CN111057211A - Hydrolysis-resistant high-peel-resistance fluorine-free wet-process polyurethane resin for synthetic leather and preparation method thereof - Google Patents
Hydrolysis-resistant high-peel-resistance fluorine-free wet-process polyurethane resin for synthetic leather and preparation method thereof Download PDFInfo
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
- D06N3/146—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes characterised by the macromolecular diols used
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Abstract
The invention discloses a hydrolysis-resistant high-peel-resistance fluorine-free wet polyurethane resin for synthetic leather, which consists of A, B two components in a weight ratio of 1: 30-20, wherein the component A comprises the following components: 36 to 50 percent of diphenylmethane-4, 4' -diisocyanate; 27% -37% of castor oil; 6.5 to 10.5 percent of methanol. 12 to 20 percent of N, N-dimethylformamide; the component B comprises the following components: 9 to 11 percent of diphenylmethane-4, 4' -diisocyanate; 5.5 to 7.5 percent of polytetrahydrofuran ether glycol; 1 to 2 percent of polypropylene oxide glycol; 6 to 10 percent of polyester diol; 2 to 2.5 percent of ethylene glycol; 70 to 73 percent of N, N-dimethylformamide. The invention also discloses a method thereof. The polyurethane resin provided by the invention has the characteristics of good film forming property, good hydrolysis resistance and high strength, and does not contain fluorine element.
Description
Technical Field
The invention belongs to the field of preparation of polyurethane resin, and particularly relates to hydrolysis-resistant high-peel-resistance fluorine-free wet-process polyurethane resin for synthetic leather and a preparation method thereof.
Background
The polyurethane resin for synthetic leather is a novel polymer material for partially replacing natural genuine leather, and with the increasing competition of the synthetic leather industry, the requirements of people on the polyurethane resin for synthetic leather are higher and higher.
Particularly in the application field of shoe leather in the shoe manufacturing industry, the polyurethane material is required to have high peel strength, certain hydrolysis resistance (namely, the polyurethane material can keep high peel strength after being soaked in an alkali solution), and good water washing performance and good surface smoothness under the condition of less or no filling.
The solution in the prior art is that the fluorine-containing acrylic acid polymer is added as a waterproof agent to reduce the surface tension of base materials such as fabrics, paper, leather and the like, and the water repellency and oil repellency of the product can be obviously improved.
The common hydrolysis-resistant high-stripping-resistance wet-process polyurethane resin product for sports shoe leather in the market is generally prepared by adding the fluorine-containing waterproof agent, and the hydrolysis resistance of the product is improved on the basis of not influencing other physical properties such as resin stripping strength, water washing property and the like.
However, the fluorocarbon segment structure in the fluorine-containing acrylate polymer can be degraded into perfluoro compounds (PFCs) with high stability and accumulation, and researches show that the PFCs have persistence and biological accumulation, the accumulation level in organisms is hundreds to thousands of times higher than that of persistent organic pollutants such as known organochlorine pesticides, and the PFCs also have various toxicities such as reproductive toxicity, mutagenic toxicity, developmental toxicity, neurotoxicity, immunotoxicity, and the like, and are environmental pollutants with systemic multi-organ toxicity.
They are stable in nature for a long period of time, have high diffusibility and are potentially harmful to the environment and human body. Currently, the european union and the united states have stated the prohibition of the use of C8 and above perfluorocompounds (such as perfluorooctanoic acid PFOA and perfluorooctane sulfonic acid PFOS of 8 carbon atoms).
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a hydrolysis-resistant high-peel-resistance fluorine-free wet-process polyurethane resin for synthetic leather. The product of the invention is a more environment-friendly product which does not contain any fluorine element, has good hydrolysis resistance and high strength.
The invention also aims to provide a preparation method of the hydrolysis-resistant high-peeling fluorine-free wet-process polyurethane resin for synthetic leather.
In order to realize one of the purposes of the invention, the adopted technical scheme is as follows:
the hydrolysis-resistant high-peel-resistance fluorine-free wet polyurethane resin for the synthetic leather consists of A, B two components in a weight ratio of 1: 30-20, wherein the component A comprises the following components in parts by weight:
the component B comprises the following components in parts by weight:
in a preferred embodiment of the invention, the molar ratio of the diphenylmethane-4, 4' -diisocyanate in the component A to the castor oil is 4:1 to 7: 1.
In a preferred embodiment of the invention, the molar ratio of the methanol in the component A to the diphenylmethane-4, 4' -diisocyanate is 1.3:1 to 1.7: 1.
