CN114085356A - Chemical-resistant biodegradable surface layer polyurethane resin for synthetic leather and preparation method thereof - Google Patents
Chemical-resistant biodegradable surface layer polyurethane resin for synthetic leather and preparation method thereof Download PDFInfo
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- CN114085356A CN114085356A CN202111407903.8A CN202111407903A CN114085356A CN 114085356 A CN114085356 A CN 114085356A CN 202111407903 A CN202111407903 A CN 202111407903A CN 114085356 A CN114085356 A CN 114085356A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—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
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- 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
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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
- C08G18/28—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
- C08G18/428—Lactides
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- 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
- C08G18/44—Polycarbonates
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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
- C08G18/28—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
- C08G18/6662—Compounds of group C08G18/42 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
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- 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
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
- D06N3/147—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes characterised by the isocyanates used
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2203/00—Macromolecular materials of the coating layers
- D06N2203/06—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06N2203/068—Polyurethanes
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/14—Properties of the materials having chemical properties
- D06N2209/143—Inert, i.e. inert to chemical degradation, corrosion resistant
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/16—Properties of the materials having other properties
- D06N2209/1607—Degradability
- D06N2209/1614—Biodegradable
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- D06N2211/00—Specially adapted uses
- D06N2211/12—Decorative or sun protection articles
- D06N2211/28—Artificial leather
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Abstract
The invention discloses a chemical-resistant biodegradable surface layer polyurethane resin for synthetic leather and a preparation method thereof, wherein the surface layer polyurethane resin is prepared from the following components in parts by mass: 26-30 parts of isocyanate, 25-35 parts of polycarbonate polyol, 30-45 parts of polylactic acid polyol, 2-4 parts of hydroxyl-containing low molecular compound, 2-4 parts of castor oil, 300 parts of organic solvent 220-. The polylactic acid is attracted by attention due to the characteristics of biodegradability and the like, and the polylactic acid polyol is used as a polyurethane soft segment material, is applied to chemical-resistant synthetic leather by innovatively utilizing the characteristics of high ester bond density and strong bond energy in the structure, widens the application field of the polylactic acid and simultaneously endows biodegradable and environment-friendly characteristics to the surface layer polyurethane resin for the synthetic leather.
Description
Technical Field
The invention belongs to the field of polyurethane resin, and particularly relates to a chemical-resistant biodegradable surface layer polyurethane resin for synthetic leather and a preparation method thereof.
Background
Because of excellent molecular designability, polyurethane resin can be used for preparing polyurethane products with different performances by selecting different raw materials and adopting different synthesis processes, so that the polyurethane resin is widely applied to the field of synthetic leather, mainly reflected in a plurality of fields such as sofas, shoes, cases, furniture, automobiles, electronic products and the like, and has strong market demand. Along with the improvement of the living quality of people and the requirement of upgrading of synthetic leather products, higher requirements are put forward on the market for the corrosion resistance of human body secretions such as sweat, oleic acid and the like, sun cream, essential balm and the like of the synthetic leather.
In addition, due to the increasing environmental and resource problems, the use of biodegradable materials instead of petroleum-based materials to solve the "white pollution" problem has become an important part of the sustainable development of the present materials industry. Polylactic acid (PLA) is a biodegradable environment-friendly material which takes renewable resources such as straws, corns and the like as raw materials, has good biocompatibility and solvent resistance, is nontoxic and harmless, has no pungent smell and large yield, is multipurpose in the field of medical instruments and food packaging at present, but has unobvious advantages and too strong plasticity in the field of polyurethane resin for synthetic leather and cannot be widely used.
The invention discloses chemical corrosion resistance, cosmetic and beverage stain resistance synthetic leather and a preparation method thereof (patent No. CN 107988810A), and discloses a method for achieving the effect of resisting corrosion of chemical products such as oleic acid, alcohol and sun cream by selecting polycarbonate synthetic dry-process surface resin. The chemical corrosion resistance effect is mainly achieved by the soft segment polycarbonate, and the biodegradation effect cannot be achieved.
