CN107602801B - Solvent-free polyurethane slurry, preparation method thereof and application thereof in hydrolysis-resistant 5-7-year vacuum grain-absorbing synthetic leather - Google Patents
Solvent-free polyurethane slurry, preparation method thereof and application thereof in hydrolysis-resistant 5-7-year vacuum grain-absorbing synthetic leather Download PDFInfo
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Abstract
The invention provides a solvent-free polyurethane slurry, a preparation method thereof and application thereof in hydrolysis-resistant 5-7 years vacuum grain-absorbing synthetic leather, wherein the solvent-free polyurethane slurry is composed of a component A and a component B according to the mass ratio of 100: 45-110, wherein the component A is composed of polytetrahydrofuran dihydric alcohol, an alcohol chain extender, tertiary water, glass fiber, a pore-opening agent, a delayed catalyst, a foam stabilizer and a photo-thermal stabilizer; the component B consists of polytetrahydrofuran diol, polyisocyanate, polymerization inhibitor and catalyst. The invention adopts the embossing process that water is taken as a foaming agent to participate in the reaction to obtain a stable cell structure, and then the vacuum grain-absorbing process is applied, so that the prepared vacuum grain-absorbing synthetic leather with the middle layer being a solvent-free polyurethane layer has soft hand feeling and strong real leather feeling.
Description
Technical Field
The invention belongs to the technical field of synthetic leather, and relates to solvent-free polyurethane slurry, a preparation method thereof and application of the solvent-free polyurethane slurry in vacuum pattern-sucking synthetic leather with hydrolysis resistance for 5-7 years.
Background
The development of the polyurethane synthetic leather industry towards the directions of environmental protection, energy conservation and emission reduction gradually becomes a trend, and the aqueous polyurethane synthetic leather, the solvent-free polyurethane synthetic leather, the TPU and the like gradually become novel materials for replacing the traditional solvent-based polyurethane synthetic leather. The solvent-free polyurethane synthetic leather has the advantages of excellent physical properties, low energy consumption in production and processing, few production procedures, excellent environmental protection performance and the like, and is gradually a research hotspot in the synthetic leather industry.
The main reason for the VOC residue of the traditional solvent-based polyurethane synthetic leather is the residue of organic solvent in the wet-process bass and dry-process bonding links, and the problem can be well solved through the research and development of solvent-free polyurethane intermediate layer resin, because the research and development of the solvent-free polyurethane resin are the premise of the research and development of solvent-free polyurethane synthetic leather products. In addition, because most solvent-free polyurethane resins form a body type network structure with high crosslinking degree, and the structure is firmer than a linear structure formed by solvent type polyurethane resins, the solvent-free polyurethane synthetic leather has higher durability and durability than the traditional solvent type polyurethane synthetic leather on the premise of the same type of polyurethane resin raw materials.
The polyurethane synthetic leather pattern and grain are obtained by mainly adopting two modes of release paper transfer veneering and embossing, and the latter mode has more advantages in the aspects of production efficiency, real leather feeling effect and the like compared with the former mode. At present, more solvent-free polyurethane resins are mainly applied to a release paper transfer veneering process to obtain the surface grain effect of synthetic leather, and few reports are made on solvent-free polyurethane full-water foaming resins which can be applied to an embossing process. The invention discloses a polyurethane synthetic leather cleaning production process based on a direct coating method, which is reported in Chinese invention patent with application number 201210233756.1, and adopts the steps of directly coating solvent-free two-component resin A, B on base cloth to form the base cloth with a solvent-free coating, then coating waterborne polyurethane on the solvent-free coating, and finally embossing to form the surface texture effect of the synthetic leather. The technology of the patent has great difficulty in practical processing: firstly, because the A, B mixture has low viscosity at the initial reaction stage, when the mixed two-component A, B material is sprayed on non-woven cloth or knitted cloth through a double-nozzle feeding system, the mixed two-component A, B material is easy to permeate into base cloth with larger pores, so that the coating and scraping of a coating and scraping machine are difficult; secondly, once the A, B mixed material is permeated into the base fabric, the base fabric is stiff in hand feeling, and the final finished product is stiff in hand feeling and is not favored by consumers. In addition, the solvent-free two-component foaming coating mentioned in the patent report adopts a physical foaming mode of compressed air, and the size of the foam pores is determined according to the mixing amount of air in a compressed air spray gun and the atomization degree of slurry; since the amount of air to be mixed is difficult to determine, the applicant believes that the size and structure of cells formed by the air mixing device have problems of great fluctuation, difficulty in control and the like.
The invention discloses a manufacturing method of embossable solvent-free synthetic leather reported in Chinese patent application No. 201410204557.7, wherein the embossing characteristic of the synthetic leather is mainly provided by a thermoplastic aqueous polyurethane foaming middle layer, while a solvent-free thermosetting foaming bottom layer only provides the physical property and hand feeling of the synthetic leather, and the aqueous polyurethane foaming resin actually plays the role of embossing effect.
