CN106479095B - Super-soft protein wet resin and preparation method and application thereof - Google Patents

Super-soft protein wet resin and preparation method and application thereof Download PDF

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CN106479095B
CN106479095B CN201610858935.2A CN201610858935A CN106479095B CN 106479095 B CN106479095 B CN 106479095B CN 201610858935 A CN201610858935 A CN 201610858935A CN 106479095 B CN106479095 B CN 106479095B
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polyvinyl alcohol
glycol
silicone oil
modified silicone
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CN106479095A (en
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钱建中
钱洪祥
巩倩
邹佳娜
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Shanghai Huide Technology Co ltd
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    • C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
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Abstract

The invention relates to super-soft protein wet resin which is prepared from 5-10% of polyester/polyether polyol, 0.3-0.7% of double-end hydroxyl polyether modified silicone oil, 0.3-1% of ethylene glycol, 2-5% of diphenylmethane-4, 4' -diisocyanate, 15-20% of polyvinyl alcohol powder, 0.15-0.25% of polyamide wax and 68-73% of N, N-dimethylformamide. The invention also discloses a preparation method of the super-soft protein wet resin. The wet synthetic leather bass made of the polyurethane polyvinyl alcohol blended wet resin synthesized by the formula and the process has strong spongy feeling, cellular network-like cellular structure similar to real leather protein fiber, fine crease, and the characteristics of softness, comfort, naturalness and warmth retention similar to real leather protein fiber.

Description

Super-soft protein wet resin and preparation method and application thereof
Technical Field
The invention relates to the technical field of preparation of blending modified polyurethane resin, in particular to polyurethane/polyvinyl alcohol blending wet resin with super-soft hand feeling similar to protein fiber, a preparation method and application thereof.
Background
The polyurethane resin for the synthetic leather is a novel polymer material for partially replacing natural leather, along with the increasing exhaustion of natural resources, natural leather resources are gradually insufficient and cannot meet the increasing market demand, and along with the increasing hardening of the competition of the synthetic leather industry, the requirements of people on the polyurethane resin for the synthetic leather are higher and higher, the common polyurethane resin cannot meet the requirements of people, and accordingly, some leather-imitated synthetic leather materials become the focus of the market.
Generally, polyurethane synthetic leather products on the market generally have low cell density, small cell holes or slender cells, and the cell density is greatly different from that of a protein fiber net structure in animal skin, so that the hand feeling of the formed synthetic leather is not soft and natural like that of natural animal skin. In order to form a reticular structure similar to real leather protein fiber, one direction for manufacturing a leather-like synthetic leather product is to form a honeycomb microporous structure, polyurethane material is singly used for manufacturing the synthetic leather wet method base fabric (note: DMF solvent, other fillers and auxiliary agents are added into polyurethane resin to prepare mixed solution, after defoaming is carried out by a vacuum machine, the mixed solution is soaked or coated on a base fabric, then the solvent is replaced by water, the polyurethane resin is gradually solidified to form a microporous polyurethane grain surface layer, and then the wet method base fabric is manufactured by rolling, drying and shaping), although micropores can be formed, the number and the density of the micropores have certain limitations. The invention mainly selects another material, namely polyvinyl alcohol and polyurethane blending modification, so that the two polymers are mixed to prepare a uniform material, and then the uniform material is used for preparing the synthetic leather wet method bass with a structure similar to real leather.
Disclosure of Invention
One of the technical problems to be solved by the invention is to provide the ultra-soft protein wet-process resin aiming at the defects in the prior art, and the wet-process synthetic leather bass prepared from the ultra-soft protein wet-process resin has strong sponge feeling, cellular reticular cell structure similar to real leather, fine crease and the characteristics of softness, comfort, nature and heat preservation similar to real leather protein fiber.
The second technical problem to be solved by the present invention is to provide a method for preparing the ultra-soft protein wet resin.
The invention also provides the application of the ultra-soft protein wet resin.
The technical problem to be solved by the invention can be realized by the following technical scheme:
the super-soft protein wet process resin is mainly prepared from the following raw materials in percentage by weight:
Figure BDA0001122069280000021
in a preferred embodiment of the present invention, the polyester/polyether polyol is one or a mixture of two of polyethylene adipate glycol-1, 4 butylene glycol, polyethylene adipate glycol, polyethylene glycol diethylene glycol adipate glycol and polytetrahydrofuran ether glycol, and the number average molecular weight of the polyester/polyether polyol is 2000 to 4000 g/mol.
