CN112482045A - Polylactic acid biodegradable polyurethane synthetic leather and preparation method thereof - Google Patents
Polylactic acid biodegradable polyurethane synthetic leather and preparation method thereof Download PDFInfo
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- 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
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- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
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- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
- D06N3/0011—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using non-woven fabrics
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- D06N3/0015—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 fibres of specified chemical or physical nature, e.g. natural silk
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Abstract
The invention provides polylactic acid biodegradable polyurethane synthetic leather and a preparation method thereof. The problem that the existing polyurethane synthetic leather cannot be biodegraded is solved, and the problem that the polylactic acid/polyurethane composite material cannot meet the general physical property requirements of the synthetic leather is also solved. The synthetic leather comprises base cloth, a polyurethane synthetic leather base layer and a polyurethane synthetic leather surface layer in sequence. The polylactic acid biodegradable polyurethane synthetic leather is formed through the processes of coating, coagulation, washing, drying, veneering and the like. The polylactic acid biodegradable polyurethane synthetic leather manufactured by the method can meet the physical properties of shoe material synthetic leather, has small wrinkles on the leather surface, is suitable for being used as a wrinkle-free product, obviously improves the natural durability of the polylactic acid material, can keep the biodegradable performance of the polylactic acid material, and is a novel environment-friendly polyurethane synthetic leather material.
Description
Technical Field
The invention belongs to the field of synthetic leather preparation, and particularly relates to polylactic acid biodegradable polyurethane synthetic leather and a preparation method thereof.
Background
Polyurethane synthetic leather is an important component of the plastic industry and is widely used in various industries of national economy. Through continuous development, the polyurethane synthetic leather is rapidly increased in product quality, variety and yield, and occupies an important position in the daily life of human beings. The traditional polyurethane synthetic leather comprises terylene or chinlon base cloth, polyurethane resin is formed by reaction of isocyanate and polyalcohol, and a new material is formed by processing the synthetic leather, so that the polyurethane synthetic leather is widely applied to the industries of shoes, packing materials, sports equipment, sofas and automobiles. The raw materials used by the material are all made of chemical stone materials, are general materials which are not degradable or are very slow to degrade, and the degradation speed is not controllable, so that the material is convenient for people to live and causes serious pollution to the environment, and under the condition, the development of a fast and efficient degradable material is urgently required to solve the problem.
The biodegradable material refers to a material which can perform biochemical reaction under the action of microbial enzymes in a natural environment to finally form carbon dioxide and water, and polylactic acid (PLA) is one of the most representative biodegradable materials. The biodegradable material does not use petroleum as a raw material, is biodegradable under normal composting conditions, is considered as a new material which has the most hopeful prospect of shaking the traditional status of petroleum-based plastics (PE, PP, PVC and the like) and petroleum-based chemical fibers (PET, PTT, PBT and the like) in the future, is a biodegradable material which has large yield, wide application range and high cost performance and is most close to petroleum-based polyester in the current biodegradable materials. Meanwhile, the production raw materials of the polylactic acid are mainly derived from grain crops such as grains, and the polylactic acid can be prepared by obtaining a lactic acid raw material through fermentation of inedible materials such as corn straws and sugarcane residues, and is low in price.
However, polylactic acid is a product obtained by polymerization, and has too wide relative molecular weight distribution, and meanwhile, the polylactic acid is a linear polymer, so that the polylactic acid material has the defects of high brittleness, difficulty in film formation, low vitrification, poor impact resistance and the like, and has certain limitation in the practical application process.
The preparation method of the polylactic acid biodegradable polyurethane synthetic leather adopts a base cloth composite blending mode, can meet the physical properties of shoe material synthetic leather, has small wrinkles on the leather surface, synthesizes a special polylactic acid/polyurethane resin, obviously improves the natural durability of the polylactic acid material, can keep the biodegradable performance of the polylactic acid material, and is a novel environment-friendly polyurethane synthetic leather material.
Disclosure of Invention
Aiming at the problems, the invention provides polylactic acid biodegradable polyurethane synthetic leather, which comprises a base cloth layer, a polyurethane synthetic leather base layer and a polyurethane synthetic leather surface layer; the polyurethane synthetic leather surface layer is prepared by coating and drying polyurethane synthetic leather resin.
Further, the polyurethane synthetic leather resin is polylactic acid/polyurethane resin.
Further, the polylactic acid/polyurethane resin comprises the following components in component proportion: 10 to 25 percent of polylactic acid polyol, 5 to 15 percent of polyether polymeric polyol, 2 to 20 percent of micromolecular chain extender, 10 to 20 percent of isocyanate, 70 to 80 percent of solvent and 0.001 to 0.005 percent of organic bismuth catalyst.
