CN110818879A - Polyurethane resin for folding white-mark-free fabric coating and preparation method thereof - Google Patents

Polyurethane resin for folding white-mark-free fabric coating and preparation method thereof Download PDF

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Publication number
CN110818879A
CN110818879A CN201911117229.2A CN201911117229A CN110818879A CN 110818879 A CN110818879 A CN 110818879A CN 201911117229 A CN201911117229 A CN 201911117229A CN 110818879 A CN110818879 A CN 110818879A
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polyurethane resin
coating
mark
isocyanate
white
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刘成刚
王旭涛
姜海龙
张泽琦
刘少勇
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JIANGSU HUADA NEW MATERIAL CO Ltd
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JIANGSU HUADA NEW MATERIAL CO Ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/4009Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08Processes
    • C08G18/10Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/42Polycondensates having carboxylic or carbonic ester groups in the main chain
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/48Polyethers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/48Polyethers
    • C08G18/4804Two or more polyethers of different physical or chemical nature
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/48Polyethers
    • C08G18/4854Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72Polyisocyanates or polyisothiocyanates
    • C08G18/74Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72Polyisocyanates or polyisothiocyanates
    • C08G18/74Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06NWALL, 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
    • D06N3/00Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12Artificial 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
    • D06N3/14Artificial 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
    • D06N3/146Artificial 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
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06NWALL, 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
    • D06N3/00Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12Artificial 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
    • D06N3/14Artificial 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
    • D06N3/147Artificial 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 isocyanates used

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention relates to polyurethane resin for a folding white-mark-free fabric coating and a preparation method thereof, wherein the raw material formula of the polyurethane resin comprises the following components: 5-15% of polyester polyol; 15-25% of polyether polyol; 10-25% of isocyanate; 1-10% of a chain extender; 45-60% of a solvent; 0.01-0.1% of stabilizer phosphoric acid; 0.05-0.2% of 1.3-butanediol serving as a blocking agent. The invention adopts polyester polyol, polyether polyol, chain extender, isocyanate, end capping agent and the like to prepare the two-liquid type polyurethane resin which is used for fabric coating, improves the bonding strength and elasticity, not only solves the problem of white marks, but also enhances the cold resistance of the coating resin.

