CN116444759B - Solvent-free polyurethane resin composition and application thereof - Google Patents

Solvent-free polyurethane resin composition and application thereof Download PDF

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Publication number
CN116444759B
CN116444759B CN202310695373.4A CN202310695373A CN116444759B CN 116444759 B CN116444759 B CN 116444759B CN 202310695373 A CN202310695373 A CN 202310695373A CN 116444759 B CN116444759 B CN 116444759B
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polyurethane prepolymer
solvent
resin composition
polyurethane resin
alkali
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CN116444759A (en
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尹凯凯
凌长水
江平
张大华
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XUCHUAN CHEMICAL (SUZHOU) CO Ltd
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XUCHUAN CHEMICAL (SUZHOU) 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
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • 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
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two 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
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene 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
    • C08G18/28—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
    • C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
    • 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
    • C08G18/8064—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with monohydroxy compounds
    • C08G18/8067—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with monohydroxy compounds phenolic 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
    • C08G18/70—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
    • C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing 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
    • C08G18/70—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
    • C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
    • C08G18/8077—Oximes
    • 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
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0011—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using non-woven fabrics
    • 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
    • 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
    • D06N2211/00—Specially adapted uses
    • D06N2211/12—Decorative or sun protection articles
    • D06N2211/28—Artificial leather
    • 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 discloses a solvent-free polyurethane resin composition, which comprises the following raw materials: a blocked polyurethane prepolymer and an amine curing agent; wherein, the blocking agent reacts with-NCO groups in the polyurethane prepolymer to prepare the blocked polyurethane prepolymer; the sealing agent consists of at least two sealing agents with different deblocking temperatures, and the difference of the deblocking temperatures is 10-30 ℃; the amine curing agent is one of polyamine, and a composition of polyamine and diamine. The invention also discloses application of the solvent-free polyurethane resin composition in leather. The invention also discloses a preparation method of the leather, which comprises the following steps: and (3) carrying out impregnation treatment on the non-woven fabric by using the solvent-free polyurethane resin composition, drying at 130-140 ℃ for 10-15min, and carrying out decrement treatment by using alkali liquor to obtain leather. The invention has good high-temperature alkali resistance, and the prepared leather has good hand feeling and meat feeling.

Description

Solvent-free polyurethane resin composition and application thereof
Technical Field
The invention relates to the technical field of leather, in particular to a solvent-free polyurethane resin composition and application thereof.
Background
The superfine fiber synthetic leather originally originates from Japan, is a polymer composite material of polyurethane resin and superfine fiber, structurally has a 'simulation' structure of leather, is used as a fourth-generation synthetic leather product, has high mechanical strength, soft and plump hand feeling and strong leather feel, and is an ideal substitute of natural leather.
Sea-island microfiber synthetic leather is divided into toluene extracted adventitious island microfiber and alkali-reduced fixed island microfiber, wherein the alkali-reduced fixed island microfiber becomes a high-end product of the microfiber synthetic leather with excellent hand feeling and vivid dyeing property. The alkali deweighting island microfiber currently mostly adopts solvent polyurethane resin, has good hand feeling, good dyeing property and excellent performance, but the DMF is used as a solvent in the production process of the product, so that the environment is polluted, the physical health of workers is damaged, and a certain amount of VOC organic solvent is also added into the solvent microfiber leather, so that the body of the user is damaged.
In recent years, environment-friendly polyurethane resin is gradually applied to the field of fixed island microfibers, and the application of the most main waterborne polyurethane in the fixed island microfibers is that the waterborne polyurethane for the fixed island microfibers is in many markets at present, but certain problems exist in the use process: 1. the waterborne polyurethane has the advantages of low molecular weight, general high-temperature hot alkali resistance, resin loss during decrement, and general custom-made island super-fiber hand feeling; 2. after the non-woven fabric is impregnated with the aqueous polyurethane, the polyurethane emulsion can migrate to the two ends of the non-woven fabric in the drying process, the problem of hollow core in the middle occurs, and the product has poor performance and general hand feeling. The above problems are still difficult to solve completely in the prior art, so that the environmental protection of polyurethane for impregnating the island-fixing microfiber is urgent.