Further, the polylactic acid polyol is polylactic acid dihydric alcohol (Anhui Feng original group, and the mark is PLA-300); the polyether polymeric polyol is polytetrahydrofuran ether glycol (Shanxi three-dimensional group GmbH, the trade name is PTMG-1000, PTMG-2000); the chain extender is a dihydric alcohol chain extender (Shanxi three-dimensional group GmbH, 1,2 propylene glycol); the isocyanate is 4, 4' -diphenylmethane diisocyanate (produced by Nicotiana tabacum, and the brand number is CD-MDI 100L); the organic bismuth catalyst is one or more of butyl bismuth and ethyl bismuth (produced by leading chemicals of the United states of America under the brand name of
8106) (ii) a The solvent is diphenylmethane diisocyanate.
Further, the polylactic acid polyol and the polyether polymer polyol form a mixed polyol, and the molar ratio of the mixed polyol to the glycol chain extender is 1: 1.4 to 1.8; the ratio of the mixed polyol to the 4, 4' -diphenylmethane diisocyanate is (calculated by the cyanide-to-hydroxyl ratio) 1.2-1.4: 1.
further, the polylactic acid/polyurethane resin comprises the following components in component proportion: 10-25% of polylactic acid polyol, 5-15% of polyether polymeric polyol, 2-10% of micromolecular chain extender, 10-20% of isocyanate, 70% of solvent and 0.001-0.005% of organic bismuth catalyst.
Further, the base cloth layer is prepared by co-spinning polylactic acid fiber/polyamide fiber; the base cloth layer is one or a plurality of composite of non-woven fabrics, woven fabrics and knitted fabrics.
The invention also provides a preparation method of the polylactic acid biodegradable polyurethane synthetic leather, which comprises the following steps:
step a, determining a polyurethane synthetic leather base cloth layer and a polyurethane synthetic leather bass layer, and bonding the base cloth layer and the bass layer;
step b, preparing polyurethane synthetic leather resin:
step b1, determining the preparation raw materials and the mixture ratio of the polyurethane synthetic leather resin: the polyurethane synthetic leather resin comprises the following raw materials in parts by weight: 80-160 parts of polylactic acid polyol, 80-160 parts of polyether polymeric polyol, 10-50 parts of chain extender, 80-120 parts of isocyanate, 750-900 parts of solvent and 0.03-0.06 part of organic bismuth catalyst;
step b2, preparing the polyurethane synthetic leather resin: adding polyether polymeric polyol, an auxiliary agent and one third of solvent into a reaction kettle, uniformly stirring, adding one half of isocyanate, and reacting for 20-30 min at 40-60 ℃; adding polylactic acid polyol and one half of chain extender into the reaction solution, and reacting for 20-30 min at 40-60 ℃ to obtain a prepolymer;
adding the remaining half of chain extender, the remaining half of isocyanate and one third of solvent into the prepolymer, reacting at 50-60 ℃, adding the remaining one third of solvent step by step along with the continuous increase of the system viscosity, adding an organic bismuth catalyst in the reaction process, controlling the final viscosity to be 180-250 Pa.S/25 ℃, and finally adding a terminator to obtain the polyurethane synthetic leather resin;
and c, coating the polyurethane synthetic leather resin on the Bass layer by a wet method, and forming the polylactic acid biodegradable polyurethane synthetic leather through the technological processes of condensation, washing, drying and veneering of the synthetic leather.
Further, the auxiliary agent is phosphoric acid; the terminator is methanol.
Further, the number average molecular weight of the polyether polymeric polyol is 1000-2000 g/mol.
The polylactic acid biodegradable polyurethane synthetic leather manufactured by the method can meet the physical properties of shoe material synthetic leather, has small wrinkles on the leather surface, is suitable for being used as a wrinkle-free product, obviously improves the natural durability of the polylactic acid material, can keep the biodegradable performance of the polylactic acid material, and is a novel environment-friendly polyurethane synthetic leather material.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the polylactic acid biodegradable polyurethane synthetic leather product prepared by the invention, the polyurethane synthetic leather base fabric is prepared by co-spinning the polylactic acid fibers/the polyamide fibers according to a certain proportion, so that the basic physical properties of the base material can be improved, the physical properties of shoe material synthetic leather are met, meanwhile, the wrinkles of the leather surface are small, and the polylactic acid biodegradable polyurethane synthetic leather product is suitable for being used as a wrinkle-free product;
2. according to the polylactic acid biodegradable polyurethane synthetic leather product prepared by the invention, the polylactic acid biodegradable polyurethane synthetic leather resin is special polylactic acid/polyurethane resin, so that the natural durability of a polylactic acid material can be obviously improved, and meanwhile, the biodegradable performance of the polylactic acid material can be kept, and the polylactic acid biodegradable polyurethane synthetic leather product is a novel environment-friendly polyurethane synthetic leather material;
3. the polylactic acid biodegradable polyurethane synthetic leather prepared by the invention is a production and processing technology of conventional polyurethane synthetic leather through processes of coating, condensation, washing, drying, veneering and the like, and has strong processing applicability and convenient production and processing process.