Description

Polyurethane resin for folding white-mark-free fabric coating and preparation method thereof
Technical Field
The invention belongs to the technical field of polyurethane resin for a fabric coating, and particularly relates to polyurethane resin for a folding white-mark-free fabric coating and a preparation method thereof.
Background
The coated fabric is a textile and the coating adhesive material forms a single or multiple layer coating in situ on one or both sides of the fabric. The adhesive material can be acrylic resin, polyurethane resin, polyvinyl chloride and the like, and is widely applied to clothes, tents, bags, curtains and the like, wherein the polyurethane coating has the advantages of full hand feeling, good membrane feeling and high popularity. The polyurethane resin coating applied to the bags, curtains and kite cloth generally requires high modulus (100 to 200 modulus) and hard hand feeling, but the existing polyurethane resin applied to the bags, curtains and kite cloth is generally in a one-liquid type, and white marks are easily formed at the fold lines during rolling and folding, and even the coating is partially broken.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an improved polyurethane resin for coating a folding white-mark-free fabric and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the polyurethane resin for the coating of the folding white-mark-free fabric comprises the following raw materials in percentage by weight:
Figure BDA0002274401040000011
according to some embodiments of the invention, the polyester polyol is one or a combination of 1500-2500 molecular weight polyester polyol prepared by polymerizing AA, EG and 1.4-BG, and 1500-2500 molecular weight polyester polyol prepared by polymerizing AA and 1.4-BG.
Preferably, the polyester polyol is one or a combination of two of a 2000 molecular weight polyester polyol prepared by polymerizing AA, EG and 1.4-BG and a 2000 molecular weight polyester polyol prepared by polymerizing AA and 1.4-BG. Such as Huada CMA-244, CMA-44.
According to some embodiments of the invention, the polyether polyol is one or a combination of PTMEG-2000, PPG-3000.
According to some embodiments of the invention, the chain extender is one or a combination of 1, 4-butanediol, neopentyl glycol.
According to some embodiments of the invention, the solvent is one or a combination of N, N-dimethylformamide and toluene.
According to some embodiments of the invention, the isocyanate is one of TDI, MDI or a combination of both.
According to some preferred embodiments of the invention, the isocyanate is TDI or a combination thereof with MDI, and when the isocyanate is a combination of TDI and MDI, the proportion of MDI does not exceed 20% of the total weight of the isocyanate.
According to some embodiments of the invention, the stabilizer is phosphoric acid.
According to some embodiments of the invention, the end-capping agent is 1, 3-butanediol.
The other technical scheme adopted by the invention is as follows: the preparation method of the polyurethane resin for the folded white-mark-free fabric coating comprises the steps of uniformly stirring polyester polyol, polyether polyol and a stabilizer at the temperature of 40-60 ℃, and then adding a stabilizer of the polyurethane resin into a mixture according to the proportion of NCO: adding a part of isocyanate into the OH with the molar ratio of 1.8-2.2, heating to 85 +/-3 ℃, reacting for 1-3 h, then adding a solvent and a chain extender, cooling, adding the rest part of isocyanate when the temperature is reduced to 60 ℃ or below, heating to 85 +/-3 ℃, reacting to the viscosity of 80-120 Pa.S/25 ℃, adding a blocking agent for blocking, cooling and discharging.
Preferably, the portion of the isocyanate is TDI and the remaining portion of the isocyanate is MDI.
The polyurethane resin prepared by the invention is a two-liquid polyurethane resin, and when the polyurethane resin is used, a curing agent, the polyurethane resin, a catalyst and a solvent are mixed according to a mass ratio of 1: 5-10: 0.1-0.2: 1.5-4, wherein the curing agent is NCO type curing agent, such as NX; the catalyst is organic bismuth catalyst, and the solvent is toluene.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
the invention adopts polyester polyol, polyether polyol, chain extender, isocyanate, end capping agent and the like to prepare the two-liquid type polyurethane resin which is used for fabric coating, improves the bonding strength and elasticity, not only solves the problem of white marks, but also enhances the cold resistance of the coating resin.
The preparation method of the polyurethane resin comprises the steps of carrying out prepolymerization reaction on polyol and isocyanate, then carrying out chain extension, and then carrying out end capping with a capping agent to prepare the two-liquid type polyurethane resin, wherein an NCO type curing agent is added during specific use.
Detailed Description
The inventor analyzes the white mark part to see that the joint of the resin and the cloth is separated, the resin coating is not restored to the original position after being stretched, and therefore, the white mark problem needs to be solved in terms of the bonding fastness of the resin and the cloth and the elasticity of the resin. The present invention is a polyurethane resin developed to improve the above problems and also to enhance the cold resistance of a coating resin.
The following examples are presented to further illustrate the practice of the invention, but the scope of the invention is not limited thereto
Example 1
The polyurethane resin for the coating of the folding white-mark-free fabric provided by the embodiment is prepared by the following method:
adding 40g of polyester polyol (CMA-244), 100g of polyether polyol (PTMEG-2000 specifically), 140g of polyether polyol (PPG-2000 specifically) and 0.03g of phosphoric acid into a reaction kettle, fully stirring, controlling the temperature at 50 ℃ and stirring for 40min, and then adding TDI according to the ratio of NCO: and adding OH with the molar ratio of 2.0 into a reaction kettle, controlling the temperature to slowly rise to 85 ℃, reacting for 2 hours, adding 180g of DMF (dimethyl formamide) and 100g of TOL (total organic solvent) for cooling, adding 33g of 1.4-BG (hydroxyl-terminated diisocyanate) and 33g of NPG (N-propylphosphate), adding 135g of MDI (diphenylmethane diisocyanate) when the temperature is reduced to below 60 ℃, slowly rising to 85 ℃, reacting until the viscosity is 40-50 Pa.S/75 ℃, then adding 1.5g of 1.3-BG (hydroxyl-terminated diisocyanate) for end capping reaction, cooling, discharging, packaging and weighing, wherein the reaction time is 5 hours.
