CN116284661A - Water-based bio-based polyurethane resin, degradable synthetic leather and preparation method thereof - Google Patents

Water-based bio-based polyurethane resin, degradable synthetic leather and preparation method thereof Download PDF

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CN116284661A
CN116284661A CN202310247697.1A CN202310247697A CN116284661A CN 116284661 A CN116284661 A CN 116284661A CN 202310247697 A CN202310247697 A CN 202310247697A CN 116284661 A CN116284661 A CN 116284661A
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parts
bio
polyurethane resin
water
based polyurethane
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李维虎
闫成成
戴家兵
赵曦
朱保凌
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Lanzhou Ketian Waterborne Polymer Material Co ltd
Hefei Ketian Waterborne Technology Co ltd
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Lanzhou Ketian Waterborne Polymer Material Co ltd
Hefei Ketian Waterborne Technology Co ltd
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Priority to CN202310247697.1A priority Critical patent/CN116284661A/en
Publication of CN116284661A publication Critical patent/CN116284661A/en
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    • D—TEXTILES; PAPER
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    • 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
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Abstract

The invention belongs to the technical field of polyurethane resin, and particularly relates to water-based bio-based polyurethane resin, degradable synthetic leather and a preparation method thereof. The aqueous polyurethane is prepared by the following processes in sequence: hydroxylation and functionalization of bio-based vegetable oil; synthesizing high molecular weight water-based bio-based polyurethane resin emulsion by adopting a bio-based soft segment and a hard segment; the high molecular weight (1-10 ten thousand) water-based bio-based polyurethane resin is prepared by compounding bio-based lignin powder, bamboo powder and bio-based polyurethane resin emulsion. On the basis, preparing slurry, adopting the same materials of the surface, the middle and the bottom, and compounding the water-based bass base material to prepare the bio-based degradable environment-friendly synthetic leather. Through high solid anaerobic environment analysis test (adopting ASTMD5511 standard), the prepared bio-based synthetic leather has biodegradability, and can realize degradation rate of more than 75% in a period of 3-5 months. Meanwhile, the whole preparation process of the method does not adopt a high-boiling-point toxic organic solvent, and the chemical resistance of the synthetic leather is good.

Description

Water-based bio-based polyurethane resin, degradable synthetic leather and preparation method thereof
Technical Field
The invention belongs to the technical field of polyurethane resin synthesis, and particularly relates to an environment-friendly bio-based water-based bio-based polyurethane resin and a preparation method of degradable synthetic leather thereof.
Background
Along with the rapid development of polyurethane synthetic technology, polyurethane system synthetic leather materials are widely applied to various aspects of daily life, production, national defense and the like of human beings. Because polyurethane synthetic leather cannot be biodegraded and is not easy to rot, a large amount of solid waste pollutants arrive for the environment, and serious influence is caused on the ecological environment and the biological circulation. The degradability of the leather is studied deeply, the contradiction between the use stability and the degradability of the leather is well treated, the biotechnology capable of improving the degradability of the leather is developed, and the method has important significance on the ecological environment and the sustainable development of the leather market in the future.
Disclosure of Invention
The invention aims to provide a preparation method of environment-friendly water-based bio-based polyurethane resin, which mainly aims to overcome the technical defect that the existing product is not degradable and provides a new solution for the green high-valued development of synthetic leather.