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 as well as the appended drawings.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and those skilled in the art can also obtain other drawings according to the drawings without creative efforts.
Fig. 1 shows a schematic structural diagram of polylactic acid biodegradable polyurethane synthetic leather in the embodiment of the invention.
1-a base fabric layer; 2-a polyurethane synthetic leather base layer; 3-polyurethane synthetic leather surface layer.
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 with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. 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.
The invention particularly relates to a preparation method of polylactic acid biodegradable polyurethane synthetic leather. The problem that the existing polyurethane synthetic leather cannot be biodegraded is solved, and the problem that the polylactic acid/polyurethane composite material cannot meet the general physical property requirements of the synthetic leather is also solved. The synthetic leather comprises base cloth, a polyurethane synthetic leather base layer and a polyurethane synthetic leather surface layer in sequence. The polylactic acid biodegradable polyurethane synthetic leather base cloth is prepared by co-spinning polylactic acid fibers/polyamide fibers according to a certain proportion. The polylactic acid biodegradable polyurethane synthetic leather resin is special polylactic acid/polyurethane resin, and the polylactic acid/polyurethane resin comprises the following components in parts by weight: the composite material comprises 10-25% of polylactic acid polyol, 5-15% of polyether polymeric polyol, 2-10% of micromolecular chain extender, 10-20% of isocyanate, 70-80% of solvent, 0.001-0.005% of organic bismuth catalyst, terminator and auxiliary agent. The polylactic acid biodegradable polyurethane synthetic leather is formed through the processes of coating, coagulation, washing, drying, veneering and the like. The polylactic acid biodegradable polyurethane synthetic leather manufactured by the method can meet the physical properties of shoe material synthetic leather, has small wrinkles on the leather surface, is suitable for being used as a wrinkle-free product, obviously improves the natural durability of the polylactic acid material, can maintain the biodegradable performance of the polylactic acid material, and is a novel environment-friendly polyurethane synthetic leather material.
Illustratively, the adjuvant is phosphoric acid; the terminating agent is methanol.
The polylactic acid biodegradable polyurethane synthetic leather comprises a base cloth layer, a polyurethane synthetic leather base layer and a polyurethane synthetic leather surface layer, wherein the polyurethane synthetic leather surface layer is prepared by coating and drying polyurethane synthetic leather resin, and the polyurethane synthetic leather resin is polylactic acid/polyurethane resin.
Illustratively, the base cloth layer is prepared by co-spinning polylactic acid fiber/polyamide fiber according to a certain proportion, and the base cloth comprises the following components in percentage by weight: the polylactic acid fiber/nylon fiber is prepared by co-spinning in different proportions of 1:4-4:1, can be adjusted according to different requirements, and can be prepared by compounding one or more of non-woven fabrics, woven fabrics or knitted fabrics.
Illustratively, the polylactic acid/polyurethane resin comprises the following components in a component ratio: 10 to 25 percent of polylactic acid polyol, 5 to 15 percent of polyether polymeric polyol, 2 to 20 percent of micromolecular chain extender, 10 to 20 percent of isocyanate, 70 to 80 percent of solvent and 0.001 to 0.005 percent of organic bismuth catalyst.
Illustratively, the polylactic acid polyol is polylactic acid diol; the polyether polymeric polyalcohol is polytetrahydrofuran ether glycol; the chain extender is a dihydric alcohol chain extender; the isocyanate is 4, 4' -diphenylmethane diisocyanate; the organic bismuth catalyst is one or more of butyl bismuth and ethyl bismuth; the solvent is dimethylformamide.
Illustratively, the polylactic acid polyol and the polyether polyol form a mixed polyol having a molar ratio of mixed polyol to glycol chain extender of 1: 1.4 to 1.8; the ratio of the mixed polyol to the 4, 4' -diphenylmethane diisocyanate is 1.2-1.4 in terms of the cyanide-to-hydroxyl ratio: 1.
illustratively, the polylactic acid polyol and the polyether polyol form a mixed polyol, wherein the polylactic acid polyol comprises 50-80 wt% of the polyol mixture, and the balance is polyether polyol. The polylactic acid polyalcohol is derived from biomass materials, such as corn, wheat, sweet potato, etc. The polyether polyol is polytetrahydrofuran ether glycol, and the number average molecular weight is 1000-2000 g/mol.
Illustratively, the polylactic acid/polyurethane resin comprises the following components in a component ratio: 10-25% of polylactic acid polyol, 5-15% of polyether polymeric polyol, 2-10% of micromolecular chain extender, 10-20% of isocyanate, 70% of solvent and 0.001-0.005% of organic bismuth catalyst.