In a preferred embodiment of the invention, the polyester polyol in the component B is any one or more of polybutylene adipate glycol, polyethylene glycol terephthalate glycol or polyethylene glycol terephthalate glycol with the number average molecular weight ranging from 2000 to 4000 g/mol.
In a preferred embodiment of the present invention, the number average molecular weight of the polytetrahydrofuran ether glycol in the B component is in the range of 1800-2000 g/mol.
In a preferred embodiment of the present invention, the number average molecular weight of the polyoxypropylene diol in the B component is in the range of 2000-3000 g/mol.
In a preferred embodiment of the present invention, the weight ratio of the polytetrahydrofuran ether glycol to the polyester diol in the component B is in a range of 1:1.5 to 1:1.
In a preferred embodiment of the present invention, the weight ratio of the polyoxypropylene glycol in the B component to the sum of the weights of the polytetrahydrofuran ether glycol and the polyester diol ranges from 1:10 to 1: 8.
In order to realize the second purpose of the invention, the adopted technical scheme is as follows:
a method for preparing hydrolysis-resistant high-peel-resistance fluorine-free wet-process polyurethane resin for synthetic leather comprises the following steps:
the preparation of the component A comprises the following steps:
putting the castor oil, diphenylmethane-4, 4' -diisocyanate and N, N-dimethylformamide into a reaction kettle, controlling the solid content and the reaction temperature of a first reaction liquid to react in an inert gas atmosphere until NCO of a system reaches a theoretical value, and adding the methanol to terminate the reaction to obtain the component A;
the preparation step of the component B:
carrying out pre-polymerization reaction on the polyester dihydric alcohol, part of diphenylmethane-4, 4' -diisocyanate and part of solvent to obtain a second reaction liquid, controlling the reaction temperature of the second reaction liquid and the solid content of the reaction liquid, and reacting until the viscosity and the vacuum degree of the second reaction liquid reach the standard, wherein the molar ratio of isocyanate groups to hydroxyl groups of the second reaction liquid is 0.92: 1-0.95: 1;
then adding the polytetrahydrofuran ether glycol and the polyoxypropylene glycol for continuous reaction, then adding the ethylene glycol and the residual solvent, stirring uniformly, adding the residual diphenylmethane-4, 4 '-diisocyanate to obtain a third reaction liquid, controlling the molar ratio of isocyanate groups to hydroxyl groups in the third reaction liquid to be 0.92: 1-0.95: 1, then controlling the reaction temperature of the third reaction liquid, and adding the last residual diphenylmethane-4, 4' -diisocyanate until the vacuum degree and the viscosity of the third reaction liquid reach the standard to obtain a component B;
mixing:
and (3) uniformly mixing the A, B components at the temperature of 60-80 ℃, and discharging to obtain the product.
In a preferred embodiment of the present invention, the controlling the solid content and the reaction temperature of the first reaction solution is specifically to control the reaction temperature at 75 to 85 ℃ and the solid content of the reaction solution at 45 to 50%.
In a preferred embodiment of the present invention, the controlling of the reaction temperature and the solid content of the reaction liquid of the second reaction liquid is specifically to control the reaction temperature at 75 to 85 ℃ and the solid content of the reaction liquid at 45 to 50%.
In a preferred embodiment of the invention, the viscosity and the vacuum degree of the second reaction solution reach the standard, specifically, when the viscosity of the reaction solution reaches 60 ℃, the vacuum degree reaches the range of 150-220 Pa · s.
In a preferred embodiment of the invention, the reaction temperature of the third reaction solution is 75-85 ℃; and the vacuum degree and the viscosity of the third reaction liquid reach the standard, wherein the vacuum degree reaches the range of 150-250 Pa.s when the final viscosity reaches 50 ℃.
The invention has the beneficial effects that:
the invention provides a hydrolysis-resistant high-stripping fluorine-free wet polyurethane resin for sports shoe leather, which has the characteristics of good film forming property, good hydrolysis resistance and high strength, does not contain fluorine element, and is more environment-friendly.
Detailed Description
The main principle of the invention is as follows:
the component A in the hydrolysis-resistant high-stripping fluorine-free wet polyurethane resin selects castor oil as a main raw material, the castor oil is a polyhydroxy compound, calculated according to hydroxyl, the castor oil contains 70% of trifunctional and 30% of difunctional, the average functionality of the hydroxyl is 2.7, and the castor oil has long-chain fatty group. Therefore, the polymer prepared by the reaction of the modified isocyanate and diisocyanate has a certain crosslinking structure and good hydrophobicity and hydrolysis resistance.