In order to achieve the above purpose, the invention adopts the following technical scheme, and the preparation method of the water-based bio-based polyurethane resin is characterized by comprising the following steps:
s11, placing 100-200 parts of vegetable oil into a reaction device, adding 15-50 parts of a thioglycollic modifier and 5-10 parts of a photoinitiator, controlling the molar ratio of C=C double bonds to sulfhydryl groups in the vegetable oil to be (0.1-1) (1-2.5), and controlling the illumination intensity to be 25-80mW/cm 2 The reaction is carried out for 1 to 4 hours at room temperature under the irradiation of an ultraviolet lamp, then the reaction is carried out for 0.5 to 3 hours under the initiation of the heat of an infrared lamp with the power of 1 to 5kW and the heating voltage of 75 to 150V, the reaction product is diluted by 80 to 100 parts of chloroform and is washed by saturated sodium chloride and distilled water in turn, finally, the reaction product is dried by anhydrous magnesium sulfate, and the modified vegetable oil polyol with the hydroxyl group of 150 to 600mgKOH/g and the C=C double bond conversion rate of more than 95 percent is obtained after the solvent is evaporated;
s12, weighing 30-120 parts of bio-based polyester polyol, 30-100 parts of sulfonic acid type polyester polyol and 30-120 parts of modified vegetable oil polyol, placing the materials at 100-105 ℃ for vacuum dehydration for 1h, mixing, adding 50-200 parts of bio-based polyisocyanate and 0.5-10 parts of catalyst, and reacting for 3-5h at 80-100 ℃;
then adding 5-20 parts of polysiloxane modifier, 3-20 parts of hydrophilic chain extender, 1-15 parts of micromolecular chain extender, 0.1-8 parts of cross-linking agent, 0.1-10 parts of catalyst and 5-10 parts of macromolecule chain extender, and continuously reacting for 2-4 hours at 75-90 ℃;
then cooling to 40-60 ℃, adding viscosity-reducing acetone, then cooling and adding 2-18 parts of neutralizing agent between 20-40 ℃ for neutralization for 3-5min, discharging, mixing with 300-900 parts of ice water for emulsification under the high-speed shearing action of an IKA (internet-Key-A) dispersing machine, simultaneously dropwise adding 5-12 parts of chain extender and 3-6 parts of auxiliary agent within 1-2min, intermittently adding acetone for viscosity reduction during the reaction period, and finally removing acetone at 40-55 ℃ to obtain the water-based bio-polyurethane resin.
As a further improvement of the above-mentioned method for producing an aqueous bio-based polyurethane resin:
preferably, the vegetable oil is a hydroxylated vegetable oil polyol having 8 to 18 carbon atoms in the molecular chain; the modified vegetable oil can be used as a soft segment to participate in the reaction.
Preferably, the hydroxylated vegetable oil polyol is one or a combination of more than two of palm oil, castor oil, soybean oil, peanut oil, olive oil, tobacco seed oil, cottonseed oil, rapeseed oil, sunflower seed oil and jatropha seed oil.
Preferably, the mercaptothiol modifier is a compound comprising a mercapto-functional group-SH and an alcoholic hydroxyl group; the main function is to graft hydroxyl groups with carbon-carbon bonds opened on the molecular chain of the vegetable oil so as to promote the reactivity.
Preferably, the mercaptoethanol modifier is one or more than two of 2-mercaptoethanol, 1-mercapto-2-propanol, 3-mercapto-1-propanol and 3-mercapto-2-butanol.
Preferably, the photoinitiator is a photosensitive energy transfer initiator, and specifically is one or a combination of more than two of benzophenone, thioxanthone 1-hydroxy-cyclohexyl-phenyl ketone and the like.
Preferably, the bio-based polyester polyol is one or a combination of more than two of polylactic acid polyol, polyhydroxyalkanoate polyol, poly 3-hydroxybutyrate, polyhydroxyvalerate, hydroxybutyrate and hydroxyvalerate copolymer polyol, and the molecular weight part of the polyol ranges from 1000 to 3000.
Preferably, the sulfonic acid type polyester polyol is a polyester polyol with a side group as a sulfonic acid hydrophilic group, specifically one or more than two types of SC1101, SC2101 and SC3101 manufactured by Hefeidae Tianshui science and technology Co-ordinates, and the molecular weight range is 1000-3000.
Preferably, the biological polyisocyanate is amino acid type isocyanate, and specifically comprises one or more of lysine biological polyisocyanate, tryptophan isocyanate, methionine isocyanate, phenylalanine isocyanate and leucine isocyanate.
Preferably, the catalyst is one or more of dibutyl tin dilaurate, zinc carboxylate, bismuth carboxylate and tetrabutyl titanate.
Preferably, the polysiloxane modifier is one or more than two of polyalkylsiloxane, polyether modified polyorganosiloxane, methyl polysiloxane and polydimethylsiloxane. The waterproof performance of the coating can be promoted, and the hand feeling comfort level of the coating is improved.
Preferably, the hydrophilic chain extender is one or a combination of more than two of A95 sulfonate chain extender and dimethylolpropionic acid.
Preferably, the macromolecular diffusion bond is an amino-terminated silicone polyester.
Preferably, the small molecule chain extender is one or more than two of 1,4 butanediol, ethylene glycol, 1,4 dimethylolcyclohexane, diethylene glycol, neopentyl glycol, dodecandiol and spiro glycol.
Preferably, the cross-linking agent is one or a combination of more than two of trimethylolpropane, silane coupling agent, aziridine, triethanolamine, carbodiimide and epichlorohydrin.
Preferably, the neutralizing agent is triethylamine.
Preferably, the back chain extender is preferably one or a combination of two or more of isophorone diamine, ethylenediamine, hexamethylenediamine, trimethylhexamethylenediamine, and diaminodicyclohexylmethane.
