CN112724654B - Wet-process polyurethane resin and preparation method and application thereof - Google Patents
Wet-process polyurethane resin and preparation method and application thereof Download PDFInfo
- Publication number
- CN112724654B CN112724654B CN202011583471.1A CN202011583471A CN112724654B CN 112724654 B CN112724654 B CN 112724654B CN 202011583471 A CN202011583471 A CN 202011583471A CN 112724654 B CN112724654 B CN 112724654B
- Authority
- CN
- China
- Prior art keywords
- component
- wet
- polyurethane resin
- diphenylmethane
- diisocyanate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/06—Polyurethanes from polyesters
-
- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
- C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
- C08G18/4213—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from terephthalic acid and dialcohols
-
- 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
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2101/00—Manufacture of cellular products
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/14—Applications used for foams
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention provides wet-process polyurethane resin and a preparation method and application thereof, wherein the wet-process polyurethane resin comprises three components A, B and C, and the preparation raw material of the component A comprises the following components: diphenylmethane-4, 4' -diisocyanate, polyester diol, a small molecular chain extender, N-dimethylformamide and alkyd resin; the preparation raw materials of the component B comprise the following components: diphenylmethane-4, 4' -diisocyanate, polyester diol, a small molecular chain extender and N, N-dimethylformamide; the preparation raw materials of the component C comprise the following components: polyvinylpyrrolidone and N, N-dimethylformamide. The wet-process bass of the adsorption pad prepared from the wet-process polyurethane resin has the characteristics of good water washability, good wear resistance, strong surface astringency and uniform cells, and can be used for suede adsorption pads.
Description
Technical Field
The invention belongs to the field of polyurethane resin preparation, relates to wet-process polyurethane resin and a preparation method and application thereof, and particularly relates to wet-process polyurethane resin for a suede adsorption pad and a preparation method and application thereof.
Background
With the development of synthetic leather technology, the application field of synthetic leather materials is more and more extensive nowadays. Due to the increasing demand of people, the high-tech digital, intelligent and networked new technology 3C products are in a wide range, and a suede adsorption pad product is produced in the field of synthetic leather and widely used as a base material of a polishing screen in the electronic industry. The suede adsorption pad is an essential component playing an important role in the chemical mechanical polishing process. In general, the adsorption pad may be made of wet urethane resin, and has grooves on the surface thereof for the bulk flow of the polishing solution and micro-pores for assisting the fine flow of the polishing solution.
The conventional adsorption pad is a technology for forming a pore structure using an inert gas or a volatile liquid-phase foaming agent, and it is difficult to precisely control the diameter of the pores, particularly to generate the pores having a uniform structure, since it is inevitable to process an uncontrollable gas phase. Compared with the traditional foamed polyurethane adsorption pad, the polyurethane adsorption pad prepared by the wet process has the advantages of strong processability, stable process, good batch stability, high production efficiency and lower comprehensive cost.
CN201810219329.5 discloses a highly astringent wet-process polyurethane resin and a preparation method thereof, the highly astringent wet-process polyurethane resin comprises two components of a and B, wherein the component a comprises polyoxypropylene glycol and diphenylmethane-4, 4' -diisocyanate; the component B comprises polytetrahydrofuran ether glycol, poly adipic acid polyester diol, polyethylene glycol oxide, ethylene glycol, diphenylmethane-4, 4' -diisocyanate and N, N-dimethylformamide. The high-astringency wet-process polyurethane resin prepared by the method has the characteristics of good film forming property, high strength, good astringency and good water absorption, but micropores with uniform structures cannot be generated.
Therefore, in the art, it is desired to develop a wet polyurethane resin for a suede absorbent pad which has good washability, good abrasion resistance, good surface astringency, and can produce micropores having a uniform structure.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a wet-process polyurethane resin and a preparation method and application thereof, and particularly provides the wet-process polyurethane resin for a suede adsorption pad and the preparation method and application thereof. The wet-process base made of the wet-process polyurethane resin has the characteristics of good washing performance, good wear resistance, good surface astringency and uniform foam pores.
In order to achieve the purpose, the invention adopts the following technical scheme:
on one hand, the invention provides a wet-process polyurethane resin which comprises three components of A, B and C, wherein the preparation raw materials of the component A comprise the following components in percentage by weight:
the preparation raw materials of the component B comprise the following components in percentage by weight:
the preparation raw materials of the component C comprise the following components in percentage by weight:
7 to 8.6 percent of polyvinylpyrrolidone;
91.4 to 93 percent of N, N-dimethylformamide.
In the invention, the addition of the alkyd resin in the component A can improve the film-forming property of the polyurethane resin, and can improve the water-washability and surface tack and astringency of the wet base made of the polyurethane resin; the polyvinyl pyrrolidone molecule has both hydrophilic group and lipophilic group, so that the polyvinyl pyrrolidone molecule can interact with a plurality of solvents, and the polyvinyl pyrrolidone molecule can be dissolved in water and organic solvents such as alcohol, carboxylic acid, amine, halogenated hydrocarbon and the like.
In the present invention, the amount of diphenylmethane-4, 4' -diisocyanate used in the preparation of the a component may be 6.7% to 7.9%, for example, 6.7%, 7%, 7.5%, 7.9%, or the like.
In the present invention, the amount of the polyester diol used in the raw material for preparing the component a may be 14.4% to 17.5%, for example, 14.4%, 15.5%, 16%, 17%, or 17.5%.
