather as described above, preferably, the polyaspartic acid ester is prepared from one of diethylenetriamine, isophorone diamine, 4-diamino dicyclohexylmethane, 3' -dimethyl-4, 4-diamino dicyclohexylmethane and diethyl maleate by Michael addition reaction.
In the solvent-free polyurethane resin for yellowing resistant synthetic leather as described above, preferably, the polymer polyol in the a component is a polyether polyol modified by grafting a styrene-acrylonitrile copolymer;
preferably, the polymer polyol has a functionality of 3 and a number average molecular weight of 4000-6000;
still preferably, the mass percent of styrene-acrylonitrile copolymer in the polymer polyol is 30-40%.
In the solvent-free polyurethane resin for yellowing resistant synthetic leather described above, preferably, the polyether glycol in the a component is a copolymerized propylene oxide-ethylene glycol; the number average molecular weight of the polyether glycol is 750-2000;
preferably, the polyether triol is a copolymerized propylene oxide-ethylene triol; the number average molecular weight of the polyether triol is 3000-5000;
still preferably, the small molecular dihydric alcohol in the component A and/or the component B is one of ethylene glycol, butanediol and methyl propylene glycol;
still preferably, the leveling agent is an organosilicon leveling agent.
In the solvent-free polyurethane resin for yellowing resistant synthetic leather, preferably, the polyether glycol in the component B is polyoxypropylene glycol with the number average molecular weight of 1000-2000;
preferably, the HDI trimer is a trimerization product of hexamethylene diisocyanate, wherein the mass percent of NCO is 20-25%.
In the solvent-free polyurethane resin for yellowing-resistant synthetic leather described above, preferably, the bismuth carboxylate is bismuth isooctanoate or bismuth neodecanoate;
the zinc carboxylate is zinc isooctanoate or zinc neodecanoate;
the carboxylate of the 1, 8-diazabicyclo [5.4.0] undecene-7 is one of isooctanoate of DBU, formate of DBU and p-toluenesulfonate of DBU;
preferably, the mass ratio of the zinc carboxylate to the bismuth carboxylate is 1:8-1:2;
the mass ratio of the zinc carboxylate to the carboxylate of the 1, 8-diazabicyclo [5.4.0] undecene-7 is 1:8-1:4.
A preparation method of solvent-free polyurethane resin for yellowing-resistant synthetic leather, which comprises the following steps:
step one, preparing a component A;
adding polymer polyol, polyether glycol, polyether triol, polyaspartic acid ester, micromolecular glycol and a flatting agent into a closed nitrogen-sealed reactor according to mass ratio, and uniformly mixing to obtain a component A;
step two, preparing a component B;
according to the mass ratio, polyether glycol, micromolecular glycol, diphenylmethane diisocyanate and hydrogenated diphenylmethane diisocyanate are placed in a closed nitrogen-sealed reactor, and then HDI trimer is added, and after uniform mixing, the component B is prepared;
step three, preparing a component C;
bismuth carboxylate, zinc carboxylate and 1, 8-diazabicyclo [5.4.0] undecene-7 carboxylate are mixed in a closed nitrogen-sealed reactor according to the mass ratio, and the mixture is uniformly mixed to prepare a component C;
and fourthly, carrying out constant temperature treatment on the component A, the component B and the component C, metering and putting into a mixer for stirring, and mixing to obtain the polyurethane resin.
In the preparation method of the solvent-free polyurethane resin for the yellowing-resistant synthetic leather, preferably, stirring is carried out for 1.5-2 hours at the temperature of 40-50 ℃ in the reactor in the first step;
preferably, in the second step, stirring and reacting for 4.5-6 hours at the temperature of 85-95 ℃ in the reactor, then adding the HDI trimer, and continuing to react for 1.5-3 hours;
still preferably, in step three, stirring is carried out in the reactor at a temperature of 25-35 ℃ for 1-2h;
still preferably, in step four, the A component, the B component and the C component are all treated at a constant temperature of 10-30 ℃.
The yellowing-resistant synthetic leather is prepared by a preparation method of solvent-free polyurethane resin for the yellowing-resistant synthetic leather.
A method for preparing yellowing-resistant synthetic leather, which comprises the following steps:
coating the polyurethane resin on release paper which is coated with aliphatic polyurethane resin in advance, bonding with a base material after prebaking, curing, cooling and stripping to obtain yellowing-resistant synthetic leather;
preferably, the temperature of the pre-baking is 110-130 ℃, and the pre-baking time is 120-200s; the bonding pressure is 0.2-0.5MPa, and the materials are put into an oven at 120-140 ℃ after bonding, cured for 8-15min, and then cooled and peeled.
