CN116478381B - Bio-based polycaprolactone diol, polyurethane resin for leather, synthetic leather and preparation method thereof - Google Patents

Bio-based polycaprolactone diol, polyurethane resin for leather, synthetic leather and preparation method thereof Download PDF

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CN116478381B
CN116478381B CN202310417187.4A CN202310417187A CN116478381B CN 116478381 B CN116478381 B CN 116478381B CN 202310417187 A CN202310417187 A CN 202310417187A CN 116478381 B CN116478381 B CN 116478381B
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bio
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parts
polycaprolactone diol
diol
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CN116478381A (en
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王湘杰
高伟
王胜军
陶志豪
彭友智
李镓豪
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Hunan Juren New Materials Co
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Hunan Juren Chemical New Material 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/664—Polyesters containing oxygen in the form of ether groups derived from hydroxy carboxylic acids
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • 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
    • 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 relates to bio-based polycaprolactone diol, polyurethane resin for leather, synthetic leather and a preparation method thereof, wherein 500-100 parts by weight of low molecular weight bio-based diol is heated to 120-130 ℃, vacuum dehydration is carried out for 2 hours, then the temperature is reduced to below 80 ℃, then 100ppm of catalyst and 1000-2500 parts by weight of epsilon-caprolactone are added, the temperature is raised to 160 ℃ under the protection of nitrogen, the temperature is kept for 6 hours, then the temperature is reduced to 140 ℃, impurities are removed in vacuum, and then the temperature is reduced to 80 ℃ for discharging, thus obtaining the bio-based polycaprolactone diol. According to the invention, low molecular weight bio-based dihydric alcohol is used for replacing dihydric alcohol of petrochemical products, so that the dependency degree of the petrochemical products can be reduced, and excellent products with better low temperature resistance can be obtained by modifying polycaprolactone, and the product has high product competitiveness and application value.

Description

Bio-based polycaprolactone diol, polyurethane resin for leather, synthetic leather and preparation method thereof
Technical Field
The invention belongs to the technical field of new polyurethane materials, and particularly relates to a substance-based polycaprolactone diol, polyurethane resin for leather, synthetic leather and a preparation method thereof.
Background
Polycaprolactone belongs to a high-end raw material in the polyurethane industry, has hydrolysis resistance, high strength and high chemical resistance, and is widely applied to coatings, adhesives, synthetic leather, waterborne polyurethane, spray polyurea, thermoplastic elastomer, casting elastomer and the like. However, the existing polycaprolactone is usually polymerized with caprolactone by using dihydric alcohols in petrochemical products, such as pentanediol, etc. With the improvement of the living standard of people, the consumption of petrochemical resources is increased, petrochemical products are non-renewable resources, the risk of petroleum exhaustion is faced in the future, and the main direction of future technology is to replace the petrochemical products with renewable resources completely or partially. In addition, low temperature resistance of polycaprolactone products obtained by polymerization of petrochemical diols with caprolactone is poor, and therefore improvements are needed.
Disclosure of Invention
Based on the background situation, the invention provides a bio-based polycaprolactone diol, polyurethane resin for bio-based polycaprolactone diol base leather, synthetic leather and a preparation method thereof in order to solve the problem of dependency of polycaprolactone diol on petrochemical products. The hydrolysis resistance, cold resistance, flex resistance and chemical resistance of the modified polyurethane are greatly improved compared with the traditional polycaprolactone diol. Can be widely applied to the fields of paint, adhesive, synthetic leather, aqueous polyurethane, spray polyurea, thermoplastic elastomer, casting elastomer, high-performance polyurethane foam plastic and the like.
The technical problems to be solved by the invention are realized by the following technical scheme:
a bio-based polycaprolactone diol comprises 500-100 parts by weight of low molecular weight bio-based diol, 1000-2500 parts by weight of epsilon-caprolactone and 100ppm of catalyst (the sum of the weight of relatively low molecular weight bio-based diol and epsilon-caprolactone); the molecular weight of the low molecular weight bio-based diol ranges from 500 to 1100.
Further improved, the chemical formula of the low molecular weight bio-based diol is as follows:
H-[O-CH 2 CH 2 CH 2 -] P the value range of the OHP is 9-18.
