CN113668256A - Regenerated polyurethane composite material and preparation method and application thereof - Google Patents
Regenerated polyurethane composite material and preparation method and application thereof Download PDFInfo
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- D06N3/0011—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using non-woven fabrics
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The invention relates to a regenerated polyurethane composite material and a preparation method thereof, wherein the preparation method comprises the following steps: mixing and dissolving the waste polyurethane composite material and dimethylformamide to obtain substrate fibers and a dissolved polyurethane material; filtering and separating the substrate fiber and the dissolved polyurethane material to respectively obtain a substrate fiber material and regenerated polyurethane slurry; transferring the regenerated polyurethane slurry to a reaction kettle to prepare slurry for a polyurethane wet method; preparing a regenerated substrate fiber material by melting, stretching, cutting, paving and reinforcing a felting needle of the substrate fiber material; and (3) carrying out wet coating, washing, drying and dry transfer veneering on the slurry for the polyurethane wet method and the regenerated base fiber material to prepare the regenerated polyurethane composite material. The preparation method ensures the structural characteristics of the polyurethane and realizes the stability of the physical properties of the polyurethane; meanwhile, the recycling of the substrate fiber material is realized, so that the 100 percent recycling of the polyurethane composite material is realized.
Description
Technical Field
The invention relates to a regenerated polyurethane composite material and a preparation method and application thereof, belonging to the field of leisure shoe polyurethane composite materials.
Background
The waste Polyurethane (PU) mainly comprises waste leftover materials of polyurethane synthetic leather production enterprises and sports and leisure shoe processing factories, or waste sports and leisure shoe recycling materials, waste polyurethane leather and the like. Polyurethane recycling methods are mainly classified into physical recycling methods, chemical recycling methods and heat recycling methods. The physical recycling method mainly comprises the steps of crushing, compression molding and recycling as a new material filler, and the recycled and prepared regenerated polyurethane has poor performance and is suitable for low-grade products. Chemical recovery methods (e.g., alcoholysis, ammonolysis, hydrolysis, etc.) refer to the degradation of polyurethane resins into components of low relative molecular mass under the action of chemical degradation agents, which greatly affect the structure of polyurethane materials, thereby degrading their properties in various respects. The heat recovery method recovers heat by burning polyurethane waste, which causes serious secondary pollution and is not basically used. The raw materials used by the polyurethane regeneration methods are generally old polyurethane foam and elastomer, but the regeneration utilization rate of the base fiber material of the polyurethane synthetic leather is not high, and the 100% regeneration of the common polyurethane synthetic leather can not be realized.
In view of the above problems, the invention provides a preparation method of a regenerated polyurethane composite material, which can realize the regeneration and utilization of a base fiber material without affecting the structural performance of polyurethane.
Disclosure of Invention
Aiming at the problems, the invention provides a preparation method of a regenerated polyurethane composite material, which comprises the following steps:
mixing and dissolving the waste polyurethane composite material and dimethylformamide to obtain substrate fibers and a dissolved polyurethane material;
filtering and separating the substrate fiber and the dissolved polyurethane material to respectively obtain a substrate fiber material and regenerated polyurethane slurry;
transferring the regenerated polyurethane slurry to a reaction kettle to prepare slurry for a polyurethane wet method;
preparing a regenerated substrate fiber material by melting, stretching, cutting, paving and reinforcing a felting needle of the substrate fiber material;
and (3) carrying out wet coating, washing, drying and dry transfer veneering on the slurry for the polyurethane wet method and the regenerated base fiber material to prepare the regenerated polyurethane composite material.
Further, before the waste polyurethane composite material is mixed with the dimethyl formamide, the waste polyurethane composite material is subjected to water washing and drying pretreatment.
Further, in the step of mixing and dissolving the waste polyurethane composite material and the dimethyl formamide, the adding amount of the dimethyl formamide is 1-3 times of the weight of the waste polyurethane composite material.
Further, in the step of mixing and dissolving the waste polyurethane composite material and the dimethylformamide, the dissolving temperature is 40-70 ℃, and the dissolving time is 1-2 hours.