The beneficial effects are that:
the invention adopts aliphatic isocyanate (namely HDI trimer) and MDI, H 12 The polyurethane resin for synthesizing the solvent-free synthetic leather by compounding MDI (methylene diphenyl diisocyanate) comprises a component B, wherein polyaspartic acid ester is matched with polyol resin as a component A, and a proper catalyst is matched, so that the reaction of hydroxyl components and NCO components has higher reaction speed, the reaction of polyaspartic acid ester and NCO is influenced by steric hindrance, the reaction speed is slower, and the resin has higher reaction speedThe invention has long operation time, the operation time reaches 600-900s, the strength is high after solidification, and the resin system can not only meet the requirement of solvent-free synthetic leather production on reaction speed, but also can effectively improve the yellowing performance of the synthetic leather product.
The solvent-free polyurethane resin for the yellowing-resistant synthetic leather is prepared into the component B by compounding the aliphatic isocyanate and the aromatic isocyanate, so that the reduction of the yellowing resistance caused by permeation of free aromatic isocyanate to a surface layer can be reduced, and simultaneously polyaspartic acid ester is added to react with the aliphatic isocyanate, so that urea bonds are introduced, and the final strength of a synthetic leather product is ensured. The UV yellowing resistance of the synthetic leather produced by using the solvent-free polyurethane resin can reach more than 4 levels, the peeling strength is not lower than 4 kg/3 cm, and the synthetic leather has wide application prospect.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which are derived by a person skilled in the art based on the embodiments of the invention, fall within the scope of protection of the invention.
The present invention will be described in detail with reference to examples. It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
The invention provides a solvent-free polyurethane resin for yellowing-resistant synthetic leather, which comprises A, B and C three solvent-free components;
the component A is a hydroxyl component, and the preparation raw materials comprise the following components in parts by weight:
30-50 parts (such as 35 parts, 40 parts and 45 parts) of polymer polyol, 350-450 parts (such as 380 parts, 400 parts, 420 parts and 440 parts) of polyether glycol, 100-150 parts (such as 110 parts, 120 parts, 130 parts and 140 parts) of polyether triol, 80-250 parts (such as 100 parts, 150 parts, 200 parts and 250 parts) of polyaspartic acid ester, 10-30 parts (such as 15 parts, 20 parts and 25 parts) of micromolecular glycol and 1-5 parts (such as 2 parts, 3 parts and 4 parts) of flatting agent.
In a specific embodiment of the invention, the polyaspartic acid ester is a hindered amine and is prepared from one of diethylenetriamine, isophorone diamine, 4-diamino dicyclohexylmethane and 3,3' -dimethyl-4, 4-diamino dicyclohexylmethane and diethyl maleate through Michael addition reaction.
In a specific embodiment of the present invention, the polymer polyol in the A-component is a styrene-acrylonitrile copolymer graft modified polyether polyol.
The polymer polyol has a functionality of 3 and a number average molecular weight of 4000-6000.
The mass percent of the styrene-acrylonitrile copolymer in the polymer polyol is 30-40% (such as 32%, 34%, 36%, 38%).
In the specific embodiment of the invention, polyether glycol in the component A is copolymerized propylene oxide-ethylene glycol; the number average molecular weight of the polyether glycol in the component A is 750-2000; wherein the ethylene oxide content is 15-35% (e.g., 18%, 20%, 22%, 24%, 26%, 28%, 30%, 32%, 34%).
The polyether triol is copolymerized propylene oxide-ethylene triol; the number average molecular weight of the polyether triol is 3000-5000; wherein the ethylene oxide content is 15-35% (e.g., 18%, 20%, 22%, 24%, 26%, 28%, 30%, 32%, 34%).
The small molecular dihydric alcohol in the component A and/or the component B is one of ethylene glycol, butanediol and methyl propylene glycol.
In a specific embodiment of the invention, the leveling agent is an organosilicon leveling agent.
The component B is isocyanate component, and the preparation raw materials comprise the following components in parts by weight:
200-350 parts (such as 250 parts, 300 parts and 350 parts) of polyether glycol, 8-20 parts (such as 10 parts, 12 parts, 14 parts, 16 parts and 18 parts) of micromolecular glycol, 200-300 parts (such as 220 parts, 240 parts, 260 parts and 280 parts) of diphenylmethane diisocyanate (MDI), hydrogenated diphenylmethane diisocyanate (H) 12 MDI) 500-600 parts (e.g. 520 parts, 540 parts, 560 parts, 580 parts), HDI trimer 150-250 parts (e.g. 180 parts, 200 parts, 220 parts, 240 parts).