The component B in the hydrolysis-resistant high-stripping fluorine-free wet polyurethane resin selects polytetrahydrofuran ether glycol, polyester diol and polyoxypropylene diol as soft segment raw materials.
Polytetrahydrofuran ether glycol and polypropylene oxide glycol have good hydrolysis resistance, but too large addition amount easily causes the conditions of strength reduction, poor surface smoothness and the like, and polyurethane resin with too high polyether diol content in a polyurethane soft segment has fast surface solidification and slow internal solidification during solidification, and a compact layer is easily formed on the surface.
While polyester diols provide better strength and slow surface set upon setting, but have poor hydrolysis resistance. The invention adopts a synthesis process that polyester polyol is prepolymerized firstly, polyether polyol (including polytetrahydrofuran ether glycol and polyoxypropylene glycol) is added after the prepolymerization reaches a certain viscosity, and then chain extension is carried out.
Experiments prove that the synthesis process ensures the compatibility of a system, can reduce the surface solidification speed of the resin with higher polyether content in a solidification stage, is difficult to form a surface compact layer on the surface, and ensures the washability and good processability in subsequent processing.
The invention is further illustrated and described by the following specific examples:
the wet-process polyurethane material of part of the disclosure is denoted as wet-process base.
Example 1
The component A comprises:
and B component:
preparing a component A:
15.5kg of castor oil, 16.84kg of MDI and 8kg of DMF are put into a reaction kettle, the reaction temperature is 80-120 ℃, the reaction is carried out for 3-4 hours in the atmosphere of inert gas, when the measured NCO of the system reaches a theoretical value, 3kg of methanol is added to terminate the reaction, and the component A is obtained after discharging.
Preparing a component B:
carrying out prepolymerization reaction on 105kg of poly (ethylene glycol butylene adipate) glycol, 8.22kg of MDI and 114kg of DMF, controlling the reaction temperature at 75-85 ℃, after the reaction is carried out for 2-4 h, testing the viscosity of the reaction solution to 60 ℃, after 190-220 Pa.s, adding 84kg of polytetrahydrofuran ether glycol and 21kg of polyoxypropylene glycol, after the reaction is carried out for 1h, continuing adding 23.53kg of ethylene glycol and 703kg of DMF, after the uniform stirring, adding 100.3kg of MDI, controlling the reaction temperature at 75-85 ℃, after the reaction is carried out for 1-2 h, adding the rest of MDI in batches, and reacting until the final viscosity is 50 ℃, 150-250 Pa.s, thus obtaining the component B.
A. Mixing the component B:
and uniformly mixing the component A and the component B, controlling the mixing temperature to be 60-80 ℃, mixing for 3-5 h, and discharging to obtain a final product.
Example 2
The component A comprises:
and B component:
preparing a component A:
and (2) putting 20kg of castor oil, 32.6kg of MDI and 9.3kg of DMF into a reaction kettle, reacting at the temperature of 80-120 ℃ in an inert gas atmosphere for 3-4 h, adding 6.68kg of methanol to terminate the reaction when the measured NCO of the system reaches a theoretical value, and discharging to obtain the component A.
Preparing a component B:
carrying out prepolymerization reaction on 100kg of polybutylene adipate glycol, 11.6kg of MDI and 130kg of DMF, controlling the reaction temperature at 75-85 ℃, after the reaction is carried out for 2-4 h, testing the viscosity of the reaction solution to 60 ℃, adding 100kg of polytetrahydrofuran ether glycol and 20kg of polyoxypropylene glycol after 150-180 Pa.s, after the reaction is carried out for 1h, continuing adding 29.94kg of ethylene glycol and 895kg of DMF, after the uniform stirring, adding 126.7kg of MDI, controlling the reaction temperature at 75-85 ℃, after the reaction is carried out for 1-2 h, adding the rest amount of MDI in batches, and reacting until the final viscosity is 50 ℃, 150-250 Pa.s, thus obtaining the component B.
A. Mixing the component B:
and uniformly mixing the component A and the component B, controlling the mixing temperature to be 60-80 ℃, mixing for 3-5 h, and discharging to obtain a final product.