The vacuum grain absorption process is an embossing process technology developed in recent years, and compared with a cold pressing process and a hot pressing process, the vacuum grain absorption process has the advantages that the synthetic leather product prepared by the vacuum grain absorption process is softer in hand feeling, stable in physical performance and the like. The double-component solvent-free polyurethane resin endows the synthetic leather with a body type cross-linked structure, and although the synthetic leather has excellent durability and durability, the synthetic leather also has certain defects: firstly, if polyester type two-component solvent-free polyurethane resin is adopted, the hydrolysis resistance of the prepared synthetic leather is difficult to ensure to be stable for more than 3 years; and secondly, if the formed body type crosslinking degree is high, the net structure of the solvent-free polyurethane resin coating is obvious, and the method is difficult to be applied to an embossing process. In addition, in order to ensure that the double-component solvent-free polyurethane resin coating continuously and stably forms a foam pore structure with consistent size and uniform pore pattern, the formed foam pores are quantified by adopting a chemical foaming mode, so that the double-component solvent-free polyurethane resin coating has an obvious production application prospect. Therefore, it is especially necessary to develop a solvent-free intermediate layer polyurethane resin product which can be applied to an embossing process and can be prepared into synthetic leather with soft hand feeling and high hydrolysis resistance.
Disclosure of Invention
The invention aims to provide a solvent-free polyurethane slurry, a preparation method thereof and application of the solvent-free polyurethane slurry in vacuum pattern-sucking synthetic leather with hydrolysis resistance for 5-7 years.
The technical scheme of the invention is as follows:
a solvent-free polyurethane slurry comprises component A and component B at a mass ratio of 100: 45-110,
wherein the component A comprises the following components in parts by mass:
80-90 parts of polytetrahydrofuran dihydric alcohol
2-5 parts of alcohol chain extender
0.5-1.5 parts of tertiary water
5-15 parts of glass fiber
0.5-2 parts of pore forming agent
0.05 to 0.5 portion of delayed type catalyst
0.05-0.5 part of foam stabilizer
0-1 part of photo-thermal stabilizer;
the component B comprises the following components in parts by mass:
35-60 parts of polytetrahydrofuran dihydric alcohol
65-40 parts of polyisocyanate
0.01 to 0.03 portion of polymerization inhibitor
0-0.1 part of catalyst.
In a further scheme, the polytetrahydrofuran diol is modified polytetrahydrofuran diol with a molecular chain containing a branched chain structure.
Preferably, the modified polytetrahydrofuran diol is one obtained by copolymerizing tetrahydrofuran and one of the side group-substituted tetrahydrofuran, neopentyl glycol and propylene oxide, and the molecular weight of the modified polytetrahydrofuran diol is 1000-4000.
In a further scheme, the alcohol chain extender is at least one of ethylene glycol, 1, 3-propylene glycol, 1, 2-propylene glycol, methyldiethanolamine and dihydroxyethylaniline.
Further, the conductivity of the tertiary water is not more than 5uS/cm at 25 ℃;
the cell opener refers to polyether polyol with the hydroxyl value of 160-180 mgKOH/g;
the glass fiber is 100-1000 mesh alkali-free glass fiber powder;
the delayed type catalyst is a special amine delayed gel type catalyst DY-215.
In the invention, tertiary water with the conductivity of not more than 5uS/cm (25 ℃) is selected as a foaming agent, and a diamine structure can be formed in the reaction process and used as a chain extender to further participate in the reaction.
The glass fiber is 100-1000 mesh alkali-free glass fiber powder, preferably 300-mesh, 500-mesh or 1000-mesh glass fiber powder, and has small influence on viscosity and easy processing as a filler.
The delayed catalyst DY-215 is a special amine delayed gel catalyst, so that the early-stage fluidity of the reaction is effectively ensured, the continuous production is ensured, the after-ripening performance of the product is not influenced, and the product shaping performance is ensured.
In a further scheme, the polyisocyanate is a mixture of diphenylmethane diisocyanate, carbodiimide modified diphenylmethane diisocyanate and MDI-50 in a mass ratio of 70-90: 5-20: 1-10, wherein the content of NCO groups is 10-20 wt%.
In a further scheme, the foam stabilizer is polyether modified organosilicon surfactant; the light-heat stabilizer is an ultraviolet absorbent, a hindered amine light stabilizer and an antioxidant.
Preferably, the polyether-modified silicone surfactant is a polysiloxane-alkylene oxide block or graft copolymer; such as DC-193, DC-2525, DC-2585, DC-3042, DC-3043 and DC-5043 of American air chemical industry, B8715 LF2, B8726 LF2 and B8738 LF2 of Germany winning and creating company, L-580, L-818, L-3002, L-3415 and the like of American Meiji corporation;
the ultraviolet absorbent is UV-1, UV-320, UV-1130, UV-P, UV-1164 or UV-234; the hindered amine light stabilizer is 292, 622, 770, 944, 5050, 5060 or 5151; the antioxidant is antioxidant 245, antioxidant 1010, antioxidant 1035, antioxidant 1076, antioxidant 1098 or antioxidant 3114.
In a further scheme, the polymerization inhibitor is phosphoric acid or benzoyl chloride; the catalyst is organic metal bismuth catalyst, such as BiCAT 8106, BiCAT 8108, BiCAT 8124, BiCAT 3228, BiCAT 4130, BiCAT 4232, MB20, etc.