In the specific embodiment of the invention, the polyether glycol in the component B is polyoxypropylene glycol with the number average molecular weight of 1000-2000.
HDI trimer is the trimerization product of hexamethylene diisocyanate, wherein the mass percent of NCO is 20-25% (e.g., 21%, 22%, 23%, 24%).
The component C is a catalyst component, and the preparation raw materials comprise the following components in parts by weight;
bismuth carboxylates, zinc carboxylates, carboxylates of 1, 8-diazabicyclo [5.4.0] undec-7 (DBU).
In a specific embodiment of the invention, the bismuth carboxylate is bismuth isooctanoate or bismuth neodecanoate;
the zinc carboxylate is zinc isooctanoate or zinc neodecanoate;
the carboxylate of 1, 8-diazabicyclo [5.4.0] undecene-7 (DBU) is one of the isooctanoate salt of DBU, the formate salt of DBU, and the p-toluenesulfonate salt of DBU.
In a specific embodiment of the invention, the mass ratio of the zinc carboxylate to the bismuth carboxylate is 1:8-1:2 (such as 1:3, 1:4, 1:5, 1:6, 1:7);
the mass ratio of the zinc carboxylate to the carboxylate of the 1, 8-diazabicyclo [5.4.0] undecene-7 is 1:8-1:4 (such as 1:5, 1:6, 1:7).
The invention also provides a preparation method of the solvent-free polyurethane resin for the yellowing-resistant synthetic leather, which comprises the following steps:
step one, preparing a component A;
adding polymer polyol, polyether glycol, polyether triol, polyaspartic acid ester, micromolecular glycol and a flatting agent into a closed nitrogen-sealed reactor according to mass ratio, and uniformly mixing to obtain a component A;
step two, preparing a component B;
according to the mass ratio, polyether glycol, micromolecular glycol, diphenylmethane diisocyanate and hydrogenated diphenylmethane diisocyanate are placed in a closed nitrogen-sealed reactor, and then HDI trimer is added, and after uniform mixing, the component B is prepared;
step three, preparing a component C;
bismuth carboxylate, zinc carboxylate and 1, 8-diazabicyclo [5.4.0] undecene-7 carboxylate are mixed in a closed nitrogen-sealed reactor according to the mass ratio, and the mixture is uniformly mixed to prepare a component C;
and fourthly, carrying out constant temperature treatment on the component A, the component B and the component C, metering and putting into a mixer for stirring, and mixing to obtain the polyurethane resin.
In an embodiment of the invention, the reactor in step one is stirred at a temperature of 40-50deg.C (e.g., 42deg.C, 44deg.C, 46℃, 48℃) for 1.5-2h (e.g., 1.6h, 1.8 h).
In the second step, the reaction is carried out in a reactor at a temperature of 85-95 ℃ (such as 88 ℃, 80 ℃, 92 ℃ and 94 ℃) with stirring for 4.5-6 hours (such as 5 hours and 5.5 hours), then HDI trimer is added, and the reaction is continued for 1.5-3 hours (such as 2 hours and 2.5 hours).
In the third step, the reactor is stirred at 25-35 ℃ (30 ℃ C., 32 ℃ C., 34 ℃ C.) for 1-2h (1.2 h, 1.5h, 1.8h, for example).
In the fourth step, the A component, the B component and the C component are all processed at constant temperature of 10-30 ℃ (such as 15 ℃, 20 ℃ and 25 ℃).
The invention provides a preparation method of yellowing-resistant synthetic leather, which comprises the following steps:
coating polyurethane resin on release paper which is coated with aliphatic polyurethane resin in advance, bonding with a base material after prebaking, curing, cooling and stripping to obtain yellowing-resistant synthetic leather;
in the specific embodiment of the invention, the pre-baking temperature is 110-130 ℃ (such as 115 ℃, 120 ℃, 125 ℃, 130 ℃), and the pre-baking time is 120-200s (such as 130s, 140s, 150s, 160s, 180 s); the bonding pressure is 0.2-0.5MPa (such as 0.3MPa and 0.4 MPa), and the materials are put into an oven with 120-140 ℃ (such as 125 ℃, 130 ℃ and 135 ℃) for curing for 8-15min (such as 10min, 12min and 14 min) after bonding, and then cooled and peeled.