Example 3
The component A comprises:
and B component:
preparing a component A:
and (2) putting 17kg of castor oil, 21.54kg of MDI and 7.9kg of DMF into a reaction kettle, reacting at the temperature of 80-120 ℃ in an inert gas atmosphere for 3-4 h, adding 4.1kg of methanol to terminate the reaction when the measured NCO of the system reaches a theoretical value, and discharging to obtain the component A.
Preparing a component B:
carrying out prepolymerization reaction on 84kg of polybutylene adipate glycol, 42kg of polyethylene glycol terephthalate glycol 14.8kg of MDI and 142kg of DMF, controlling the reaction temperature at 75-85 ℃, after the reaction is carried out for 2-4 h, testing the viscosity of the reaction solution to 60 ℃, adding 84kg of polytetrahydrofuran ether glycol and 26kg of polyoxypropylene glycol after 190-220 Pa.s, after the reaction is carried out for 1h, continuously adding 29.54kg of ethylene glycol and 870kg of DMF, stirring uniformly, adding 123.8kg of MDI, controlling the reaction temperature at 75-85 ℃, after the reaction is carried out for 1-2 h, adding the rest of MDI in batches, and reacting until the final viscosity is 50 ℃, 150-250 Pa.s to obtain the component B.
A. Mixing the component B:
and uniformly mixing the component A and the component B, controlling the mixing temperature to be 60-80 ℃, mixing for 3-5 h, and discharging to obtain a final product.
Example 4
The component A comprises:
and B component:
preparing a component A:
16kg of castor oil, 23.17kg of MDI and 7.5kg of DMF are put into a reaction kettle, the reaction temperature is 80-120 ℃, the reaction is carried out for 3-4 h in the atmosphere of inert gas, when the measured NCO of the system reaches a theoretical value, 4.6kg of methanol is added to terminate the reaction, and the component A is obtained after discharging.
Preparing a component B:
carrying out prepolymerization reaction on 110kg of polybutylene adipate glycol, 6.5kg of MDI and 136kg of DMF, controlling the reaction temperature at 75-85 ℃, after the reaction is carried out for 2-4 h, testing the viscosity of the reaction solution to 60 ℃, adding 90kg of polytetrahydrofuran ether glycol and 22kg of polyoxypropylene glycol after 150-180 Pa.s, after the reaction is carried out for 1h, continuously adding 28.03kg of ethylene glycol and 784kg of DMF, after the uniform stirring, adding 118.6kg of MDI, controlling the reaction temperature at 75-85 ℃, after the reaction is carried out for 1-2 h, adding the rest amount of MDI in batches, and reacting until the final viscosity is 50 ℃, 150-250 Pa.s to obtain the component B.
A. Mixing the component B:
and uniformly mixing the component A and the component B, controlling the mixing temperature to be 60-80 ℃, mixing for 3-5 h, and discharging to obtain a final product.
Parallel comparative example 1
The component A comprises:
and B component:
preparing a component A:
and (2) putting 7.75kg of castor oil, 8.42kg of MDI and 4kg of DMF into a reaction kettle, reacting at the temperature of 80-120 ℃ in an inert gas atmosphere for 3-4 h, adding 1.5kg of methanol to terminate the reaction when the measured NCO of the system reaches a theoretical value, and discharging to obtain the component A.
Preparing a component B:
carrying out prepolymerization reaction on 110kg of polybutylene adipate glycol, 6.5kg of MDI and 136kg of DMF, controlling the reaction temperature at 75-85 ℃, after the reaction is carried out for 2-4 h, testing the viscosity of the reaction solution to 60 ℃, adding 90kg of polytetrahydrofuran ether glycol and 22kg of polyoxypropylene glycol after 150-180 Pa.s, after the reaction is carried out for 1h, continuously adding 28.03kg of ethylene glycol and 784kg of DMF, after the uniform stirring, adding 118.6kg of MDI, controlling the reaction temperature at 75-85 ℃, after the reaction is carried out for 1-2 h, adding the rest amount of MDI in batches, and reacting until the final viscosity is 50 ℃, 150-250 Pa.s to obtain the component B.
A. Mixing the component B:
and uniformly mixing the component A and the component B, controlling the mixing temperature to be 60-80 ℃, mixing for 3-5 h, and discharging to obtain a final product.
Parallel comparative example 2
The component A comprises:
and B component:
preparing a component A:
and (2) putting 20kg of castor oil, 32.6kg of MDI and 9.3kg of DMF into a reaction kettle, reacting at the temperature of 80-120 ℃ in an inert gas atmosphere for 3-4 h, adding 6.68kg of methanol to terminate the reaction when the measured NCO of the system reaches a theoretical value, and discharging to obtain the component A.
