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 PDFInfo
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- 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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- China
- Prior art keywords
- polyurethane resin
- coating
- mark
- isocyanate
- white
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- Pending
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- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 40
- 239000004744 fabric Substances 0.000 title claims abstract description 36
- 239000011248 coating agent Substances 0.000 title claims abstract description 34
- 238000000576 coating method Methods 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 21
- 239000012948 isocyanate Substances 0.000 claims abstract description 19
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 19
- 229920005862 polyol Polymers 0.000 claims abstract description 19
- 150000003077 polyols Chemical class 0.000 claims abstract description 19
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 18
- 229920000570 polyether Polymers 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 9
- 239000004970 Chain extender Substances 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000003381 stabilizer Substances 0.000 claims abstract description 7
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002981 blocking agent Substances 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 238000001816 cooling Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 230000000379 polymerizing effect Effects 0.000 claims description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 230000000903 blocking effect Effects 0.000 claims description 2
- 235000019437 butane-1,3-diol Nutrition 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- 229920005989 resin Polymers 0.000 abstract description 7
- 239000011347 resin Substances 0.000 abstract description 7
- 239000007788 liquid Substances 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 description 19
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 16
- 125000005442 diisocyanate group Chemical group 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 6
- 238000004806 packaging method and process Methods 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 230000000630 rising effect Effects 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- SZHZCPHKDJWHNG-UHFFFAOYSA-N dipropyl butanedioate Chemical compound CCCOC(=O)CCC(=O)OCCC SZHZCPHKDJWHNG-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
- D06N3/146—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes characterised by the macromolecular diols used
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
- D06N3/147—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes characterised by the isocyanates used
Landscapes
- 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
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:
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
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.
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