The anti-yellowing synthetic leather produced by the solvent-free polyurethane resin has the anti-UV yellowing performance reaching more than 4 levels, and the peeling strength not lower than 4 kg/3 cm.
Example 1
The solvent-free polyurethane resin for the yellowing-resistant synthetic leather provided by the embodiment comprises A, B and C three solvent-free components;
the component A is a hydroxyl component, and the preparation raw materials comprise the following components in parts by weight:
30 parts of polymer polyol, 350 parts of polyether glycol, 120 parts of polyether triol, 80 parts of polyaspartic acid ester, 10 parts of micromolecular glycol and 1 part of flatting agent.
The polymer polyol in the component A is polyether polyol grafted by vinyl polymer, the functionality is 3, the number average molecular weight is 4000, and the content of the vinyl polymer is 30%;
the polyether glycol is polyoxypropylene-ethylene glycol with the number average molecular weight of 1000, and the ethylene oxide content is 18%;
the polyether triol is polyoxypropylene-ethylene diol with a number average molecular weight of 3000, and the ethylene oxide content is 25%;
the polyaspartic acid ester is prepared by a Michael addition reaction of 4, 4-diamino dicyclohexylmethane and diethyl maleate;
the small molecular dihydric alcohol is ethylene glycol;
the leveling agent is BYK9565.
The component B is isocyanate component, and the preparation raw materials comprise the following components in parts by weight:
200 parts of polyether glycol, 8 parts of small molecular glycol, 200 parts of diphenylmethane diisocyanate (MDI) and hydrogenated diphenylmethane diisocyanate (H 12 MDI) 550 parts, HDI trimer 250 parts.
The polyether glycol is polyoxypropylene glycol with the number average molecular weight of 1000;
the small molecular dihydric alcohol is butanediol.
The NCO mass content in the HDI trimer was 20%.
The component C is a catalyst component, and the preparation raw materials comprise the following components in parts by weight;
bismuth isooctanoate, zinc isooctanoate, and DBU formate in a mass ratio of zinc isooctanoate to bismuth isooctanoate of 1:3 and zinc isooctanoate to (DBU) formate of 1:4.
When in use, the mass ratio of the component A to the component B is 1:0.9, and the mass of the component C is 1.5 percent of the sum of the mass of the components A, B.
The preparation method of the solvent-free polyurethane resin for the yellowing synthetic leather provided by the embodiment of the invention comprises the following steps:
the preparation method of the component A comprises the following steps: and (3) stirring the raw materials of each component in the component A for 1.5 hours at the temperature of 40 ℃ in a closed nitrogen-sealed reactor to obtain the component A.
The component B is prepared by a step method: polyether glycol, small molecular glycol, diphenylmethane diisocyanate (MDI), hydrogenated diphenylmethane diisocyanate (H) 12 MDI) was reacted in a closed nitrogen-sealed reactor at 85 c with stirring for 6 hours, and HDI trimer was added and the reaction was continued for 1.5 hours to prepare the B component.
And (3) preparation of a component C: the carboxylic acid salts of the bismuth carboxylate, the zinc carboxylate and the 1, 8-diazabicyclo [5.4.0] undecene-7 (DBU) are stirred for 1 hour in a closed nitrogen-sealed reactor at the temperature of 35 ℃ to prepare the component C.
The component A, the component B and the component C are processed at the constant temperature of 15 ℃, are put into a high-speed mixer according to the metering and stirred, and the mixed materials have the operation time of 900 seconds and are mixed to prepare the polyurethane resin.
Coating polyurethane resin on release paper which is pre-coated with aliphatic polyurethane resin, pre-baking the coated material, attaching the coated material to a base material, wherein the pre-baking temperature is 130 ℃, the pre-baking time is 150 seconds, the attaching pressure is 0.3MPa, placing the attached material into a 140 ℃ oven for curing for 10 minutes, cooling and stripping to obtain the yellowing-resistant solvent-free polyurethane synthetic leather, wherein the yellowing resistance of the yellowing-resistant synthetic leather can reach more than 4 grades, and the stripping strength is 4.5 kg/3 cm.
Example 2
The solvent-free polyurethane resin for the yellowing-resistant synthetic leather provided by the embodiment comprises A, B and C three solvent-free components;
the component A is a hydroxyl component, and the preparation raw materials comprise the following components in parts by weight:
50 parts of polymer polyol, 450 parts of polyether glycol, 150 parts of polyether triol, 150 parts of polyaspartic acid ester, 25 parts of micromolecular glycol and 3 parts of flatting agent.