The second invention of the present invention is to provide a method for preparing the above solvent-free polyurethane slurry, which comprises the following steps:
(1) putting polytetrahydrofuran dihydric alcohol and an alcohol chain extender into a reaction kettle, stirring and heating to 60-80 ℃, adding tertiary water, cooling to 30-40 ℃, adding a pore-opening agent, a foam stabilizer and a light-heat stabilizer, and stirring for 2-3 hours to obtain a mixture;
(2) putting polyisocyanate into a reaction kettle according to the mass ratio, adding a polymerization inhibitor, heating to 50-60 ℃, and stirring until the mixture is clear and transparent; then adding polytetrahydrofuran dihydric alcohol and a catalyst, heating to 65-90 ℃, reacting for 2-4h, and carrying out vacuum defoaming for 2-3h under-0.08 MPa to-0.1 MPa after the NCO content is detected to reach 10-20wt%, so as to obtain a component B;
(3) adding glass fiber and a delayed catalyst into the mixture prepared in the step (1), and mixing to form a component A; and then fully mixing the component A and the component B according to the mass ratio of 100: 45-110 to form the solvent-free polyurethane slurry.
The mixture in the solvent-free polyurethane slurry component A, the glass fiber, the delayed catalyst and the component B are poured on the solvent-based surface layer for foaming and reaction to form the solvent-free foamed middle layer when the mixture, the glass fiber, the delayed catalyst and the component B are mixed for use.
The third purpose of the invention is to provide the application of the solvent-free polyurethane slurry, wherein the solvent-free polyurethane slurry is used as the middle layer slurry of the vacuum pattern-sucking synthetic leather with hydrolysis resistance for 5-7 years.
In a further scheme, the preparation method of the hydrolysis-resistant vacuum grain-sucking synthetic leather for 5-7 years comprises the following steps:
(1) putting polytetrahydrofuran dihydric alcohol and an alcohol chain extender into a reaction kettle, stirring and heating to 60-80 ℃, adding tertiary water, cooling to 30-40 ℃, adding a pore-opening agent, a foam stabilizer and a light-heat stabilizer, and stirring for 2-3 hours to obtain a mixture;
(2) putting polyisocyanate into a reaction kettle according to the mass ratio, adding a polymerization inhibitor, heating to 50-60 ℃, and stirring until the mixture is clear and transparent; then adding polytetrahydrofuran dihydric alcohol and a catalyst, heating to 65-90 ℃, reacting for 2-4h, and carrying out vacuum defoaming for 2-3h under-0.08 MPa to-0.1 MPa after the NCO content is detected to reach 10-20wt%, so as to obtain a component B;
(3) coating solvent type surface layer sizing agent on the plain release paper, drying and forming to obtain a solvent type surface layer;
(4) adding glass fiber and a delayed catalyst into the mixture prepared in the step (1) and mixing to form a component A; then, fully mixing the component A and the component B according to the mass ratio of 100: 45-110 to form solvent-free polyurethane slurry; pouring the solvent-free polyurethane slurry on the solvent-based surface layer in the step (3) back and forth in a reciprocating manner through a reaction injection molding continuous casting machine, reacting at the temperature of 100-120 ℃ and chemically foaming to form a cell structure; then placing the mixture at the temperature of 100-120 ℃ for pre-reaction for 1-2min to form a solvent-free foaming middle layer;
(5) adhering the solvent-free foaming intermediate layer to the base cloth, and then placing the base cloth at the temperature of 130-150 ℃ for continuous high-temperature reaction to cure and form the base cloth; then peeling off the plain release paper to obtain a synthetic leather bottom blank;
(6) and (3) quickly pre-drying the prepared synthetic leather base blank at the temperature of 160-250 ℃, and then carrying out grain suction process under the conditions of-0.1 to-0.05 MPa pressure and 10-25m/min vehicle speed to obtain expected grains, thus obtaining the hydrolysis-resistant vacuum grain suction synthetic leather for 5-7 years.
In a further scheme, the sizing agent of the solvent-based surface layer is polyurethane resin, the polyurethane resin is soft segment prepared by copolymerizing polyester diol and polyether diol, and the polyurethane resin is hard segment prepared by copolymerizing ethylene glycol, the solid content of the polyurethane resin is 25%, and the viscosity of the polyurethane resin is 80-120 Pa.s.
Preferably, the polyester diol is a polyester diol with molecular weight of 2000 prepared from adipic acid and ethylene glycol, and the polyether diol is polytetrahydrofuran diol with molecular weight of 2000.
Compared with the prior art, the invention has the following obvious advantages:
(1) according to the invention, water is used as a foaming agent to participate in the reaction to obtain an embossing process of a stable cell structure, and then a vacuum grain suction process is applied, so that the prepared vacuum grain suction synthetic leather with the solvent-free middle layer has soft hand feeling and strong real leather feeling;
(2) the solvent-free polyurethane slurry adopts the all polyether formula, has good embossing performance and excellent durability and durability, and effectively ensures the service performance of synthetic leather products; the hydrolysis resistance of the prepared vacuum line-sucking solvent-free polyurethane synthetic leather product (jungle test: 95% humidity, 70 ℃) can reach the level of 5-7 years; the point is different from the contradiction between the hydrolysis resistance and the embossing performance of the traditional solvent type polyurethane synthetic leather;
(3) according to the invention, the glass fiber material and the polyurethane resin are compounded and cooperated, so that the heat resistance of the solvent-free polyurethane slurry can be improved besides the enhancement and toughening of the polyurethane resin, the damage of temperature and pressure to the molecular chain of the polyurethane resin in the middle layer in the embossing process can be effectively prevented, and the influence on the physical performance of the finished leather is reduced; meanwhile, the formed glass fiber reinforced composite coating structure makes up the problems of molecular chain pyrolysis and mechanical property reduction caused by insufficient temperature resistance and few crosslinking points of a polyether material in a molecular structure, and ensures continuous and stable production of vacuum suction lines.