Preparing a component B:
carrying out prepolymerization reaction on 100kg of polybutylene adipate glycol, 23.8kg of MDI, 100kg of polytetrahydrofuran ether glycol, 20kg of polyoxypropylene glycol and 286kg of DMF, controlling the reaction temperature at 75-85 ℃, after reacting for 2-4 h, adding 29.94kg of ethylene glycol and 739kg of DMF, stirring uniformly, adding 114.5kg of MDI, controlling the reaction temperature at 75-85 ℃, after reacting for 1-2 h, adding the rest MDI in batches, and reacting until the final viscosity is 50 ℃ and 150-250 Pa.s to obtain the component B.
A. Mixing the component B:
and uniformly mixing the component A and the component B, controlling the mixing temperature to be 60-80 ℃, mixing for 3-5 h, and discharging to obtain a final product.
Test results
1. Diluting the hydrolysis-resistant high-peel-off fluorine-free wet-process resin prepared in the embodiments 1-4 and the fluorine-containing hydrolysis-resistant high-peel-off wet-process resin HDW-100HE obtained by Shanghai Congo technology respectively according to a certain proportion to prepare a coating liquid;
2. soaking 1.0mm non-woven fabric in impregnating resin (HDD-5030 HNF obtained by Shanghai Confucius science and technology), controlling the impregnating sizing amount to be 400-450 g/m2, controlling a certain water content through solidification and extrusion, coating and scraping the non-woven fabric on the impregnating resin at a knife distance of 2.4mm, and obtaining the wet-process base through solidification, washing and drying.
3. Testing of wet base tear strength: cutting two sample strips with the width of 3cm from the test sample, cutting 2cm from the middle of the test sample in the width direction, testing the tearing strength on a tensile machine, testing in the warp direction and the weft direction, and recording the average value of the warp direction test data and the weft direction test data.
4. Hydrolysis resistance test
The wet-process bass prepared in the above steps was completely immersed in a 10% aqueous solution of sodium hydroxide at 25 ℃ for 24 hours, then washed with water and dried, and the results of the peel strength before and after hydrolysis resistance were measured are shown in table 1.
TABLE 1
In parallel with comparative example 1 and example 1, the weight ratio of component A/component B was 1:53.85, outside the claimed range: within 1: 30-20, and other formula processes are the same. Compared with the wet base prepared in examples 1-4, the wet base prepared by the method has slightly lower tearing strength, the peel retention rate after 24 hours of hydrolysis resistance is only 62.8%, and the hydrolysis resistance is obviously poorer than that of the wet base prepared in examples 1-4. It can be seen that too low a content of component a affects the hydrolysis resistance of the resin.
The formula adopted in parallel with the comparative example 2 is the same as that in the example 2, but the synthesis process is different, and polyester and polyether are prepolymerized together instead of being prepolymerized step by step, so that the surface of the prepared wet-process base is solidified too fast, the internal solidification is slow, the replacement of DMF in the solidification process is difficult, the base is washed by water and is difficult to wash, a large amount of DMF remains, and the DMF corrodes the surface of the base during drying to cause surface rotting, so that the peeling strength cannot be tested.
The non-fluorine containing wet base prepared in examples 1-4 has better surface smoothness than the conventional wet base prepared by the fluorine containing resin HDW-100 HE.
And the hydrolysis resistance of the wet base prepared in the embodiments 1 to 4 reaches the effect of the wet base prepared by the fluorine-containing resin HDW-100HE, namely the peel strength retention rate exceeds 90 percent after hydrolysis resistance is carried out for 24 hours.
In addition, the tear strength data show that the tear strength of the wet base prepared from the resins of examples 1-4 is higher than that of the wet base prepared from the fluorine-containing resin HDW-100 HE.
Therefore, the wet base prepared by the method can play a good product substitution role for the wet base prepared by the conventional fluorine-containing resin HDW-100HE, and provides a more environment-friendly product selection direction.
Claims (10)
1. The hydrolysis-resistant high-peel-resistance fluorine-free wet polyurethane resin for the synthetic leather consists of A, B two components in a weight ratio of 1: 30-20, and is characterized in that the component A comprises the following components in parts by weight:
the component B comprises the following components in parts by weight:
2. the wet-process polyurethane resin for hydrolysis-resistant high-peel-resistance fluorine-free synthetic leather as claimed in claim 1, wherein the molar ratio of diphenylmethane-4, 4' -diisocyanate in the component A to the castor oil is 4: 1-7: 1.