Preferably, the post-addition auxiliary agent is neopentyl glycol glycidyl ether, so that yellowing resistance and strength can be improved;
the second object of the present invention is to provide an aqueous bio-based polyurethane resin prepared by any one of the above preparation methods.
The invention also provides the degradable synthetic leather which is prepared from the water-based bio-based polyurethane resin.
The invention aims at providing a preparation method of degradable synthetic leather, which comprises the following steps:
s21, preparing aqueous bio-based polyurethane resin slurry: adding 0.1-10 parts of cross-linking agent, 0.1-5 parts of defoaming agent, 0.1-10 parts of film forming auxiliary agent, 0.05-5 parts of thickening agent, 0.1-5 parts of leveling wetting agent, 1-10 parts of color paste, 5-10 parts of lignin powder and 20-40 parts of bamboo powder into the prepared water-based bio-based polyurethane resin, stirring and mixing uniformly at a slow speed for 10-20min, and preparing to obtain water-based bio-based polyurethane resin slurry;
s22, preparing synthetic leather through a wet process: coating the prepared aqueous bio-based polyurethane resin slurry on the upper surface and the lower surface of release paper by adopting a release paper transfer method to respectively serve as a fabric layer and a middle fabric layer, wherein the coating amount is 100-300g/m 2 Drying by gradient heating at room temperature to 130deg.C at a heating rate of 2-5deg.C/min to dry;
coating the prepared aqueous bio-based polyurethane resin slurry on a middle material layer with the coating weight of 100-200g/m 2 A wet pasting method is adopted to attach the biological base type 630R water-based space leather bass; and then drying at the temperature ranging from room temperature to 150 ℃ at the heating rate of 3-5 ℃/min in a gradient heating mode, and stripping to prepare the degradable synthetic leather of the full-aqueous system.
As a further improvement of the preparation method of the degradable synthetic leather, the following steps are adopted:
preferably, the cross-linking agent is selected from one or more than two of trimethylolpropane, silane coupling agent, aziridine, triethanolamine, carbodiimide and epichlorohydrin.
Preferably, the defoamer is a polysiloxane copolymer defoamer;
preferably, the film forming aid is dodecanol ester;
preferably, the thickener is hydroxymethyl cellulose and polyether associative thickener;
preferably, the leveling wetting agent is a dicarboxylic acid alkyl ammonium salt propylene glycol solution.
Compared with the prior art, the invention has the beneficial effects that:
1) The invention relates to a preparation method of water-based bio-based polyurethane resin, which is characterized in that biomass oil modified polyol, bio-based polyester polyol, sulfonic acid side group polyester polyol, lysine isocyanate and other materials are adopted to autonomously design and synthesize the water-based bio-based polyurethane resin with high molecular weight (1-10 ten thousand). The method specifically comprises the following steps:
hydroxylation and functionalization of bio-based vegetable oils: because the double bond of the vegetable oil is in the molecular main chain, the activity is lower when the vegetable oil directly participates in polymerization, and high temperature or severe catalysis conditions are needed, the unsaturated double bond in the structure is less utilized. The invention promotes the addition reaction between the sulfur hydrogen bond and the carbon-carbon double bond by adopting the synchronization effect of the solvophobic-alkene click ultraviolet irradiation chemical reaction and the infrared light irradiation heat initiation, thereby opening and connecting the double bond in the vegetable oil with the active hydroxyl group, and further improving the reaction activity.
Synthesizing high molecular weight water-based bio-based polyurethane resin emulsion by adopting a bio-based soft segment and a hard segment; the method is characterized in that the introduction of the sulfonic acid type macromolecule soft segment and the coordination of the sulfonic acid chain extender introduce hydrophilic groups to form a mixed ionic structure of sulfonic acid type and carboxylic acid type, and simultaneously the synchronous action of the amino-terminated silicone polyester ensures that the coating layer has the effects of softness, non-adhesion and good water resistance.
2) The invention also provides a preparation method of the biodegradable synthetic leather, which comprises the steps of firstly compounding the bio-based lignin powder, the bamboo powder and the bio-based polyurethane resin emulsion to prepare the water-based bio-based polyurethane resin slurry, and then compounding the water-based bass base materials with the same materials of the surface, the middle and the bottom, and carrying out gradient drying to prepare the bio-based biodegradable environment-friendly synthetic leather. The gradient drying and heating are adopted, so that the coating film is heated uniformly, the problems of early stripping and the like are not easy to occur, and the coating film is dried rapidly.