The synthetic leather obtained by the invention patent of 'biodegradable synthetic leather and a preparation method thereof' (patent number CN 108708185A) is degradable, low-carbon, environment-friendly and soft in hand feeling, bagasse and cassava starch polylactic acid is used in the formula of the bottom layer of the synthetic leather, but the synthetic leather is only in a physical change process, does not relate to chemical reaction, is not connected with a polyurethane resin main chain, and has large limitation on the application range.
The patent "a polylactic acid biodegradable polyurethane synthetic leather and its preparation method" (patent No. CN202011209669.3) uses polylactic acid and polyether glycol as soft segment in polyurethane synthesis, which solves the problem that the prior polyurethane wet synthetic leather can not be degraded and the polyurethane/polylactic acid composite material can not meet the general physical property requirements of synthetic leather such as durability. Therefore, the chemically-resistant biodegradable top resin for synthetic leather provided by the invention has obvious technical creativity and market demand.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a chemical-resistant biodegradable surface layer polyurethane resin for synthetic leather and a preparation method thereof.
The purpose of the invention is realized by the following technical scheme:
a chemical-resistant biodegradable surface layer polyurethane resin for synthetic leather is prepared from the following components in parts by mass: 26-30 parts of isocyanate, 25-35 parts of polycarbonate polyol, 30-45 parts of polylactic acid polyol, 2-4 parts of hydroxyl-containing low molecular compound, 2-4 parts of castor oil, 300 parts of organic solvent 220-; wherein:
the isocyanate is 4, 4' -diphenylmethane diisocyanate;
the number average molecular weight of the polycarbonate polyol is 1000-2000 g/mol; the initiator adopted by the polycarbonate polyol is one or two of 1, 6-hexanediol, 3-methylpentanediol, 1, 4-butanediol and 1, 5-pentanediol;
the number average molecular weight of the polylactic acid polyol is 1000-2000 g/mol; the synthetic method of the polylactic acid polyol is one of a direct lactic acid polycondensation method and a lactide ring opening method;
the molecular weight of the hydroxyl-containing low molecular compound is 60-120, and the hydroxyl-containing low molecular compound is selected from at least one of ethylene glycol, 1, 4-butanediol, neopentyl glycol and 1, 6-hexanediol;
the organic solvent is dimethylformamide; the antioxidant is an antioxidant 1010; the catalyst is an organic bismuth catalyst; the reaction terminator is methanol.
The invention also provides a preparation method of the chemical-resistant biodegradable surface layer polyurethane resin for synthetic leather, which comprises the following steps:
preparing a prepolymer: adding 9-14 parts of isocyanate, 25-35 parts of polycarbonate polyol, 30-45 parts of polylactic acid polyol, 0.01-0.04 part of antioxidant and 0.02-0.06 part of catalyst into 60-80 parts of organic solvent to form a mixed solution, and reacting at the temperature of 70-80 ℃ for 0.5-1.5h to obtain a prepolymer;
preparing a surface layer polyurethane resin: adding 2-4 parts of low molecular weight compound containing hydroxyl and 2-4 parts of castor oil into the prepolymer, carrying out chain extension reaction at the temperature of 70-80 ℃, adding the residual isocyanate into the reaction system for multiple times during the chain extension reaction, and adding the residual organic solvent and the reaction terminator after the reaction is carried out until the isocyanate is sticky, thus obtaining the target product.
Compared with the prior art, the invention has the beneficial effects that:
polylactic acid is attracting much attention because of its biodegradable properties, but it has not been widely used in the field of polyurethane synthetic leather. According to the invention, polylactic acid polyol is taken as a polyurethane soft segment material, and the characteristics of high ester bond density and strong bond energy in the structure of the polylactic acid polyol are innovatively utilized to apply the polylactic acid polyol to chemical-resistant synthetic leather, so that the application field of polylactic acid is widened, and meanwhile, the biodegradable and environment-friendly characteristics of the surface layer polyurethane resin for the synthetic leather are also endowed.
Castor Oil (CO) is a biobased triglyceride containing 70% trifunctional castor oil and 30% difunctional castor oil, with an average hydroxyl functionality of about 2.7. The castor oil can bring biodegradability, toughening effect and the like to the polyurethane resin, and the biodegradable surface layer polyurethane resin for the synthetic leather, which has stable performance and can resist chemicals, is prepared by the combined action of the polylactic acid polyol and the castor oil.