Example 2
The polyurethane resin for the coating of the folding white-mark-free fabric provided by the embodiment is prepared by the following method:
adding 80g of polyester polyol (CMA-44), 60g of polyether polyol (PTMEG-2000 specifically) and 140g of polyether polyol (PPG-3000 specifically) 0.035g of phosphoric acid into a reaction kettle, fully stirring, controlling the temperature at 50 ℃ and the stirring time at 40min, and then adding TDI according to the NCO: adding OH with the molar ratio of 2.0 into a reaction kettle, controlling the temperature to slowly rise to 85 ℃, reacting for 2 hours, adding 180g of DMF (dimethyl formamide) and 100g of TOL (total organic solvent) for cooling, adding 32g of 1.4-BG (hydroxyl-terminated diisocyanate) and 32g of NPG (N-propylsuccinate), adding 136.6g of MDI (diphenyl diisocyanate) when the temperature is reduced to below 60 ℃, slowly rising to 82 ℃, reacting until the viscosity is 40-50 Pa.S/25 ℃, then adding 1.2g of 1.3-BG (hydroxyl-terminated diisocyanate) for end capping reaction, and cooling, discharging, packaging and weighing, wherein the reaction time is 5.5.
Example 3
The polyurethane resin for the coating of the folding white-mark-free fabric provided by the embodiment is prepared by the following method:
adding 80g of polyester polyol (CMA-44), 100g of polyether polyol (PTMEG-2000 specifically) and 0.025g of phosphoric acid of 100g of polyether polyol (PPG-2000 specifically) into a reaction kettle, fully stirring, controlling the temperature at 50 ℃ and stirring for 40min, and then adding TDI according to the ratio of NCO: and adding OH with the molar ratio of 2.0 into a reaction kettle, controlling the temperature to slowly rise to 85 ℃, reacting for 2 hours, adding 180g of DMF (dimethyl formamide) and 100g of TOL (total organic solvent) for cooling, adding 33g of 1.4-BG (hydroxyl-terminated diisocyanate) and 33g of NPG (N-propylphosphate), adding 135g of MDI (diphenylmethane diisocyanate) when the temperature is reduced to below 60 ℃, slowly rising to 85 ℃, reacting until the viscosity is 40-60 Pa.S/25 ℃, then adding 1.2g of 1.3-BG (hydroxyl-terminated diisocyanate) for end capping reaction, and cooling, discharging, packaging and weighing, wherein the reaction time is 5.5 hours.
Comparative example 1
The polyurethane resin for the fabric coating provided by the comparative example is prepared by the following method:
adding 140g of polyester polyol (CMA-244), 140g of polyether polyol (specifically PPG-2000) and 0.02g of phosphoric acid into a reaction kettle, fully stirring, controlling the temperature at 50 ℃, stirring for 40min, and then adding TDI according to the ratio of NCO: and adding OH with the molar ratio of 2.0 into a reaction kettle, controlling the temperature to slowly rise to 85 ℃, reacting for 2 hours, adding 180g of DMF (dimethyl formamide) and 100g of TOL (total organic solvent) for cooling, adding 33g of 1.4-BG (hydroxyl-terminated diisocyanate) and 33g of NPG (N-propylphosphate), adding 135g of MDI (diphenylmethane diisocyanate) when the temperature is reduced to below 60 ℃, slowly rising to 85 ℃, reacting until the viscosity is 40-50 Pa.S/25 ℃, then adding 1.2g of 1.3-BG (hydroxyl-terminated diisocyanate) for terminating the reaction, cooling, discharging, packaging and weighing, wherein the reaction time is 4.5 hours.
Comparative example 2
The polyurethane resin for the fabric coating provided by the comparative example is prepared by the following method:
160g of polyester polyol (CMA-44), 40g of polyether polyol (PTMEG-2000 in particular) and 80g of polyether polyol (PPG-2000 in particular) of 0.03g of phosphoric acid are added into a reaction kettle, fully stirred, the temperature is controlled at 50 ℃, the stirring time is 40min, and then TDI is added according to the ratio of NCO: and adding OH with the molar ratio of 2.0 into a reaction kettle, controlling the temperature to slowly rise to 85 ℃, reacting for 2 hours, adding 180g of DMF (dimethyl formamide) and 100g of TOL (total organic solvent) for cooling, adding 33g of 1.4-BG (hydroxyl-terminated diisocyanate) and 33g of NPG (N-propylphosphate), adding 135g of MDI (diphenylmethane diisocyanate) when the temperature is reduced to below 60 ℃, slowly rising to 85 ℃, reacting until the viscosity is 40-50 Pa.S/25 ℃, then adding 1.2g of 1.3-BG (hydroxyl-terminated diisocyanate) for end capping reaction, cooling, discharging, packaging and weighing, wherein the reaction time is 5 hours.
Comparative example 3
The polyurethane resin for the fabric coating provided by the comparative example is prepared by the following method:
adding 80g of polyester polyol (CMA-44), 160g of polyether polyol (specifically PPG-2000) and 0.03g of phosphoric acid into a reaction kettle, fully stirring, controlling the temperature at 40 ℃, stirring for 40min, and then adding TDI according to the ratio of NCO: and adding OH with the molar ratio of 2.0 into a reaction kettle, controlling the temperature to slowly rise to 88 ℃, reacting for 2 hours, adding 180g of DMF (dimethyl formamide) and 100g of TOL (total organic solvent) for cooling, adding 33g of 1.4-BG (hydroxyl-terminated diisocyanate) and 33g of NPG (N-propylphosphate), adding 135g of MDI (diphenylmethane diisocyanate) when the temperature is reduced to below 60 ℃, slowly raising the temperature to 85 ℃, reacting until the viscosity is 40-50 Pa.S/75 ℃, then adding 1.5g of 1.3-BG (hydroxyl-terminated diisocyanate) for end capping reaction, and cooling, discharging, packaging and weighing, wherein the reaction time is 5.5 hours.
The polyurethane resins prepared in examples 1 to 3 and comparative examples 1 to 3 were mixed as a polyurethane resin: NCO type curing agent NX: organic bismuth-based catalyst: the mass ratio of the toluene solvent is 100: 12: 2: 30, then coating the oxford fabric on the fabric, curing to obtain a fabric sample, and then carrying out performance test, wherein the results are shown in table 1.
Table 1 shows the results of the performance test of the polyurethane resins prepared in examples 1 to 3 and comparative examples 1 to 3
Figure BDA0002274401040000041
Figure BDA0002274401040000051
The test method comprises the following steps:
white mark test: the fabric sample was repeatedly folded and kneaded over 100 times to observe the white mark condition.
Cold resistance test: the fabric sample was flexed 1 ten thousand times at-15 ℃ and observed for cracking and white marking.
Elongation percentage: tensile machine testing
Tensile strength: tensile machine testing
Rebound resilience: tensile machine testing
Peel strength: testing on tensile machine after PU strip is pasted
Modulus: tensile machine testing
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.