In the present invention, in the raw material for preparing the component a, the amount of the small molecule chain extender may be 1.4% to 2.5%, for example, 1.4%, 2%, or 2.5%.
In the present invention, in the raw material for preparing the component a, the amount of N, N-dimethylformamide may be 70% to 73%, for example, 70%, 71%, 72%, 73%, etc.
In the present invention, the alkyd resin may be used in an amount of 3% to 5%, for example, 3%, 4%, or 5% in the raw material for preparing the a component.
In the present invention, the amount of diphenylmethane-4, 4' -diisocyanate used in the preparation of the B component may be 6.5% to 7.5%, for example, 6.5%, 7%, 7.5%, or the like.
In the present invention, the amount of the polyester diol used in the raw material for preparing the component B may be 19.1% to 22.6%, for example, 19.1%, 20%, 20.5%, 21%, 22.6%, etc.
In the present invention, in the raw material for preparing the B component, the small molecule chain extender may be used in an amount of 0.9% to 2.3%, for example, 0.9%, 1.5%, 2%, or 2.3%.
In the present invention, the amount of N, N-dimethylformamide used in the raw material for preparing the B component may be 70% to 73%, for example, 70%, 71%, 72%, 73%, etc.
In the present invention, in the raw material for preparing the C component, the polyvinylpyrrolidone may be used in an amount of 7% to 8.6%, for example, 7%, 7.5%, 8%, 8.6%, or the like.
In the present invention, in the raw material for preparing the C component, N-dimethylformamide may be used in an amount of 91.4% to 93%, for example, 91.4%, 92%, 92.5%, 93%, or the like.
In the present invention, the polyester diol in the component A is a polyester diol having a number average molecular weight of 3000 to 4000g/mol (e.g., 3000g/mol, 3500g/mol, 4000g/mol, etc.).
Preferably, the polyester diol in the A component is selected from any one of or a combination of at least two of poly (1, 4-butylene adipate) glycol, poly (ethylene butylene adipate) glycol, poly (diethylene glycol terephthalate) glycol or poly (ethylene glycol terephthalate) glycol having a number average molecular weight of 3000 to 4000g/mol (e.g., 3000g/mol, 3500g/mol, 4000g/mol, etc.). Combinations of the at least two, for example, poly-1, 4-butylene adipate glycol and poly-ethylene glycol butylene adipate glycol, poly-diethylene glycol butylene adipate glycol and poly-diethylene glycol terephthalate glycol, and poly-ethylene glycol terephthalate glycol, and the like.
In the invention, the small molecular chain extenders in the A component and the B component are independently ethylene glycol and/or 1, 4-butanediol.
In the invention, the alkyd resin is castor oil modified short oil alkyd resin.
In the present invention, the polyester diol in the component B is a polyester diol having a number average molecular weight of 2000 to 4000g/mol (e.g., 2000g/mol, 3000g/mol, 4000g/mol, etc.).
Preferably, the polyester diol in the B component is any one of or a combination of at least two of poly (1, 4-butylene adipate) glycol, poly (ethylene glycol butylene adipate) glycol, or poly (diethylene glycol butylene adipate) glycol, having a number average molecular weight in the range of 2000 to 4000g/mol (e.g., 2000g/mol, 3000g/mol, 4000g/mol, etc.). Combinations of the at least two, such as poly-1, 4-butylene adipate glycol and poly-ethylene glycol butylene adipate glycol, poly-1, 4-butylene adipate glycol and poly-diethylene glycol butylene adipate glycol, and the like.
In the present invention, the polyvinylpyrrolidone is a polyvinylpyrrolidone having a K value of 30 to 90 (e.g., 30, 60, or 90, etc.).
In the present invention, the weight ratio of the a component to the B component is 2.5; the C component accounts for 3-5 percent of the total weight of the A, B and C components, such as 3 percent, 4 percent or 5 percent.
In another aspect, the present invention provides a method for preparing the wet process polyurethane resin as described above, comprising the steps of:
(1) Preparing a component A: carrying out prepolymerization reaction on polyester diol, part of diphenylmethane-4, 4' -diisocyanate and part of N, N-dimethylformamide to obtain a prepolymer; adding a small molecular chain extender and the rest of N, N-dimethylformamide into the prepolymer, uniformly stirring, adding part of diphenylmethane-4, 4 '-diisocyanate for reaction, adding the rest of diphenylmethane-4, 4' -diisocyanate, reacting until the viscosity of a reaction solution reaches 200-260 Pa.s (such as 200 Pa.s, 240 Pa.s or 260 Pa.s) at 25 ℃, adding alkyd resin, and stirring to obtain a component A;
(2) B, preparation of a component: uniformly mixing polyester diol, a small-molecule chain extender and N, N-dimethylformamide, adding part of diphenylmethane-4, 4 '-diisocyanate into the mixture to react, then adding the rest diphenylmethane-4, 4' -diisocyanate, and reacting until the viscosity of a reaction solution reaches 50-80 Pa.s (such as 50 Pa.s, 60 Pa.s, 70 Pa.s or 80 Pa.s) at 25 ℃ to obtain a component B;
(3) C, preparation of a component: adding polyvinylpyrrolidone into N, N-dimethylformamide, and uniformly stirring to obtain a component C;
(4) And mixing the component A, the component B and the component C to obtain the wet-process polyurethane resin.