3) The prepared bio-based synthetic leather has biodegradability through high solid anaerobic environment analysis test (using ASTM D5511 standard), and can achieve degradation rate of more than 75% in a period of 3-5 months. Meanwhile, the whole preparation process of the method does not adopt a high-boiling-point toxic organic solvent, and the chemical resistance of the synthetic leather is good.
Detailed Description
Other advantages and effects of the present invention will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present invention with reference to specific examples. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention.
Note that "%" and "parts" shown in the description herein refer to "% by mass" and "parts by mass", respectively, unless otherwise specified.
Example 1
The embodiment provides a preparation method of bio-based polyurethane resin and degradable synthetic leather thereof, which specifically comprises the following steps:
(1) Synthesis of high molecular weight bio-based polyurethane resin: 135 parts of vegetable oil (palm oil) were placed in a reaction apparatus, and then 15 parts of a thiothiol modifier (1-mercapto-2-propanol modifier) and 5 parts of a photoinitiator (thioxanthone 1-hydroxy-cyclohexyl-phenyl ketone) were added, followed by irradiation with ultraviolet light (light intensity 65mW/cm 2 ) Reacting for 3 hours at room temperature under irradiation, then continuously reacting for 1 hour under the thermal initiation of an infrared lamp (the power is 1kW and the heating voltage is 100V), diluting a reaction product with 90 parts of chloroform, repeatedly washing with saturated sodium chloride and distilled water for 3-5 times, finally drying with anhydrous magnesium sulfate, steaming for 2 hours at the temperature of 90 ℃ in a rotary way, and steaming to remove a solvent to obtain the modified vegetable oil polyol with the hydroxyl group at 550mgKOH/g and the C=C double bond conversion rate of 95%;
(2) Weighing 55 parts of bio-based polyester Polyol (PHA), 30 parts of sulfonic acid type polyester polyol (astronomical SC 1101) and 60 parts of modified vegetable oil polyol prepared by the steps, placing the components at 100 ℃ for vacuum dehydration for 1h, then mixing, adding 75 parts of bio-based polyisocyanate (lysine diisocyanate) and 1 part of catalyst (organobismuth catalyst), and reacting for 3h at 85 ℃;
then 5 parts of polysiloxane modifier, hydrophilic chain extender (8 parts of A95 sulfonate chain extender, 6 parts of dimethylolpropionic acid), 5 parts of small molecule chain extender (diethylene glycol), 1 part of cross-linking agent (trimethylolpropane), 1 part of catalyst (organobismuth catalyst), 5 parts of macromolecular chain extender (amino-terminated silicone polyurethane) and continuing to react for 4 hours at 75 ℃;
then continuously cooling to 50 ℃, adding viscosity-reducing acetone, then cooling, adding 5 parts of neutralizing agent (triethylamine) between 30 ℃ for neutralization for 3min, discharging, mixing with 400 parts of deionized ice water for emulsification under the high-speed shearing action of an IKA (internet-based acrylic acid) dispersing machine, simultaneously dropwise adding 5 parts of rear chain extender (isophorone diamine) and 3 parts of neopentyl glycol glycidyl ether within 1-2min, intermittently adding 50 parts of acetone for viscosity reduction during the reaction period, and finally removing acetone at 50 ℃ to obtain the water-based bio-polyurethane resin;
(3) Then adding 2 parts of cross-linking agent (aziridine), 3 parts of defoaming agent (polysiloxane copolymer type defoaming agent), 2 parts of film forming auxiliary agent (dodecyl alcohol ester), 2 parts of thickening agent (hydroxymethyl cellulose), 0.5 part of leveling wetting agent (dicarboxylic acid alkyl ammonium salt propylene glycol solution), 5 parts of water-based color paste, 5 parts of lignin powder and 10 parts of bamboo powder into the prepared water-based bio-based polyurethane resin, stirring and mixing uniformly for 10 minutes at a slow speed, and preparing the water-based bio-based polyurethane resin slurry.
(4) The aqueous biological base 630R space leather aqueous base is taken as a base material, the prepared aqueous biological base polyurethane resin slurry is coated on the upper surface and the lower surface of the release paper by adopting a release paper transfer method and the same materials of the surface, the surfaces and the bottom are respectively taken as a fabric layer and a middle fabric layer, and the coating amount is 180g/m 2 Drying by adopting a gradient heating mode at the temperature of between room temperature and 130 ℃, wherein the heating rate is 2 ℃/min, and drying;
then the prepared aqueous bio-based polyurethane resin slurry is coated on a middle material layer with the coating amount of 200g/m 2 A wet pasting method is adopted to attach the biological base type 630R water-based space leather bass; and then drying at the temperature of between room temperature and 150 ℃ at the heating rate of 5 ℃/min in a gradient heating mode, and stripping to prepare the full-aqueous system bio-based degradable synthetic leather product.