A preparation method of polylactic acid biodegradable polyurethane synthetic leather comprises the following steps:
step a, determining a polyurethane synthetic leather base cloth layer and a polyurethane synthetic leather bass layer, and bonding the base cloth layer and the bass layer;
step b, preparing polyurethane synthetic leather resin:
step b1, determining the preparation raw materials and the mixture ratio of the polyurethane synthetic leather resin: the polyurethane synthetic leather resin comprises the following raw materials in parts by weight: 80-160 parts of polylactic acid polyol, 80-160 parts of polyether polymeric polyol, 10-50 parts of chain extender, 80-120 parts of isocyanate, 750-900 parts of solvent and 0.03-0.06 part of organic bismuth catalyst;
step b2, preparing the polyurethane synthetic leather resin: adding polyether polymeric polyol, an auxiliary agent and one third of solvent into a reaction kettle, uniformly stirring, adding one half of isocyanate, and reacting for 20-30 min at 40-60 ℃; adding polylactic acid polyol and one half of chain extender into the reaction solution, and reacting for 20-30 min at 40-60 ℃ to obtain a prepolymer;
adding the remaining half of chain extender, the remaining half of isocyanate and one third of solvent into the prepolymer, reacting at 50-60 ℃, adding the remaining one third of solvent step by step along with the continuous increase of the system viscosity, adding an organic bismuth catalyst in the reaction process, controlling the final viscosity to be 180-250 Pa.S/25 ℃, and finally adding a terminator to obtain the polyurethane synthetic leather resin;
and c, coating the polyurethane synthetic leather resin on the Bass layer by a wet method, and forming the polylactic acid biodegradable polyurethane synthetic leather through the technological processes of condensation, washing, drying and veneering of the synthetic leather.
The present invention is further illustrated by the following specific examples and comparative examples, but it should be noted that the specific material ratios, process conditions, results, etc. described in the examples of the present invention are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered by the scope of the present invention.
Example one
A preparation method of polylactic acid biodegradable polyurethane synthetic leather comprises the following steps:
step a, determining a polyurethane synthetic leather base cloth layer and a polyurethane synthetic leather bass layer, and bonding the base cloth layer and the bass layer;
the polyurethane synthetic leather base cloth layer is a needle-punched non-woven fabric, wherein the ratio of polylactic acid fiber to polyamide fiber is 1: 4;
step b, preparing polyurethane synthetic leather resin:
step b1, determining the preparation raw materials and the mixture ratio of the polyurethane synthetic leather resin: the polyurethane synthetic leather resin comprises the following raw materials in parts by weight: 100 parts of polylactic acid dihydric alcohol, 120 parts of polytetrahydrofuran ether glycol, 12 parts of ethylene glycol, 85 parts of 4, 4' -diphenylmethane diisocyanate, 750 parts of dimethylformamide and 0.04 part of organic bismuth catalyst;
step b2, preparing the polyurethane synthetic leather resin: adding polytetrahydrofuran ether glycol, phosphoric acid and one third of dimethylformamide into a reaction kettle, uniformly stirring, adding one half of 4, 4' -diphenylmethane diisocyanate, and reacting for 20-30 min at 40-60 ℃; adding polylactic acid dihydric alcohol and half of glycol into the reaction solution, and reacting at 40-60 ℃ for 20-30 min to obtain a prepolymer;
adding the remaining half of ethylene glycol, the remaining half of 4, 4' -diphenylmethane diisocyanate and one third of dimethylformamide into the prepolymer, reacting at 50-60 ℃, adding the remaining one third of dimethylformamide step by step along with the continuous increase of the system viscosity, adding an organic bismuth catalyst in the reaction process, controlling the final viscosity to be 180-250 Pa.S/25 ℃, and finally adding methanol to obtain the polyurethane synthetic leather resin;
and c, coating the polyurethane synthetic leather resin on the Bass layer by a wet method, and forming the polylactic acid biodegradable polyurethane synthetic leather through the technological processes of condensation, washing, drying and veneering of the synthetic leather.