Detailed Description
The present invention will be further described with reference to the following examples.
The types and suppliers of reagents used in the following examples were as follows:
PC1000 is a polycarbonate polyol with a molecular weight of 1000g/mol starting materials 1, 6-hexanediol, 1, 5-pentanediol (Asahi Kasei corporation, trade name T5651);
PC2000 is a polycarbonate polyol with a molecular weight of 2000g/mol starting materials 1, 6-hexanediol, 1, 5-pentanediol (Asahi Kasei corporation, trade name T5652);
PLA1000 and PLA2000 are polylactic acid polyol with molecular weight of 1000g/mol and 2000g/mol respectively (produced by Shenzhen Guanghua Webster Limited and with the brand numbers of PLA210M and PLA 220M);
CO is castor oil (produced by Shanghai Michelin Biochemical technology Co., Ltd.) and EG is ethylene glycol (produced by Shanxi three-dimensional group Co., Ltd.);
MDI is 4, 4' -diphenylmethane diisocyanate (produced by Tantawa;
MB20 is an organic bismuth reaction catalyst (manufactured by air chemical products company);
DMF is N, N' -dimethylformamide (produced by Qilu petrochemical industry), CH3OH is a reaction terminator methanol (produced by national drug group chemical reagent company, Ltd.), an antioxidant 1010 is an antioxidant (produced by Germany Basff), PTMG-1000 is polytetrahydrofuran ether glycol with a molecular weight of 1000 (produced by Shanxi three-dimensional group company, Ltd.), SP-2000 is polyester polyol with a molecular weight of 2000, the used raw materials and the formula are 8000kg of adipic acid, 2500kg of ethylene glycol and 2000kg of 1, 4-butanediol, and the preparation method is as follows: polyurethane resin and application thereof, chemical industry publisher (2011.11), Liu Yijun, production method and material calculation of P62 polyester polyol.
The reagents are provided only for illustrating the sources and components of the reagents used in the experiments of the present invention, so as to be fully disclosed, and do not indicate that the present invention cannot be realized by using other reagents of the same type or other reagents supplied by other suppliers.
Example 1:
a preparation method of a surface layer polyurethane resin for chemical-resistant biodegradable synthetic leather comprises the following experiments according to the relation of the material dosage in Table 1:
1) preparing a prepolymer: mixing 35g of polycarbonate polyol PC1000, 35g of polylactic acid polyol PLA2000, 0.04g of antioxidant 1010 and 11.8g of isocyanate MDI, adding the mixture into 60g of organic solvent DMF, uniformly mixing, adding 0.06g of catalyst MB20, and reacting at 75 ℃ for 0.5h to obtain a prepolymer;
2) preparing a surface layer polyurethane resin: adding 3g of low molecular weight compound EG containing hydroxyl and 3g of castor oil CO into the prepolymer to carry out chain extension reaction at 75 ℃, adding the rest isocyanate into the reaction system for multiple times, adding 0.4g of reaction terminator CH after the reaction is carried out until the viscosity is 14 ten thousand CPS/75 DEG C3OH and residual DMF to obtain the target product.
Example 2:
a preparation method of a surface layer polyurethane resin for chemical-resistant biodegradable synthetic leather comprises the following experiments according to the relation of the material dosage in Table 1:
1) preparing a prepolymer: mixing 30g of polycarbonate polyol PC1000, 30g of polylactic acid polyol PLA1000, 0.04g of antioxidant 1010 and 13.5g of isocyanate MDI, adding the mixture into 60g of organic solvent DMF, uniformly mixing, adding 0.06g of catalyst MB20, and reacting at 75 ℃ for 0.5h to obtain a prepolymer;
2) preparing a surface layer polyurethane resin: adding 3g of low molecular weight compound EG containing hydroxyl and 3g of castor oil CO into the prepolymer to carry out chain extension reaction at 75 ℃, adding the rest isocyanate into the reaction system for multiple times, adding 0.4g of reaction terminator CH after the reaction is carried out until the viscosity is 14 ten thousand CPS/75 DEG C3OH and residual DMF to obtain the target product.