(4) The invention is a solvent-free polyurethane slurry which is developed specially for a vacuum line-sucking process and is used as a middle layer of vacuum line-sucking synthetic leather, wherein water is used as a foaming agent on one hand, quantitative and stable foam holes are formed through chemical reaction, and the polyurethane slurry has soft hand feeling before vacuum line-sucking; on the other hand, a certain amount of MDI-50 is introduced into the isocyanate prepolymer of the component B, so that the crystallinity of the isocyanate prepolymer is reduced, and the softness of finished leather can be further increased on the premise of not influencing the setting performance;
(5) the synthetic leather prepared by the invention adopts a vacuum line-absorbing process, and compared with a roller type embossing process such as hot pressing, cold pressing and the like, the original cellular structure of the synthetic leather can be pressed into a flat cellular structure, so that the hand feeling is hard, and the original cellular structure of the synthetic leather can be changed into a vertical cellular structure by adopting the vacuum line-absorbing process, so that the hand feeling is softer and is closer to the real leather feeling effect;
(6) the solvent-free polyurethane slurry formula adopts modified polytetrahydrofuran diol with a molecular chain containing a branched chain structure, wherein the polytetrahydrofuran diol is taken as a main body, and has higher strength compared with polypropylene oxide diol, so that the strength of resin and the temperature resistance in the embossing process can be improved, and the branched chain structure is used for improving the opening property of a formed cell structure and avoiding quality hidden troubles such as foam collapse, foam explosion and the like caused by closed cells in the embossing high-temperature process; and the synthetic leather prepared by the method has hydrolysis resistance of 5-7 years;
(7) no matter the component A in the solvent-free polyurethane slurry is used as polyether diol of a soft segment or chain extender of a hard segment, the component A adopts a 2-functionality structure, which is the premise of ensuring that the solvent-free middle layer polyurethane resin can be subjected to vacuum embossing; in addition, by introducing carbodiimide modified MDI with functionality degree slightly larger than 2 into the component B, a small amount of crosslinking points are formed in the leather forming process, and the mechanical property of the solvent-free middle-layer polyurethane resin is improved to the maximum extent on the premise of not influencing the embossing performance; ensures that the synthetic leather manufactured by the method has embossing feasibility
(8) According to the invention, tertiary water as a chemical foaming agent participates in the reaction to form a diamine structure which further participates in the reaction as a chain extender, and a certain amount of polyurea structure is formed to provide good support for the solvent-free polyurethane coating in the vacuum grain absorption processing process, so that the reduction of the plumpness and the definition of patterns on the leather surface caused by insufficient support of the middle layer in the vacuum grain absorption process is prevented, and the problem of the formation of the patterns on the leather surface is effectively prevented.
Detailed Description
The present invention is further illustrated by the following specific examples, but it should be noted that the specific material ratios, process conditions, results, etc. described in the examples of the present invention are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and all equivalent changes and modifications made according to the spirit of the present invention should be covered by the scope of the present invention.
Example 1:
a solvent-free polyurethane slurry for a vacuum line-sucking synthetic leather intermediate layer slurry with hydrolysis resistance of 5-7 years is composed of a component A and a component B:
wherein the component A consists of the following components:
polytetrahydrofuran diol (PTG-L3000) 80 parts
2 portions of alcohol chain extender (ethylene glycol)
0.5 part of tertiary water
15 portions of glass fiber
2 portions of pore-forming agent (GJ-170)
0.5 part of delayed type catalyst (DY-215)
Foam stabilizer (DC-193) 0.5 part
0.1 portion of photo-thermal stabilizer (UV-1)
0.1 part of photo-thermal stabilizer (Chisorb 292)
0.05 part of photo-thermal stabilizer (Chinox 1010)
The component B consists of the following components:
polytetrahydrofuran diol (PTG-L2000) 35 parts
65 parts of polyisocyanate
Polymerization inhibitor (phosphoric acid) 0.03 part
0.1 part of catalyst (BiCAT 8108).
The polytetrahydrofuran diols PTG-L3000 and PTG-L2000 are respectively modified polytetrahydrofuran diol produced by Nippon Baogu chemical industries, and produced by the company of molecular weight 3000 and 2000, and modified polytetrahydrofuran diol copolymerized by side group substituted tetrahydrofuran;
the methyldiethanolamine chain extender is a product of BASF company, the third-level water is self-made water with the conductivity of not more than 5uS/cm (25 ℃), the pore-forming agent GJ-170 is polyether polyol with the hydroxyl value of 160-180mgKOH/g produced by Shanghai Gaoqiao petrochemical company, the glass fiber is 500-mesh alkali-free glass fiber powder produced by Shenzhen Ci Adita science and technology Limited company, and the delayed catalyst DY-215 is a delayed gel catalyst produced by Shanghai Desheng chemical company;
the polyisocyanate is a mixture of diphenylmethane diisocyanate, carbodiimide modified diphenylmethane diisocyanate and MDI-50 at a mass ratio of 70: 20: 10, wherein the content of NCO groups is 10-20 wt%. The diphenylmethane diisocyanate was Wannate MDI-100 produced by Nicotiana Wawawa polyurethane, Inc., the carbodiimide-modified diphenylmethane diisocyanate was Wannate MDI-100LL produced by Nicotiana Wawa polyurethane, Inc., and the MDI-50 was a mixture of 4,4 '-MDI and 2, 4' -MDI produced by Nicotiana Wawa polyurethane, Inc.