The synthetic leather prepared from the bio-based polycaprolactone diol is characterized by comprising 100-200 parts by weight of the bio-based polycaprolactone diol, 20-22.1 parts by weight of ethylene glycol, 700 parts by weight of solvent and 105 parts by weight of diphenylmethane diisocyanate;
further improved, the structural formula of the bio-based polycaprolactone diol is shown as follows:
H-[O-CH 2 CH 2 CH 2 CH 2 CH 2 -CO] m -[O-CH 2 CH 2 CH 2 -O] p -[CO-CH 2 CH 2 CH 2 CH 2 CH 2 ] n -OH
wherein m and n are caprolactone repeating units, p is a bio-base diol 1.3-propanediol repeating unit, the value range of p is 9-18, the value range of m is 5-8, and the value range of n is 5-8.
Further improved, the epsilon-caprolactone is an industrial grade product with the purity of 95.00-99.99 percent.
Further improved, the catalyst is one or more of tetraisobutyl titanate, tetraisopropyl titanate, dibutyl tin dilaurate and stannous octoate.
A preparation method of bio-based polycaprolactone diol comprises the following steps:
heating 500-100 parts by weight of low molecular weight bio-based dihydric alcohol to 120-130 ℃, dehydrating in vacuum for 2 hours, then reducing the temperature to below 80 ℃, then adding 100ppm of catalyst and 1000-2500 parts by weight of epsilon-caprolactone, heating to 160 ℃ under the protection of nitrogen, preserving heat for 6 hours, then reducing the temperature to 140 ℃, removing impurities in vacuum, reducing the temperature to 80 ℃ and discharging to obtain the bio-based polycaprolactone dihydric alcohol.
The polyurethane resin for the bio-based polycaprolactone diol leather comprises 200 parts by weight of bio-based polycaprolactone diol, 20-22.1 parts by weight of ethylene glycol, 700 parts by weight of solvent, 105 parts by weight of diphenylmethane diisocyanate and 0.3-0.5 part by weight of methanol; the bio-based polycaprolactone diol is as shown in any one of claims 1-5.
Further improved, the solvent is one or more of N, N-dimethylformamide, toluene, butanone, ethyl acetate, dimethyl carbonate and butyl acetate.
A preparation method of polyurethane resin for bio-based polycaprolactone diol leather comprises the following steps:
adding 200 parts by weight of bio-based polycaprolactone dihydric alcohol, 20-22.1 parts by weight of ethylene glycol and 700 parts by weight of solvent into a reaction kettle, stirring for 30 minutes, adding 105 parts by weight of diphenylmethane diisocyanate, uniformly stirring, heating to 50-90 ℃, increasing the system viscosity to 12 kiloCPS/25 ℃, and adding 0.3-0.5 part by weight of methanol to terminate the reaction to obtain the polyurethane resin for the bio-based polycaprolactone dihydric alcohol leather; the bio-based polycaprolactone diol is as described above.
A synthetic leather, the method of making the synthetic leather comprising: adding 100 parts by weight of polyurethane resin for bio-based polycaprolactone diol leather, 5 parts by weight of color paste, 50 parts by weight of dimethylformamide and 50 parts by weight of butanone into a dispersing cup, uniformly stirring, defoaming by a centrifugal machine, coating the mixture on release paper, putting the release paper into a baking oven for baking, then coating a layer of resin, baking the release paper until the release paper is semi-dried, attaching the release paper to a base, and putting the release paper into the baking oven for baking after attaching the release paper to obtain synthetic leather; the polyurethane resin for bio-based polycaprolactone diol-based leather is as described above.
The invention has the advantages that:
according to the invention, low molecular weight bio-based dihydric alcohol is used for replacing dihydric alcohol of petrochemical products, so that the dependency degree of the petrochemical products can be reduced, and excellent products with better low temperature resistance can be obtained by modifying polycaprolactone, and the product has high product competitiveness and application value.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention as defined in the claims.
The testing method comprises the following steps:
the number average molecular weight Mn of the product was determined by GPC with tetrahydrofuran as mobile phase and polystyrene as standard reference.