Application performance and biodegradability test: the prepared water-based bio-based polyurethane resin is applied to sofa or clothing leather, and the obtained full-water-based system bio-based polyurethane resin can be degraded and is subjected to mechanical indexes such as tensile strength, peel strength, tearing strength and joint strength of a film material tested by an Instron universal tester; the wear resistance of the synthetic leather is tested by adopting a Talbot method, and the normal and low temperature folding resistance of the synthetic leather is tested by adopting a folding strength tester. Biodegradability under anaerobic conditions is tested according to ASTM D5511.
Example 2
The invention relates to a preparation method of bio-based polyurethane resin and degradable synthetic leather thereof, which specifically comprises the following steps:
(1) Synthesis of high molecular weight bio-based polyurethane resin: 70 parts of vegetable oil (palm oil), 80 parts of vegetable oil (castor oil) are placed in a reaction apparatus, 25 parts of a mercaptothiol modifier (1-mercapto-2-propanol modifier) and 10 parts of a photoinitiator (thioxanthone 1-hydroxy-cyclohexyl-phenyl ketone) are then added, and the mixture is irradiated with light of 85mW/cm intensity under ultraviolet light 2 ) Reacting for 3 hours at room temperature under irradiation, then continuously reacting for 1 hour under the thermal initiation of an infrared lamp (the power is 1kW and the heating voltage is 100V), diluting the product obtained by the reaction with 90 parts of chloroform, repeatedly washing with saturated sodium chloride and distilled water for 3-5 times, finally drying with anhydrous magnesium sulfate, steaming for 2 hours at the temperature of 90 ℃ in a rotary way, and steaming to remove the solvent to obtain the modified vegetable oil polyol with the hydroxyl group at 580mgKOH/g and the C=C double bond conversion rate at 96.5%;
(2) Weighing 75 parts of bio-based polyester Polyol (PLA), 30 parts of sulfonic acid type polyester polyol (astronomical SC 2101) and 80 parts of modified vegetable oil polyol prepared by the steps, vacuum dehydrating at 100 ℃ for 1h, mixing, adding 150 parts of bio-based polyisocyanate (lysine diisocyanate) and 2 parts of catalyst (organobismuth catalyst), and reacting at 85 ℃ for 3h;
then 6 parts of polysiloxane modifier, hydrophilic chain extender (5 parts of A95 sulfonate chain extender, 8 parts of dimethylolpropionic acid), 7 parts of small molecule chain extender (ethylene glycol), 3.5 parts of cross-linking agent (trimethylolpropane), 1 part of catalyst (organobismuth catalyst), 6 parts of large molecule chain extender (amino-terminated silicone polyester) and continuing to react for 4 hours at 75 ℃;
then continuously cooling to 50 ℃, adding viscosity-reducing acetone, then cooling, adding 5 parts of neutralizing agent (triethylamine) between 30 ℃ for neutralization for 5min, discharging, mixing with 650 parts of deionized ice water for emulsification under the high-speed shearing action of an IKA (internet-of-a-technology) dispersing machine, simultaneously dropwise adding 12 parts of rear chain extender (isophorone diamine) and 6 parts of neopentyl glycol glycidyl ether within 1min, intermittently adding 50 parts of acetone for viscosity reduction during the reaction period, and finally removing acetone at 50 ℃ to obtain the water-based bio-polyurethane resin;
(3) Then adding 3 parts of cross-linking agent (aziridine), 3 parts of defoaming agent (polysiloxane copolymer type defoaming agent), 2 parts of film forming auxiliary agent (dodecyl alcohol ester), 3 parts of thickening agent (hydroxymethyl cellulose), 1 part of leveling wetting agent (dicarboxylic acid alkyl ammonium salt propylene glycol solution), 2 parts of water-based color paste, 10 parts of lignin powder and 30 parts of bamboo powder into the prepared water-based bio-based polyurethane resin, stirring and slowly stirring and uniformly mixing for 20 minutes, and preparing the water-based bio-based polyurethane resin slurry.