Disclosure of Invention
Based on the technical problems existing in the background technology, the invention provides a solvent-free polyurethane resin composition and application thereof; the whole preparation process of the solvent-free polyurethane resin composition has no solvent intervention and no solvent residue; through reasonable formula design, the polyurethane resin has good high-temperature alkali resistance, and the prepared leather has good hand feeling and meat feel, so that the problem that the waterborne polyurethane resin migrates to two ends of the non-woven fabric when being dried is avoided; meanwhile, the solvent-free polyurethane resin composition can react and emit heat when being dried, so that the energy consumption required by resin drying and molding can be obviously reduced, and the solvent-free polyurethane resin composition is a low-carbon green environment-friendly product.
The invention provides a solvent-free polyurethane resin composition, which comprises the following raw materials: a blocked polyurethane prepolymer and an amine curing agent;
wherein, the blocking agent reacts with-NCO groups in the polyurethane prepolymer to prepare the blocked polyurethane prepolymer; the sealing agent consists of at least two sealing agents with different deblocking temperatures, and the difference of the deblocking temperatures is 10-30 ℃; the amine curing agent is one of polyamine, and a composition of polyamine and diamine.
Preferably, the blocking agent is at least two of butanone oxime, acetoxime, 3, 5-dimethylpyrazole and phenol.
Preferably, the amine curing agent is a combination of a polyamine and a diamine.
Preferably, the polyamine is one or more of diethylenetriamine and triethylenetetramine.
Preferably, the diamine is one or more of ethylenediamine, isophoronediamine, 1, 5-pentanediamine, aminopolyether.
Preferably, the weight ratio of polyamine to diamine is 1:8.59-25.9.
Preferably, the-NCO content of the blocked polyurethane prepolymer is 0.
Preferably, when the solvent-free polyurethane resin composition is used, the molar ratio of the amino groups in the amine-based curing agent to the-NCO groups in the polyurethane prepolymer before blocking is 1:1 to 1.05.
Preferably, the raw materials of the closed polyurethane prepolymer include: diisocyanate, polyol compound, chain extender, catalyst and blocking agent.
Preferably, the raw materials of the closed polyurethane prepolymer comprise the following components in percentage by weight: 18-26% of diisocyanate, 67-74% of polyol compound, 0.5-0.9% of chain extender, 0.001-0.005% of catalyst and 4-8% of sealing agent, wherein the sum of the weight percentages of the raw materials is 100%.
Preferably, the diisocyanate is one or more of 4, 4-diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate or 4, 4-dicyclohexylmethane diisocyanate.
Preferably, the polyol compound is a polyether polyol.
Preferably, the polyether polyol has a relative molecular weight of 1000 to 8000g/mol.
Preferably, the polyether polyol is one or more of polytetrahydrofuran diol, polypropylene oxide ether diol, or polytetrahydrofuran propylene oxide copolyether diol.
Preferably, the chain extender is a glycol.
Preferably, the catalyst is an organobismuth catalyst.
Preferably, the preparation method of the closed polyurethane prepolymer comprises the following steps: uniformly mixing a polyol compound, a chain extender, diisocyanate and a catalyst, and performing a prepolymerization reaction; and then adding a blocking agent to carry out a blocking reaction until the content of-NCO groups is 0, thus obtaining the blocked polyurethane prepolymer.
Preferably, the temperature of the prepolymerization reaction is 70-85 ℃ and the time is 2-4h.
Preferably, the temperature of the blocking reaction is 70-80 ℃.
Preferably, the prepolymerization and the blocking reaction are carried out in an inert gas atmosphere.
The invention also provides polyurethane resin, and the polyurethane resin is obtained by taking the solvent-free polyurethane resin composition and curing.
Preferably, the curing temperature is 130-140 ℃.
The invention also provides application of the solvent-free polyurethane resin composition in leather.
Preferably, the leather is a microfiber synthetic leather.
The invention also provides a preparation method of the leather, which comprises the following steps: and (3) carrying out impregnation treatment on the non-woven fabric by using the solvent-free polyurethane resin composition, drying at 130-140 ℃ for 10-15min, and carrying out decrement treatment by using alkali liquor to obtain leather.