In a preferred embodiment of the present invention, the hydroxyl-terminated polyether modified silicone oil is hydroxyl-terminated polyether modified silicone oil having a number average molecular weight of 2000 to 3000 g/mol.
In a preferred embodiment of the invention, the mass ratio of the hydroxyl-terminated polyether modified silicone oil to the total mass of the polyester/polyether polyol is 1:20 to 1: 10.
In a preferred embodiment of the present invention, the polyvinyl alcohol powder is one or two kinds of polyvinyl alcohol powders having an average polymerization degree of 300 to 2400.
In a preferred embodiment of the present invention, the polyvinyl alcohol powder is one or a mixture of two of polyvinyl alcohol powder with 86% alcoholysis degree and polyvinyl alcohol powder with 88% alcoholysis degree.
In a preferred embodiment of the present invention, the mass ratio of the mass of the polyvinyl alcohol powder to the total mass of the polyurethane solid content is: 2.5: 1-1: 1; the total mass of the polyurethane solid components is as follows: polyester/polyether polyol, ethylene glycol, hydroxyl terminated polyether modified silicone oil and isocyanate.
The preparation method of the ultra-soft protein wet process resin as the second aspect of the invention comprises the following steps:
(1) putting polyester/polyether polyol, double-end hydroxyl polyether modified silicone oil, diphenylmethane-4, 4' -diisocyanate and a part of solvent into a reaction kettle for prepolymerization reaction, controlling the molar ratio of isocyanate groups to hydroxyl groups in a reaction liquid to be 0.95: 1-0.98: 1, controlling the reaction temperature to be 75-85 ℃, controlling the solid content of the reaction liquid to be 40-60%, and finishing the first-step reaction when the viscosity of the reaction liquid reaches 10-150 Pa.s/50 ℃ after the reaction is carried out for 2-3 hours;
(2) adding ethylene glycol, diphenylmethane-4, 4' -diisocyanate and the rest solvent into a reaction kettle to carry out chain extension reaction, controlling the reaction temperature to be 50-80 ℃, adding polyvinyl alcohol powder and polyamide wax to carry out blending reaction when the reaction solution viscosity reaches 50 ℃ and 5-30 pas, reacting for 4-6 hours, and finishing the reaction when the test reaction solution viscosity reaches 10-200 pas/50 ℃.
The application of the super-soft protein wet-process resin as the third aspect of the invention is used for manufacturing synthetic leather wet-process bass, and the manufactured wet-process bass has a honeycomb-shaped cellular structure similar to dermal protein fibers.
The super-soft protein wet resin is mainly prepared by physically blending polyurethane and polyvinyl alcohol. The blending of the polymer can obtain new characteristics, and the blending material of the invention can change the cell structure of the traditional polyurethane synthetic leather.
In the invention, polyurethane is used as a main polymer, and polyester/polyether polyol and hydroxyl-terminated polyether modified silicone oil are mainly used as soft segment macromolecular polyol. Because the polyurethane/polyvinyl alcohol blending material often encounters the problems of poor leveling and the like in the leather making process, the double-end hydroxyl polyether modified silicone oil is reacted on a macromolecular chain, so that the compatibility is improved when the polyurethane/polyvinyl alcohol blending material is blended with polyvinyl alcohol powder by changing the surface tension of macromolecules of the polyurethane. In addition, the polyamide wax is added mainly for preventing the polyvinyl alcohol from settling and ensuring the stability of the system.
The super-soft protein wet resin is a polyurethane/polyvinyl alcohol blending material, is applied to the aspect of leather making, utilizes the characteristic that polyvinyl alcohol powder which is swelled and uniformly dispersed occupies space when being solidified in the leather making process and is dissolved in water to leave micropores when being washed, can change the traditional cellular structure to form a cellular micropore structure which is closer to the reticular structure of dermal protein fibers, has strong sponge feeling and fine creases, and has the characteristics of softness, comfort, nature and warm keeping.