Example two
A preparation method of polylactic acid biodegradable polyurethane synthetic leather comprises the following steps:
step a, determining a polyurethane synthetic leather base cloth layer and a polyurethane synthetic leather bass layer, and bonding the base cloth layer and the bass layer;
the polyurethane synthetic leather base cloth layer is a needle-punched non-woven fabric, wherein the ratio of polylactic acid fiber to polyamide fiber is 1: 1;
step b, preparing polyurethane synthetic leather resin:
step b1, determining the preparation raw materials and the mixture ratio of the polyurethane synthetic leather resin: the polyurethane synthetic leather resin comprises the following raw materials in parts by weight: 100 parts of polylactic acid dihydric alcohol, 120 parts of polytetrahydrofuran ether glycol, 12 parts of ethylene glycol, 85 parts of 4, 4' -diphenylmethane diisocyanate, 750 parts of dimethylformamide and 0.04 part of organic bismuth catalyst;
step b2, preparing the polyurethane synthetic leather resin: adding polytetrahydrofuran ether glycol, phosphoric acid and one third of dimethylformamide into a reaction kettle, uniformly stirring, adding one half of 4, 4' -diphenylmethane diisocyanate, and reacting for 20-30 min at 40-60 ℃; adding polylactic acid dihydric alcohol and half of glycol into the reaction solution, and reacting at 40-60 ℃ for 20-30 min to obtain a prepolymer;
adding the remaining half of ethylene glycol, the remaining half of 4, 4' -diphenylmethane diisocyanate and one third of dimethylformamide into the prepolymer, reacting at 50-60 ℃, adding the remaining one third of dimethylformamide step by step along with the continuous increase of the system viscosity, adding an organic bismuth catalyst in the reaction process, controlling the final viscosity to be 180-250 Pa.S/25 ℃, and finally adding methanol to obtain the polyurethane synthetic leather resin;
and c, coating the polyurethane synthetic leather resin on the Bass layer by a wet method, and forming the polylactic acid biodegradable polyurethane synthetic leather through the technological processes of condensation, washing, drying and veneering of the synthetic leather.
EXAMPLE III
A preparation method of polylactic acid biodegradable polyurethane synthetic leather comprises the following steps:
step a, determining a polyurethane synthetic leather base cloth layer and a polyurethane synthetic leather bass layer, and bonding the base cloth layer and the bass layer;
the polyurethane synthetic leather base cloth layer is a needle-punched non-woven fabric, wherein the ratio of polylactic acid fiber to polyamide fiber is 4: 1;
step b, preparing polyurethane synthetic leather resin:
step b1, determining the preparation raw materials and the mixture ratio of the polyurethane synthetic leather resin: the polyurethane synthetic leather resin comprises the following raw materials in parts by weight: 100 parts of polylactic acid dihydric alcohol, 120 parts of polytetrahydrofuran ether glycol, 12 parts of ethylene glycol, 85 parts of 4, 4' -diphenylmethane diisocyanate, 750 parts of dimethylformamide and 0.04 part of organic bismuth catalyst;
step b2, preparing the polyurethane synthetic leather resin: adding polytetrahydrofuran ether glycol, phosphoric acid and one third of dimethylformamide into a reaction kettle, uniformly stirring, adding one half of 4, 4' -diphenylmethane diisocyanate, and reacting for 20-30 min at 40-60 ℃; adding polylactic acid dihydric alcohol and half of glycol into the reaction solution, and reacting at 40-60 ℃ for 20-30 min to obtain a prepolymer;
adding the remaining half of ethylene glycol, the remaining half of 4, 4' -diphenylmethane diisocyanate and one third of dimethylformamide into the prepolymer, reacting at 50-60 ℃, adding the remaining one third of dimethylformamide step by step along with the continuous increase of the system viscosity, adding an organic bismuth catalyst in the reaction process, controlling the final viscosity to be 180-250 Pa.S/25 ℃, and finally adding methanol to obtain the polyurethane synthetic leather resin;
and c, coating the polyurethane synthetic leather resin on the Bass layer by a wet method, and forming the polylactic acid biodegradable polyurethane synthetic leather through the technological processes of condensation, washing, drying and veneering of the synthetic leather.
Example four
A preparation method of polylactic acid biodegradable polyurethane synthetic leather comprises the following steps:
step a, determining a polyurethane synthetic leather base cloth layer and a polyurethane synthetic leather bass layer, and bonding the base cloth layer and the bass layer;
the polyurethane synthetic leather base cloth layer is a needle-punched non-woven fabric, wherein the ratio of polylactic acid fiber to polyamide fiber is 1: 1;
step b, preparing polyurethane synthetic leather resin:
step b1, determining the preparation raw materials and the mixture ratio of the polyurethane synthetic leather resin: the polyurethane synthetic leather resin comprises the following raw materials in parts by weight: 160 parts of polylactic acid dihydric alcohol, 80 parts of polytetrahydrofuran ether glycol, 12 parts of ethylene glycol, 85 parts of 4, 4' -diphenylmethane diisocyanate, 750 parts of dimethylformamide and 0.04 part of organic bismuth catalyst;
step b2, preparing the polyurethane synthetic leather resin: adding polytetrahydrofuran ether glycol, phosphoric acid and one third of dimethylformamide into a reaction kettle, uniformly stirring, adding one half of 4, 4' -diphenylmethane diisocyanate, and reacting for 20-30 min at 40-60 ℃; adding polylactic acid dihydric alcohol and half of glycol into the reaction solution, and reacting at 40-60 ℃ for 20-30 min to obtain a prepolymer;
adding the remaining half of ethylene glycol, the remaining half of 4, 4' -diphenylmethane diisocyanate and one third of dimethylformamide into the prepolymer, reacting at 50-60 ℃, adding the remaining one third of dimethylformamide step by step along with the continuous increase of the system viscosity, adding an organic bismuth catalyst in the reaction process, controlling the final viscosity to be 180-250 Pa.S/25 ℃, and finally adding methanol to obtain the polyurethane synthetic leather resin;
and c, coating the polyurethane synthetic leather resin on the Bass layer by a wet method, and forming the polylactic acid biodegradable polyurethane synthetic leather through the technological processes of condensation, washing, drying and veneering of the synthetic leather.