Further, transferring the regenerated polyurethane slurry to a reaction kettle, and preparing the slurry for the polyurethane wet process, wherein the slurry for the polyurethane wet process comprises the following raw materials in parts by weight:
further, the slurry raw material for the polyurethane wet method also comprises resin, wherein the weight part ratio of the resin is 100 parts.
Further, the viscosity of the slurry for the wet method of polyurethane prepared by transferring the regenerated polyurethane slurry to a reaction kettle is 5000 mPa.s-12000 mPa.s/25 ℃.
Further, the waste polyurethane composite material comprises one or two of polyurethane synthetic leather and waste leftover materials of sports and leisure processing shoe factories.
Further, the base fiber material is one or more of terylene, chinlon and cotton.
The invention also provides a regenerated polyurethane composite material prepared by the method.
The invention also provides an application of the regenerated polyurethane composite material, and the regenerated polyurethane composite material is used for manufacturing sports casual shoes, sofa furniture or balls.
Compared with the prior art, the invention has the beneficial effects that:
according to the preparation method of the regenerated polyurethane composite material and the regenerated polyurethane composite material, provided by the invention, on one hand, the structural characteristics of polyurethane are ensured, and the stability of physical properties of the polyurethane is realized; on the other hand, the regeneration and utilization of the substrate fiber material are realized, so that the 100 percent regeneration and utilization of the polyurethane composite material is realized. Meanwhile, the preparation method has simple process and less pollution, and meets the requirement of environmental protection.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims hereof.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, and not all of the 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.
Example 1:
(1) washing the waste polyurethane composite material with water to remove surface metal products, then putting the waste polyurethane composite material into a drying oven for drying treatment for 1h, and taking out for later use (the washed and dried waste polyurethane composite material is marked as SW-A);
(2) taking 100 parts by weight of SW-A in the step (1), adding 150 parts by weight of Dimethylformamide (DMF) into a solution tank for dissolving, starting a heating stirrer, stirring and dissolving at 60 ℃ for 1 hour, completely dissolving, and cooling to room temperature to recover a polyurethane surface layer and a foaming layer after dissolving; the base fiber is not dissolved in this step;
(3) filtering the substrate fiber in the solution tank, the dissolved polyurethane surface layer and the foaming layer material to obtain regenerated polyurethane slurry (marked as SW-B), and washing, drying and separating the substrate fiber to obtain a substrate fiber material (marked as SW-C); the viscosity of SW-B in the step can reach 20000mPa & s/25 ℃;
(4) transferring the SW-B obtained in the step (3) to a reaction kettle device, and preparing new slurry for the polyurethane wet process according to the following proportion (all parts by weight):
wherein HY-608 is produced by Jinhuo county Jinling auxiliary factory in Huaian city, Huai province, Jiangsu province, and RB-89W-B is produced by Shanghai Nippon Hongyun trade company Limited. The viscosity of the slurry for the polyurethane wet method prepared in the step is 10000mPa & s/25 ℃;
(5) and (4) classifying and disinfecting the SW-C obtained in the step (3), then melting the substrate fiber, stretching the substrate fiber into filaments, softening the filaments in hot water, stretching, curling and drying the filaments to obtain long fibers, cutting the long fibers into short fibers, opening, carding and paving the short fibers into a fiber net, and finally repeatedly puncturing and reinforcing the fiber net into cloth to obtain the regenerated substrate fiber material. The thickness and grammage of the new fibrous base material may be adjusted as desired, in this example between 0.75mm and 0.85mm, gramThe weight is 190g/m2-220g/m2；
(6) And (4) carrying out wet coating, washing, drying and dry transfer veneering on the slurry for the polyurethane wet process obtained in the step (4) and the regenerated base fiber material obtained in the step (5) again to obtain the regenerated polyurethane composite material.