(4) The aqueous biological base 630R space leather aqueous base is taken as a base material, the prepared aqueous biological base polyurethane resin slurry is coated on the upper surface and the lower surface of the release paper by adopting a release paper transfer method and the same materials of the surface, the surfaces and the bottom are respectively taken as a fabric layer and a middle fabric layer, and the coating amount is 180g/m 2 Drying by adopting a gradient heating mode at the temperature of between room temperature and 130 ℃, wherein the heating rate is 2 ℃/min, and drying;
then the prepared aqueous bio-based polyurethane resin slurry is coated on a middle material layer with the coating amount of 200g/m 2 A wet pasting method is adopted to attach the biological base type 630R water-based space leather bass; and then drying at the temperature of between room temperature and 150 ℃ at the heating rate of 5 ℃/min in a gradient heating mode, and stripping to prepare the full-aqueous system bio-based degradable synthetic leather product.
Application performance and biodegradability test: the prepared water-based bio-based polyurethane resin is applied to sofa or clothing leather, and the obtained full-water-based system bio-based polyurethane resin can be degraded and is subjected to mechanical indexes such as tensile strength, peel strength, tearing strength and joint strength of a film material tested by an Instron universal tester; the wear resistance of the synthetic leather is tested by adopting a Talbot method, and the normal and low temperature folding resistance of the synthetic leather is tested by adopting a folding strength tester. Biodegradability under anaerobic conditions is tested according to ASTM D5511.
Example 3
The embodiment provides a preparation method of bio-based polyurethane resin and degradable synthetic leather thereof, which specifically comprises the following steps:
(1) Synthesis of high molecular weight bio-based polyurethane resin: first, 150 parts of vegetable oil (castor oil) was placed in a reaction apparatus, followed by addition of 25 parts of a thiothiol modifier (1-mercapto-2-propanol modifier) and 10 parts of a photoinitiator (thioxanthone 1-hydroxy-cyclohexyl-phenyl ketone), followed by irradiation with light of 85mW/cm intensity 2 ) And (3) reacting for 4 hours at room temperature under irradiation, then continuously reacting for 2 hours under the thermal initiation of an infrared lamp (the power is 1kW and the heating voltage is 100V), diluting the product obtained by the reaction with 90 parts of chloroform, repeatedly washing with saturated sodium chloride and distilled water for 3-5 times, finally drying with anhydrous magnesium sulfate, steaming for 2 hours at the temperature of 90 ℃ in a rotary way, and steaming to remove the solvent to obtain the modified vegetable oil polyol with the hydroxyl group at 600mgKOH/g and the C=C double bond conversion rate at 97%.
(2) Weighing 45 parts of bio-based polyester Polyol (PHA), 45 parts of bio-based polyester Polyol (PLA), 30 parts of sulfonic acid type polyester polyol (astronomical water SC 3101) and 200 parts of modified mixed vegetable oil polyol prepared by the steps, placing the mixture at 100 ℃ for vacuum dehydration for 1 hour, adding 100 parts of bio-based polyisocyanate (lysine diisocyanate) and 2 parts of catalyst (organobismuth catalyst) after mixing, and reacting for 3 hours at 85 ℃;
then 6 parts of polysiloxane modifier, hydrophilic chain extender (3 parts of A95 sulfonate chain extender, 10 parts of dimethylolpropionic acid), 2 parts of cross-linking agent (trimethylolpropane), 4 parts of small molecule chain extender (1, 4 butanediol), 1 part of catalyst (organobismuth catalyst), 5 parts of macromolecular chain extender (amino-terminated silicone polyurethane) and continuing to react for 4 hours at 75 ℃;
then continuously cooling to 50 ℃, adding viscosity-reducing acetone, then cooling, adding 10 parts of neutralizing agent (triethylamine) between 30 ℃, discharging, mixing and emulsifying with 650 parts of deionized ice water under the high-speed shearing action of an IKA (internet-of-gravity) dispersing machine, simultaneously dropwise adding 8 parts of rear chain extender (isophorone diamine) and 8 parts of rear chain extender (ethylenediamine) within 2min, intermittently adding 50 parts of acetone during the reaction to reduce the viscosity, and finally removing acetone at 50 ℃ to obtain the water-based bio-polyurethane resin;
(3) Then adding 3 parts of cross-linking agent (aziridine), 3 parts of defoaming agent (polysiloxane copolymer type defoaming agent), 2 parts of film forming auxiliary agent (dodecyl alcohol ester), 3 parts of thickening agent (hydroxymethyl cellulose), 1 part of leveling wetting agent (dicarboxylic acid alkyl ammonium salt propylene glycol solution), 2 parts of water-based color paste, 10 parts of lignin powder and 30 parts of bamboo powder into the prepared water-based bio-based polyurethane resin, stirring and slowly stirring and uniformly mixing for 20 minutes, and preparing to obtain water-based bio-based polyurethane resin slurry;
(4) The aqueous biological base 630R space leather aqueous base is taken as a base material, the prepared aqueous biological base polyurethane resin slurry is coated on the upper surface and the lower surface of the release paper by adopting a release paper transfer method and the same materials of the surface, the surfaces and the bottom are respectively taken as a fabric layer and a middle fabric layer, and the coating amount is 180g/m 2 Drying by adopting a gradient heating mode at the temperature of between room temperature and 130 ℃, wherein the heating rate is 2 ℃/min, and drying;
then the prepared aqueous bio-based polyurethane resin slurry is coated on a middle material layer with the coating amount of 200g/m 2 A wet pasting method is adopted to attach the biological base type 630R water-based space leather bass; and then drying at the temperature of between room temperature and 150 ℃ at the heating rate of 5 ℃/min in a gradient heating mode, and stripping to prepare the full-aqueous system bio-based degradable synthetic leather product.