EXAMPLE five
A preparation method of polylactic acid biodegradable polyurethane synthetic leather comprises the following steps:
step a, determining a polyurethane synthetic leather base cloth layer and a polyurethane synthetic leather bass layer, and bonding the base cloth layer and the bass layer;
the polyurethane synthetic leather base cloth layer is a needle-punched non-woven fabric, wherein the ratio of polylactic acid fiber to polyamide fiber is 1: 1;
step b, preparing polyurethane synthetic leather resin:
step b1, determining the preparation raw materials and the mixture ratio of the polyurethane synthetic leather resin: the polyurethane synthetic leather resin comprises the following raw materials in parts by weight: 80 parts of polylactic acid dihydric alcohol, 160 parts of polytetrahydrofuran ether glycol, 12 parts of ethylene glycol, 85 parts of 4, 4' -diphenylmethane diisocyanate, 750 parts of dimethylformamide and 0.04 part of organic bismuth catalyst;
step b2, preparing the polyurethane synthetic leather resin: adding polytetrahydrofuran ether glycol, phosphoric acid and one third of dimethylformamide into a reaction kettle, uniformly stirring, adding one half of 4, 4' -diphenylmethane diisocyanate, and reacting for 20-30 min at 40-60 ℃; adding polylactic acid dihydric alcohol and half of glycol into the reaction solution, and reacting at 40-60 ℃ for 20-30 min to obtain a prepolymer;
adding the remaining half of ethylene glycol, the remaining half of 4, 4' -diphenylmethane diisocyanate and one third of dimethylformamide into the prepolymer, reacting at 50-60 ℃, adding the remaining one third of dimethylformamide step by step along with the continuous increase of the system viscosity, adding an organic bismuth catalyst in the reaction process, controlling the final viscosity to be 180-250 Pa.S/25 ℃, and finally adding methanol to obtain the polyurethane synthetic leather resin;
and c, coating the polyurethane synthetic leather resin on the Bass layer by a wet method, and forming the polylactic acid biodegradable polyurethane synthetic leather through the technological processes of condensation, washing, drying and veneering of the synthetic leather.
Comparative example 1
A preparation method of polylactic acid biodegradable polyurethane synthetic leather comprises the following steps:
step a, determining a polyurethane synthetic leather base cloth layer and a polyurethane synthetic leather bass layer, and bonding the base cloth layer and the bass layer;
the polyurethane synthetic leather base cloth layer is a needle-punched non-woven fabric, wherein the ratio of polylactic acid fiber to polyamide fiber is 1: 0;
step b, preparing polyurethane synthetic leather resin:
step b1, determining the preparation raw materials and the mixture ratio of the polyurethane synthetic leather resin: the polyurethane synthetic leather resin comprises the following raw materials in parts by weight: 100 parts of polylactic acid dihydric alcohol, 120 parts of polytetrahydrofuran ether glycol, 12 parts of ethylene glycol, 85 parts of 4, 4' -diphenylmethane diisocyanate, 750 parts of dimethylformamide and 0.04 part of organic bismuth catalyst;
step b2, preparing the polyurethane synthetic leather resin: adding polytetrahydrofuran ether glycol, phosphoric acid and one third of dimethylformamide into a reaction kettle, uniformly stirring, adding one half of 4, 4' -diphenylmethane diisocyanate, and reacting for 20-30 min at 40-60 ℃; adding polylactic acid dihydric alcohol and half of glycol into the reaction solution, and reacting at 40-60 ℃ for 20-30 min to obtain a prepolymer;
adding the remaining half of ethylene glycol, the remaining half of 4, 4' -diphenylmethane diisocyanate and one third of dimethylformamide into the prepolymer, reacting at 50-60 ℃, adding the remaining one third of dimethylformamide step by step along with the continuous increase of the system viscosity, adding an organic bismuth catalyst in the reaction process, controlling the final viscosity to be 180-250 Pa.S/25 ℃, and finally adding methanol to obtain the polyurethane synthetic leather resin;
and c, coating the polyurethane synthetic leather resin on the Bass layer by a wet method, and forming the polylactic acid biodegradable polyurethane synthetic leather through the technological processes of condensation, washing, drying and veneering of the synthetic leather.