Example 2:
(1) washing the waste polyurethane composite material with water to remove surface metal products, then putting the waste polyurethane composite material into a drying oven for drying treatment for 1h, and taking out for later use (the washed and dried waste polyurethane composite material is marked as SW-A);
(2) taking 100 parts by weight of SW-A in the step (1), adding 200 parts by weight of Dimethylformamide (DMF) into a solution tank for dissolving, starting a heating stirrer, stirring and dissolving at 50 ℃ for 1.5 hours, completely dissolving, and cooling to room temperature to recover a polyurethane surface layer and a foaming layer after dissolving; the base fiber is not dissolved in this step;
(3) filtering the substrate fiber in the solution tank, the dissolved polyurethane surface layer and the foaming layer material to obtain regenerated polyurethane slurry (marked as SW-B), and washing, drying and separating the substrate fiber to obtain a substrate fiber material (marked as SW-C); the viscosity of SW-B in the step can reach 16000mPa & s/25 ℃;
(4) transferring the SW-B obtained in the step (3) to a reaction kettle device, and preparing new slurry for the polyurethane wet process according to the following proportion (all parts by weight):
wherein HY-608 is produced by Jinhui county Jinling auxiliary agent factory in Huaian city, Huai province, Jiangsu province, RB-89W-B is produced by Shanghai Nippon Hongyun Co Ltd, and the viscosity of the slurry for the polyurethane wet process prepared in the step is 8000mPa & s/25 ℃;
(5) classifying and sterilizing the SW-C obtained in the step (3), then melting the substrate fiber, stretching the substrate fiber into long filaments, softening the filaments in hot water, stretching, curling and drying the filaments to obtain long fibers, cutting the long fibers into short fibers, opening, carding and paving the short fibers into a fiber net, and finally enabling the fibers to be in a fiber net shapeAnd repeatedly puncturing and reinforcing the net into cloth to obtain the regenerated base fiber material. The thickness and the gram weight of the novel fiber base material can be adjusted according to requirements, the thickness is 0.75mm-0.85mm in the embodiment, and the gram weight is 190g/m2-220 g/m2；
(6) And (4) carrying out wet coating, washing, drying and dry transfer veneering on the slurry for the polyurethane wet process obtained in the step (4) and the regenerated base fiber material obtained in the step (5) again to obtain the regenerated polyurethane composite material.
Example 3:
(1) washing the waste polyurethane composite material with water to remove surface metal products, then putting the waste polyurethane composite material into a drying oven for drying treatment for 1h, and taking out for later use (the washed and dried waste polyurethane composite material is marked as SW-A);
(2) taking 100 parts by weight of SW-A in the step (1), adding 300 parts by weight of Dimethylformamide (DMF) into a solution tank for dissolving, starting a heating stirrer, stirring and dissolving for 2 hours at 40 ℃, completely dissolving, and cooling to room temperature to recover a polyurethane surface layer and a foaming layer after dissolving; the base fiber is not dissolved in this step;
(3) filtering the substrate fiber in the solution tank, the dissolved polyurethane surface layer and the foaming layer material to obtain regenerated polyurethane slurry (marked as SW-B), and washing, drying and separating the substrate fiber to obtain a substrate fiber material (marked as SW-C); the viscosity of SW-B in the step can reach 12000mPa & s/25 ℃;
(4) transferring the SW-B obtained in the step (3) to a reaction kettle device, and preparing new slurry for the polyurethane wet process according to the following proportion (all parts by weight):
wherein HY-608 is produced by Jinhuo county Jinling auxiliary agent factory in Huaian city, Huai province, Jiangsu province, RB-89W-B is produced by Shanghai Nippon Hongyun Co Ltd, and the viscosity of the slurry for the polyurethane wet process prepared in the step is 6000 mPa.s/25 ℃;
(5) classifying and sterilizing the SW-C obtained in the step (3), and then melting the substrate fiberThen drawing into long filaments, softening in hot water, obtaining long fibers through drawing, curling and drying, cutting into short fibers, opening, carding and paving into a fiber net, and finally repeatedly puncturing and reinforcing the fiber net into cloth to obtain the regenerated base fiber material. The thickness and the gram weight of the novel fiber base material can be adjusted according to requirements, the thickness is 0.75mm-0.85mm in the embodiment, and the gram weight is 190g/m2-220 g/m2；
(6) And (4) carrying out wet coating, washing, drying and dry transfer veneering on the slurry for the polyurethane wet process obtained in the step (4) and the regenerated base fiber material obtained in the step (5) again to obtain the regenerated polyurethane composite material.