Example 3:
a preparation method of a surface layer polyurethane resin for chemical-resistant biodegradable synthetic leather comprises the following experiments according to the relation of the material dosage in Table 1:
1) preparing a prepolymer: mixing 25g of polycarbonate polyol PC2000, 10g of polycarbonate polyol PC1000, 35g of polylactic acid polyol PLA2000, 0.04g of antioxidant 1010 and 9g of isocyanate MDI, adding the mixture into 60g of organic solvent DMF, uniformly mixing, adding 0.06g of catalyst MB20, and reacting at 75 ℃ for 0.5h to obtain a prepolymer;
2) preparing a surface layer polyurethane resin: adding 3g of hydroxyl-containing low molecular weight compound EG and 3g of castor oil CO into the prepolymer to perform chain extension reaction at 75 ℃, adding the rest isocyanate into the reaction system for multiple times, adding 0.4g of reaction terminator CH after the reaction is carried out until the viscosity is 14 ten thousand CPS/75 DEG C3OH and residual DMF to obtain the target product.
Example 4:
a preparation method of a surface layer polyurethane resin for chemical-resistant biodegradable synthetic leather comprises the following experiments according to the relation of the material dosage in Table 1:
1) preparing a prepolymer: mixing 35g of polycarbonate polyol PC1000, 20g of polylactic acid polyol PLA1000, 15g of polylactic acid polyol PLA2000, 0.04g of antioxidant 1010 and 14g of isocyanate MDI, adding the mixture into 80g of organic solvent DMF, uniformly mixing, adding 0.06g of catalyst MB20, and reacting at 75 ℃ for 0.5h to obtain a prepolymer;
2) preparing a surface layer polyurethane resin: adding 3g of hydroxyl-containing low molecular weight compound EG and 4g of castor oil CO into the prepolymer to carry out chain extension reaction at 75 ℃, adding the rest isocyanate into the reaction system for multiple times, adding 0.4g of reaction terminator CH after the reaction is carried out until the viscosity is 14 ten thousand CPS/75 DEG C3OH and residual DMF to obtain the target product.
Example 5:
a preparation method of a surface layer polyurethane resin for chemical-resistant biodegradable synthetic leather comprises the following experiments according to the relation of the material dosage in Table 1:
1) preparing a prepolymer: mixing 12g of polycarbonate polyol PC1000, 20g of polycarbonate polyol PC2000, 20g of polylactic acid polyol PLA1000, 20g of polylactic acid polyol PLA2000, 0.01g of antioxidant 1010 and 11.7g of isocyanate MDI, adding the mixture into 100g of organic solvent DMF, uniformly mixing, adding 0.02g of catalyst MB20, and reacting at 75 ℃ for 0.5h to obtain a prepolymer;
2) preparation of the Top polyurethaneResin: adding 4g of hydroxyl-containing low molecular weight compound EG and 2g of castor oil CO into the prepolymer to carry out chain extension reaction at 75 ℃, adding the rest isocyanate into the reaction system for multiple times, adding 0.2g of reaction terminator CH after the reaction is carried out until the viscosity is 13 ten thousand CPS/75 DEG C3OH and residual DMF to obtain the target product.
Comparative example 1
Compared with example 1, comparative example 1 is different in that polylactic acid polyol and castor oil are not added in the preparation process, wherein the polylactic acid polyol is replaced by polycarbonate polyol with the same molecular weight, and the castor oil is replaced by ethylene glycol with the same molar amount to maintain the formulation contrast.
Comparative example 2
Comparative example 2 is distinguished from example 1 in that no castor oil is added during the preparation, and the castor oil is replaced by the same molar amount of ethylene glycol to maintain formulation contrast.
Comparative example 3
In comparison with example 1, comparative example 3 differs in that the usual polyester and polyether raw materials are used in the preparation process, the PTMG-1 polyether polyol having a molecular weight of 1000g/mol and the polyester polyol SP2000 having a molecular weight of 2000g/mol replacing PC1000 and PLA2000, respectively, in the original formulation.