In the invention, the component A is synthesized by a prepolymerization method, so that the molecular regularity of a high polymer material is improved, the solidification speed and the wear resistance of the polyurethane resin are improved, and the good washing performance of the polyurethane resin can be ensured; the invention selects the polyurethane resin B component synthesized by a one-step synthesis process and the polyurethane resin A component synthesized by a prepolymerization process for compounding and blending, and aims to provide a component with a relatively large difference in solidification speed, so that the surface solidification speed and the internal solidification speed of the resin are closer in the solidification process, and a more uniform cell structure is favorably formed.
Preferably, the partial diphenylmethane-4, 4' -diisocyanate in step (1) is in an amount such that the molar ratio of isocyanate groups to hydroxyl groups in the reaction solution is from 0.82.
Preferably, the portion of N, N-dimethylformamide in step (1) is in an amount such that the solid content in the prepolymerization reaction solution is 60 to 70% (e.g., 60%, 65%, 70%, etc.).
Preferably, the temperature of the prepolymerization reaction in the step (1) is 60-80 ℃ (for example, 60 ℃, 70 ℃ or 80 ℃, etc.), and the time of the prepolymerization reaction is 1-4 h, for example, 1h, 2h, 3h or 4h, etc.
Preferably, the viscosity of the reaction solution after the prepolymerization in the step (1) is 1 to 4 pas, for example, 1 pas, 2 pas, 3 pas or 4 pas, at 60 ℃.
Preferably, the portion of diphenylmethane-4, 4' -diisocyanate charged in step (1) is in an amount such that the molar ratio of isocyanate groups to hydroxyl groups in the reaction liquid is from 0.93 to 1.96 (e.g., 0.93, 1, 0.95, 1 or 0.96.
Preferably, the temperature for charging part of the diphenylmethane-4, 4' -diisocyanate to react in step (1) is 60 to 80 ℃ (for example 60 ℃, 70 ℃ or 80 ℃ and the like), and the reaction time is 1 to 4 hours, for example 1 hour, 2 hours, 3 hours or 4 hours and the like.
Preferably, the mixing time after adding the alkyd resin in step (1) is 1-2 h, such as 1h, 1.5h or 2h.
Preferably, the partial diphenylmethane-4, 4' -diisocyanate in step (2) is in an amount such that the molar ratio of isocyanate groups to hydroxyl groups in the reaction solution is from 0.93 to 1 to 0.96 (e.g., 0.93, 1, 0.95, 1 or 0.96.
Preferably, the temperature for adding part of the diphenylmethane-4, 4' -diisocyanate to carry out the reaction in the step (2) is 60-80 ℃ (for example 60 ℃, 70 ℃ or 80 ℃ and the like), and the reaction time is 2-4 h, for example 2h, 3h or 4h and the like.
Preferably, the stirring time in step (3) is 2 to 4 hours, such as 2 hours, 3 hours, 4 hours and the like.
Preferably, the mixing temperature in step (4) is 60-80 ℃ (e.g. 60 ℃, 70 ℃ or 80 ℃, etc.), and the mixing time is 3-5 h, e.g. 3h, 4h or 5h, etc.
In another aspect, the invention provides an application of the wet-process polyurethane resin in preparation of a suede adsorption pad.
Compared with the prior art, the invention has the following beneficial effects:
(1) The addition of the alkyd resin in the component A can improve the film forming property of the polyurethane resin, and can improve the water washing property and the surface sticky and unsmooth feeling of wet base made of the polyurethane resin; the component A adopts a synthesis process of a prepolymerization method, so that the molecular regularity of a high polymer material can be improved, the solidification speed and the wear resistance of the polyurethane resin can be improved, and the good washing performance of the polyurethane resin can be ensured;
(2) The addition of polyvinylpyrrolidone in the component C can improve the hydrophilicity of the polyurethane resin, so that the polyurethane resin has larger foam pores formed in the solidification process and better water washing property;
(3) The component B of the polyurethane resin synthesized by the one-step synthesis process and the component A synthesized by the prepolymerization process are compounded and blended, so that a component with a relatively large difference in solidification speed can be provided, the surface solidification speed and the internal solidification speed of the polyurethane resin are closer in the solidification process, and a more uniform cell structure is favorably formed.
(4) The blending scheme of the components A, B and C integrates the crystallinity of the resin, thereby not only ensuring the water washability (level 1), the wear resistance (weight loss rate after wear resistance: 1.9-2.6%) and the surface touch (strong surface astringency) of the resin, but also forming a more uniform cell structure in the solidification process. The wet adsorption pad base prepared from the polyurethane resin has uniform size of the foam hole, so that the liquid crystal screen is not easily scratched when the surface polishing solution flows to polish the liquid crystal screen in a large quantity.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitation of the present invention.
Example 1
In this embodiment, a wet process polyurethane resin is provided, where the wet process polyurethane resin includes three components a, B, and C, and the preparation raw materials of the component a include, by weight:
the preparation raw materials of the component B comprise the following components in percentage by weight:
the preparation raw materials of the component C comprise the following components in percentage by weight:
8.3% of polyvinylpyrrolidone (K value of 30);
91.7 percent of N, N-dimethylformamide.
Wherein the number average molecular weight of the poly adipic acid-1, 4-butanediol ester diol in the component A is 3000g/mol, and the number average molecular weight of the poly adipic acid-1, 4-butanediol ester diol in the component B is 2000g/mol; the weight ratio of the component A to the component B is 2.7; the component C accounts for 5 percent of the total weight of the components A, B and C.