The hydroxyl number was determined by the acetic anhydride-pyridine method using industry standard HG 2709-1995-T.
Mobility was determined by industry standard HG/T4454-2012.
The synthetic leather was cut into 35 x 70mm size samples.
The elongation at break and the tensile strength are tested by a universal tensile machine according to national standard GB/T1040-1992.
The normal low temperature flex test is carried out by a normal low temperature flex tester according to QB/T2714-2005.
Example 1
500 g of bio-based dihydric alcohol with the molecular weight of 500-700 (H-650 of DuPont company of U.S.) is added into a reaction kettle, the temperature is raised to 120-130 ℃, the mixture is dehydrated for 2 hours in vacuum, then the temperature is reduced to below 80 ℃, then 100ppm stannous octoate and 1500 g of caprolactone are added, the mixture is heated to 160 ℃ under the protection of nitrogen, the mixture is kept for 6 hours for reaction, then the mixture is cooled to 140 ℃ and the impurities are removed in vacuum for 3 hours, and the mixture is discharged after the temperature is reduced to 80 ℃. The test acid value was 0.25mgKOH/g, and the hydroxyl value was: 55.85mgKOH/g to obtain the bio-based polycaprolactone diol BP-1.
Adding the bio-based polycaprolactone diol BP-1200 g, ethylene glycol 20 g and dimethylformamide 700 g into a reaction kettle, stirring for 30 minutes, adding diphenylmethane diisocyanate 105 g, uniformly stirring, heating to 50-90 ℃, increasing the system viscosity to 12 ten thousand CPS/25 ℃, and adding 0.3g of methanol to terminate the reaction to obtain the bio-based polycaprolactone diol-based polyurethane resin BPU-1.
Adding 100 g of BPU-1, 5g of color paste, 50 g of dimethylformamide and 50 g of butanone into a dispersing cup, uniformly stirring, defoaming by a centrifugal machine, coating on release paper, putting into a baking oven for baking, coating a layer of resin, baking to be semi-dry, attaching to a bass, and putting into the baking oven for baking after attaching. And taking out the synthetic leather SL-1 from the baking oven for cooling, and stripping the release paper to obtain the synthetic leather SL-1 prepared from the bio-based polycaprolactone diol.
Example 2
500 g of bio-based dihydric alcohol with the molecular weight of 500-700 (H-650 of DuPont company of U.S.) is added into a reaction kettle, the temperature is raised to 120-130 ℃, the mixture is dehydrated in vacuum for 2 hours, then the temperature is reduced to below 80 ℃, then 100ppm stannous octoate and 2500 g of caprolactone are added, the mixture is heated to 160 ℃ under the protection of nitrogen, the mixture is kept for 6 hours, the mixture is cooled to 140 ℃ and the impurities are removed in vacuum for 3 hours, and the mixture is discharged after the temperature is reduced to 80 ℃. The test acid value was 0.23mgKOH/g, and the hydroxyl value was: 37.63mgKOH/g to give biobased polycaprolactone diol BP-2.
Adding the bio-based polycaprolactone diol BP-2200 g, ethylene glycol 22.1 g and dimethylformamide 700 g into a reaction kettle, stirring for 30 minutes, adding diphenylmethane diisocyanate 105 g, stirring uniformly, heating to 50-90 ℃, increasing the system viscosity to 12 ten thousand CPS/25 ℃, and adding 0.5g of methanol to terminate the reaction to obtain the polyurethane resin BPU-2 for the bio-based polycaprolactone diol leather.
Adding 100 g of BPU-2, 5g of color paste, 50 g of dimethylformamide and 50 g of butanone into a dispersing cup, uniformly stirring, defoaming by a centrifugal machine, coating on release paper, putting into a baking oven for baking, coating a layer of resin, baking to be semi-dry, attaching to a bass, and putting into the baking oven for baking after attaching. And taking out the synthetic leather SL-2 prepared from the bio-based polycaprolactone diol from the oven, cooling, and stripping the release paper.