The ethylene glycol chain extender and the phosphoric acid polymerization inhibitor are commercially available raw materials, the foam stabilizer DC-193 is a polyether modified organic silicon foam stabilizer produced by American air chemical company, the light and heat stabilizer UV-1 is an ultraviolet absorber produced by Kunming dye chemical company Limited, the light and heat stabilizer Chisorb 292 is a hindered amine light stabilizer produced by Taiwan double bond chemical company Limited, the light and heat stabilizer Chinox 1010 is a hindered phenol antioxidant produced by Taiwan double bond chemical company Limited, and the catalyst BiCAT 8108 is an organic bismuth catalyst produced by American advanced chemical company.
The solvent-free polyurethane slurry is used as an intermediate slurry of the vacuum line-sucking synthetic leather with hydrolysis resistance for 5-7 years, and the preparation method comprises the following steps:
(1) putting polytetrahydrofuran diol PTG-L3000, ethylene glycol and methyldiethanolamine into a reaction kettle according to a formula ratio, stirring and heating to 60 ℃, adding tertiary water, then cooling to 30 ℃, adding a pore-forming agent GJ-170, a foam stabilizer DC-193, a photo-thermal stabilizer UV-1, Chisorb 292 and Chinox 1010, stirring for 2 hours to prepare a mixture, and sealing and packaging for later use;
(2) putting polyisocyanate into a reaction kettle, adding a polymerization inhibitor phosphoric acid, heating to 60 ℃, stirring until the mixture is clear and transparent, then putting polytetrahydrofuran diol PTG-L2000 and a catalyst BiCAT 8108, heating to 90 ℃, reacting for 2 hours, carrying out vacuum defoamation for 2 hours under-0.08 MPa after the NCO content is detected to reach 10-20wt%, and preparing a component B, and sealing and packaging for later use;
(3) coating solvent type surface layer sizing agent on the plain release paper, drying and forming to obtain a solvent type surface layer; the solvent-based surface layer sizing agent is polyurethane resin, the polyurethane resin is soft segment formed by copolymerization of polyester diol and polyether diol, and ethylene glycol is hard segment, the solid content of the polyurethane resin is 25%, and the viscosity of the polyurethane resin is 80-120 Pa.s. Wherein the polyester diol is prepared from adipic acid and ethylene glycol, the molecular weight of the polyester diol is 2000, and the polyether diol is polytetrahydrofuran diol with the molecular weight of 2000.
(4) Adding 500-mesh alkali-free glass fiber powder and a delayed catalyst DY-215 into the mixture prepared in the step (1) and mixing to form a component A; fully mixing the component A and the component B according to the mass ratio of 100: 45 to form solvent-free polyurethane slurry; pouring the solvent-free polyurethane slurry on the solvent-based surface layer in the step (3) back and forth in a reciprocating manner through a reaction injection molding continuous casting machine, reacting at 100 ℃ and chemically foaming to form a cellular structure; pre-reacting at 100 deg.C for 2min to form a solvent-free foamed intermediate layer;
(5) adhering the solvent-free foaming intermediate layer to the base cloth, and then placing the base cloth at 130 ℃ for continuous high-temperature reaction to cure and form the base cloth; then peeling off the plain release paper to obtain a synthetic leather bottom blank;
(6) and (3) quickly pre-drying the prepared synthetic leather base blank at 160 ℃, and then carrying out grain suction process under the conditions of-0.05 MPa pressure and 10m/min vehicle speed to obtain expected grains, thus obtaining the hydrolysis-resistant vacuum grain suction synthetic leather for 5-7 years.
The vacuum grain-absorbing synthetic leather product prepared by the embodiment has soft hand feeling and full patterns, and the hydrolysis resistance (jungle test: 95% RH, 70 ℃) can reach the 5-year level.
Example 2:
a solvent-free polyurethane slurry for a vacuum line-sucking synthetic leather intermediate layer slurry with hydrolysis resistance of 5-7 years is composed of a component A and a component B:
the component A comprises the following components:
polytetrahydrofuran diol (PTXG-1800) 90 parts
4 parts of alcohol chain extender (1, 2-propylene glycol)
Alcohol chain extender (dihydroxyethylaniline) 1 part
Tertiary water 1.5 parts
5 parts of glass fiber
0.5 part of pore forming agent (GJ-170)
0.05 part of delayed type catalyst (DY-215)
Foam stabilizer (B8726 LF 2) 0.05 part
0.3 part of photo-thermal stabilizer (UV-1130)
0.2 part of photo-thermal stabilizer (Chisorb 944)
0.1 part of photo-thermal stabilizer (Chinox 1076)
The component B consists of the following components:
polytetrahydrofuran diol (PTXG-1000) 60 parts
40 parts of polyisocyanate
Polymerization inhibitor (phosphoric acid) 0.01 part
The polytetrahydrofuran diols PTXG-1800 and PTXG-1000 are branched polytetrahydrofuran diols having molecular weights of 1800 and 1000 produced by Asahi chemical Co., Ltd, Japan, respectively; the dihydroxyethyl aniline chain extender is a product of Tongyuan chemical company of Hainin, Zhejiang province, the third-level water is self-made water with the conductivity of less than or equal to 5uS/cm (25 ℃), the pore-forming agent GJ-170 is polyether polyol with the hydroxyl value of 160 and 180mgKOH/g, which is produced by Shanghai Gaoqiao petrochemical company, the glass fiber is 300-mesh alkali-free glass fiber powder produced by Adita science and technology Limited company, Shenzhen city, and the delayed catalyst DY-215 is a delayed gel catalyst produced by Shanghai De Sound chemical company;
the polyisocyanate is prepared from diphenylmethane diisocyanate, carbodiimide modified diphenylmethane diisocyanate and MDI-50 according to a mass ratio of 90: 5: 1, wherein the NCO group content is from 10 to 20% by weight. The diphenylmethane diisocyanate was Wannate MDI-100 produced by Nicotiana Wawawa polyurethane, Inc., the carbodiimide-modified diphenylmethane diisocyanate was Wannate MDI-100LL produced by Nicotiana Wawa polyurethane, Inc., and the MDI-50 was a mixture of 4,4 '-MDI and 2, 4' -MDI produced by Nicotiana Wawa polyurethane, Inc.