The preparation method comprises the following steps:
(1) Preparation of a component A: carrying out prepolymerization reaction on poly (1, 4-butanediol adipate) glycol, part of diphenylmethane-4, 4' -diisocyanate and part of N, N-dimethylformamide to ensure that the molar ratio of isocyanate groups to hydroxyl groups in a reaction solution is 0.82 and the solid content of the reaction solution is 60%, and reacting for 1h at 60 ℃ until the viscosity of the reaction solution reaches 4 Pa.s at 60 ℃ to finish the reaction to obtain a prepolymer; adding ethylene glycol and the rest of N, N-dimethylformamide into the prepolymer, uniformly stirring, adding part of diphenylmethane-4, 4 '-diisocyanate to react, enabling the molar ratio of isocyanate groups to hydroxyl groups in the reaction liquid to be 0.93, reacting at 60 ℃ for 1 hour, then adding the rest of diphenylmethane-4, 4' -diisocyanate, reacting until the viscosity of the reaction liquid reaches 250 Pa.s at 25 ℃, then adding alkyd resin, and stirring for 2 hours to obtain a component A;
(2) B, preparation of a component: uniformly mixing poly (1, 4-butanediol adipate) glycol, ethylene glycol and N, N-dimethylformamide, adding part of diphenylmethane-4, 4 '-diisocyanate into the mixture to react, so that the molar ratio of isocyanate groups to hydroxyl groups in the reaction liquid is 0.94 to react for 3 hours at 60 ℃, then adding the rest diphenylmethane-4, 4' -diisocyanate, and reacting until the viscosity of the reaction liquid reaches 60 Pa.s at 25 ℃ to obtain a component B;
(3) C, preparation of a component: adding polyvinylpyrrolidone into N, N-dimethylformamide, and stirring for 3h to obtain a component C;
(4) And mixing the component A, the component B and the component C at 60 ℃ for 4h to obtain the wet-process polyurethane resin.
Example 2
In this embodiment, a wet process polyurethane resin is provided, where the wet process polyurethane resin includes three components, i.e., a component a, a component B, and a component C, and the preparation raw material of the component a includes the following components by weight percent:
the component B comprises the following raw materials in percentage by weight:
the preparation raw materials of the component C comprise the following components in percentage by weight:
7.5 percent of polyvinylpyrrolidone (K value is 60);
92.5% of N, N-dimethylformamide.
Wherein the number average molecular weight of the poly (diethylene glycol butylene adipate) glycol in the component A is 4000g/mol, and the number average molecular weight of the poly (ethylene glycol butylene adipate) glycol in the component B is 3000g/mol; the weight ratio of the component A to the component B is 2.5; the component C accounts for 5 percent of the total weight of the components A, B and C.
The preparation method comprises the following steps:
(1) Preparation of a component A: carrying out prepolymerization reaction on polyethylene glycol adipate butanediol, part of diphenylmethane-4, 4' -diisocyanate and part of N, N-dimethylformamide to ensure that the molar ratio of isocyanate groups to hydroxyl groups in a reaction solution is 0.83 to 1 and the solid content of the reaction solution is 70%, reacting for 2h at 70 ℃ until the viscosity of the reaction solution reaches 1 Pa.s at 60 ℃, and finishing the reaction to obtain a prepolymer; adding 1, 4-butanediol and the rest of N, N-dimethylformamide into the prepolymer, uniformly stirring, adding part of diphenylmethane-4, 4 '-diisocyanate to react to ensure that the molar ratio of isocyanate groups to hydroxyl groups in the reaction liquid is 0.96 to 1, reacting at 75 ℃ for 2 hours, then adding the rest of diphenylmethane-4, 4' -diisocyanate, reacting until the viscosity of the reaction liquid reaches 200Pa s at 25 ℃, then adding alkyd resin, and stirring for 1.5 hours to obtain a component A;
(2) B, preparation of a component: uniformly mixing polyethylene glycol butanediol adipate, glycol and N, N-dimethylformamide, adding part of diphenylmethane-4, 4' -diisocyanate into the mixture to react, so that the molar ratio of isocyanate groups to hydroxyl groups in reaction liquid is 0.96;
(3) Preparing a component C: adding polyvinylpyrrolidone into N, N-dimethylformamide, and stirring for 4h to obtain a component C;
(4) And mixing the component A, the component B and the component C at 70 ℃ for 5h to obtain the wet-process polyurethane resin.
Example 3
In this embodiment, a wet process polyurethane resin is provided, where the wet process polyurethane resin includes three components a, B, and C, and the preparation raw materials of the component a include, by weight:
the preparation raw materials of the component B comprise the following components in percentage by weight:
the preparation raw materials of the component C comprise the following components in percentage by weight:
polyvinylpyrrolidone (K value 90) 7%;
93% of N, N-dimethylformamide.
Wherein the number average molecular weight of the polyethylene glycol butanediol adipate in the component A is 3000g/mol, and the number average molecular weight of the polyethylene glycol butanediol adipate in the component B is 3000g/mol; the weight ratio of the component A to the component B is 3.7; the component C accounts for 3 percent of the total weight of the components A, B and C.