Example 3
Adding 1000 g of bio-based dihydric alcohol with 900-1100 molecular weight (H-1000 of DuPont company of America) into a reaction kettle, heating to 120-130 ℃, vacuum dehydrating for 2 hours, then reducing the temperature to below 80 ℃, adding 100ppm stannous octoate and 1000 g of caprolactone, heating to 160 ℃ under the protection of nitrogen, preserving heat for 6 hours, then cooling to 140 ℃, vacuum removing impurities for 3 hours, and discharging after reducing the temperature to 80 ℃. The test acid value was 0.29mgKOH/g, and the hydroxyl value was: 56.24mgKOH/g to obtain the bio-based polycaprolactone diol BP-3.
Adding the bio-based polycaprolactone diol BP-3200 g, 20 g of ethylene glycol and 700 g of dimethylformamide into a reaction kettle, stirring for 30 minutes, adding 105 g of diphenylmethane diisocyanate, uniformly stirring, heating to 50-90 ℃, increasing the system viscosity to 12 ten thousand CPS/25 ℃, and adding 0.3g of methanol to terminate the reaction to obtain the polyurethane resin BPU-3 for the bio-based polycaprolactone diol leather.
Adding 100 g of BPU-3, 5g of color paste, 50 g of dimethylformamide and 50 g of butanone into a dispersing cup, uniformly stirring, defoaming by a centrifugal machine, coating on release paper, putting into a baking oven for baking, coating a layer of resin, baking to be semi-dry, attaching to a bass, and putting into the baking oven for baking after attaching. And taking out the synthetic leather SL-3 prepared from the bio-based polycaprolactone diol after cooling from the oven, and stripping the release paper.
Comparative example 1
5.2 g of neopentyl glycol, 100ppm of stannous octoate and 995 g of caprolactone are added into a reaction kettle, the mixture is stirred and heated to 70 ℃, the mixture is dehydrated in vacuum for 2 hours, the mixture is heated to 160 ℃ after being pumped in nitrogen to break vacuum, the mixture is reacted for 6 hours in a heat preservation way, the mixture is cooled to 140 ℃ and is discharged after the mixture is cooled to 80 ℃ after the mixture is cooled to remove impurities in vacuum for 3 hours. The test acid value was 0.29mgKOH/g, and the hydroxyl value was: 56.24mgKOH/g to obtain the bio-based polycaprolactone diol BP-4.
Adding the polycaprolactone dihydric alcohol BP-4200 g, the ethylene glycol 20 g and the dimethylformamide 700 g into a reaction kettle, stirring for 30 minutes, adding the diphenylmethane diisocyanate 105 g, uniformly stirring, heating to 50-90 ℃, increasing the system viscosity to 12 ten thousand CPS/25 ℃, and adding the methanol 0.3g to terminate the reaction to obtain the polyurethane resin BPU-4 for the polycaprolactone dihydric alcohol leather.
Adding 100 g of BPU-4, 5g of color paste, 50 g of dimethylformamide and 50 g of butanone into a dispersing cup, uniformly stirring, defoaming by a centrifugal machine, coating on release paper, putting into a baking oven for baking, coating a layer of resin, baking to be semi-dry, attaching to a bass, and putting into the baking oven for baking after attaching. And taking out the synthetic leather SL-4 prepared from polycaprolactone diol from the oven, cooling, and stripping the release paper.
Comparative example 2
5.2 g of neopentyl glycol, 100ppm of stannous octoate and 1495 g of caprolactone are added into a reaction kettle, stirred and heated to 70 ℃, dehydrated in vacuum for 2 hours, heated to 160 ℃ after being pumped in nitrogen to break vacuum, and reacted for 6 hours in a heat preservation mode, cooled to 140 ℃ and removed in vacuum for 3 hours, and discharged after being cooled to 80 ℃. The test acid value was 0.23mgKOH/g, and the hydroxyl value was: 38.13mgKOH/g to give polycaprolactone diol BP-5.
Adding the polycaprolactone dihydric alcohol BP-5200 g, ethylene glycol 22.1 g and dimethylformamide 700 g into a reaction kettle, stirring for 30 minutes, adding 105 g of diphenylmethane diisocyanate, uniformly stirring, heating to 50-90 ℃, increasing the system viscosity to 12 ten thousand CPS/25 ℃, and adding 0.3g of methanol to terminate the reaction to obtain the polyurethane resin BPU-5 for the polycaprolactone dihydric alcohol leather.