Application performance and biodegradability test: the prepared water-based bio-based polyurethane resin is applied to sofa or clothing leather, and the obtained full-water-based system bio-based polyurethane resin can be degraded and is subjected to mechanical indexes such as tensile strength, peel strength, tearing strength and joint strength of a film material tested by an Instron universal tester; the wear resistance of the synthetic leather is tested by adopting a Talbot method, and the normal and low temperature folding resistance of the synthetic leather is tested by adopting a folding strength tester. Biodegradability under anaerobic conditions is tested according to ASTM D5511. Wherein "-indicates that there is temporarily no standard requirement for the relevant biodegradation of synthetic leather.
TABLE 1 test Performance results for examples 1-3
Figure SMS_1
Figure SMS_2
The invention only adopts the automobile synthetic leather standard with strict and strict synthetic leather performance requirements for reference comparison, but is not limited to be applied to automobile leather, and can be further popularized to the industrial fields of other multifunctional application synthetic leather such as clothing leather, sofa leather and the like. From the test results, the prepared bio-based synthetic leather has biodegradability, and the degradation rate can be more than 75% in a period of 3-5 months. Meanwhile, the whole preparation process of the method does not adopt a high-boiling-point toxic organic solvent, and the chemical resistance of the synthetic leather is good.
Description of Table 1: the second column is an index standard, and it can be seen that the performance tests of examples 1 to 4 all meet the standards. The preparation method of the invention realizes the biodegradability and simultaneously ensures the practical application performance of the synthetic leather; provides a new solution idea and approach for the green high-valued development of the future synthetic leather.
Those skilled in the art will appreciate that the foregoing is merely a few, but not all, embodiments of the invention. The above-described embodiments are merely illustrative of the principles of the present invention and its capabilities and are not intended to limit the present invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.

Claims (10)

1. The preparation method of the water-based bio-based polyurethane resin is characterized by comprising the following steps of:
s11, placing 100-200 parts of vegetable oil into a reaction device,adding 15-50 parts of a hydrophobic mercaptan modifier and 5-10 parts of a photoinitiator, controlling the molar ratio of C=C double bonds to mercapto groups in the vegetable oil to be (0.1-1) (1-2.5), and controlling the illumination intensity to be 25-80mW/cm 2 The reaction is carried out for 1 to 4 hours at room temperature under the irradiation of an ultraviolet lamp, then the reaction is carried out for 0.5 to 3 hours under the initiation of the heat of an infrared lamp with the power of 1 to 5kW and the heating voltage of 75 to 150V, the reaction product is diluted by 80 to 100 parts of chloroform and is washed by saturated sodium chloride and distilled water in turn, finally, the reaction product is dried by anhydrous magnesium sulfate, and the modified vegetable oil polyol with the hydroxyl group of 150 to 600mgKOH/g and the C=C double bond conversion rate of more than 95 percent is obtained after the solvent is evaporated;
s12, weighing 30-120 parts of bio-based polyester polyol, 30-100 parts of sulfonic acid type polyester polyol and 30-120 parts of modified vegetable oil polyol, placing the materials at 100-105 ℃ for vacuum dehydration for 1h, mixing, adding 50-200 parts of bio-based polyisocyanate and 0.5-10 parts of catalyst, and reacting for 3-5h at 80-100 ℃;
then adding 5-20 parts of polysiloxane modifier, 3-20 parts of hydrophilic chain extender, 1-15 parts of micromolecular chain extender, 0.1-8 parts of cross-linking agent, 0.1-10 parts of catalyst and 5-10 parts of macromolecule chain extender, and continuously reacting for 2-4 hours at 75-90 ℃;
then cooling to 40-60 ℃, adding viscosity-reducing acetone, then cooling and adding 2-18 parts of neutralizing agent between 20-40 ℃ for neutralization for 3-5min, discharging, mixing with 300-900 parts of ice water for emulsification under the high-speed shearing action of an IKA (internet-Key-A) dispersing machine, simultaneously dropwise adding 5-12 parts of chain extender and 3-6 parts of auxiliary agent within 1-2min, intermittently adding acetone for viscosity reduction during the reaction period, and finally removing acetone at 40-55 ℃ to obtain the water-based bio-polyurethane resin.