3. The wet-process polyurethane resin for hydrolysis-resistant high-peel-resistance fluorine-free synthetic leather as claimed in claim 1, wherein the molar ratio of methanol in the component A to the diphenylmethane-4, 4' -diisocyanate is 1.3:1 to 1.7: 1.
4. The wet polyurethane resin for synthetic leather with hydrolysis resistance and high peel resistance and no fluorine content as claimed in claim 1, wherein the polyester polyol in the component B is any one or more of polybutylene adipate glycol, polyethylene glycol terephthalate glycol or polyethylene glycol terephthalate glycol with number average molecular weight ranging from 2000 to 4000 g/mol.
5. The wet polyurethane resin for synthetic leather with hydrolysis resistance and high peeling performance and no fluorine content as claimed in claim 1, wherein the number average molecular weight of the polytetrahydrofuran ether glycol in the component B is 1800-2000 g/mol; the number average molecular weight of the polyoxypropylene glycol in the component B is 2000-3000 g/mol.
6. The wet polyurethane resin for synthetic leather with hydrolysis resistance and high peeling performance and no fluorine content as claimed in claim 1, wherein the weight ratio of polytetrahydrofuran ether glycol to polyester diol in the component B is 1: 1.5-1: 1.
7. The wet polyurethane resin for synthetic leather with hydrolysis resistance and high peeling performance and no fluorine content as claimed in claim 1, wherein the weight ratio of the polyoxypropylene glycol in the component B to the sum of the weight of the polytetrahydrofuran ether glycol and the weight of the polyester diol is 1: 10-1: 8.
8. The method for preparing the hydrolysis-resistant high-peel-ability fluorine-free wet-process polyurethane resin for synthetic leather according to any one of claims 1 to 7, which comprises the following steps:
the preparation of the component A comprises the following steps:
putting the castor oil, diphenylmethane-4, 4' -diisocyanate and N, N-dimethylformamide into a reaction kettle, controlling the solid content and the reaction temperature of a first reaction liquid to react in an inert gas atmosphere until NCO of a system reaches a theoretical value, and adding the methanol to terminate the reaction to obtain the component A;
the preparation step of the component B:
carrying out pre-polymerization reaction on the polyester dihydric alcohol, part of diphenylmethane-4, 4' -diisocyanate and part of solvent to obtain a second reaction liquid, controlling the reaction temperature of the second reaction liquid and the solid content of the reaction liquid, and reacting until the viscosity and the vacuum degree of the second reaction liquid reach the standard, wherein the molar ratio of isocyanate groups to hydroxyl groups of the second reaction liquid is 0.92: 1-0.95: 1;
then adding the polytetrahydrofuran ether glycol and the polyoxypropylene glycol for continuous reaction, then adding the ethylene glycol and the residual solvent, stirring uniformly, adding the residual diphenylmethane-4, 4 '-diisocyanate to obtain a third reaction liquid, controlling the molar ratio of isocyanate groups to hydroxyl groups in the third reaction liquid to be 0.92: 1-0.95: 1, then controlling the reaction temperature of the third reaction liquid, and adding the last residual diphenylmethane-4, 4' -diisocyanate until the vacuum degree and the viscosity of the third reaction liquid reach the standard to obtain a component B;
mixing:
and (3) uniformly mixing the A, B components at the temperature of 60-80 ℃, and discharging to obtain the product.
9. The method for preparing the hydrolysis-resistant high-peel-resistance fluorine-free wet-process polyurethane resin for synthetic leather according to claim 8, wherein the solid content and the reaction temperature of the first reaction liquid are controlled to be 75-85 ℃ and the solid content of the reaction liquid is controlled to be 45-50%.
10. The method for preparing the hydrolysis-resistant high-peel-resistance fluorine-free wet-process polyurethane resin for synthetic leather according to claim 8,
the step of controlling the reaction temperature and the solid content of the second reaction solution is to control the reaction temperature to be 75-85 ℃ and the solid content of the reaction solution to be 45-50%;
the viscosity and the vacuum degree of the second reaction liquid reach the standard, specifically, when the viscosity of the reaction liquid reaches 60 ℃, the vacuum degree reaches the range of 150-220 Pa.s;
the reaction temperature of the third reaction solution is 75-85 ℃; and the vacuum degree and the viscosity of the third reaction liquid reach the standard, wherein the vacuum degree reaches the range of 150-250 Pa.s when the final viscosity reaches 50 ℃.
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