Comparative example No. two
A preparation method of polylactic acid biodegradable polyurethane synthetic leather comprises the following steps:
step a, determining a polyurethane synthetic leather base cloth layer and a polyurethane synthetic leather bass layer, and bonding the base cloth layer and the bass layer;
the polyurethane synthetic leather base cloth layer is a needle-punched non-woven fabric, wherein the ratio of polylactic acid fiber to polyamide fiber is 1: 1;
step b, preparing polyurethane synthetic leather resin:
step b1, determining the preparation raw materials and the mixture ratio of the polyurethane synthetic leather resin: the polyurethane synthetic leather resin comprises the following raw materials in parts by weight: 240 parts of polylactic acid dihydric alcohol, 0 part of polytetrahydrofuran ether glycol, 12 parts of ethylene glycol, 85 parts of 4, 4' -diphenylmethane diisocyanate, 750 parts of dimethylformamide and 0.04 part of organic bismuth catalyst;
step b2, preparing the polyurethane synthetic leather resin: adding phosphoric acid and one third of dimethylformamide into a reaction kettle, uniformly stirring, adding one half of 4, 4' -diphenylmethane diisocyanate, and reacting for 20-30 min at 40-60 ℃; adding polylactic acid dihydric alcohol and half of glycol into the reaction solution, and reacting at 40-60 ℃ for 20-30 min to obtain a prepolymer;
adding the remaining half of ethylene glycol, the remaining half of 4, 4' -diphenylmethane diisocyanate and one third of dimethylformamide into the prepolymer, reacting at 50-60 ℃, adding the remaining one third of dimethylformamide step by step along with the continuous increase of the system viscosity, adding an organic bismuth catalyst in the reaction process, controlling the final viscosity to be 180-250 Pa.S/25 ℃, and finally adding methanol to obtain the polyurethane synthetic leather resin;
and c, coating the polyurethane synthetic leather resin on the Bass layer by a wet method, and forming the polylactic acid biodegradable polyurethane synthetic leather through the technological processes of condensation, washing, drying and veneering of the synthetic leather.
Comparative example No. three
A preparation method of polylactic acid biodegradable polyurethane synthetic leather comprises the following steps:
step a, determining a polyurethane synthetic leather base cloth layer and a polyurethane synthetic leather bass layer, and bonding the base cloth layer and the bass layer;
the polyurethane synthetic leather base cloth layer is a needle-punched non-woven fabric, wherein the ratio of polylactic acid fiber to polyamide fiber is 1: 1;
step b, preparing polyurethane synthetic leather resin:
step b1, determining the preparation raw materials and the mixture ratio of the polyurethane synthetic leather resin: the polyurethane synthetic leather resin comprises the following raw materials in parts by weight: 0 part of polylactic acid dihydric alcohol, 240 parts of polytetrahydrofuran ether glycol, 12 parts of ethylene glycol, 85 parts of 4, 4' -diphenylmethane diisocyanate, 750 parts of dimethylformamide and 0.04 part of organic bismuth catalyst;
step b2, preparing the polyurethane synthetic leather resin: adding polytetrahydrofuran ether glycol, phosphoric acid and one third of dimethylformamide into a reaction kettle, uniformly stirring, adding one half of 4, 4' -diphenylmethane diisocyanate, and reacting for 20-30 min at 40-60 ℃; then, adding half of ethylene glycol into the reaction liquid, and reacting for 20-30 min at 40-60 ℃ to obtain a prepolymer;
adding the remaining half of ethylene glycol, the remaining half of 4, 4' -diphenylmethane diisocyanate and one third of dimethylformamide into the prepolymer, reacting at 50-60 ℃, adding the remaining one third of dimethylformamide step by step along with the continuous increase of the system viscosity, adding an organic bismuth catalyst in the reaction process, controlling the final viscosity to be 180-250 Pa.S/25 ℃, and finally adding methanol to obtain the polyurethane synthetic leather resin;
and c, coating the polyurethane synthetic leather resin on the Bass layer by a wet method, and forming the polylactic acid biodegradable polyurethane synthetic leather through the technological processes of condensation, washing, drying and veneering of the synthetic leather.
Physical properties of the polyurethane synthetic leather prepared in the examples and the comparative examples and the commercially available common polyurethane synthetic leather are respectively compared as follows;
wherein: the alkali liquor soaking is as follows: 10% NaOH, at 25 ℃ for 24 hours.
Biodegradability: under the condition of compost, the temperature is 58 ℃, the humidity is 98 percent and the microorganism condition is adopted for 2 months, the decomposition degree of the waste is recorded, and the 1-10 biodegradability is sequentially strengthened.