2. The method for preparing an aqueous bio-based polyurethane resin according to claim 1, wherein the vegetable oil in the present invention is a hydroxylated vegetable oil polyol having 8 to 18 carbon atoms in the molecular chain.
3. The method for producing an aqueous bio-based polyurethane resin according to claim 1, wherein the thiol-modifier is a compound containing a mercapto-functional group-SH and an alcoholic hydroxyl group.
4. The method for producing an aqueous bio-based polyurethane resin according to claim 1, wherein the bio-based polyester polyol is one or a combination of two or more of polylactic acid polyol, polyhydroxyalkanoate polyol, poly-3-hydroxybutyrate, polyhydroxyvalerate, hydroxybutyric acid and hydroxyvalerate copolymer polyol, and the molecular weight part of the polyol ranges from 1000 to 3000.
5. The method for preparing an aqueous bio-based polyurethane resin according to claim 1, wherein the sulfonic acid type polyester polyol is a polyester polyol having a pendant sulfonic acid hydrophilic group, and has a molecular weight in the range of 1000 to 3000.
6. The method for producing an aqueous bio-based polyurethane resin according to claim 1, wherein the polysiloxane modifier is one or a combination of two or more of polyalkylsiloxane, polyether-modified polyorganosiloxane, methylpolysiloxane, and polydimethylsiloxane.
7. The method for producing an aqueous bio-based polyurethane resin according to claim 1, wherein the hydrophilic chain extender is one or a combination of two or more of an a95 sulfonate chain extender and dimethylolpropionic acid.
8. An aqueous bio-based polyurethane resin prepared by the preparation method of any one of the above claims 1 to 7.
9. A degradable synthetic leather made from the aqueous bio-based polyurethane resin of claim 8.
10. A method of making the degradable synthetic leather of claim 9, comprising the steps of:
s21, preparing aqueous bio-based polyurethane resin slurry: adding 0.1-10 parts of cross-linking agent, 0.1-5 parts of defoaming agent, 0.1-10 parts of film forming auxiliary agent, 0.05-5 parts of thickening agent, 0.1-5 parts of leveling wetting agent, 1-10 parts of color paste, 5-10 parts of lignin powder and 20-40 parts of bamboo powder into the prepared water-based bio-based polyurethane resin, stirring and mixing uniformly at a slow speed for 10-20min, and preparing to obtain water-based bio-based polyurethane resin slurry;
s22, preparing synthetic leather through a wet process: coating the prepared aqueous bio-based polyurethane resin slurry on the upper surface and the lower surface of release paper by adopting a release paper transfer method to respectively serve as a fabric layer and a middle fabric layer, wherein the coating amount is 100-300g/m 2 Drying by gradient heating at room temperature to 130deg.C at a heating rate of 2-5deg.C/min to dry;
coating the prepared aqueous bio-based polyurethane resin slurry on a middle material layer with the coating weight of 100-200g/m 2 A wet pasting method is adopted to attach the biological base type 630R water-based space leather bass; and then drying at the temperature ranging from room temperature to 150 ℃ at the heating rate of 3-5 ℃/min in a gradient heating mode, and stripping to prepare the degradable synthetic leather of the full-aqueous system.
CN202310247697.1A 2023-03-15 2023-03-15 Water-based bio-based polyurethane resin, degradable synthetic leather and preparation method thereof Pending CN116284661A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
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CN116693802A (en) * 2023-08-04 2023-09-05 张家港市顾乐仕生活家居科技有限公司 Bio-based polyurethane buffer material

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116693802A (en) * 2023-08-04 2023-09-05 张家港市顾乐仕生活家居科技有限公司 Bio-based polyurethane buffer material
CN116693802B (en) * 2023-08-04 2023-10-13 张家港市顾乐仕生活家居科技有限公司 Bio-based polyurethane buffer material

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