Drawings
FIG. 1 is a schematic diagram showing the cell structure of the cross section of a wet process bass produced from the ultra-soft protein wet process resins of examples 1 and 2 of the present invention.
FIG. 2 is a schematic diagram showing the cell structure of the cross section of the wet process bass produced from the ultra-soft protein wet process resins of examples 3 and 4 of the present invention.
FIG. 3 is a schematic diagram showing the cell structure of the cross section of the wet process shellfish prepared by the ultra-soft protein wet process resin of example 5 of the present invention and the cell structure of the cross section of the wet process shellfish prepared in comparative example 1.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1
1. Formulation of
Figure BDA0001122069280000041
2. Preparation method
100kg of poly (ethylene adipate) -1, 4-butanediol glycol (with the number average molecular weight of 4000g/mol), 50kg of poly (tetrahydrofuran ether glycol) (with the number average molecular weight of 2000g/mol), 10kg of double-end hydroxyl polyether modified silicone oil (with the number average molecular weight of 2000), 13.1kg of diphenylmethane-4, 4 '-diisocyanate (MDI) and 260kg of N, N-dimethylformamide are added into a reaction kettle for pre-polymerization reaction, the reaction temperature is controlled to be 75-85 ℃, after the reaction is carried out for 2-3 h, the viscosity of the reaction solution reaches 10-20 Pa.s/50 ℃, 11.81kg of ethylene glycol, 48.26kg of diphenylmethane-4, 4' -diisocyanate and 1892kg of N, N-dimethylformamide are added into the reaction kettle for chain extension reaction, the reaction temperature is controlled to be 60-70 ℃, when the viscosity of the reaction solution reaches 50 ℃, 5-10 Pa.s, adding 597kg of polyvinyl alcohol 0388 powder and 6kg of polyamide wax for a blending reaction, reacting for 4-6 h, and ending the reaction when the viscosity of the reaction solution is tested to reach 170-200 pas/50 ℃.
Example 2
1. Formulation of
Figure BDA0001122069280000051
2. Preparation method
188kg of polyethylene glycol adipate glycol (with the number average molecular weight of 3000g/mol), 10kg of double-end hydroxyl polyether modified silicone oil (with the number average molecular weight of 3000g/mol), 16.11kg of diphenylmethane-4, 4 '-diisocyanate (MDI) and 143kg of N, N-dimethylformamide are added into a reaction kettle for pre-polymerization reaction, the reaction temperature is controlled to be 75-85 ℃, after the pre-polymerization reaction is carried out for 2-3 hours, when the viscosity of a reaction liquid reaches 130-150 Pa.s/50 ℃, 18.25kg of ethylene glycol, 74kg of diphenylmethane-4, 4' -diisocyanate and 1305kg of N, N-dimethylformamide are added into the reaction kettle for chain extension reaction, the reaction temperature is controlled to be 50-60 ℃, when the viscosity of the reaction liquid reaches 50 ℃ and 20-30 Pa.s, 207kg of polyvinyl alcohol 0588 powder and 103.5kg of polyvinyl alcohol 2488 powder are added into the reaction kettle, And 4kg of polyamide wax is subjected to blending reaction for 4-6 h, and the reaction is finished when the viscosity of the reaction solution reaches 10-30 Pa.s/50 ℃ in a test.
Example 3
1. Formulation of
Figure BDA0001122069280000052
Figure BDA0001122069280000061
2. Preparation method
Adding 180kg of polytetrahydrofuran ether glycol (with the number average molecular weight of 3000g/mol), 18kg of double-end hydroxyl polyether modified silicone oil (with the number average molecular weight of 2000g/mol), 16.6kg of diphenylmethane-4, 4 '-diisocyanate (MDI) and 198kg of N, N-dimethylformamide into a reaction kettle for prepolymerization reaction, controlling the reaction temperature to be 75-85 ℃, adding 14.55kg of ethylene glycol, 59.3kg of diphenylmethane-4, 4' -diisocyanate and 2195kg of N, N-dimethylformamide into the reaction kettle for chain extension reaction after the reaction temperature reaches 50-70 Pa.s/50 ℃ after the reaction is carried out for 2-3 hours, controlling the reaction temperature to be 70-80 ℃, adding 296.5kg of polyvinyl alcohol 1788 powder, 296.5kg of polyvinyl alcohol 0386 powder and 8kg of polyamide wax for blending reaction when the reaction liquid viscosity reaches 50 ℃ and 8-12 Pa.s, and (4) reacting for 4-6 h, and finishing the reaction when the viscosity of the reaction solution is tested to reach 150-190 Pa.s/50 ℃.