Claims (9)

1. The polyurethane resin for the coating of the folding white-mark-free fabric is characterized by comprising the following raw materials in percentage by weight:
5-15% of polyester polyol;
15-25% of polyether polyol;
10-25% of isocyanate;
1-10% of a chain extender;
45-60% of a solvent;
0.01-0.1% of a stabilizer;
0.05 to 0.2 percent of end-capping agent,
the end-capping agent is 1, 3-butanediol.
2. The polyurethane resin for coating a folding white-mark-free fabric according to claim 1, wherein: the polyester polyol is 1500-2500 molecular weight polyester polyol prepared by polymerizing AA, EG and 1.4-BG, and one or the combination of 1500-2500 molecular weight polyester polyol prepared by polymerizing AA and 1.4-BG.
3. The polyurethane resin for coating a folding white-mark-free fabric according to claim 1, wherein: the polyether polyol is one or two of PTMEG-2000, PPG-2000 and PPG-3000.
4. The polyurethane resin for coating a folding white-mark-free fabric according to claim 1, wherein: the chain extender is one or the combination of 1, 4-butanediol and neopentyl glycol.
5. The polyurethane resin for coating a folding white-mark-free fabric according to claim 1, wherein: the solvent is one or the combination of N, N-dimethylformamide and toluene.
6. The polyurethane resin for coating a folding white-mark-free fabric according to claim 1, wherein: the isocyanate is TDI or MDI or the combination of the TDI and the MDI.
7. The polyurethane resin for coating a folding white-mark-free fabric according to claim 6, wherein: the isocyanate is TDI or a combination thereof with MDI, and when the isocyanate is TDI and MDI, the proportion of the MDI is not more than 20% of the total weight of the isocyanate.
8. The polyurethane resin for coating a folding white-mark-free fabric according to claim 1, wherein: the stabilizer is phosphoric acid.
9. A method for preparing the polyurethane resin for the coating of the folded white-mark-free fabric according to any one of claims 1 to 8, wherein the method comprises the following steps: the preparation method comprises the steps of uniformly stirring polyester polyol, polyether polyol and a stabilizer at the temperature of 40-60 ℃, and then adding NCO: adding a part of isocyanate into the OH with the molar ratio of 1.8-2.2, heating to 85 +/-3 ℃, reacting for 1-3 h, then adding a solvent and a chain extender, cooling, adding the rest part of isocyanate when the temperature is reduced to 60 ℃ or below, heating to 85 +/-3 ℃, reacting to the viscosity of 80-120 Pa.S/25 ℃, adding a blocking agent for blocking, cooling and discharging.
CN201911117229.2A 2019-11-15 2019-11-15 Polyurethane resin for folding white-mark-free fabric coating and preparation method thereof Pending CN110818879A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113072676A (en) * 2021-03-26 2021-07-06 扬州工业职业技术学院 Low-temperature flexible polyurethane coating resin for clothes and preparation method thereof
CN114106286A (en) * 2020-08-31 2022-03-01 江苏奥斯佳材料科技股份有限公司 Liquid polyurethane coating and preparation method and application thereof
CN114539503A (en) * 2022-03-23 2022-05-27 江苏华大新材料有限公司 Flame-retardant polyurethane resin for fabric coating and preparation method thereof
CN115044015A (en) * 2022-06-22 2022-09-13 烟台云泷化学制品有限公司 Fast-drying textile auxiliary and preparation method thereof