Example 4:
(1) washing the waste polyurethane composite material with water to remove surface metal products, then putting the waste polyurethane composite material into a drying oven for drying treatment for 1h, and taking out for later use (the washed and dried waste polyurethane composite material is marked as SW-A);
(2) taking 100 parts by weight of SW-A in the step (1), adding 100 parts by weight of Dimethylformamide (DMF) into a solution tank for dissolving, starting a heating stirrer, stirring and dissolving at 70 ℃ for 1 hour, completely dissolving, and cooling to room temperature to recover a polyurethane surface layer and a foaming layer after dissolving; the base fiber is not dissolved in this step;
(3) filtering the substrate fiber in the solution tank, the dissolved polyurethane surface layer and the foaming layer material to obtain regenerated polyurethane slurry (marked as SW-B), and washing, drying and separating the substrate fiber to obtain a substrate fiber material (marked as SW-C); the viscosity of SW-B in the step can reach 25000mPa & s/25 ℃;
(4) transferring the SW-B obtained in the step (3) to a reaction kettle device, and preparing new slurry for the polyurethane wet process according to the following proportion (all parts by weight):
wherein HY-608 is produced by Jinhuo county Jinling auxiliary agent factory in Huaian city, Huai province, Jiangsu province, RB-89W-B is produced by Shanghai Nippon Hongyun Co Ltd, and the viscosity of the slurry for the polyurethane wet process prepared in the step is 12000mPa & s/25 ℃;
(5) and (4) classifying and disinfecting the SW-C obtained in the step (3), then melting the substrate fiber, stretching the substrate fiber into filaments, softening the filaments in hot water, stretching, curling and drying the filaments to obtain long fibers, cutting the long fibers into short fibers, opening, carding and paving the short fibers into a fiber net, and finally repeatedly puncturing and reinforcing the fiber net into cloth to obtain the regenerated substrate fiber material. The thickness and the gram weight of the novel fiber base material can be adjusted according to requirements, the thickness is 0.75mm-0.85mm in the embodiment, and the gram weight is 190g/m2-220 g/m2；
(6) And (4) carrying out wet coating, washing, drying and dry transfer veneering on the slurry for the polyurethane wet process obtained in the step (4) and the regenerated base fiber material obtained in the step (5) again to obtain the regenerated polyurethane composite material.
Comparative example 1:
(1) washing the waste polyurethane composite material with water to remove surface metal products, then putting the waste polyurethane composite material into a drying oven for drying treatment for 1h, and taking out for later use (the washed and dried waste polyurethane composite material is marked as SW-A);
(2) taking 100 parts by weight of SW-A in the step (1), adding 200 parts by weight of Dimethylformamide (DMF) into a solution tank for dissolving, starting a heating stirrer, stirring and dissolving at 50 ℃ for 1.5 hours, completely dissolving, and cooling to room temperature to recover a polyurethane surface layer and a foaming layer after dissolving; the base fiber is not dissolved in this step;
(3) filtering the substrate fiber in the solution tank, the dissolved polyurethane surface layer and the foaming layer material to obtain regenerated polyurethane slurry (marked as SW-B), and washing, drying and separating the substrate fiber to obtain a substrate fiber material (marked as SW-C); the viscosity of SW-B in the step can reach 16000mPa & s/25 ℃;
(4) transferring the SW-B obtained in the step (3) to a reaction kettle device, and preparing new slurry for the polyurethane wet process according to the following proportion (all parts by weight):
wherein HY-608 is produced by Jinling auxiliary agent factories in Jinhucounty, Huaian, Huai province, Jiangsu province, SW-6102A is produced by Anli polyurethane new material company Limited in Hefei city, Anhui province, RB-89W-B is produced by Shanghai Nihong trade company Limited, and the viscosity of the slurry for the polyurethane wet process prepared in the step is 8000mPa s/25 ℃;
(5) and (4) classifying and disinfecting the SW-C obtained in the step (3), then melting the substrate fiber, stretching the substrate fiber into filaments, softening the filaments in hot water, stretching, curling and drying the filaments to obtain long fibers, cutting the long fibers into short fibers, opening, carding and paving the short fibers into a fiber net, and finally repeatedly puncturing and reinforcing the fiber net into cloth to obtain the regenerated substrate fiber material. The thickness and the gram weight of the novel fiber base material can be adjusted according to requirements, the thickness is 0.75mm-0.85mm in the embodiment, and the gram weight is 190g/m2-220 g/m2；
(6) And (4) carrying out wet coating, washing, drying and dry transfer veneering on the slurry for the polyurethane wet process obtained in the step (4) and the regenerated base fiber material obtained in the step (5) again to obtain the regenerated polyurethane composite material.