Adding 100 g of BPU-5, 5g of color paste, 50 g of dimethylformamide and 50 g of butanone into a dispersing cup, uniformly stirring, defoaming by a centrifugal machine, coating on release paper, putting into a baking oven for baking, coating a layer of resin, baking to be semi-dry, attaching to a bass, and putting into the baking oven for baking after attaching. And taking out the synthetic leather SL-5 prepared from polycaprolactone diol from the oven, cooling, and stripping the release paper.
Comparative example 3
1000 g of polytetrahydrofuran dihydric alcohol with the molecular weight is added into a reaction kettle, the temperature is raised to 120-130 ℃, the vacuum dehydration is carried out for 2 hours, then the temperature is reduced to below 80 ℃, then 100ppm stannous octoate and 1000 g of caprolactone are added, the temperature is raised to 160 ℃ under the protection of nitrogen, the temperature is kept for 6 hours, the reaction is carried out, the temperature is reduced to 140 ℃, the vacuum impurity removal is carried out for 3 hours, and the material is discharged after the temperature is reduced to 80 ℃. The test acid value was 0.29mgKOH/g, and the hydroxyl value was: 57.34mgKOH/g to obtain polyether ester diol BP-6.
Adding the above polyether-ester diol BP-3200 g, 20 g of ethylene glycol and 700 g of dimethylformamide into a reaction kettle, stirring for 30 minutes, adding 105 g of diphenylmethane diisocyanate, uniformly stirring, heating to 50-90 ℃, increasing the viscosity of the system to 12 ten thousand CPS/25 ℃, and adding 0.3g of methanol to terminate the reaction to obtain the polyurethane resin BPU-6 for the polyether-ester diol leather.
Adding 100 g of BPU-6, 5g of color paste, 50 g of dimethylformamide and 50 g of butanone into a dispersing cup, uniformly stirring, defoaming by a centrifugal machine, coating on release paper, putting into a baking oven for baking, coating a layer of resin, baking to be semi-dry, attaching to a bass, and putting into the baking oven for baking after attaching. And taking out the synthetic leather SL-6 prepared from polyether ester diol from the baking oven, cooling, and stripping the release paper.
The synthetic leather samples prepared in the above examples were subjected to performance test comparison, and the results are shown in the following table:
description: the normal temperature flexibility test condition is 20 ℃, and the low temperature flexibility test condition is-20 ℃.
As can be seen from the above table, in the embodiments 1 to 3, the larger the ratio of caprolactone in the bio-based polycaprolactone diol, the larger the final strength of the product, the elongation at break and the number of times of normal temperature flex resistance are not much affected, but the number of times of low temperature flex resistance is reduced. The tensile strength was reduced as compared with comparative examples 2 and 3, the elongation was not changed much, the number of normal temperature flex resistance was increased as compared with comparative examples 2 to 3 in examples 1 to 3, and the increase was relatively large as compared with comparative examples 1 to 2 in examples 1 to 3 in the low temperature flex resistance test. Example 3 the product of example 3 has a lower modulus, better hand feel, and more excellent low temperature flexure resistance than comparative example 3, and is more suitable for soft super cold resistant synthetic leather products. Example 3 had a slight decrease in tensile strength compared to comparative example 2, with other properties being substantially equal. Demonstrating that the performance in synthetic leather is very similar in bio-based polycaprolactone diol prepared with 1000 molecular weight bio-based diol and in polyether ester prepared with 1000 molecular weight polytetrahydrofuran diol. From the above experimental data, the bio-based polycaprolactone diol prepared by taking the bio-based diol as the initiator can replace or partially replace petrochemical polyether ester diol in actual production and life, and the bio-based product is used for replacing petrochemical products in the field of synthetic leather, so that the bio-based polycaprolactone diol has more excellent performance in low-temperature cold resistance and can reduce the dependency degree on the petrochemical products.
The above detailed description is only specific for the practical embodiments of the present invention, and they are not intended to limit the scope of the present invention, and various changes made by those skilled in the art without departing from the spirit of the present invention.