The preparation method comprises the following steps:
(1) Preparing a component A: carrying out prepolymerization reaction on polyethylene glycol butanediol adipate, part of diphenylmethane-4, 4' -diisocyanate and part of N, N-dimethylformamide to ensure that the molar ratio of isocyanate groups to hydroxyl groups in a reaction solution is 0.84 and the solid content of the reaction solution is 65%, reacting for 3h at 80 ℃ until the viscosity of the reaction solution reaches 2 Pa.s at 60 ℃, and finishing the reaction to obtain a prepolymer; adding ethylene glycol, 1, 4-butanediol and the rest of N, N-dimethylformamide into the prepolymer, stirring uniformly, adding part of diphenylmethane-4, 4 '-diisocyanate to react, so that the molar ratio of isocyanate groups to hydroxyl groups in the reaction liquid is 0.95 to react for 2 hours at 80 ℃, then adding the rest of diphenylmethane-4, 4' -diisocyanate, reacting until the viscosity of the reaction liquid reaches 240 Pa.s at 25 ℃, then adding alkyd resin, and stirring for 1 hour to obtain a component A;
(2) B, preparation of a component: uniformly mixing polydiethylene glycol adipate butanediol, glycol, 1, 4-butanediol and N, N-dimethylformamide, adding part of diphenylmethane-4, 4 '-diisocyanate into the mixture to react, so that the molar ratio of isocyanate groups to hydroxyl groups in the reaction liquid is 0.95 to react for 2 hours at 70 ℃, then adding the rest diphenylmethane-4, 4' -diisocyanate, and reacting until the viscosity of the reaction liquid reaches 80 Pa.s at 25 ℃ to obtain a component B;
(3) C, preparation of a component: adding polyvinylpyrrolidone into N, N-dimethylformamide, and stirring for 2h to obtain a component C;
(4) And mixing the component A, the component B and the component C at 75 ℃ for 3h to obtain the wet-process polyurethane resin.
Example 4
In this embodiment, a wet process polyurethane resin is provided, where the wet process polyurethane resin includes three components a, B, and C, and the preparation raw materials of the component a include, by weight:
the preparation raw materials of the component B comprise the following components in percentage by weight:
the preparation raw materials of the component C comprise the following components in percentage by weight:
8.6 percent of polyvinylpyrrolidone (K value of 30);
91.4% of N, N-dimethylformamide.
Wherein the number average molecular weight of polyethylene terephthalate glycol diethylene glycol terephthalate glycol diol in the component A is 4000g/mol, and the number average molecular weight of polyethylene diethylene glycol butanediol adipate glycol in the component B is 4000g/mol; the weight ratio of the component A to the component B is 2.6; the component C accounts for 4 percent of the total weight of the components A, B and C.
The preparation method comprises the following steps:
(1) Preparing a component A: carrying out prepolymerization reaction on polyethylene glycol terephthalate glycol, part of diphenylmethane-4, 4' -diisocyanate and part of N, N-dimethylformamide to ensure that the molar ratio of isocyanate groups to hydroxyl groups in a reaction solution is 0.85 to ensure that the solid content of the reaction solution is 60%, and reacting for 4h at 75 ℃ until the viscosity of the reaction solution reaches 3 Pa.s at 60 ℃ to finish the reaction to obtain a prepolymer; adding ethylene glycol and the rest of N, N-dimethylformamide into the prepolymer, uniformly stirring, adding part of diphenylmethane-4, 4' -diisocyanate to react, so that the molar ratio of isocyanate groups to hydroxyl groups in the reaction liquid is 0.94;
(2) B, preparation of a component: uniformly mixing polydiethylene glycol adipate butanediol glycol, 1, 4-butanediol and N, N-dimethylformamide, adding part of diphenylmethane-4, 4 '-diisocyanate into the mixture to react, so that the molar ratio of isocyanate groups to hydroxyl groups in a reaction liquid is 0.93, reacting for 4 hours at 80 ℃, then adding the rest diphenylmethane-4, 4' -diisocyanate, and reacting until the viscosity of the reaction liquid reaches 70 Pa.s at 25 ℃ to obtain a component B;
(3) Preparing a component C: adding polyvinylpyrrolidone into N, N-dimethylformamide, and stirring for 2.5h to obtain a component C;
(4) And mixing the component A, the component B and the component C at 80 ℃ for 5h to obtain the wet-process polyurethane resin.
Example 5
In this embodiment, a wet process polyurethane resin is provided, where the wet process polyurethane resin includes three components, i.e., a component a, a component B, and a component C, and the preparation raw material of the component a includes the following components by weight percent:
the component B comprises the following raw materials in percentage by weight:
the preparation raw materials of the component C comprise the following components in percentage by weight:
7.3% of polyvinylpyrrolidone (K value of 60);
92.7 percent of N, N-dimethylformamide.
Wherein the number average molecular weight of the polyethylene glycol butanediol adipate in the component A is 3000g/mol, and the number average molecular weight of the polyethylene glycol diethylene glycol butanediol adipate in the component B is 2000g/mol; the weight ratio of the component A to the component B is 3.3; the component C accounts for 4 percent of the total weight of the components A, B and C.
The preparation method comprises the following steps:
(1) Preparing a component A: carrying out prepolymerization reaction on polyethylene glycol butanediol adipate, part of diphenylmethane-4, 4' -diisocyanate and part of N, N-dimethylformamide to ensure that the molar ratio of isocyanate groups to hydroxyl groups in reaction liquid is 0.83 to 1 and the solid content of the reaction liquid is 70%, reacting for 4h at 65 ℃ until the viscosity of the reaction liquid reaches 2 Pa.s at 60 ℃, and finishing the reaction to obtain a prepolymer; adding ethylene glycol and the rest of N, N-dimethylformamide into the prepolymer, uniformly stirring, adding part of diphenylmethane-4, 4 '-diisocyanate to react to ensure that the molar ratio of isocyanate groups to hydroxyl groups in the reaction liquid is 0.95 to 1, reacting at 65 ℃ for 3 hours, then adding the rest of diphenylmethane-4, 4' -diisocyanate, reacting until the viscosity of the reaction liquid reaches 230 pas at 25 ℃, then adding alkyd resin, and stirring for 2 hours to obtain a component A;
(2) B, preparation of a component: uniformly mixing polyethylene glycol adipate butanediol glycol, ethylene glycol, 1, 4-butanediol and N, N-dimethylformamide, adding part of diphenylmethane-4, 4 '-diisocyanate into the mixture to react, so that the molar ratio of isocyanate groups to hydroxyl groups in the reaction liquid is 0.95 to react for 3 hours at 65 ℃, then adding the rest diphenylmethane-4, 4' -diisocyanate, and reacting until the viscosity of the reaction liquid reaches 60 Pa.s at 25 ℃ to obtain a component B;
(3) C, preparation of a component: adding polyvinylpyrrolidone into N, N-dimethylformamide, and stirring for 3h to obtain a component C;
(4) And mixing the component A, the component B and the component C at 70 ℃ for 4h to obtain the wet-process polyurethane resin.