TABLE 1 amounts (unit: g) of raw materials of each component in examples 1 to 5
In order to verify the chemical resistance of the products prepared in the implementation of the invention, the products prepared in the above examples and comparative examples were subjected to dry proofing and then attached to the same wet crust leather to obtain leather samples, and then the tests of oleic acid resistance, essential balm resistance and sunscreen cream resistance were performed. The test method comprises the following steps: the test sample is evenly smeared on the surface of leather in a range of 1cm x 1cm, the leather is placed for 24 hours at normal temperature, soapy water is pasted by cotton cloth to wipe the surface of the leather clean, and the change of the surface of the leather is observed, and the resin has excellent chemical resistance as shown in the table 2, is obviously improved compared with the comparative example 3 synthesized by polyether PTMG-1 and polyester polyol SP2000, and is equivalent to the comparative example 1 synthesized by using all-polycarbonate polyol.
TABLE 2 Corrosion protection test data for products made in each of the examples and comparative examples
| Sample | Oleic acid | Essential balm | Sunscreen cream |
| Comparative example 1 | 3 | 3 | 3 |
| Comparative example 2 | 3 | 3 | 3 |
| Comparative example 3 | 2 | 1 | 1 |
| Example 1 | 3 | 3 | 3 |
| Example 2 | 3 | 3 | 3 |
| Example 3 | 3 | 3 | 3 |
| Example 4 | 3 | 3 | 3 |
| Example 5 | 3 | 3 | 3 |
Grade: 1-poor (severe bulging of the leather surface, cracking); 2-general (slight bulging of the leather surface, slight cracking); 3-good (leather surface without bulge and crack)
In order to verify the biodegradability of the products obtained in the above-described practice of the present invention, the biodegradation test was performed on the products obtained in the above-described examples and comparative examples by peeling the films on the same glass plate. The test method comprises the following steps: the test skin is mixed with fresh biomass waste in an accurate proportion and then placed in a composting environment, and the composting process is naturally initiated by a microbial population ubiquitous in nature. In the embodiment of the invention, the mass loss rate of the film in three months under the composting condition is 45-50%, a large number of mildew points appear on the surface of the residual film, and the mass loss rate of the resin film in the comparative example 1 is lower than 10%; comparative example 2 the resin film quality loss rate was 41%, and the residual film surface mold was less; comparative example 3 the resin film mass loss rate was 15%. The polylactic acid polyol and the castor oil bring obvious biodegradation performance to the polyurethane resin.
It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (7)
1. A chemical-resistant biodegradable surface layer polyurethane resin for synthetic leather is characterized in that: the adhesive is prepared from the following components in parts by mass: 26-30 parts of isocyanate, 25-35 parts of polycarbonate polyol, 30-45 parts of polylactic acid polyol, 2-4 parts of hydroxyl-containing low molecular compound, 2-4 parts of castor oil, 300 parts of organic solvent 220-.
2. The chemical-resistant biodegradable top layer polyurethane resin for synthetic leather according to claim 1, wherein: the isocyanate is 4, 4' -diphenylmethane diisocyanate.
3. The chemical-resistant biodegradable top layer polyurethane resin for synthetic leather according to claim 1, wherein: the number average molecular weight of the polycarbonate polyol is 1000-2000 g/mol; the initiator adopted by the polycarbonate polyol is one or two of 1, 6-hexanediol, 3-methylpentanediol, 1, 4-butanediol and 1, 5-pentanediol.
4. The chemical-resistant biodegradable top layer polyurethane resin for synthetic leather according to claim 1, wherein: the number average molecular weight of the polylactic acid polyol is 1000-2000 g/mol; the synthetic method of the polylactic acid polyol is one of a direct lactic acid polycondensation method and a lactide ring opening method.
5. The chemical-resistant biodegradable top layer polyurethane resin for synthetic leather according to claim 1, wherein: the molecular weight of the hydroxyl-containing low molecular compound is 60-120, and the hydroxyl-containing low molecular compound is at least one selected from ethylene glycol, 1, 4-butanediol, neopentyl glycol and 1, 6-hexanediol.
6. The chemical-resistant biodegradable top layer polyurethane resin for synthetic leather according to claim 1, wherein: the organic solvent is dimethylformamide; the antioxidant is an antioxidant 1010; the catalyst is an organic bismuth catalyst; the reaction terminator is methanol.