Comparative example 2:
(1) washing the waste polyurethane composite material with water to remove surface metal products, then putting the waste polyurethane composite material into a drying oven for drying treatment for 1h, and taking out for later use (the washed and dried waste polyurethane composite material is marked as SW-A);
(2) taking 100 parts by weight of SW-A in the step (1), adding 200 parts by weight of Dimethylformamide (DMF) into a solution tank for dissolving, starting a heating stirrer, stirring and dissolving at 50 ℃ for 1.5 hours, completely dissolving, and cooling to room temperature to recover a polyurethane surface layer and a foaming layer after dissolving; the base fiber is not dissolved in this step;
(3) filtering the substrate fiber in the solution tank, the dissolved polyurethane surface layer and the foaming layer material to obtain regenerated polyurethane slurry (marked as SW-B), and washing, drying and separating the substrate fiber to obtain a substrate fiber material (marked as SW-C); the viscosity of SW-B in the step can reach 16000mPa & s/25 ℃;
(4) transferring the SW-B obtained in the step (3) to a reaction kettle device, and preparing new slurry for the polyurethane wet process according to the following proportion (all parts by weight):
wherein HY-608 is produced by Jinhui county Jinling auxiliary agent factory in Huaian city, Huai province, Jiangsu province, RB-89W-B is produced by Shanghai Nippon Hongyun Co Ltd, and the viscosity of the slurry for the polyurethane wet process prepared in the step is 8000mPa & s/25 ℃;
(5) classifying and disinfecting the SW-C obtained in the step (3), then melting the substrate fiber, stretching the substrate fiber into filaments, softening the filaments in hot water, stretching, curling and drying the filaments to obtain long fibers, cutting the long fibers to form short fibers, co-spinning the short fibers and non-regenerated polyester short fibers according to the mass ratio of 1:1, opening, carding and paving the short fibers into a fiber net, and finally repeatedly puncturing and reinforcing the fiber net into cloth to obtain the regenerated substrate fiber material.
(6) And (4) carrying out wet coating, washing, drying and dry transfer veneering on the slurry for the polyurethane wet process obtained in the step (4) and the regenerated base fiber material obtained in the step (5) again to obtain the regenerated polyurethane composite material.
Comparative example 3:
the polyurethane composite material for the commercial non-regenerative sports leisure shoes.
The performance tests of the polyurethane composite materials prepared in the above examples 1 to 4 and comparative examples 1 to 3 include the latitudinal and longitudinal breaking strength, latitudinal and longitudinal elongation, latitudinal and longitudinal tearing strength, peeling strength, bursting strength and hydrolysis resistance tests of the polyurethane composite materials, wherein in the hydrolysis resistance tests, the condition parameters of the alkali soaking solution are set to 25 ℃ 10% NaOH 16H. The relevant test data are shown in table 1.
Table 1 polyurethane composite Performance test data
The performance test data in the table 1 show that the physical properties (including the breaking strength in the warp and weft directions, the elongation in the warp and weft directions, the tearing strength in the warp and weft directions, the peeling strength, the bursting strength and the hydrolysis resistance) of the regenerated polyurethane composite material obtained by the preparation method are basically equivalent to those of the conventional non-regenerated material polyurethane synthetic leather on the market in all aspects, so that the requirements of sports and leisure shoes can be met, the market requirements can be met, and the full-environment-friendly requirement can be realized.
According to the preparation method, the invention also designs and obtains the regenerated polyurethane composite material.