The 1, 2-propylene glycol chain extender and the polymerization inhibitor phosphoric acid are commercially available raw materials, the foam stabilizer B8726 LF2 is a polyether modified organic silicon surfactant produced by Germany winning and creating company, the light and heat stabilizer UV-1130 is an ultraviolet absorbent produced by Guangzhou Zhi chemical engineering Co., Ltd, the light and heat stabilizer Chisorb 944 is a hindered amine light stabilizer produced by Taiwan double bond chemical engineering Co., Ltd, and the light and heat stabilizer Chinox 1076 is a hindered phenol antioxidant produced by Taiwan double bond chemical engineering Co., Ltd.
The solvent-free polyurethane slurry is used as an intermediate slurry of the vacuum line-sucking synthetic leather with hydrolysis resistance for 5-7 years, and the preparation method comprises the following steps:
(1) putting polytetrahydrofuran diol PTXG-1800, 1, 2-propylene glycol and diethanoaniline into a reaction kettle according to a formula ratio, stirring and heating to 80 ℃, adding tertiary water, then cooling to 40 ℃, adding a pore-forming agent GJ-170, a foam stabilizer B8726 LF2, a light and heat stabilizer UV-1130, a Chisorb 944 and a Chinox 1076, stirring for 3 hours, preparing a mixture, and sealing and packaging for later use;
(2) putting polyisocyanate into a reaction kettle, adding a polymerization inhibitor phosphoric acid, heating to 50 ℃, stirring until the mixture is clear and transparent, then putting polytetrahydrofuran diol PTXG-1000, heating to 65 ℃, reacting for 4 hours, carrying out vacuum defoamation for 3 hours under-0.1 MPa after the NCO content is detected to reach 10-20wt%, and sealing and packaging to obtain a component B for later use;
(3) coating solvent type surface layer sizing agent on the plain release paper, drying and forming to obtain a solvent type surface layer;
(4) adding 300-mesh alkali-free glass fiber powder and a delayed type catalyst DY-215 into the mixture prepared in the step (1), fully mixing the mixture with the component B according to the mass ratio of 100: 110, then using a reaction injection molding continuous casting machine to perform reciprocating casting back and forth to coat the mixture on a solvent type surface layer, reacting at 110 ℃ and performing chemical foaming to form a cellular structure, and then placing the cellular structure at 110 ℃ for pre-reaction for 1.5min to form a solvent-free foaming middle layer;
(5) adhering the solvent-free foaming intermediate layer to the base cloth, and then placing the base cloth at 140 ℃ for continuous high-temperature reaction to cure and form the base cloth; then peeling off the plain release paper to obtain a synthetic leather bottom blank;
(6) and (3) quickly pre-drying the prepared synthetic leather base blank at 190 ℃, and then carrying out grain suction process under the conditions of-0.08 MPa pressure and 20m/min vehicle speed to obtain expected grains, thus obtaining the hydrolysis-resistant vacuum grain suction synthetic leather for 5-7 years.
The vacuum grain-absorbing synthetic leather product prepared by the embodiment has soft hand feeling and full patterns, and the hydrolysis resistance (forest test: 95% RH, 70 ℃) can reach 6-year level.
Example 3:
a solvent-free polyurethane slurry of a vacuum line-sucking synthetic leather intermediate layer slurry resistant to hydrolysis for 5-7 years is composed of a component A and a component B:
the component A comprises the following components:
polytetrahydrofuran diol (polycyrine DCB-4000) 85 parts
2 parts of alcohol chain extender (1, 3-propylene glycol)
2 portions of alcohol chain extender (methyldiethanolamine)
Tertiary water 1.0 part
Glass fiber 10 parts
1 part of pore forming agent (GJ-170)
0.3 portion of delayed type catalyst (DY-215)
0.3 part of foam stabilizer (L-580)
0.4 part of photo-thermal stabilizer (UV-1164)
0.2 part of photo-thermal stabilizer (Tinuvin 5050)
0.4 part of photo-thermal stabilizer (Chinox 1098)
The component B consists of the following components:
50 parts of polytetrahydrofuran dihydric alcohol (polycyrine DCB-2000)
50 parts of polyisocyanate
0.02 portion of polymerization inhibitor (benzoyl chloride)
0.05 part of catalyst (BiCAT 3228)
The polytetrahydrofuran diol Polycerine DCB-4000 and Polycerine DCB-2000 are tetrahydrofuran-propylene oxide copolyether glycol with molecular weight of 4000 and 2000, respectively, produced by Nippon oil Co., Ltd; the 1, 3-propylene glycol chain extender is a product of DuPont company in America, the methyldiethanolamine chain extender is a product of BASF company, the third-level water is self-made water with the conductivity of less than or equal to 5uS/cm (at 25 ℃), the pore-forming agent GJ-170 is polyether polyol with the hydroxyl value of 160-;
the polyisocyanate is a mixture of diphenylmethane diisocyanate, carbodiimide modified diphenylmethane diisocyanate and MDI-50 at a mass ratio of 70: 20: 10, wherein the content of NCO groups is 10-20 wt%. The diphenylmethane diisocyanate was Wannate MDI-100 produced by Nicotiana Wawawa polyurethane, Inc., the carbodiimide-modified diphenylmethane diisocyanate was Wannate MDI-100LL produced by Nicotiana Wawa polyurethane, Inc., and the MDI-50 was a mixture of 4,4 '-MDI and 2, 4' -MDI produced by Nicotiana Wawa polyurethane, Inc.