Example 4
1. Formulation of
Figure BDA0001122069280000062
2. Preparation method
Adding 180kg of polyethylene glycol diethylene glycol adipate glycol (with the number average molecular weight of 4000g/mol), 15kg of double-end hydroxyl polyether modified silicone oil (with the number average molecular weight of 2000g/mol), 12.8kg of diphenylmethane-4, 4 '-diisocyanate (MDI) and 310kg of N, N-dimethylformamide into a reaction kettle for pre-polymerization reaction, controlling the reaction temperature to be 75-85 ℃, adding 14.02kg of ethylene glycol, 56.87kg of diphenylmethane-4, 4' -diisocyanate and 1154kg of N, N-dimethylformamide into the reaction kettle for chain extension reaction when the viscosity of a reaction solution reaches 20-30 pas/50 ℃ after the reaction is carried out for 2-3 hours, controlling the reaction temperature to be 60-70 ℃, adding 405.3kg of polyvinyl alcohol 0588 powder and 5kg of polyamide wax for blending reaction when the viscosity of the reaction solution reaches 50 ℃ and 15-20 pas, and (4) reacting for 4-6 h, and finishing the reaction when the viscosity of the reaction solution is tested to reach 100-120 Pa.s/50 ℃.
Example 5
1. Formulation of
Figure BDA0001122069280000071
2. Preparation method
200kg of poly (ethylene adipate) glycol-1, 4-butanediol glycol diol (with the number average molecular weight of 4000g/mol), 10kg of double-end hydroxyl polyether modified silicone oil (with the number average molecular weight of 2000g/mol), 13.2kg of diphenylmethane-4, 4 '-diisocyanate (MDI) and 273kg of N, N-dimethylformamide are added into a reaction kettle for pre-polymerization reaction, the reaction temperature is controlled to be 75-85 ℃, after the reaction is carried out for 2-3 h, when the viscosity of a reaction solution reaches 10-20 Pa.s/50 ℃, 13.95kg of ethylene glycol, 56.8kg of diphenylmethane-4, 4' -diisocyanate and 1587kg of N, N-dimethylformamide are added into the reaction kettle for reaction, the reaction temperature is controlled to be 50-60 ℃, when the viscosity of the reaction solution reaches 50 ℃, and when the chain extension is 5-10 Pa.s, 1788 kg of polyvinyl alcohol powder 498kg and 498kg of polyvinyl alcohol are added, 5kg of polyamide wax is subjected to blending reaction for 4-6 h, and the reaction is finished when the viscosity of the reaction solution reaches 60-80 Pa.s/50 ℃ in a test.
The inventors conducted a test using the ultra-soft protein wet process resins prepared in examples 1 to 5 of the present invention together with comparative example HDW-20 to compare the cell difference in synthetic leather bass using the above resins.
The experimental steps are as follows:
(1) adding the soft full polyether type hydrolysis-resistant low-foam wet-process polyurethane resin prepared in the embodiment 1-5 into color paste, filling and a solvent, and uniformly stirring to prepare working slurry with the viscosity of 8-15 pas/25 ℃; adding color paste, filling and solvent into the common soft wet process resin HDW-30 of Shanghai Confucius science and technology Limited company to prepare working slurry with the temperature of 8-15 pas/25 ℃.
(2) And (3) coating and scraping the cotton-like base cloth woven fabric with the thickness of 0.9mm, and carrying out solidification, washing and drying to obtain the wet-process bass.
Test results
The cell structure of the cross-sections of the wet base made according to examples 1 to 5 and comparative example HDW-30 of the ultra-soft protein wet resin of the present invention are shown in fig. 1 to 3 (magnified 100 times by a digital microscope):
as shown in fig. 1 to 3, it is apparent that the cross-sectional cells of the bass made of the ultra-soft protein wet process resin of the present invention are honeycomb-shaped and have a larger thickness of the bass, while the cells of the bass made of the general wet process resin are vertical and have a certain stacking layer, and the thickness of the bass is thin, and the honeycomb-shaped cells of examples 1 to 5 cannot be adjusted by filling with the general wet process resin. Therefore, the wet-process bass made of the blended resin material has a cellular cell structure different from that of the traditional wet-process resin, is closer to a net structure of dermal protein fibers, has strong sponge feeling and fine creases, and has the characteristics of softness, comfort, naturalness and warmth retention.