In addition, the invention also relates to the application of the regenerated polyurethane composite material prepared by the preparation method, and the regenerated polyurethane composite material prepared by the method is used for polyurethane composite materials of sports and leisure shoes, sofa furniture or balls, wherein the balls are basketballs, football or volleyballs.
In conclusion, the preparation method of the regenerated polyurethane composite material and the regenerated polyurethane composite material provided by the invention ensure the structural characteristics of polyurethane and realize the stability of physical properties; on the other hand, the regeneration and utilization of the substrate fiber material are realized, so that the 100 percent regeneration and utilization of the polyurethane composite material is realized. Meanwhile, the preparation method has simple process and less pollution, and meets the requirement of environmental protection.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (11)
1. A method for preparing a recycled polyurethane composite, the method comprising:
mixing and dissolving the waste polyurethane composite material and dimethylformamide to obtain substrate fibers and a dissolved polyurethane material;
filtering and separating the substrate fiber and the dissolved polyurethane material to respectively obtain a substrate fiber material and regenerated polyurethane slurry;
transferring the regenerated polyurethane slurry to a reaction kettle to prepare slurry for a polyurethane wet method;
preparing a regenerated substrate fiber material by melting, stretching, cutting, paving and reinforcing a felting needle of the substrate fiber material;
and (3) carrying out wet coating, washing, drying and dry transfer veneering on the slurry for the polyurethane wet method and the regenerated base fiber material to prepare the regenerated polyurethane composite material.
2. The method according to claim 1, wherein the waste polyurethane composite material is pretreated by washing with water and drying before being mixed with dimethylformamide.
3. The method as claimed in claim 1, wherein in the step of mixing and dissolving the waste polyurethane composite material with dimethylformamide, the amount of dimethylformamide added is 1-3 times of the weight of the waste polyurethane composite material.
4. The method as claimed in claim 1, wherein in the step of mixing and dissolving the waste polyurethane composite material and the dimethylformamide, the dissolving temperature is 40-70 ℃, and the dissolving time is 1-2 hours.
5. The method according to claim 1, wherein in the step of transferring the regenerated polyurethane slurry to a reaction kettle to prepare the slurry for the wet polyurethane process, the slurry for the wet polyurethane process comprises the following raw materials in parts by weight:
6. the method as claimed in claim 5, wherein the slurry raw material for the wet process of polyurethane further comprises resin, and the weight ratio of the resin is 100 parts.
7. The method according to claim 4 or 5, wherein the viscosity of the slurry for wet polyurethane prepared by transferring the regenerated polyurethane slurry to a reaction kettle is 5000-12000 mPa-s/25 ℃.
8. The method of any one of claims 1-6, wherein the waste polyurethane composite material comprises one or both of polyurethane synthetic leather, sports and leisure processing shoe factory waste scrap.
9. The method of claim 1, wherein the base fiber material is one or more of polyester, nylon, and cotton.
10. A recycled polyurethane composite prepared by the method of any one of claims 1 to 6.
11. Use of the recycled polyurethane composite of claim 10 for the manufacture of sports casual shoes, sofa furniture or balls.
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| CN103031737A (en) * | 2011-09-29 | 2013-04-10 | 昆山协兴合成革有限公司 | Production method of hydrolysis resistance regenerating resin synthetic leather |
| CN103031738A (en) * | 2011-09-29 | 2013-04-10 | 昆山协兴合成革有限公司 | Method for manufacturing netted sandwich cloth synthetic leather |
| CN104213432A (en) * | 2014-09-26 | 2014-12-17 | 江西豪普高科涂层织物有限公司 | Polyurethane (PU) synthetic leather production process allowing solid waste recycling |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103031737A (en) * | 2011-09-29 | 2013-04-10 | 昆山协兴合成革有限公司 | Production method of hydrolysis resistance regenerating resin synthetic leather |
| CN103031738A (en) * | 2011-09-29 | 2013-04-10 | 昆山协兴合成革有限公司 | Method for manufacturing netted sandwich cloth synthetic leather |
| CN104213432A (en) * | 2014-09-26 | 2014-12-17 | 江西豪普高科涂层织物有限公司 | Polyurethane (PU) synthetic leather production process allowing solid waste recycling |
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