Advantageous effects
1. After the solvent-free polyurethane resin composition disclosed by the invention is impregnated into non-woven fabrics, drying is carried out at a proper temperature, deblocking is carried out on the closed polyurethane prepolymer, and chain extension and crosslinking reaction is carried out on the deblocked-NCO group and an amine curing agent; according to the invention, at least two blocking agents with different deblocking temperatures (such as butanone oxime and 3, 5-dimethylpyrazole) are selected for blocking treatment on the-NCO groups in the polyurethane prepolymer, the-NCO groups can be deblocked at different temperatures, and the polyamine or the combination of the polyamine and the diamine is used as the curing agent in a matching manner, so that the crosslinking selectivity of the amine curing agent can be improved, the molecular weight of the polyurethane is improved, and meanwhile, the proper crosslinking degree is realized, so that the high-temperature alkali resistance of the polyurethane resin is ensured, the loss of the resin during alkali reduction is reduced, and the hand feeling of leather is improved.
2. The solvent-free polyurethane resin composition uses the raw materials of the composition as solvents, and no other solvents are additionally used in the preparation process, so that the composition is an environment-friendly product; and after the non-woven fabric is impregnated with the solvent-free polyurethane resin composition, the phenomenon that similar aqueous polyurethane resin migrates to two ends of the non-woven fabric is avoided in the process of drying and forming the resin, and the problems of hollow middle and poor performance are avoided.
3. The chain extension and crosslinking reaction of the unpacked-NCO group and the amine curing agent is carried out, and the whole process is exothermic, so that the energy consumption is reduced when the product is prepared, and the low-carbonization production requirement is met.
4. The invention selects polyether polyol (such as polytetrahydrofuran glycol, polypropylene oxide ether glycol and the like) of proper types as a resin soft segment, so that the alkali resistance of polyurethane resin can be further improved; and the invention has good stability and can be stored for a long time through reasonable formula design.
Drawings
FIG. 1 is a graph showing the dispersion of resin in a custom-made island microfiber synthetic leather prepared by the present invention.
FIG. 2 is a graph showing the dispersion of resins in the custom-made island microfiber synthetic leather prepared by using comparative example 3.
Detailed Description
The invention relates to a solvent-free polyurethane resin composition, which comprises the following raw materials: a blocked polyurethane prepolymer and an amine curing agent;
wherein, the blocking agent reacts with-NCO groups in the polyurethane prepolymer to prepare the blocked polyurethane prepolymer; the sealing agent consists of at least two sealing agents with different deblocking temperatures, and the difference of the deblocking temperatures is 10-30 ℃; the amine curing agent is one of polyamine, and a composition of polyamine and diamine.
Preferably, the difference in deblocking temperatures is 15-20 ℃.
The blocking agent contains blocking groups, and can react with-NCO groups in polyurethane prepolymer to generate chemical bonds to obtain the blocked polyurethane prepolymer, wherein the chemical bonds are stable at normal temperature and can be broken when heated at a proper temperature (namely deblocking temperature), so that the blocking groups and-NCO groups are regenerated.
The polyamine is an amine having three or more amino groups in the molecule.
After the solvent-free polyurethane resin composition disclosed by the invention is impregnated into non-woven fabrics, drying is carried out at a proper temperature, deblocking is carried out on the closed polyurethane prepolymer, and chain extension and crosslinking reaction is carried out on the deblocked-NCO group and an amine curing agent; according to the invention, at least two blocking agents with different deblocking temperatures (such as butanone oxime and 3, 5-dimethylpyrazole) are selected for blocking treatment on the-NCO groups in the polyurethane prepolymer, the-NCO groups can be deblocked at different temperatures, and the polyamine or the combination of the polyamine and the diamine is used as a curing agent in a matching manner, so that the selectivity of molecular chain crosslinking can be improved, the molecular weight of the polyurethane is improved, and meanwhile, the polyurethane resin has proper crosslinking degree, thereby ensuring the high-temperature alkali-resistant performance of the polyurethane resin, reducing the loss of the resin during alkali decrement and improving the hand feeling of leather.
The solvent-free polyurethane resin composition disclosed by the invention uses the self raw materials as the solvent, and no other solvent is additionally used in the preparation process, so that the solvent-free polyurethane resin composition is an environment-friendly product; and after the non-woven fabric is impregnated with the solvent-free polyurethane resin composition, the phenomenon that similar aqueous polyurethane resin migrates to two ends of the non-woven fabric is avoided in the process of drying and forming the resin, and the problems of hollow middle and poor performance are avoided.