The data show that the biodegradability of the polylactic acid material can be obviously improved when the polylactic acid material is introduced into the polyurethane synthetic leather, but the alkali resistance of the polylactic acid material is reduced due to the physical property characteristics of the polylactic acid material, but the physical property of the polylactic acid material can be improved when the blended chinlon component is introduced into the base fabric and the polylactic acid polyol and the polytetrahydrofuran are introduced into the processing resin, and meanwhile, the natural durability of the shoe material can be met
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 (10)
1. The polylactic acid biodegradable polyurethane synthetic leather is characterized by comprising a base cloth layer, a polyurethane synthetic leather base layer and a polyurethane synthetic leather surface layer;
the polyurethane synthetic leather surface layer is prepared by coating and drying polyurethane synthetic leather resin.
2. A polylactic acid biodegradable polyurethane synthetic leather according to claim 1, wherein said polyurethane synthetic leather resin is polylactic acid/polyurethane resin.
3. The polylactic acid biodegradable polyurethane synthetic leather according to claim 2, wherein the polylactic acid/polyurethane resin comprises the following components in component ratio: 10 to 25 percent of polylactic acid polyol, 5 to 15 percent of polyether polymeric polyol, 2 to 20 percent of micromolecular chain extender, 10 to 20 percent of isocyanate, 70 to 80 percent of solvent and 0.001 to 0.005 percent of organic bismuth catalyst.
4. The polylactic acid biodegradable polyurethane synthetic leather according to claim 3, wherein the polylactic acid polyol is polylactic acid diol; the polyether polymeric polyalcohol is polytetrahydrofuran ether glycol; the chain extender is a dihydric alcohol chain extender; the isocyanate is 4, 4' -diphenylmethane diisocyanate; the organic bismuth catalyst is one or more of butyl bismuth and ethyl bismuth; the solvent is diphenylmethane diisocyanate.
5. A polylactic acid biodegradable polyurethane synthetic leather according to claim 4, wherein the polylactic acid polyol and the polyether polymer polyol form a mixed polyol, and the molar ratio of the mixed polyol to the glycol chain extender is 1: 1.4 to 1.8; the ratio of the mixed polyol to the 4, 4' -diphenylmethane diisocyanate is (calculated by the cyanide-to-hydroxyl ratio) 1.2-1.4: 1.
6. the polylactic acid biodegradable polyurethane synthetic leather according to claim 3, wherein the polylactic acid/polyurethane resin comprises the following components in component ratio: 10-25% of polylactic acid polyol, 5-15% of polyether polymeric polyol, 2-10% of micromolecular chain extender, 10-20% of isocyanate, 70% of solvent and 0.001-0.005% of organic bismuth catalyst.
7. The polylactic acid biodegradable polyurethane synthetic leather according to claim 1, wherein the base fabric layer is prepared by co-spinning polylactic acid fiber/polyamide fiber; the base cloth layer is one or a plurality of composite of non-woven fabrics, woven fabrics and knitted fabrics.
8. A method for preparing polylactic acid biodegradable polyurethane synthetic leather according to any one of claims 1 to 7, wherein the method comprises the following steps:
step a, determining a polyurethane synthetic leather base cloth layer and a polyurethane synthetic leather bass layer, and bonding the base cloth layer and the bass layer;
step b, preparing polyurethane synthetic leather resin:
step b1, determining the preparation raw materials and the mixture ratio of the polyurethane synthetic leather resin: the polyurethane synthetic leather resin comprises the following raw materials in parts by weight: 80-160 parts of polylactic acid polyol, 80-160 parts of polyether polymeric polyol, 10-50 parts of chain extender, 80-120 parts of isocyanate, 750-900 parts of solvent and 0.03-0.06 part of organic bismuth catalyst;
step b2, preparing the polyurethane synthetic leather resin: adding polyether polymeric polyol, an auxiliary agent and one third of solvent into a reaction kettle, uniformly stirring, adding one half of isocyanate, and reacting for 20-30 min at 40-60 ℃; adding polylactic acid polyol and one half of chain extender into the reaction solution, and reacting for 20-30 min at 40-60 ℃ to obtain a prepolymer;
adding the remaining half of chain extender, the remaining half of isocyanate and one third of solvent into the prepolymer, reacting at 50-60 ℃, adding the remaining one third of solvent step by step along with the continuous increase of the system viscosity, adding an organic bismuth catalyst in the reaction process, controlling the final viscosity to be 180-250 Pa.S/25 ℃, and finally adding a terminator to obtain the polyurethane synthetic leather resin;
and c, coating the polyurethane synthetic leather resin on the Bass layer by a wet method, and forming the polylactic acid biodegradable polyurethane synthetic leather through the technological processes of condensation, washing, drying and veneering of the synthetic leather.
9. The method for preparing polylactic acid biodegradable polyurethane synthetic leather according to claim 8, wherein the auxiliary agent is phosphoric acid; the terminator is methanol.
10. The method for preparing polylactic acid biodegradable polyurethane synthetic leather according to claim 8, wherein the number average molecular weight of the polyether polymer polyol is 1000-2000 g/mol.
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