Claims (3)

1. The super-soft protein wet process resin is mainly prepared from the following raw materials in percentage by weight:
Figure FDF0000008651860000011
the polyester/polyether polyol is one or a mixture of more than two of poly (ethylene adipate-1, 4-butanediol) glycol, poly (ethylene adipate) glycol, poly (ethylene glycol diethylene glycol adipate) glycol and poly (tetrahydrofuran ether glycol) with the number average molecular weight of 2000-4000 g/mol, and the hydroxyl terminated polyether modified silicone oil is hydroxyl terminated polyether modified silicone oil with the number average molecular weight of 2000-3000 g/mol;
the mass ratio of the mass of the polyvinyl alcohol to the total mass of the solid polyurethane is as follows: 2.5: 1-1: 1; the total mass of the polyurethane solid components is as follows: the mass sum of polyester/polyether polyol, ethylene glycol, double-end hydroxyl polyether modified silicone oil and isocyanate; the polyurethane solid and polyvinyl alcohol are physically blended, the polyvinyl alcohol powder is swelled to occupy space when tanning is solidified, and the swelled polyvinyl alcohol powder is dissolved in water after being washed with water to leave micropores; the polyvinyl alcohol powder is one or a mixture of two of polyvinyl alcohol powders with the average polymerization degree of 300-2400; the polyvinyl alcohol powder is one or a mixture of two of polyvinyl alcohol powder with alcoholysis degree of 86% and polyvinyl alcohol powder with alcoholysis degree of 88%;
the preparation method of the ultra-soft protein wet resin is characterized by comprising the following steps:
(1) putting polyester/polyether polyol, double-end hydroxyl polyether modified silicone oil, diphenylmethane-4, 4' -diisocyanate and a part of solvent into a reaction kettle for prepolymerization reaction, controlling the molar ratio of isocyanate groups to hydroxyl groups in a reaction liquid to be 0.95: 1-0.98: 1, controlling the reaction temperature to be 75-85 ℃, controlling the solid content of the reaction liquid to be 40-60%, and finishing the first-step reaction when the viscosity of the reaction liquid reaches 10-150 Pa.s/50 ℃ after the reaction is carried out for 2-3 hours;
(2) adding ethylene glycol, diphenylmethane-4, 4' -diisocyanate and the rest solvent into a reaction kettle to carry out chain extension reaction, controlling the reaction temperature to be 50-80 ℃, adding polyvinyl alcohol powder and polyamide wax when the reaction liquid viscosity reaches 50 ℃ and 5-30 Pa.s, carrying out blending reaction to swell the polyvinyl alcohol powder for 4-6 h, and finishing the reaction when the test reaction liquid viscosity reaches 10-200 Pa.s/50 ℃.
2. The super-soft protein wet process resin as claimed in claim 1, wherein the mass ratio of the hydroxyl-terminated polyether modified silicone oil to the total mass of the polyester/polyether polyol is 1: 20-1: 10;
3. use of the ultra-soft protein wet process resin of any one of claims 1 to 2 for making a synthetic leather wet process base having a cellular cell structure resembling a dermal protein fiber structure.
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CN102010496B (en) * 2010-09-29 2013-12-04 上海汇得化工有限公司 Ultra-soft wet process embossing-type polyurethane resin and preparation method and application thereof
CN104194014B (en) * 2014-09-03 2017-02-15 东北电力大学 Polyaniline pincushion array film having electric field responding hydrophilic/hydrophobic change and preparation method thereof
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US3460969A (en) * 1965-08-18 1969-08-12 Goodrich Co B F Process for producing microporous coatings on a textile fabric
US3526531A (en) * 1966-12-01 1970-09-01 Kanebo Ltd Method for making microporous sheet material
CN102449045A (en) * 2009-05-25 2012-05-09 Dic株式会社 Process for producing porous object, and porous object, layered product, and leather-like sheet each obtained thereby

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