Comparative example 1
This comparative example differs from example 1 only in that component C makes up 1% of the total weight of the three components A, B and C.
Comparative example 2
This comparative example differs from example 1 only in that component C makes up 7% of the total weight of the three components A, B and C.
Comparative example 3
This comparative example differs from example 1 only in that the castor oil-modified short oil alkyd resin in the a component is 1% by weight. The weight percentage of the preparation raw materials of the component A is as follows:
comparative example 4
This comparative example differs from example 1 only in that the castor oil-modified short oil alkyd resin in component a is 7% by weight. The weight percentage of the preparation raw materials of the component A is as follows:
comparative example 5
Commercially available technical suede resin HDW-50M.
The wet-process polyurethane resins prepared in examples 1-5 and comparative examples 1-4 and the technical suede resin HDW-50M obtained in comparative example 5 are respectively diluted according to a certain proportion to prepare a coating and scraping solution, the coating and scraping solution is coated on a PET film at a knife distance of 1.8mm, and wet-process bass is obtained after solidification, water washing and drying, and the performance of the wet-process bass is tested by the following test method:
(1) And (3) water washability test: and (3) washing and extruding the wet-process bass with hot water at 45 ℃ for 10 times, cutting 1 sample strip, washing and extruding for 10 times again, cutting 1 sample strip, washing and extruding for 10 times finally, putting the obtained product together with the 2 sample strips into a dryer, and drying the product to compare the surface conditions of the sample strips. (the first sample strip is evaluated as 1 grade water washing for good water washing performance, the second sample strip is evaluated as 2 grade water washing for good water washing performance, and the final sample is evaluated as 3 grade water washing for good water washing performance);
(2) And (3) testing the wear resistance: grinding the dried wet-process bass (together with a PET film) to the same thickness by 180-mesh abrasive paper, cutting a standard sample piece with the outer diameter of 108mm and the inner diameter of 8mm by using a sampler, attaching the sample piece to paper with the same size, selecting a CS-10 grinding wheel with the load of 500g, and testing the weight loss rate of the leather sample before and after 1000 times of friction on a TABER (wear resistance before-wear resistance after) and the weight loss rate of 100 percent before wear resistance;
(3) And (3) testing the pore diameter of the micropores: the cross section of the wet base was photographed at a focal length of 200 times by using a lens of Z100 of a VHX-2000E digital microscope system and the inner diameter of the cells was measured, and the number of cells within a length of 0.15cm and the range of the inner diameter of the cells were recorded.
The results of the performance tests are shown in table 1.
TABLE 1
As can be seen from Table 1, the wet-process bass produced in comparative example 1 has significantly reduced water washability and smaller and finer cells and a larger number of cells per unit length than the wet-process bass produced in example 1 because the proportion (1%) of the C component in the A, B and C components in comparative example 1 is lower than the given range;
the wet-process bass abrasion resistance made by comparative example 2 was inferior to that made by example 1, the cells were large and coarse, and the maximum inner diameter range of each cell per unit length was too wide, i.e., the uniformity of the cells was insufficient, because the ratio (7%) of the C component in the three components a, B, and C in comparative example 2 was out of the given range;
the wet-process bass made with comparative example 3 was less astringent, less washable, and less abrasion resistant than the wet-process bass made in example 1 because the weight percent (1%) of alkyd resin in component a in comparative example 3 was below the range given;
the wet-process bass made with comparative example 4 had less uniform cells than the wet-process bass made in example 1 because the weight percent (7%) of alkyd resin in comparative example 4 in component a was outside the range given.
Compared with the wet-process bass made of the suede resin HDW-50M of the science and technology in the comparative example 5, the wet-process bass made in the examples 1-5 has the advantages of good washing performance (grade 1), good wear resistance (weight loss rate after wear resistance: 1.9% -2.6%), strong surface astringency and relatively uniform cells.
The applicant states that the present invention is illustrated by the above examples of the wet process polyurethane resin of the present invention and the preparation method thereof, but the present invention is not limited to the above examples, that is, it does not mean that the present invention must be implemented depending on the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (21)
1. The wet-process polyurethane resin is characterized by comprising three components of A, B and C, wherein the preparation raw materials of the component A comprise the following components in percentage by weight:
the preparation raw materials of the component B comprise the following components in percentage by weight:
the preparation raw materials of the component C comprise the following components in percentage by weight:
7 to 8.6 percent of polyvinylpyrrolidone;
91.4 to 93 percent of N, N-dimethylformamide;
the weight ratio of the component A to the component B is (2.5); the component C accounts for 3-5% of the total weight of the components A, B and C.