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005063904A1 (en) * 2003-12-23 2005-07-14 Basf Corporation Coating compositions for adhesion to olefinic substrates
CN101503861A (en) * 2008-12-19 2009-08-12 安徽安利合成革股份有限公司 Two-liquid type rapid stripping synthetic leather composite overlay
CN102352100A (en) * 2011-06-15 2012-02-15 浙江华峰合成树脂有限公司 Fast cured two-liquid type non-yellowing polyurethane bonding layer resin for synthetic leather and preparation method thereof
CN102533201A (en) * 2011-12-26 2012-07-04 合肥安利聚氨酯新材料有限公司 Preparation method of two-liquid type instant immediately peeled polyurethane resin bonding agent for synthetic leather
CN102634318A (en) * 2012-05-02 2012-08-15 江苏华大新材料有限公司 Low-temperature-resisting solvent type polyurethane bonding agent and preparation method thereof
CN102911332A (en) * 2012-09-29 2013-02-06 嘉兴禾欣化学工业有限公司 Method for preparing polyurethane resin with high elongation at break
CN103351456A (en) * 2013-05-28 2013-10-16 江苏华大新材料有限公司 Wet method polyurethane resin for clothing leather, and preparation method thereof
CN106750084A (en) * 2016-11-25 2017-05-31 上海华峰超纤材料股份有限公司 High solids content two-liquid type bonding layer polyurethane resin and preparation method thereof
CN107189036A (en) * 2017-06-27 2017-09-22 郑鑫 A kind of environment-friendlyink ink polyurethane resin and preparation method thereof

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005063904A1 (en) * 2003-12-23 2005-07-14 Basf Corporation Coating compositions for adhesion to olefinic substrates
CN101503861A (en) * 2008-12-19 2009-08-12 安徽安利合成革股份有限公司 Two-liquid type rapid stripping synthetic leather composite overlay
CN102352100A (en) * 2011-06-15 2012-02-15 浙江华峰合成树脂有限公司 Fast cured two-liquid type non-yellowing polyurethane bonding layer resin for synthetic leather and preparation method thereof
CN102533201A (en) * 2011-12-26 2012-07-04 合肥安利聚氨酯新材料有限公司 Preparation method of two-liquid type instant immediately peeled polyurethane resin bonding agent for synthetic leather
CN102634318A (en) * 2012-05-02 2012-08-15 江苏华大新材料有限公司 Low-temperature-resisting solvent type polyurethane bonding agent and preparation method thereof
CN102911332A (en) * 2012-09-29 2013-02-06 嘉兴禾欣化学工业有限公司 Method for preparing polyurethane resin with high elongation at break
CN103351456A (en) * 2013-05-28 2013-10-16 江苏华大新材料有限公司 Wet method polyurethane resin for clothing leather, and preparation method thereof
CN106750084A (en) * 2016-11-25 2017-05-31 上海华峰超纤材料股份有限公司 High solids content two-liquid type bonding layer polyurethane resin and preparation method thereof
CN107189036A (en) * 2017-06-27 2017-09-22 郑鑫 A kind of environment-friendlyink ink polyurethane resin and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
邬花元等: "高固体份聚氨酯树脂在超细纤维合成革中的应用", 《西部皮革》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114106286A (en) * 2020-08-31 2022-03-01 江苏奥斯佳材料科技股份有限公司 Liquid polyurethane coating and preparation method and application thereof
CN113072676A (en) * 2021-03-26 2021-07-06 扬州工业职业技术学院 Low-temperature flexible polyurethane coating resin for clothes and preparation method thereof
CN114539503A (en) * 2022-03-23 2022-05-27 江苏华大新材料有限公司 Flame-retardant polyurethane resin for fabric coating and preparation method thereof
CN114539503B (en) * 2022-03-23 2024-02-27 江苏华大新材料有限公司 Flame-retardant polyurethane resin for fabric coating and preparation method thereof
CN115044015A (en) * 2022-06-22 2022-09-13 烟台云泷化学制品有限公司 Fast-drying textile auxiliary and preparation method thereof

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Application publication date: 20200221