Claims (9)

1. The bio-based polycaprolactone diol is characterized by comprising 500-100 parts by weight of low molecular weight bio-based diol, 1000-2500 parts by weight of epsilon-caprolactone and 100ppm of catalyst;
the molecular weight of the low molecular weight bio-based diol ranges from 500 to 1100; the chemical formula of the low molecular weight bio-based diol is shown as follows:
the value range of P is 9-18.
2. The bio-based polycaprolactone diol of claim 1, wherein the bio-based polycaprolactone diol has the structural formula:
H-[O-CH 2 CH 2 CH 2 CH 2 CH 2 -CO] m -[O-CH 2 CH 2 CH 2 -O] p -[CO-CH 2 CH 2 CH 2 CH 2 CH 2 ] n -OH wherein m, n is a caprolactone repeating unit, p is a bio-based diol 1.3-propanediol repeating unit, the value of p ranges from 9 to 18, the value of m ranges from 5 to 8, and the value of n ranges from 5 to 8.
3. The biobased polycaprolactone diol of claim 1, wherein the epsilon-caprolactone is an industrial grade product having a purity of 95.00 to 99.99%.
4. The bio-based polycaprolactone diol of claim 1, wherein the catalyst is one or more of tetraisobutyl titanate, tetraisopropyl titanate, dibutyltin dilaurate, stannous octoate.
5. The preparation method of the bio-based polycaprolactone diol is characterized by comprising the following steps of:
heating 500-100 parts by weight of low molecular weight bio-based dihydric alcohol to 120-130 ℃, dehydrating in vacuum for 2 hours, then reducing the temperature to below 80 ℃, then adding 100ppm of catalyst and 1000-2500 parts by weight of epsilon-caprolactone, heating to 160 ℃ under the protection of nitrogen, preserving heat for 6 hours, then reducing the temperature to 140 ℃, removing impurities in vacuum, reducing the temperature to 80 ℃ and discharging to obtain the bio-based polycaprolactone dihydric alcohol according to any one of claims 1-4.
6. The polyurethane resin for the bio-based polycaprolactone diol leather is characterized by comprising 200 parts by weight of bio-based polycaprolactone diol, 20-22.1 parts by weight of ethylene glycol, 700 parts by weight of solvent, 105 parts by weight of diphenylmethane diisocyanate and 0.3-0.5 part by weight of methanol; the bio-based polycaprolactone diol is as shown in any one of claims 1-4.
7. The polyurethane resin for bio-based polycaprolactone diol leather according to claim 6, wherein the solvent is one or more of N, N-dimethylformamide, toluene, butanone, ethyl acetate, dimethyl carbonate, and butyl acetate.
8. The preparation method of the polyurethane resin for the bio-based polycaprolactone diol leather is characterized by comprising the following steps of: adding 200 parts by weight of bio-based polycaprolactone dihydric alcohol, 20-22.1 parts by weight of ethylene glycol and 700 parts by weight of solvent into a reaction kettle, stirring for 30 minutes, adding 105 parts by weight of diphenylmethane diisocyanate, uniformly stirring, heating to 50-90 ℃, increasing the viscosity of the system to 12 kiloCPS/25 ℃, and adding 0.3-0.05 part by weight of methanol by mass for terminating reaction to obtain the polyurethane resin for the bio-based polycaprolactone dihydric alcohol leather; the bio-based polycaprolactone diol is as described in any one of claims 1-4.
9. The synthetic leather is characterized by comprising the following preparation method: adding 100 parts by weight of polyurethane resin for bio-based polycaprolactone diol leather, 5 parts by weight of color paste, 50 parts by weight of dimethylformamide and 50 parts by weight of butanone into a dispersing cup, uniformly stirring, defoaming by a centrifugal machine, coating the mixture on release paper, putting the release paper into a baking oven for baking, then coating a layer of resin, baking the release paper until the release paper is semi-dried, attaching the release paper to a base, and putting the release paper into the baking oven for baking after attaching the release paper to obtain synthetic leather; a polyurethane resin for bio-based polycaprolactone diol-based leather is shown in claim 6.
CN202310417187.4A 2023-04-19 2023-04-19 Bio-based polycaprolactone diol, polyurethane resin for leather, synthetic leather and preparation method thereof Active CN116478381B (en)

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