2. The wet-process polyurethane resin as claimed in claim 1, wherein the polyester diol in the component A is a polyester diol having a number average molecular weight of 3000 to 4000 g/mol.
3. The wet-process polyurethane resin as claimed in claim 1, wherein the polyester diol in the A component is selected from any one or a combination of at least two of poly (1, 4-butylene adipate) glycol, poly (ethylene glycol butylene adipate) glycol, poly (diethylene glycol terephthalate) glycol, or poly (ethylene glycol terephthalate) glycol having a number average molecular weight of 3000 to 4000 g/mol.
4. The wet process polyurethane resin of claim 1, wherein the small molecule chain extender in the A and B components is independently ethylene glycol and/or 1, 4-butanediol.
5. The wet-process polyurethane resin of claim 1, wherein the alkyd resin is a castor oil-modified short oil alkyd resin.
6. The wet-process polyurethane resin according to claim 1, wherein the polyester diol in the component B is a polyester diol having a number average molecular weight of 2000 to 4000 g/mol.
7. The wet-process polyurethane resin according to claim 1, wherein the polyester diol in the B component is any one of or a combination of at least two of poly-1, 4-butanediol adipate diol, poly-ethylene glycol butanediol adipate diol or poly-diethylene glycol butanediol adipate diol with a number average molecular weight in the range of 2000 to 4000 g/mol.
8. The wet-process polyurethane resin according to claim 1, wherein the polyvinylpyrrolidone is a polyvinylpyrrolidone having a K value of 30 to 90.
9. The method for preparing a wet-process polyurethane resin according to any one of claims 1 to 8, wherein the preparation method comprises the steps of:
(1) Preparing a component A: carrying out prepolymerization reaction on polyester dihydric alcohol, part of diphenylmethane-4, 4' -diisocyanate and part of N, N-dimethylformamide to obtain a prepolymer; adding a micromolecular chain extender and the residual N, N-dimethylformamide into the prepolymer, uniformly stirring, adding part of diphenylmethane-4, 4 '-diisocyanate for reaction, then adding the residual diphenylmethane-4, 4' -diisocyanate, reacting until the viscosity of a reaction solution reaches 200-260 Pa.s at 25 ℃, then adding alkyd resin, and stirring to obtain a component A;
(2) B, preparation of a component: uniformly mixing polyester diol, a micromolecular chain extender and N, N-dimethylformamide, adding part of diphenylmethane-4, 4 '-diisocyanate into the mixture for reaction, then adding the rest diphenylmethane-4, 4' -diisocyanate, and reacting until the viscosity of a reaction solution reaches 50-80 Pa.s at 25 ℃ to obtain a component B;
(3) C, preparation of a component: adding polyvinylpyrrolidone into N, N-dimethylformamide, and uniformly stirring to obtain a component C;
(4) And mixing the component A, the component B and the component C to obtain the wet-process polyurethane resin.
10. The production method according to claim 9, characterized in that the partial diphenylmethane-4, 4' -diisocyanate in the step (1) is in such an amount that the molar ratio of isocyanate groups to hydroxyl groups in the reaction liquid is from 0.82 to 1.85.
11. The method according to claim 9, wherein the portion of N, N-dimethylformamide in the step (1) is in an amount such that the solid content in the prepolymerization reaction solution is 60 to 70%.
12. The method of claim 9, wherein the prepolymerization temperature in step (1) is 60-80 ℃ and the prepolymerization time is 1-4 hours.
13. The method according to claim 9, wherein the viscosity of the reaction solution after the prepolymerization in step (1) is 1 to 4 pas at 60 ℃.
14. The production method according to claim 9, wherein the portion of diphenylmethane-4, 4' -diisocyanate to be reintroduced in step (1) is in an amount such that the molar ratio of isocyanate groups to hydroxyl groups in the reaction liquid is 0.93 to 0.96.
15. The method of claim 9, wherein the temperature for reacting the input portion of diphenylmethane-4, 4' -diisocyanate in step (1) is 60 to 80 ℃, and the reaction time is 1 to 4 hours.
16. The method according to claim 9, wherein the mixing time after the alkyd resin is added in step (1) is 1-2 h.
17. The production method according to claim 9, wherein the partial diphenylmethane-4, 4' -diisocyanate in the step (2) is in an amount such that the molar ratio of isocyanate groups to hydroxyl groups in the reaction liquid is from 0.93 to 1.96.
18. The method according to claim 9, wherein the reaction temperature of the step (2) is 60-80 ℃ and the reaction time is 2-4 h.
19. The method according to claim 9, wherein the stirring time in the step (3) is 2 to 4 hours.
20. The method of claim 9, wherein the mixing in step (4) is carried out at a temperature of 60 to 80 ℃ for a time of 3 to 5 hours.