The polymer polyol in the component A is polyether polyol grafted by vinyl polymer, the functionality is 3, the number average molecular weight is 5000, and the content of the vinyl polymer is 40%;
the polyether glycol is polyoxypropylene-ethylene glycol with the number average molecular weight of 2000, and the ethylene oxide content is 30%;
the polyether triol is polyoxypropylene-ethylene glycol with the number average molecular weight of 5000, and the content of ethylene oxide is 35%;
the polyaspartic acid ester is prepared by a Michael addition reaction of diamino dicyclohexylmethane and diethyl maleate;
the small molecular dihydric alcohol is butanediol;
the leveling agent is Yingchangdi high TEGO1484.
The component B is isocyanate component, and the preparation raw materials comprise the following components in parts by weight:
300 parts of polyether glycol, 15 parts of small molecular glycol, 300 parts of diphenylmethane diisocyanate (MDI) and hydrogenated diphenylmethane diisocyanate (H 12 MDI) 600 parts, HDI trimer 250 parts.
The polyether glycol is polyoxypropylene glycol with the number average molecular weight of 2000.
The small molecular dihydric alcohol is butanediol.
The NCO mass content in the HDI trimer was 25%.
The component C is a catalyst component, and the preparation raw materials comprise the following components in parts by weight;
bismuth neodecanoate, zinc neodecanoate, and isooctanoate of DBU in a mass ratio of 1:6, and zinc neodecanoate to (DBU) in a mass ratio of 1:8.
When in use, the mass ratio of the component A to the component B is 1:1.1, and the mass of the component C is 3 percent of the sum of the mass of the components A, B.
The preparation method of the solvent-free polyurethane resin for the yellowing synthetic leather provided by the embodiment of the invention comprises the following steps:
the preparation method of the component A comprises the following steps: and (3) stirring the raw materials of each component in the component A for 3 hours in a sealed nitrogen-sealed reactor at the temperature of 50 ℃ to obtain the component A.
The component B is prepared by a step method: polyether glycol, small molecular glycol, diphenylmethane diisocyanate (MDI), hydrogenated diphenylmethane diisocyanate (H) 12 MDI) in a closed nitrogen-sealed reactor at 95 ℃ for 5 hours with stirring, adding HDI trimer, and continuing the reaction for 3 hours to obtain the B component.
And (3) preparation of a component C: the carboxylic acid salts of bismuth carboxylate, zinc carboxylate and 1, 8-diazabicyclo [5.4.0] undecene-7 (DBU) are stirred in a closed nitrogen-sealed reactor at the temperature of 25 ℃ for 2 hours to obtain a component C.
The component A, the component B and the component C are processed at the constant temperature of 30 ℃, are put into a high-speed mixer according to the metering and stirred, and the mixed materials have the operational time of 600 seconds and are mixed to prepare the polyurethane resin.
Coating polyurethane resin on release paper which is pre-coated with aliphatic polyurethane resin, pre-baking the coated material, attaching the coated material to a base material, wherein the pre-baking temperature is 110 ℃, the pre-baking time is 120 seconds, the attaching pressure is 0.5MPa, placing the attached material into a baking oven at 120 ℃, curing for 8 minutes, cooling and stripping to obtain the yellowing-resistant solvent-free polyurethane synthetic leather, wherein the yellowing resistance of the yellowing-resistant synthetic leather can reach more than 4 grades, and the stripping strength is 6.5 kg/3 cm.
Example 3
The solvent-free polyurethane resin for the yellowing-resistant synthetic leather provided by the embodiment comprises A, B and C three solvent-free components;
the A component and the preparation method in this example are the same as in example 1, the B component and the preparation method are the same as in example 2, and the C component and the preparation method are the same as in example 1.
When in use, the mass ratio of the component A to the component B is 1:1.2, and the mass of the component C is 2.5 percent of the sum of the mass of the components A, B.
The preparation method of the yellowing-resistant synthetic leather provided by the embodiment comprises the following steps:
the component A, the component B and the component C are processed at the constant temperature of 30 ℃, are put into a high-speed mixer according to the metering and stirred, and the mixed materials have the operational time of 800 seconds and are mixed to prepare the polyurethane resin.
Coating polyurethane resin on release paper which is pre-coated with aliphatic polyurethane resin, pre-baking the coated material, attaching the coated material to a base material, wherein the pre-baking temperature is 110 ℃, the pre-baking time is 180 seconds, the attaching pressure is 0.4MPa, placing the attached material into a baking oven at 130 ℃, curing for 15 minutes, cooling and stripping to obtain the yellowing-resistant solvent-free polyurethane synthetic leather, wherein the yellowing resistance of the yellowing-resistant synthetic leather can reach more than 4 grades, and the stripping strength is 7.5 kg/3 cm.
Example 4
The solvent-free polyurethane resin for the yellowing-resistant synthetic leather provided by the embodiment comprises A, B and C three solvent-free components;
the A component and the preparation method in this example are the same as in example 2, the B component and the preparation method are the same as in example 1, and the C component and the preparation method are the same as in example 2.
When in use, the mass ratio of the component A to the component B is 1:0.8, and the mass of the component C is 3 percent of the sum of the mass of the components A, B.
The preparation method of the yellowing-resistant synthetic leather provided by the embodiment comprises the following steps:
the component A, the component B and the component C are processed at the constant temperature of 30 ℃, are put into a high-speed mixer according to the metering and stirred, and the mixed materials have the operational time of 750 seconds and are mixed to prepare the polyurethane resin.
Coating polyurethane resin on release paper which is pre-coated with aliphatic polyurethane resin, pre-baking the coated material, attaching the coated material to a base material, wherein the pre-baking temperature is 130 ℃, the pre-baking time is 120 seconds, the attaching pressure is 0.2MPa, placing the attached material into a baking oven at 130 ℃, curing for 10 minutes, cooling and stripping to obtain the yellowing-resistant solvent-free polyurethane synthetic leather, wherein the yellowing resistance of the yellowing-resistant synthetic leather can reach more than 4 grades, and the stripping strength is 5.5 kg/3 cm.
Comparative example 1
The comparative example differs from example 2 in that the polyaspartic acid ester in the A component is changed to 0 part, and the preparation method of the A component is the same as that of example 2, and the preparation methods of the B and C components and the preparation method of the C component are the same as that of example 2.
When in use, the mass ratio of the component A to the component B is 1:0.9, and the mass of the component C is 3 percent of the sum of the mass of the components A, B.
A method for preparing synthetic leather by solvent-free polyurethane resin for yellowing-resistant synthetic leather comprises the following steps: the A, B, C components are firstly kept at a constant temperature of 30 ℃, and are added into a high-speed mixer according to the measurement to be stirred, and after A, B, C components are mixed, the mixed materials have an operable time of 600 seconds; coating the product on release paper which is pre-coated with aliphatic polyurethane resin, pre-baking the coated product, attaching the product to a base material, wherein the pre-baking temperature is 110 ℃, the pre-baking time is 120 seconds, the attaching pressure is 0.5MPa, attaching the product, placing the product in a 120 ℃ oven, curing for 8 minutes, cooling and stripping the product to obtain the yellowing-resistant solvent-free polyurethane synthetic leather, wherein the yellowing resistance of the yellowing-resistant synthetic leather can reach more than 4 grades, and the stripping strength is 2.2 kg/3 cm.
Comparative example 2
The present comparative example differs from example 2 in that hydrogenated diphenylmethane diisocyanate (H 12 MDI), HDI trimer were all changed to 0 parts, diphenylmethane diisocyanate (MDI) was changed to 1000 parts; the preparation method of the component B is the same as that of the example 2; A. component C and its preparation method are the same as in example 2.
When the composition is used, the mass ratio of the component A to the component B is 1:1, and the mass of the component C is 3% of the sum of the mass of the components A, B.
A method for preparing synthetic leather by solvent-free polyurethane resin for yellowing-resistant synthetic leather comprises the following steps: the A, B, C components are firstly kept at a constant temperature of 30 ℃, and are added into a high-speed mixer according to the measurement to be stirred, and after A, B, C components are mixed, the mixed materials have an operable time of 450 seconds; coating the non-solvent polyurethane synthetic leather on release paper which is pre-coated with aliphatic polyurethane resin, pre-baking the coated material, bonding the coated material with the base material, wherein the pre-baking temperature is 110 ℃, the pre-baking time is 100 seconds, the bonding pressure is 0.5MPa, placing the bonded material into a baking oven at 120 ℃, curing for 5 minutes, cooling and stripping to obtain the non-solvent polyurethane synthetic leather, wherein the yellowing resistance of the non-solvent polyurethane synthetic leather is about 3 grades, and the stripping strength is 6.3 kg/3 cm.
The yellowing resistance and peel strength data of the synthetic leather prepared in examples and comparative examples are shown in table 1 below.
Table 1 yellowing resistance and peel strength of synthetic leather of examples and comparative examples
Figure BDA0004027428800000131
As shown in the table, the solvent-free polyurethane resin for the yellowing-resistant synthetic leather prepared in the embodiment of the invention has longer operable time which reaches 600-900s, and the prolonged operable time is beneficial to coating operation in the preparation of the synthetic leather, and reduces the phenomenon of sticking to the knife caused by resin solidification in the operation process, thereby reducing the defective rate of synthetic leather products. By adding polyaspartic acid ester to react with aliphatic isocyanate and introducing urea bond, the peeling strength of the synthetic leather product can be improved, and the strength after solidification is high; the component B is prepared by compounding aliphatic isocyanate and aromatic isocyanate, so that the reduction of yellowing resistance caused by permeation of free aromatic isocyanate to a surface layer can be reduced, and the yellowing resistance of the synthetic leather is improved. The resin system can meet the requirement of solvent-free synthetic leather production on the reaction speed, and can effectively improve the yellowing performance of the synthetic leather product.
To sum up: the invention adopts aliphatic isocyanate (namely HDI trimer) and MDI, H 12 The polyurethane resin for the solvent-free synthetic leather is compounded by MDI, the polyaspartic acid ester is matched with the polyol resin as the component A, and a proper catalyst is matched, so that the reaction of the hydroxyl component and the NCO component has a high reaction speed, the reaction of the polyaspartic acid ester and the NCO is influenced by steric hindrance, the reaction speed is low, the resin has a long operation time, the operable time of the polyurethane resin reaches 600-900s, the strength is high after solidification, and the resin system can not only meet the requirement of solvent-free synthetic leather production on the reaction speed, but also can effectively improve the yellowing performance of synthetic leather products.
The solvent-free polyurethane resin for the yellowing-resistant synthetic leather is prepared by compounding the aliphatic isocyanate and the aromatic isocyanate, so that the yellowing resistance reduction caused by permeation of free aromatic isocyanate to a surface layer can be reduced, polyaspartic acid ester is added to react with the aliphatic isocyanate, and urea bonds are introduced to ensure the final strength of a synthetic leather product. The UV yellowing resistance of the synthetic leather produced by using the solvent-free polyurethane resin can reach more than 4 levels, the peeling strength is not lower than 4 kg/3 cm, and the synthetic leather has wide application prospect.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A solvent-free polyurethane resin for yellowing-resistant synthetic leather, which is characterized by comprising A, B and C three solvent-free components;
the component A is a hydroxyl component, and the preparation raw materials comprise the following components in parts by weight:
30-50 parts of polymer polyol, 350-450 parts of polyether glycol, 100-150 parts of polyether triol, 80-250 parts of polyaspartic acid ester, 10-30 parts of micromolecular glycol and 1-5 parts of flatting agent;
the component B is isocyanate component, and the preparation raw materials comprise the following components in parts by weight:
200-350 parts of polyether glycol, 8-20 parts of micromolecular glycol, 200-300 parts of diphenylmethane diisocyanate, 500-600 parts of hydrogenated diphenylmethane diisocyanate and 150-250 parts of HDI trimer;
the component C is a catalyst component, and the preparation raw materials comprise the following components in parts by weight;
bismuth carboxylate, zinc carboxylate, carboxylate of 1, 8-diazabicyclo [5.4.0] undecene-7.
2. The solvent-free polyurethane resin for yellowing resistant synthetic leather according to claim 1, wherein the polyaspartic acid ester is prepared from one of diethylenetriamine, isophorone diamine, 4-diamino dicyclohexylmethane and 3,3' -dimethyl-4, 4-diamino dicyclohexylmethane and diethyl maleate through Michael addition reaction.
3. The solvent-free polyurethane resin for yellowing resistant synthetic leather according to claim 1, wherein the polymer polyol in the a component is a styrene-acrylonitrile copolymer graft modified polyether polyol;
preferably, the polymer polyol has a functionality of 3 and a number average molecular weight of 4000-6000;
still preferably, the mass percent of styrene-acrylonitrile copolymer in the polymer polyol is 30-40%.