The foam stabilizer L-580 is a polyether modified organic silicon surfactant produced by American Meiji corporation, the light and heat stabilizer UV-1164 is an ultraviolet absorbent produced by Yuntangsheng chemical Co., Ltd, the light and heat stabilizer Tinuvin 5050 is a composite light stabilizing additive produced by Germany Basff corporation, Chinox 1098 is a hindered phenol antioxidant produced by Taiwan double bond chemical Co., Ltd, the polymerization inhibitor benzoyl chloride is a commercially available 322raw material, and the catalyst BiCAT 8 is an organic bismuth catalyst produced by American advanced chemical Co., Ltd.
The solvent-free polyurethane slurry is used as an intermediate slurry of the vacuum line-sucking synthetic leather with hydrolysis resistance for 5-7 years, and the preparation method comprises the following steps:
(1) putting polytetrahydrofuran dihydric alcohol polycerin DCB-4000, 1, 3-propylene glycol and methyldiethanolamine into a reaction kettle according to a formula proportion, stirring and heating to 70 ℃, adding tertiary water, then cooling to 35 ℃, adding a pore-forming agent GJ-170, a foam stabilizer L-580, a light and heat stabilizer UV-1164, Tinuvin 5050 and Chinox 1098, stirring for 2.5 hours to prepare a mixture, and sealing and packaging for later use;
(2) putting polyisocyanate into a reaction kettle, adding a polymerization inhibitor benzoyl chloride, heating to 55 ℃, stirring until the mixture is clear and transparent, then putting polytetrahydrofuran diol polycyrine DCB-2000 and a catalyst BiCAT 3228, heating to 80 ℃, reacting for 3 hours, carrying out vacuum defoamation for 2.5 hours under-0.09 MPa after NCO content detection reaches 10-20wt%, and preparing a component B, and sealing and packaging for later use;
(3) coating solvent type surface layer sizing agent on the plain release paper, drying and forming to obtain a solvent type surface layer;
(4) adding 1000-mesh alkali-free glass fiber powder and a delayed type catalyst DY-215 into the mixture prepared in the step (1), fully mixing the mixture with the component B according to the mass ratio of 100: 80, then using a reaction injection molding continuous casting machine to perform reciprocating casting to coat the mixture on the release paper with the solvent type surface layer, performing reaction at 120 ℃ and chemical foaming to form a cellular structure, and then placing the cellular structure at 120 ℃ for pre-reaction for 1min to form a solvent-free foamed middle layer;
(5) adhering the solvent-free foaming intermediate layer to the base cloth, and then placing the base cloth at the temperature of 150 ℃ for continuous high-temperature reaction to cure and form the base cloth; then peeling off the plain release paper to obtain a synthetic leather bottom blank;
(6) and (3) quickly pre-drying the prepared synthetic leather base blank at 250 ℃, and then carrying out grain suction process under the conditions of-0.1 MPa pressure and 25m/min vehicle speed to obtain expected grains, thus obtaining the hydrolysis-resistant vacuum grain suction synthetic leather for 5-7 years.
The vacuum grain-absorbing synthetic leather product prepared by the embodiment has soft hand feeling and full patterns, and the hydrolysis resistance (jungle test: 95% RH, 70 ℃) can reach the 7-year level.
Claims (10)
1. The application of the solvent-free polyurethane slurry as the intermediate layer slurry of the hydrolysis-resistant 5-7-year vacuum grain-sucking synthetic leather is characterized in that: the solvent-free polyurethane slurry consists of a component A and a component B according to the mass ratio of 100: 45-110,
wherein the component A comprises the following components in parts by mass:
the component B comprises the following components in parts by mass:
the polytetrahydrofuran diol is modified polytetrahydrofuran diol with a molecular chain containing a branched chain structure;
the modified polytetrahydrofuran diol is obtained by copolymerizing tetrahydrofuran and one of side group-substituted tetrahydrofuran, neopentyl glycol and propylene oxide, and has the molecular weight of 1000-4000;
the polyisocyanate is a mixture of diphenylmethane diisocyanate, carbodiimide modified diphenylmethane diisocyanate and MDI-50 according to a mass ratio of 70-90: 5-20: 1-10, wherein the content of NCO groups is 10-20 wt%.
2. Use according to claim 1, characterized in that: the alcohol chain extender is at least one of ethylene glycol, 1, 3-propylene glycol, 1, 2-propylene glycol, methyldiethanolamine and dihydroxyethylaniline.