21. Use of the wet process polyurethane resin according to any one of claims 1 to 8 in the preparation of a suede absorbent pad.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011583471.1A CN112724654B (en) | 2020-12-28 | 2020-12-28 | Wet-process polyurethane resin and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011583471.1A CN112724654B (en) | 2020-12-28 | 2020-12-28 | Wet-process polyurethane resin and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112724654A CN112724654A (en) | 2021-04-30 |
| CN112724654B true CN112724654B (en) | 2022-10-21 |
Family
ID=75606715
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011583471.1A Active CN112724654B (en) | 2020-12-28 | 2020-12-28 | Wet-process polyurethane resin and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112724654B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114149560B (en) * | 2021-12-14 | 2023-05-05 | 福建汇得新材料有限公司 | Wet polyurethane resin and preparation method and application thereof |
| CN114316206B (en) * | 2021-12-14 | 2023-10-24 | 福建汇得新材料有限公司 | Wet polyurethane resin and preparation method and application thereof |
| CN116622050B (en) * | 2023-07-21 | 2023-12-05 | 山东一诺威聚氨酯股份有限公司 | Low-density wear-resistant anti-skid polyurethane sole resin and preparation method and application thereof |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4336206A1 (en) * | 1993-10-23 | 1995-04-27 | Hoechst Ag | Aqueous self-crosslinking polyurethane-vinyl hybrid dispersions |
| JP4403684B2 (en) * | 2002-05-21 | 2010-01-27 | Ｄｉｃ株式会社 | Aqueous dry laminate adhesive composition for synthetic leather and method for producing synthetic leather using the same |
| US20070116929A1 (en) * | 2003-12-26 | 2007-05-24 | Dai Nippon Printing Co., Ltd. | Embossed release paper for synthetic leather production and support therefor, and synthetic leather using the release paper and process for producing the synthetic leather |
| DE102006054237A1 (en) * | 2006-11-17 | 2008-05-21 | Bayer Materialscience Ag | Polyurethane-modified alkyd resin dispersions |
| CN102417573B (en) * | 2011-11-01 | 2013-01-09 | 吴江市北厍盛源纺织品助剂厂 | Method for preparing polyurethane coating agent for artificial chamois leather |
| ES2729067T3 (en) * | 2013-09-26 | 2019-10-30 | Mitsui Chemicals Inc | 1,4-bis (isocyanomethyl) cyclohexane, polyisocyanate composition, polyurethane resin, molded article, eye product material, eye product mount and lens |
| CN108250399B (en) * | 2017-12-01 | 2020-07-07 | 上海汇得科技股份有限公司 | Wet polyurethane resin for labor protection gloves with high demolding performance and good wear resistance and preparation method thereof |
| CN109720015A (en) * | 2018-12-29 | 2019-05-07 | 扬州市德运塑业科技股份有限公司 | A kind of ventilative PU synthetic leather and preparation method thereof |
| WO2020174899A1 (en) * | 2019-02-25 | 2020-09-03 | Dic株式会社 | Aqueous dispersion of urethane resin, leather sheet, and method for producing leather sheet |
| CN110452359A (en) * | 2019-08-15 | 2019-11-15 | 台州禾欣高分子新材料有限公司 | A kind of preparation and application of PU mirror surface leather polyurethane wet resin |
| CN111303369B (en) * | 2020-04-03 | 2022-05-03 | 浙江华峰合成树脂有限公司 | High color-developing polyurethane resin, polyurethane synthetic leather and preparation method thereof |
-
2020
- 2020-12-28 CN CN202011583471.1A patent/CN112724654B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN112724654A (en) | 2021-04-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112724654B (en) | Wet-process polyurethane resin and preparation method and application thereof | |
| EP3327054B1 (en) | Moisture curable hot melt urethane composition, method for producing cured foam of same, synthetic leather and method for producing synthetic leather | |
| US20110009510A1 (en) | Process for producing alcohol soluble urethane resin composition, polyurethane porous body, and moisture permeable film | |
| CN109851748B (en) | Sulfonic acid type waterborne polyurethane and preparation method and application thereof | |
| CN110229301A (en) | A kind of preparation method of waterborne polyurethane resin and its synthetic leather | |
| CN104211899B (en) | Polyacetals modified carboxylic acid nonionic polyurethane aqueous dispersion and preparation method thereof and the application in coating | |
| CN108047421B (en) | Superfine fiber synthetic leather resin for automotive interior and preparation method thereof | |
| CN102796447B (en) | Aqueous Polyurethane Leather Finishing Agent and preparation method thereof | |
| CN115058176A (en) | Epoxy modified self-extinction waterborne polyurethane emulsion and preparation method thereof | |
| CN111019078A (en) | Waterborne polyurethane curing agent and preparation method and application thereof | |
| TWI274060B (en) | Thermoplastic polyurethanes and method of fabricating the same | |
| CN114276519A (en) | Self-extinction waterborne polyurethane and preparation method thereof | |
| CN111349213B (en) | Polyurethane resin composition and polishing pad | |
| KR102350417B1 (en) | Synthetic leather manufacturing method | |
| CN111777887A (en) | Flame-retardant heat-resistant waterborne polyurethane coating and preparation method thereof | |
| CN114736596B (en) | Quick-drying type single-component polyurethane waterproof coating and preparation method thereof | |
| CN111138963A (en) | Synthesis process of high-performance self-crosslinking waterborne polyurethane self-extinction resin | |
| CN107236511B (en) | Polyurethane adhesive composition for shoes and preparation method thereof | |
| CN114085351A (en) | Composition for preparing waterborne polyurethane, preparation method and application of waterborne polyurethane, and method for preparing microfiber leather | |
| WO2005049685A1 (en) | Polyurethane resin for artificial leather and porous sheet material | |
| CN112708098A (en) | Wet-process polyurethane resin and preparation method and application thereof | |
| CN110606930A (en) | Waterborne polyurethane resin and preparation method and application thereof | |
| CN115354505B (en) | Bio-based solvent-free polyurethane surface layer resin for synthetic leather and preparation method thereof | |
| JP2005232277A (en) | Aqueous disperse system of polyurethane, its manufacturing method and use | |
| CN114106286B (en) | Liquid polyurethane coating and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |