CN112724654A - Wet-process polyurethane resin and preparation method and application thereof - Google Patents
Wet-process polyurethane resin and preparation method and application thereof Download PDFInfo
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- CN112724654A CN112724654A CN202011583471.1A CN202011583471A CN112724654A CN 112724654 A CN112724654 A CN 112724654A CN 202011583471 A CN202011583471 A CN 202011583471A CN 112724654 A CN112724654 A CN 112724654A
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- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4205—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
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- 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
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- 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
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2101/00—Manufacture of cellular products
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- C08L2203/00—Applications
- C08L2203/14—Applications used for foams
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- 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
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- C—CHEMISTRY; METALLURGY
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- 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
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Abstract
The invention provides a wet-process polyurethane resin and a preparation method and application thereof, wherein the wet-process polyurethane resin comprises A, B, C three components, and the preparation raw materials of the component A comprise 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 base made of the wet-process polyurethane resin has the characteristics of good washing performance, good wear resistance, strong surface astringency and uniform foam pores, 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 A, B two components, wherein the component a comprises polyoxypropylene glycol and diphenylmethane-4, 4' -diisocyanate; the component B comprises polytetrahydrofuran ether glycol, poly adipic acid polyester diol, polyoxyethylene glycol, 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 a wet-process polyurethane resin for a suede adsorption pad and a 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:
in one aspect, the invention provides a wet-process polyurethane resin, which comprises A, B, C three components, 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 washing property and the surface sticky feeling of wet base made of the polyurethane resin; the polyvinylpyrrolidone has hydrophilic group and lipophilic group in its molecule, so that it can interact with many solvents, and can be dissolved in water, alcohol, carboxylic acid, amine, halohydrocarbon and other organic solvents.
In the present invention, in the raw material for preparing the component a, the amount of diphenylmethane-4, 4' -diisocyanate used 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, in the raw material for preparing the B component, the amount of the diphenylmethane-4, 4' -diisocyanate used 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, in the raw material for preparing the B component, N-dimethylformamide may be used in an amount of 70% to 73%, for example, 70%, 71%, 72%, 73%, or the like.
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 invention, the polyester diol in the component A is polyester diol with the number average molecular weight of 3000-4000 g/mol (such as 3000g/mol, 3500g/mol or 4000 g/mol).
Preferably, the polyester diol in the component A is selected from any one 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 with the number average molecular weight of 3000-4000 g/mol (such as 3000g/mol, 3500g/mol or 4000 g/mol). 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 invention, the polyester diol in the component B is polyester diol with the number average molecular weight of 2000-4000 g/mol (such as 2000g/mol, 3000g/mol or 4000 g/mol).
Preferably, the polyester diol in the component B is any one or a combination of at least two of poly adipic acid-1, 4-butanediol ester diol, poly adipic acid ethylene glycol butanediol ester diol or poly adipic acid diethylene glycol butanediol ester diol with the number average molecular weight ranging from 2000 to 4000g/mol (such as 2000g/mol, 3000g/mol or 4000 g/mol). 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 invention, the weight ratio of the component A to the component B is 2.5: 1-3.7: 1 (such as 2.5:1, 3:1 or 3.7: 1); the C component accounts for 3-5%, such as 3%, 4% or 5% of the total weight of the A, B, C three components.
In another aspect, the present invention provides a method for preparing the wet process polyurethane resin as described above, comprising the steps of:
(1) preparation of 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 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 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 (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 0.82:1 to 0.85:1 (e.g., 0.82:1, 0.83:1, 0.85:1, etc.).
Preferably, the N, N-dimethylformamide in the step (1) is used in an amount such that the solid content in the prepolymerization reaction solution is 60-70% (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 ℃ and the like), and the time of the prepolymerization reaction is 1-4 h, for example, 1h, 2h, 3h or 4h and the like.
Preferably, the viscosity of the reaction solution after the prepolymerization in 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 to be reintroduced in step (1) is in an amount such that the molar ratio of isocyanate groups to hydroxyl groups in the reaction solution is from 0.93:1 to 0.96:1 (e.g., 0.93:1, 0.95:1, or 0.96: 1).
Preferably, the temperature for charging part of the diphenylmethane-4, 4' -diisocyanate to carry out the reaction in step (1) is 60 to 80 ℃ (for example, 60 ℃, 70 ℃ or 80 ℃) and the reaction time is 1 to 4 hours, for example, 1 hour, 2 hours, 3 hours or 4 hours.
Preferably, the mixing time after adding the alkyd resin in the step (1) is 1-2 h, such as 1h, 1.5h or 2 h.
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 0.93:1 to 0.96:1 (e.g., 0.93:1, 0.95:1, or 0.96: 1).
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 the step (3) is 2-4 h, such as 2h, 3h or 4 h.
Preferably, the mixing temperature in the step (4) is 60-80 ℃ (for example, 60 ℃, 70 ℃ or 80 ℃ and the like), and the mixing time is 3-5 h, for example, 3h, 4h or 5h and the like.
In a further aspect, the invention provides the use of a wet process polyurethane resin as described above in the preparation of a suede absorbent 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) A, B, C the blending scheme of three components integrates the crystallinity of the resin, not only ensures 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), but also can form more uniform cell structure in the solidification process. The wet-process adsorption pad base made of the polyurethane resin has uniform size of the foam pores, so that the wet-process adsorption pad base is not easy to scratch a liquid crystal screen when surface polishing liquid flows to polish the liquid crystal screen in a large amount.
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 limitations of the present invention.
Example 1
In this embodiment, a wet-process polyurethane resin is provided, where the wet-process polyurethane resin includes A, B, C three components, and the preparation raw materials of the component a include 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:
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 2000 g/mol; the weight ratio of the component A to the component B is 2.7: 1; the C component accounts for 5 percent of the total weight of the A, B, C three components.
The preparation method comprises the following steps:
(1) preparation of a component A: carrying out prepolymerization reaction on 1, 4-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 0.82:1 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 ℃, and finishing the reaction to obtain a prepolymer; adding ethylene glycol 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 0.93:1, reacting at 60 ℃ for 1h, 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 2h to obtain a component A;
(2) b, preparation of a component: uniformly mixing poly (1, 4-butanediol adipate) glycol, 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 0.94:1, reacting 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 A, B, C three components, and the preparation raw materials of the component a include 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:
7.5 percent of polyvinylpyrrolidone (K value is 60);
92.5% of N, N-dimethylformamide.
Wherein the number average molecular weight of the polyethylene glycol butanediol adipate in the component A is 4000g/mol, and the number average molecular weight of the polyethylene glycol butanediol adipate in the component B is 3000 g/mol; the weight ratio of the component A to the component B is 2.5: 1; the C component accounts for 5 percent of the total weight of the A, B, C three components.
The preparation method comprises the following steps:
(1) preparation of 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 liquid is 0.83:1 and the solid content of the reaction liquid is 70%, and reacting for 2h at 70 ℃ until the viscosity of the reaction liquid reaches 1 Pa.s at 60 ℃ to finish the reaction to obtain a prepolymer; adding 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 0.96:1, reacting at 75 ℃ for 2 hours, then adding the rest of diphenylmethane-4, 4' -diisocyanate, reacting until the viscosity of the reaction liquid reaches 200 Pa.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, 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 a reaction liquid is 0.96:1, reacting for 2.5 hours at 75 ℃, then adding the rest diphenylmethane-4, 4' -diisocyanate, and reacting until the viscosity of the reaction liquid reaches 50 Pa.s at 25 ℃ to obtain a component B;
(3) c, preparation of a component: 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 A, B, C three components, and the preparation raw materials of the component a include 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% of polyvinylpyrrolidone (K value of 90);
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 3000 g/mol; the weight ratio of the component A to the component B is 3.7: 1; the C component accounts for 3 percent of the total weight of the A, B, C three components.
The preparation method comprises the following steps:
(1) preparation of 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 liquid is 0.84:1 and the solid content of the reaction liquid is 65%, reacting for 3 hours at 80 ℃ until the viscosity of the reaction liquid 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 0.95:1, reacting at 80 ℃ for 2 hours, 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 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 0.95:1, reacting 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 A, B, C three components, and the preparation raw materials of the component a include 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:
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 4000 g/mol; the weight ratio of the component A to the component B is 2.6: 1; the C component accounts for 4 percent of the total weight of the A, B, C three components.
The preparation method comprises the following steps:
(1) preparation of 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 0.85:1 and 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, 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 0.94:1, reacting for 4 hours at 70 ℃, then adding the rest of diphenylmethane-4, 4' -diisocyanate, reacting until the viscosity of the reaction liquid reaches 260 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 polyethylene 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 0.93:1, 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) c, preparation of a component: 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 A, B, C three components, and the preparation raw materials of the component a include 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:
7.3% 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 butanediol adipate in the component B is 2000 g/mol; the weight ratio of the component A to the component B is 3.3: 1; the C component accounts for 4 percent of the total weight of the A, B, C three components.
The preparation method comprises the following steps:
(1) preparation of 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 0.83:1 and the solid content of the reaction solution is 70%, reacting for 4h at 65 ℃ until the viscosity of the reaction solution 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, 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 0.95:1, 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 0.95:1, reacting 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 the C component makes up 1% of the total weight of the A, B, C three components.
Comparative example 2
This comparative example differs from example 1 only in that the C component makes up 7% of the total weight of the A, B, C three components.
Comparative example 3
This comparative example differs from example 1 only in that the castor oil-modified short oil alkyd resin in component a has a weight percent of 1%. 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 by hot water at 45 ℃ for 10 times, cutting 1 sample strip, washing and extruding for 10 times, cutting 1 sample strip, finally washing and extruding for 10 times, putting the obtained sample strips together with the 2 sample strips into a drying machine, and comparing the surface conditions of the sample strips after drying. (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 leather sample is evaluated as 3-grade water washing for good water washing performance);
(2) and (3) wear resistance test: grinding the dried wet base (together with the 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) on a 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 with 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, C three 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 inside diameter range of each cell per unit length was too wide, i.e., the cell uniformity was insufficient, because the ratio (7%) of the component C in the A, B, C three components 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, i.e., it does not mean that the present invention must be implemented by relying 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 (10)
1. The wet-process polyurethane resin is characterized by comprising A, B, C components, 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.
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;
preferably, the polyester diol in the component A is selected from any one or a combination of at least two of poly (1, 4-butylene adipate) diol, poly (ethylene glycol butylene adipate) diol, poly (diethylene glycol terephthalate) diol or poly (ethylene glycol terephthalate) diol with the number average molecular weight of 3000-4000 g/mol.
3. The wet process polyurethane resin of claim 1 or 2, wherein the small molecule chain extenders in the a and B components are independently ethylene glycol and/or 1, 4-butanediol.
4. The wet-process polyurethane resin of any one of claims 1-3, wherein the alkyd resin is a castor oil-modified short oil alkyd resin.
5. The wet-process polyurethane resin according to any one of claims 1 to 4, wherein the polyester diol in the B component is a polyester diol having a number average molecular weight of 2000 to 4000 g/mol;
preferably, the polyester diol in the component B is any one or a combination of at least two of poly adipic acid-1, 4-butanediol ester diol, poly ethylene glycol butanediol adipate diol or poly diethylene glycol butanediol adipate diol with the number average molecular weight ranging from 2000 to 4000 g/mol.
6. The wet-process polyurethane resin according to any one of claims 1 to 5, wherein the polyvinylpyrrolidone is a polyvinylpyrrolidone having a K value of 30 to 90.
7. The wet-process polyurethane resin as claimed in any one of claims 1 to 6, wherein the weight ratio of the A component to the B component is 2.5:1 to 3.7: 1; the component C accounts for 3-5% of the total weight of the A, B, C three components.
8. The method for preparing a wet-process polyurethane resin according to any one of claims 1 to 7, wherein the preparation method comprises the steps of:
(1) preparation of 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 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 at 25 ℃, adding alkyd resin, and stirring to obtain a component A;
(2) b, preparation of a component: uniformly mixing polyester diol, a small-molecular 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.
9. The production method according to claim 8, wherein the partial diphenylmethane-4, 4' -diisocyanate obtained in step (1) is preferably in an amount such that the molar ratio of isocyanate groups to hydroxyl groups in the reaction solution is 0.82:1 to 0.85: 1;
preferably, the part of N, N-dimethylformamide in the step (1) is an amount which enables the solid content in the prepolymerization reaction liquid to be 60-70%;
preferably, the temperature of the prepolymerization reaction in the step (1) is 60-80 ℃, and the time of the prepolymerization reaction is 1-4 h;
preferably, the viscosity of the reaction solution after the prepolymerization reaction in the step (1) reaches 1-4 Pa.s at 60 ℃;
preferably, part of the diphenylmethane-4, 4' -diisocyanate added in step (1) is in an amount such that the molar ratio of isocyanate groups to hydroxyl groups in the reaction solution is from 0.93:1 to 0.96: 1;
preferably, the temperature for adding part of the diphenylmethane-4, 4' -diisocyanate to react in the step (1) is 60-80 ℃, and the reaction time is 1-4 h;
preferably, the mixing time after the alkyd resin is added in the step (1) is 1-2 h;
preferably, the part of 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 0.93:1 to 0.96: 1;
preferably, the temperature for adding part of the diphenylmethane-4, 4' -diisocyanate to carry out the reaction in the step (2) is 60-80 ℃, and the reaction time is 2-4 h;
preferably, the stirring time in the step (3) is 2-4 h;
preferably, the mixing temperature in the step (4) is 60-80 ℃, and the mixing time is 3-5 h.
10. Use of the wet process polyurethane resin according to any one of claims 1 to 7 in the preparation of a suede absorbent pad.
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| CN114316206A (en) * | 2021-12-14 | 2022-04-12 | 福建汇得新材料有限公司 | Wet-process polyurethane resin and preparation method and application thereof |
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| 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 |
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