In addition, the unpacked-NCO group and the amine curing agent undergo chain extension crosslinking reaction, and the whole process is exothermic reaction, so that the energy consumption is reduced when the product is prepared, and the low-carbonization production requirement is met.
Preferably, the blocking agent is at least two of butanone oxime, acetoxime, 3, 5-dimethylpyrazole and phenol.
More preferably, the blocking agent consists of two blocking agents with different deblocking temperatures; preferably, the weight ratio of the blocking agent with low deblocking temperature to the blocking agent with high deblocking temperature is 1:0.6-1.4.
More preferably, the blocking agent is a combination of 3, 5-dimethylpyrazole, butanone oxime; preferably, the weight ratio of the 3, 5-dimethylpyrazole to the butanone oxime is 1:0.6-1.4.
The deblocking temperature of the butanone oxime after the butanone oxime reacts with the-NCO group is more than or equal to 140 ℃.
The deblocking temperature of the acetone oxime after the reaction with the-NCO group is more than or equal to 120 ℃.
The deblocking temperature of the 3, 5-dimethylpyrazole after the reaction with the-NCO group is more than or equal to 110 ℃.
The deblocking temperature of the phenol after the reaction with the-NCO group is more than or equal to 135 ℃.
Preferably, the amine curing agent is a combination of a polyamine and a diamine.
Preferably, the polyamine is one or more of diethylenetriamine and triethylenetetramine.
Preferably, the diamine is one or more of ethylenediamine, isophoronediamine, 1, 5-pentanediamine, aminopolyether.
Preferably, the weight ratio of polyamine to diamine is 1:8.59-25.9.
More preferably, the amine curing agent is a combination of diethylenetriamine, ethylenediamine and aminopolyether; preferably, the weight ratio of diethylenetriamine to ethylenediamine to aminopolyether is 1:0.34-0.6:8.25-25.3.
Preferably, the-NCO content of the blocked polyurethane prepolymer is 0.
The closed polyurethane prepolymer and the amine curing agent can be uniformly mixed and stored for standby; or sealing and storing separately, and mixing the two materials; the dosage of the two is not limited, and the effective crosslinking and curing can be realized; preferably, when the solvent-free polyurethane resin composition is used, the molar ratio of the amino groups in the amine curing agent to the-NCO groups in the polyurethane prepolymer before blocking is 1:1-1.05; more preferably 1:1.02.
The weight ratio of the closed polyurethane prepolymer to the amine curing agent can be 100:3-25, and the composition can be carried out within the weight ratio range so that the molar ratio of amino groups in the amine curing agent to-NCO groups in the polyurethane prepolymer before closing is 1:1-1.05, and the polyurethane resin is obtained by heating and curing.
Preferably, the raw materials of the closed polyurethane prepolymer include: diisocyanate, polyol compound, chain extender, catalyst and blocking agent.
The usage amount of each raw material in the closed polyurethane prepolymer is not limited, and the closed polyurethane prepolymer can be obtained; the amount of each raw material may be further selected to be more suitable.
Preferably, the raw materials of the closed polyurethane prepolymer comprise the following components in percentage by weight: 18-26% of diisocyanate, 67-74% of polyol compound, 0.5-0.9% of chain extender, 0.001-0.005% of catalyst and 4-8% of sealing agent, wherein the sum of the weight percentages of the raw materials is 100%.
The raw materials of the closed polyurethane prepolymer can also contain an antioxidant; the antioxidant can be one or more of pentaerythritol tetra (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 2' -methylenebis (4-methyl-6-tert-butylphenol) and the like; the amount of antioxidant in the blocked polyurethane prepolymer may be 0.02 to 0.1% by weight.
The invention has good stability and can be stored for a long time by selecting proper formula and proportion.
Preferably, the diisocyanate is one or more of 4, 4-diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate or 4, 4-dicyclohexylmethane diisocyanate.
Preferably, the polyol compound is a polyether polyol.
Preferably, the polyether polyol has a relative molecular weight of 1000 to 8000g/mol.
Preferably, the polyether polyol is one or more of polytetrahydrofuran diol, polypropylene oxide ether diol, or polytetrahydrofuran propylene oxide copolyether diol.
The invention selects polyether polyol of proper kind as the resin soft segment, which can further improve the alkali resistance of polyurethane resin.
Preferably, the chain extender is a glycol.
Preferably, the catalyst is an organobismuth catalyst.
The dihydric alcohol can be one or more of ethylene glycol, 1, 4-butanediol, neopentyl glycol, 1, 2-propanediol and the like.
The catalyst may be an organobismuth catalyst MB20 or the like.
Preferably, the preparation method of the closed polyurethane prepolymer comprises the following steps: uniformly mixing a polyol compound, a chain extender, diisocyanate and a catalyst, and performing a prepolymerization reaction; and then adding a blocking agent to carry out a blocking reaction until the content of-NCO groups is 0, thus obtaining the blocked polyurethane prepolymer.
Preferably, the temperature of the prepolymerization reaction is 70-85 ℃ and the time is 2-4h.
Preferably, the temperature of the blocking reaction is 70-80 ℃.
Preferably, the prepolymerization and the blocking reaction are carried out in an inert gas atmosphere. The inert gas may be nitrogen or the like.
The invention also provides polyurethane resin, and the polyurethane resin is obtained by taking the solvent-free polyurethane resin composition and curing.
Preferably, the curing temperature is 130-140 ℃.
The curing time is not limited, and the solvent-free polyurethane resin composition can be cured; it may also be more preferable that the curing time is 10 to 15 minutes.
The invention also provides application of the solvent-free polyurethane resin composition in leather.
Preferably, the leather is a microfiber synthetic leather.
The superfine fiber synthetic leather can be sea-island superfine fiber synthetic leather, such as toluene extracted indefinite island superfine fiber synthetic leather, alkali reduced definite island superfine fiber synthetic leather and the like; preferably, the superfine fiber synthetic leather is alkali-reduced island-fixed superfine fiber synthetic leather.
The invention also provides a preparation method of the leather, which comprises the following steps: and (3) carrying out impregnation treatment on the non-woven fabric by using the solvent-free polyurethane resin composition, drying at 130-140 ℃ for 10-15min, and carrying out decrement treatment by using alkali liquor to obtain leather.
The alkali liquor can be sodium hydroxide aqueous solution with the mass fraction of 5-15 wt%; preferably, the alkali liquor is a 10wt% sodium hydroxide aqueous solution.
The temperature of the above-mentioned decrement treatment can be 85-95 deg.C, and the time can be 25-35min; the temperature of the decrement treatment is preferably 90℃for 30 minutes.
After the weight reduction treatment, the leather is obtained through water washing and drying treatment.
The technical scheme of the invention is described in detail through specific embodiments.
The raw material information used in the following examples and comparative examples is shown in table 1.
Example 1
A solvent-free polyurethane resin composition comprises the following raw materials: a blocked polyurethane prepolymer and an amine curing agent;
wherein, the raw materials of the closed polyurethane prepolymer comprise: 76.8g of 4, 4-diphenylmethane diisocyanate, 200g of PTMG-2000 g, 2.1g of ethylene glycol, 0.007g of organobismuth catalyst MB, 0.2g of antioxidant I-1010, 8.1g of 3, 5-dimethylpyrazole and 11.1g of butanone oxime;
the difference of the deblocking temperatures of the 3, 5-dimethylpyrazole and butanone oxime is 30 ℃;
the amine curing agent comprises 0.5g of ethylenediamine, 0.8g of diethylenetriamine and 20.22g of 1000 molecular weight aminopolyether;
the preparation method of the closed polyurethane prepolymer comprises the following steps:
adding PTMG-2000, glycol and antioxidant I-1010 into a reaction bottle, stirring and mixing at 45-50deg.C; under the protection of nitrogen, adding 4, 4-diphenylmethane diisocyanate and an organobismuth catalyst MB20, uniformly mixing, preserving heat at 80 ℃ for a prepolymerization reaction for 3 hours, detecting the content of-NCO groups in a reaction system, and obtaining a polyurethane prepolymer when the content of-NCO groups reaches a theoretical value;
under the protection of nitrogen, adding 3, 5-dimethylpyrazole and butanone oxime into the polyurethane prepolymer, uniformly mixing, and carrying out a sealing reaction for 3 hours at the temperature of 80 ℃ by preserving heat, and detecting that the content of-NCO groups in a system is 0, thereby obtaining the sealing polyurethane prepolymer.
Example 2
A solvent-free polyurethane resin composition comprises the following raw materials: a blocked polyurethane prepolymer and an amine curing agent;
wherein, the raw materials of the closed polyurethane prepolymer comprise: 76.8g of 4, 4-diphenylmethane diisocyanate, 150g of PTMG-2000, 2000-50 g of PPG, 2.1g of ethylene glycol, 20.007 g of organobismuth catalyst MB, 0.2g of antioxidant I-1010, 12.1g of 3, 5-dimethylpyrazole and 7.36g of butanone oxime;
the difference of the deblocking temperatures of the 3, 5-dimethylpyrazole and butanone oxime is 30 ℃;
the amine curing agent comprises 0.5g of ethylenediamine, 0.8g of diethylenetriamine and 20.22g of 1000 molecular weight aminopolyether;
the preparation method of the closed polyurethane prepolymer comprises the following steps:
adding PTMG-2000, PPG-2000, ethylene glycol and antioxidant I-1010 into a reaction bottle, stirring and mixing at 45-50deg.C; under the protection of nitrogen, adding 4, 4-diphenylmethane diisocyanate and an organobismuth catalyst MB20, uniformly mixing, preserving heat at 80 ℃ for a prepolymerization reaction for 3 hours, detecting the content of-NCO groups in a reaction system, and obtaining a polyurethane prepolymer when the content of-NCO groups reaches a theoretical value;
under the protection of nitrogen, adding 3, 5-dimethylpyrazole and butanone oxime into the polyurethane prepolymer, uniformly mixing, and carrying out a sealing reaction for 3 hours at the temperature of 80 ℃ by preserving heat, and detecting that the content of-NCO groups in a system is 0, thereby obtaining the sealing polyurethane prepolymer.
Example 3
A solvent-free polyurethane resin composition comprises the following raw materials: a blocked polyurethane prepolymer and an amine curing agent;
wherein, the raw materials of the closed polyurethane prepolymer comprise: 76.8g of 4, 4-diphenylmethane diisocyanate, 150g of PTMG-2000, 2000-50 g of PPG, 2.1g of ethylene glycol, 20.007 g of organobismuth catalyst MB, 0.2g of antioxidant I-1010, 12.1g of 3, 5-dimethylpyrazole and 7.36g of butanone oxime;
the difference of the deblocking temperatures of the 3, 5-dimethylpyrazole and butanone oxime is 30 ℃;
the amine curing agent comprises 0.5g of ethylenediamine, 1.47g of diethylenetriamine and 12.13g of 1000 molecular weight aminopolyether;
the preparation method of the closed polyurethane prepolymer comprises the following steps:
adding PTMG-2000, PPG-2000, ethylene glycol and antioxidant I-1010 into a reaction bottle, stirring and mixing at 45-50deg.C; under the protection of nitrogen, adding 4, 4-diphenylmethane diisocyanate and an organobismuth catalyst MB20, uniformly mixing, preserving heat at 80 ℃ for a prepolymerization reaction for 3 hours, detecting the content of-NCO groups in a reaction system, and obtaining a polyurethane prepolymer when the content of-NCO groups reaches a theoretical value;
under the protection of nitrogen, adding 3, 5-dimethylpyrazole and butanone oxime into the polyurethane prepolymer, uniformly mixing, and carrying out a sealing reaction for 3 hours at the temperature of 80 ℃ by preserving heat, and detecting that the content of-NCO groups in a system is 0, thereby obtaining the sealing polyurethane prepolymer.
Example 4
A solvent-free polyurethane resin composition comprises the following raw materials: a blocked polyurethane prepolymer and an amine curing agent;
wherein, the raw materials of the closed polyurethane prepolymer comprise: 53.4g of toluene diisocyanate, 200g of PTMG-2000, 1.5g of ethylene glycol, 0.01g of organobismuth catalyst MB, 0.2g of antioxidant I-1010, 9.5g of 3, 5-dimethylpyrazole and 6g of acetone oxime;
the difference of the deblocking temperatures of the 3, 5-dimethylpyrazole and the acetoxime is 10 ℃;
the amine curing agent comprises 0.5g of 1, 5-pentanediamine, 1.47g of diethylenetriamine and 12.13g of 1000 molecular weight aminopolyether;
the preparation method of the closed polyurethane prepolymer comprises the following steps:
adding PTMG-2000, glycol and antioxidant I-1010 into a reaction bottle, stirring and mixing at 45-50deg.C; under the protection of nitrogen, adding 4, 4-diphenylmethane diisocyanate and an organobismuth catalyst MB20, uniformly mixing, preserving heat at 70 ℃ for a prepolymerization reaction for 4 hours, detecting the content of-NCO groups in a reaction system, and obtaining a polyurethane prepolymer when the content of-NCO groups reaches a theoretical value;
under the protection of nitrogen, adding 3, 5-dimethylpyrazole and butanone oxime into the polyurethane prepolymer, uniformly mixing, and carrying out a sealing reaction for 4 hours at the temperature of 70 ℃ by preserving heat, and detecting that the content of-NCO groups in a system is 0, thereby obtaining the sealed polyurethane prepolymer.
Example 5
A solvent-free polyurethane resin composition comprises the following raw materials: a blocked polyurethane prepolymer and an amine curing agent;
wherein, the raw materials of the closed polyurethane prepolymer comprise: 68.2g of isophorone diisocyanate, 150g of PTMG-2000, 50g of PPG-2000, 2.6g of 1, 4-butanediol, 20.004 g of organobismuth catalyst MB, 0.2g of antioxidant I-1010, 10g of 3, 5-dimethylpyrazole and 13.7g of butanone oxime;
the difference of the deblocking temperatures of the 3, 5-dimethylpyrazole and butanone oxime is 30 ℃;
the amine curing agent is ethylenediamine 0.5g, triethylene tetramine 1.47g and amino polyether of 1000 molecular weight 12.13g;
the preparation method of the closed polyurethane prepolymer comprises the following steps:
adding PTMG-2000, PPG-2000, ethylene glycol and antioxidant I-1010 into a reaction bottle, stirring and mixing at 45-50deg.C; under the protection of nitrogen, adding 4, 4-diphenylmethane diisocyanate and an organobismuth catalyst MB20, uniformly mixing, preserving heat at 85 ℃ for a prepolymerization reaction for 2 hours, detecting the content of-NCO groups in a reaction system, and obtaining a polyurethane prepolymer when the content of-NCO groups reaches a theoretical value;
under the protection of nitrogen, adding 3, 5-dimethylpyrazole and butanone oxime into the polyurethane prepolymer, uniformly mixing, preserving heat at 75 ℃ for sealing reaction for 2 hours, and detecting that the content of-NCO groups in the system is 0 to obtain the sealed polyurethane prepolymer.
Comparative example 1
8.1g of "3, 5-dimethylpyrazole and 11.1g of butanone oxime were replaced with 18.41g of" butanone oxime ", and the same as in example 1 was repeated.
Comparative example 2
The amine curing agent was 1.23g of ethylenediamine and 20.22g of 1000 molecular weight aminopolyether, otherwise identical to example 2.
Taking the closed polyurethane prepolymer prepared in the examples 1-5 and the comparative examples 1-2 and the amine curing agent, respectively mixing according to the molar ratio of amino groups in the amine curing agent to-NCO groups in the polyurethane prepolymer before closing of 1:1.02, stirring and uniformly mixing, respectively soaking sea-island fiber non-woven fabrics, drying in a drying oven at 130-140 ℃ for 10-15min, taking out, putting into a sodium hydroxide aqueous solution with the mass fraction of 10wt%, soaking for 30min at 90 ℃ for decrement treatment, taking out, washing with water, and drying to obtain the fixed-island superfine fiber synthetic leather.
Comparative examples 3-4 the island fiber cloth was impregnated with 2 aqueous polyurethane resins (comparative example 3 was purchased from Hangzhou chemical and comparative example 4 was purchased from Shanghai chemical) on the market, dried in an oven at 130-140 c for 30min, taken out, put in a 10wt% aqueous sodium hydroxide solution, soaked for 30min at 90 c for decrement treatment, then taken out, washed with water, and dried to obtain the island-fixing ultrafine fiber synthetic leather (suede).
The results of testing the properties of the custom-made island microfiber synthetic leather of each group are shown in Table 2 and FIGS. 1-2.
FIG. 1 is a graph showing the dispersion of resin in a custom-made island microfiber synthetic leather prepared by the present invention.
FIG. 2 is a graph showing the dispersion of resins in the custom-made island microfiber synthetic leather prepared by using comparative example 3.
As can be seen from fig. 1-2: in the island superfine fiber synthetic leather prepared by the solvent-free polyurethane resin composition, the resin is uniformly dispersed; in the island-shaped superfine fiber synthetic leather prepared in the comparative example 3, resin is unevenly dispersed, and a cavity appears in the middle.
As can be seen from Table 2, the island-shaped superfine fiber synthetic leather prepared by the method has better resin retention rate, uniform resin dispersion and good hand feeling and meat feel.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.

Claims (5)

1. The alkali-reduced island microfiber synthetic leather is characterized by comprising non-woven fabrics and a solvent-free polyurethane resin composition, wherein the solvent-free polyurethane resin composition comprises the following raw materials: a blocked polyurethane prepolymer and an amine curing agent;
wherein, the blocking agent reacts with-NCO groups in the polyurethane prepolymer to prepare the blocked polyurethane prepolymer; the sealing agent consists of two sealing agents with different deblocking temperatures, and the difference of the deblocking temperatures is 10-30 ℃; the weight ratio of the blocking agent with low deblocking temperature to the blocking agent with high deblocking temperature is 1:0.6-1.4;
the amine curing agent is a composition of diethylenetriamine, ethylenediamine and aminopolyether; the weight ratio of the diethylenetriamine to the ethylenediamine to the aminopolyether is 1:0.34-0.6:8.25-25.3;
the raw materials of the closed polyurethane prepolymer comprise the following components in percentage by weight: 18-26% of diisocyanate, 67-74% of polyol compound, 0.5-0.9% of chain extender, 0.001-0.005% of catalyst and 4-8% of sealing agent, wherein the sum of the weight percentages of the raw materials is 100%.
2. The alkali-reduced island microfiber synthetic leather of claim 1, wherein the blocking agent is two of butanone oxime, acetoxime, 3, 5-dimethylpyrazole, phenol.
3. The alkali-reduced island microfiber synthetic leather of claim 1, wherein the molar ratio of amino groups in the amine curing agent to-NCO groups in the polyurethane prepolymer before blocking is 1:1-1.05 when the solvent-free polyurethane resin composition is used.
4. The alkali-reduced island microfiber synthetic leather of claim 1, wherein the preparation method of the closed polyurethane prepolymer comprises the following steps: uniformly mixing a polyol compound, a chain extender, diisocyanate and a catalyst, and performing a prepolymerization reaction; and then adding a blocking agent to carry out a blocking reaction until the content of-NCO groups is 0, thus obtaining the blocked polyurethane prepolymer.
5. A method for preparing the alkali-reduced island-free microfiber synthetic leather according to any one of claims 1 to 4, comprising the steps of: and (3) carrying out impregnation treatment on the non-woven fabric by using the solvent-free polyurethane resin composition, drying for 10-15min at 130-140 ℃, and then carrying out decrement treatment by using alkali liquor to obtain the alkali decrement island-fixed microfiber synthetic leather.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0403044A2 (en) * 1989-06-16 1990-12-19 Hunter Douglas Industries B.V. Blocked isocyanates and their production and use
CN105399921A (en) * 2015-12-23 2016-03-16 上海华峰超纤材料股份有限公司 High solid content flame retardant wet-method foaming polyurethane used for synthetic leather and preparation method and application thereof
CN108314768A (en) * 2018-01-19 2018-07-24 东莞市高示新材料有限公司 A kind of monocomponent polyurethane, a kind of microfiber leather and preparation method thereof
CN116023626A (en) * 2023-01-05 2023-04-28 浙江禾欣科技有限公司 Hydrolysis-resistant high-solid-content closed polyurethane resin composition and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0403044A2 (en) * 1989-06-16 1990-12-19 Hunter Douglas Industries B.V. Blocked isocyanates and their production and use
CN105399921A (en) * 2015-12-23 2016-03-16 上海华峰超纤材料股份有限公司 High solid content flame retardant wet-method foaming polyurethane used for synthetic leather and preparation method and application thereof
CN108314768A (en) * 2018-01-19 2018-07-24 东莞市高示新材料有限公司 A kind of monocomponent polyurethane, a kind of microfiber leather and preparation method thereof
CN116023626A (en) * 2023-01-05 2023-04-28 浙江禾欣科技有限公司 Hydrolysis-resistant high-solid-content closed polyurethane resin composition and preparation method thereof

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