7. The method of preparing a top layer polyurethane resin for chemical-resistant biodegradable synthetic leather according to any of claims 1 to 6, wherein: the method comprises the following steps:
preparing a prepolymer: adding 9-14 parts of isocyanate, 25-35 parts of polycarbonate polyol, 30-45 parts of polylactic acid polyol, 0.01-0.04 part of antioxidant and 0.02-0.06 part of catalyst into 60-80 parts of organic solvent to form a mixed solution, and reacting at the temperature of 70-80 ℃ for 0.5-1.5h to obtain a prepolymer;
preparing a surface layer polyurethane resin: adding 2-4 parts of low molecular weight compound containing hydroxyl and 2-4 parts of castor oil into the prepolymer, carrying out chain extension reaction at the temperature of 70-80 ℃, adding the residual isocyanate into the reaction system for multiple times during the chain extension reaction, and adding the residual organic solvent and the reaction terminator after the reaction is carried out until the isocyanate is sticky, thus obtaining the target product.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115449049A (en) * | 2022-10-11 | 2022-12-09 | 合肥珝润生物科技有限公司 | All-bio-based environment-friendly polyurethane resin material and preparation method and application thereof |
| CN115806652A (en) * | 2022-12-14 | 2023-03-17 | 合肥安利聚氨酯新材料有限公司 | Low-carbon environment-friendly polyurethane resin and preparation method thereof |
| WO2024062300A1 (en) * | 2022-09-20 | 2024-03-28 | SDIP Innovations Pty Ltd | Biodegradable elastomeric copolymer |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101240056A (en) * | 2008-03-07 | 2008-08-13 | 华中科技大学 | Method for preparing castor oil plasticizing polylactic acid type polyurethane |
| CN107988810A (en) * | 2017-12-01 | 2018-05-04 | 南亚塑胶工业（南通）有限公司 | A kind of resistance to cosmetics of chemicals-resistant burn into, the dirty synthetic leather of beverage and preparation method thereof |
| CN108484873A (en) * | 2018-02-10 | 2018-09-04 | 合肥安利聚氨酯新材料有限公司 | A kind of use for synthetic leather high solid content polyurethane surface layer resin and preparation method thereof |
| CN111393596A (en) * | 2020-04-02 | 2020-07-10 | 上海应用技术大学 | Castor oil modified waterborne polyurethane nano-emulsion and preparation method thereof |
| CN112482045A (en) * | 2020-11-03 | 2021-03-12 | 安徽安利材料科技股份有限公司 | Polylactic acid biodegradable polyurethane synthetic leather and preparation method thereof |
-
2021
- 2021-11-19 CN CN202111407903.8A patent/CN114085356A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101240056A (en) * | 2008-03-07 | 2008-08-13 | 华中科技大学 | Method for preparing castor oil plasticizing polylactic acid type polyurethane |
| CN107988810A (en) * | 2017-12-01 | 2018-05-04 | 南亚塑胶工业（南通）有限公司 | A kind of resistance to cosmetics of chemicals-resistant burn into, the dirty synthetic leather of beverage and preparation method thereof |
| CN108484873A (en) * | 2018-02-10 | 2018-09-04 | 合肥安利聚氨酯新材料有限公司 | A kind of use for synthetic leather high solid content polyurethane surface layer resin and preparation method thereof |
| CN111393596A (en) * | 2020-04-02 | 2020-07-10 | 上海应用技术大学 | Castor oil modified waterborne polyurethane nano-emulsion and preparation method thereof |
| CN112482045A (en) * | 2020-11-03 | 2021-03-12 | 安徽安利材料科技股份有限公司 | Polylactic acid biodegradable polyurethane synthetic leather and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 中国轻工总会: "《轻工业技术装备手册》", vol. 1, 中国轻工业出版社, pages: 1284 - 1285 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024062300A1 (en) * | 2022-09-20 | 2024-03-28 | SDIP Innovations Pty Ltd | Biodegradable elastomeric copolymer |
| CN115449049A (en) * | 2022-10-11 | 2022-12-09 | 合肥珝润生物科技有限公司 | All-bio-based environment-friendly polyurethane resin material and preparation method and application thereof |
| CN115806652A (en) * | 2022-12-14 | 2023-03-17 | 合肥安利聚氨酯新材料有限公司 | Low-carbon environment-friendly polyurethane resin and preparation method thereof |
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