4. The solvent-free polyurethane resin for yellowing resistant synthetic leather according to claim 1, wherein the polyether glycol in the a component is a copolymerized propylene oxide-ethylene glycol; the number average molecular weight of the polyether glycol in the component A is 750-2000;
preferably, the polyether triol is a copolymerized propylene oxide-ethylene triol; the number average molecular weight of the polyether triol is 3000-5000;
still preferably, the small molecular dihydric alcohol in the component A and/or the component B is one of ethylene glycol, butanediol and methyl propylene glycol;
still preferably, the leveling agent is an organosilicon leveling agent.
5. The solvent-free polyurethane resin for yellowing resistant synthetic leather according to claim 1, wherein the polyether glycol in the component B is polyoxypropylene glycol with a number average molecular weight of 1000-2000;
preferably, the HDI trimer is a trimerization product of hexamethylene diisocyanate, wherein the mass percent of NCO is 20-25%.
6. The solvent-free polyurethane resin for yellowing resistant synthetic leather according to claim 1, wherein the bismuth carboxylate is bismuth isooctanoate or bismuth neodecanoate;
the zinc carboxylate is zinc isooctanoate or zinc neodecanoate;
the carboxylate of the 1, 8-diazabicyclo [5.4.0] undecene-7 is one of isooctanoate of DBU, formate of DBU and p-toluenesulfonate of DBU;
preferably, the mass ratio of the zinc carboxylate to the bismuth carboxylate is 1:8-1:2;
the mass ratio of the zinc carboxylate to the carboxylate of the 1, 8-diazabicyclo [5.4.0] undecene-7 is 1:8-1:4.
7. A method for preparing the solvent-free polyurethane resin for yellowing-resistant synthetic leather according to any one of claims 1 to 6, comprising the steps of:
step one, preparing a component A;
adding polymer polyol, polyether glycol, polyether triol, polyaspartic acid ester, micromolecular glycol and a flatting agent into a closed nitrogen-sealed reactor according to mass ratio, and uniformly mixing to obtain a component A;
step two, preparing a component B;
according to the mass ratio, polyether glycol, micromolecular glycol, diphenylmethane diisocyanate and hydrogenated diphenylmethane diisocyanate are placed in a closed nitrogen-sealed reactor, and then HDI trimer is added, and after uniform mixing, the component B is prepared;
step three, preparing a component C;
bismuth carboxylate, zinc carboxylate and 1, 8-diazabicyclo [5.4.0] undecene-7 carboxylate are mixed in a closed nitrogen-sealed reactor according to the mass ratio, and the mixture is uniformly mixed to prepare a component C;
and fourthly, carrying out constant temperature treatment on the component A, the component B and the component C, metering and putting into a mixer for stirring, and mixing to obtain the polyurethane resin.
8. The method for preparing a solvent-free polyurethane resin for yellowing resistant synthetic leather according to claim 7, wherein the stirring is carried out for 1.5-2h at a temperature of 40-50 ℃ in the reactor in the first step;
preferably, in the second step, stirring and reacting for 4.5-6 hours at the temperature of 85-95 ℃ in the reactor, then adding the HDI trimer, and continuing to react for 1.5-3 hours;
still preferably, in step three, stirring is carried out in the reactor at a temperature of 25-35 ℃ for 1-2h;
still preferably, in step four, the A component, the B component and the C component are all treated at a constant temperature of 10-30 ℃.
9. The yellowing-resistant synthetic leather is characterized in that the yellowing-resistant synthetic leather is prepared by the preparation method of the solvent-free polyurethane resin for the yellowing-resistant synthetic leather according to claim 7 or 8.
10. A method for preparing the yellowing resistant synthetic leather according to claim 9, wherein the method comprises the following steps:
coating the polyurethane resin on release paper which is coated with aliphatic polyurethane resin in advance, bonding with a base material after prebaking, curing, cooling and stripping to obtain yellowing-resistant synthetic leather;
preferably, the temperature of the pre-baking is 110-130 ℃, and the pre-baking time is 120-200s; the bonding pressure is 0.2-0.5MPa, and the materials are put into an oven at 120-140 ℃ after bonding, cured for 8-15min, and then cooled and peeled.
CN202211711000.3A 2022-12-29 2022-12-29 Solvent-free polyurethane resin for yellowing-resistant synthetic leather, and preparation method and application thereof Pending CN116178671A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117645858A (en) * 2024-01-29 2024-03-05 山东世纪联合新材料科技有限公司 Zero yellowing glue material and preparation method and application thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117645858A (en) * 2024-01-29 2024-03-05 山东世纪联合新材料科技有限公司 Zero yellowing glue material and preparation method and application thereof

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