3. Use according to claim 1, characterized in that: the conductivity of the tertiary water is not more than 5uS/cm at 25 ℃;
the cell opener refers to polyether polyol with the hydroxyl value of 160-180 mgKOH/g;
the glass fiber is 100-1000 mesh alkali-free glass fiber powder;
the delayed type catalyst is a special amine delayed gel type catalyst DY-215.
4. Use according to claim 1, characterized in that: the foam stabilizer is polyether modified organosilicon surfactant; the light-heat stabilizer is an ultraviolet absorbent, a hindered amine light stabilizer and an antioxidant.
5. Use according to claim 4, characterized in that: the polyether modified organosilicon surfactant is polysiloxane-alkylene oxide block or graft copolymer; the ultraviolet absorbent is UV-1, UV-320, UV-1130, UV-P, UV-1164 or UV-234; the hindered amine light stabilizer is 292, 622, 770, 944, 5050, 5060 or 5151; the antioxidant is antioxidant 245, antioxidant 1010, antioxidant 1035, antioxidant 1076, antioxidant 1098 or antioxidant 3114.
6. Use according to claim 1, characterized in that: the polymerization inhibitor is phosphoric acid or benzoyl chloride; the catalyst is an organic metal bismuth catalyst.
7. Use according to claim 1, characterized in that: the preparation method of the solvent-free polyurethane slurry comprises the following steps:
(1) putting polytetrahydrofuran dihydric alcohol and an alcohol chain extender into a reaction kettle, stirring and heating to 60-80 ℃, adding tertiary water, cooling to 30-40 ℃, adding a pore-opening agent, a foam stabilizer and a light-heat stabilizer, and stirring for 2-3 hours to obtain a mixture;
(2) putting polyisocyanate into a reaction kettle according to the mass ratio, adding a polymerization inhibitor, heating to 50-60 ℃, and stirring until the mixture is clear and transparent; then adding polytetrahydrofuran dihydric alcohol and a catalyst, heating to 65-90 ℃, reacting for 2-4h, and carrying out vacuum defoaming for 2-3h under-0.08 MPa to-0.1 MPa after the NCO content is detected to reach 10-20wt%, so as to obtain a component B;
(3) adding glass fiber and a delayed catalyst into the mixture prepared in the step (1), and mixing to form a component A; and then fully mixing the component A and the component B according to the mass ratio of 100: 45-110 to form the solvent-free polyurethane slurry.
8. Use according to claim 1, characterized in that: the preparation method of the hydrolysis-resistant 5-7 years vacuum grain-absorbing synthetic leather comprises the following steps:
(1) putting polytetrahydrofuran dihydric alcohol and an alcohol chain extender into a reaction kettle, stirring and heating to 60-80 ℃, adding tertiary water, cooling to 30-40 ℃, adding a pore-opening agent, a foam stabilizer and a light-heat stabilizer, and stirring for 2-3 hours to obtain a mixture;
(2) putting polyisocyanate into a reaction kettle according to the mass ratio, adding a polymerization inhibitor, heating to 50-60 ℃, and stirring until the mixture is clear and transparent; then adding polytetrahydrofuran dihydric alcohol and a catalyst, heating to 65-90 ℃, reacting for 2-4h, and carrying out vacuum defoaming for 2-3h under-0.08 MPa to-0.1 MPa after the NCO content is detected to reach 10-20wt%, so as to obtain a component B;
(3) coating solvent type surface layer sizing agent on the plain release paper, drying and forming to obtain a solvent type surface layer;
(4) adding glass fiber and a delayed catalyst into the mixture prepared in the step (1) and mixing to form a component A; then, fully mixing the component A and the component B according to the mass ratio of 100: 45-110 to form solvent-free polyurethane slurry; pouring the solvent-free polyurethane slurry on the solvent-based surface layer in the step (3) back and forth in a reciprocating manner through a reaction injection molding continuous casting machine, reacting at the temperature of 100-120 ℃ and chemically foaming to form a cell structure; then placing the mixture at the temperature of 100-120 ℃ for pre-reaction for 1-2min to form a solvent-free foaming middle layer;
(5) adhering the solvent-free foaming intermediate layer to the base cloth, and then placing the base cloth at the temperature of 130-150 ℃ for continuous high-temperature reaction to cure and form the base cloth; then peeling off the plain release paper to obtain a synthetic leather bottom blank;
(6) and (3) quickly pre-drying the prepared synthetic leather base blank at the temperature of 160-250 ℃, and then carrying out grain suction process under the conditions of-0.1 to-0.05 MPa pressure and 10-25m/min vehicle speed to obtain expected grains, thus obtaining the hydrolysis-resistant vacuum grain suction synthetic leather for 5-7 years.
9. Use according to claim 8, characterized in that: the sizing agent of the solvent-based surface layer is polyurethane resin, the polyurethane resin is soft segment formed by copolymerization of polyester diol and polyether diol, ethylene glycol is hard segment, the solid content is 25%, and the viscosity is 80-120 Pa.s.
10. Use according to claim 9, characterized in that: the polyester diol is prepared from adipic acid and ethylene glycol, the molecular weight of the polyester diol is 2000, and the polyether diol is polytetrahydrofuran diol with the molecular weight of 2000.
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| CN108341983B (en) * | 2018-02-12 | 2021-03-30 | 华南理工大学 | Composite film with foaming coating with open pore structure and preparation method thereof |
| CN114621659A (en) * | 2022-03-22 | 2022-06-14 | 福建中裕新材料技术有限公司 | Solvent-free polyurethane slurry for sports shoes based on direct coating process and preparation method thereof |
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