CN112300353B - Flexible sulfonic acid type hydrophilic chain extender and preparation method and application thereof - Google Patents
Flexible sulfonic acid type hydrophilic chain extender and preparation method and application thereof Download PDFInfo
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- CN112300353B CN112300353B CN202011295246.8A CN202011295246A CN112300353B CN 112300353 B CN112300353 B CN 112300353B CN 202011295246 A CN202011295246 A CN 202011295246A CN 112300353 B CN112300353 B CN 112300353B
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- sulfonic acid
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- 239000004970 Chain extender Substances 0.000 title claims abstract description 83
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- -1 ether diamine Chemical class 0.000 claims abstract description 34
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000004705 aldimines Chemical class 0.000 claims abstract description 14
- 239000013067 intermediate product Substances 0.000 claims abstract description 14
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 13
- 239000003377 acid catalyst Substances 0.000 claims abstract description 9
- 230000009471 action Effects 0.000 claims abstract description 5
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract 4
- 238000006243 chemical reaction Methods 0.000 claims description 40
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 22
- 229920003009 polyurethane dispersion Polymers 0.000 claims description 20
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 12
- 239000012279 sodium borohydride Substances 0.000 claims description 10
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229920005862 polyol Polymers 0.000 claims description 6
- 150000003077 polyols Chemical class 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000012948 isocyanate Substances 0.000 claims description 4
- 150000002513 isocyanates Chemical class 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- BEOOHQFXGBMRKU-UHFFFAOYSA-N sodium cyanoborohydride Chemical compound [Na+].[B-]C#N BEOOHQFXGBMRKU-UHFFFAOYSA-N 0.000 claims description 4
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 3
- 239000012321 sodium triacetoxyborohydride Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229920002635 polyurethane Polymers 0.000 abstract description 57
- 239000004814 polyurethane Substances 0.000 abstract description 57
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 32
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 16
- 239000007787 solid Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 239000011734 sodium Substances 0.000 description 9
- 229910052708 sodium Inorganic materials 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 125000003010 ionic group Chemical group 0.000 description 8
- 230000001376 precipitating effect Effects 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 238000010008 shearing Methods 0.000 description 7
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 7
- 150000001299 aldehydes Chemical class 0.000 description 6
- 125000001033 ether group Chemical group 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 239000010985 leather Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000012855 volatile organic compound Substances 0.000 description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 229920006264 polyurethane film Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000013068 control sample Substances 0.000 description 2
- UUKHCUPMVISNFW-UHFFFAOYSA-L disodium;4-formylbenzene-1,3-disulfonate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)C1=CC=C(C=O)C(S([O-])(=O)=O)=C1 UUKHCUPMVISNFW-UHFFFAOYSA-L 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000004632 polycaprolactone Substances 0.000 description 2
- 229920005906 polyester polyol Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000013074 reference sample Substances 0.000 description 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000011850 water-based material Substances 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 1
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 1
- 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 1
- RSSPAUNIKXELLR-UHFFFAOYSA-N C(C)[Na].C(CN)N Chemical compound C(C)[Na].C(CN)N RSSPAUNIKXELLR-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- OVDVGECZCGXFJO-UHFFFAOYSA-N benzene-1,3-diamine;sodium Chemical compound [Na].NC1=CC=CC(N)=C1 OVDVGECZCGXFJO-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000921 polyethylene adipate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- ADPUQRRLAAPXGT-UHFFFAOYSA-M sodium;2-formylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1C=O ADPUQRRLAAPXGT-UHFFFAOYSA-M 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000002023 wood Substances 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
-
- 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
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
-
- 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
- C08G18/4833—Polyethers containing oxyethylene units
-
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
-
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a flexible sulfonic acid type hydrophilic chain extender and a preparation method and application thereof. The molecular structure general formula of the flexible sulfonic acid type hydrophilic chain extender is shown as I:
wherein R is H or CH3(ii) a m is 1 or 2; n is any integer of 1-20; x is 1 or 2. The preparation method comprises the steps of reacting aldehyde containing sulfonic acid ion groups with ether diamine under the action of an acid catalyst to generate an aldimine intermediate product, and reducing the aldimine intermediate product by using a reducing agent to prepare the flexible sulfonic acid type hydrophilic chain extender. The invention also provides an application of the flexible sulfonic acid type hydrophilic chain extender or the flexible sulfonic acid type hydrophilic chain extender prepared by the preparation method in the synthesis of the aqueous polyurethane dispersoid. The chain extender further improves the toughness of the polyurethane on the basis of improving the emulsibility and the water resistance of the polyurethane.
Description
Technical Field
The invention relates to the field of polyurethane materials, in particular to a flexible sulfonic acid type hydrophilic chain extender and a preparation method and application thereof.
Background
With the increasingly strict global requirements on environmental protection, solvent-based materials with high Volatile Organic Compounds (VOCs) are gradually forbidden to be used, water-based materials with environmental protection, safety and low VOCs emission become competitive development alternative materials of various industries, and water-based materials become a mainstream direction of global industrial development.
The waterborne polyurethane takes polyurethane resin as a base material, water replaces an organic solvent to serve as a dispersion medium, and the dispersion liquid of the waterborne polyurethane does not contain or contains a little organic solvent, so that the waterborne polyurethane can be widely applied to the industries of textile printing and dyeing, leather processing, coating, adhesives, wood processing, biomedicine, electronic tags and the like due to the combination of the advantages of high performance of the solvent type polyurethane and low VOCs content of waterborne materials. Introducing hydrophilic groups into polyurethane molecular chains is a key for realizing polyurethane hydration, and among a plurality of synthetic means, introducing hydrophilic groups into a chain extender containing hydrophilic groups through a chain extender is the most common method at present, and reported chain extenders comprise: 2, 2-dimethylolpropionic acid, 2-dimethylolbutyric acid, tartaric acid, ethylenediamine ethyl sodium sulfonate, 2, 4-diaminobenzene sodium sulfonate, 1, 2-dihydroxy-3-propane sodium sulfonate, 1, 4-butanediol-2-sodium sulfonate and the like. These hydrophilic chain extenders have the common feature that each chain extender contains only one ionic group. When the chain extenders are used for preparing the waterborne polyurethane, the content of hydrophilic groups on a polyurethane molecular chain is mainly determined by the using amount of the chain extenders. At a lower chain extender consumption, the obtained waterborne polyurethane is difficult to form a waterborne polyurethane dispersion with stable performance because of less hydrophilic groups introduced into the polyurethane molecular chain. However, the higher amount of the chain extender increases the proportion of hydrophilic chain segments in polyurethane molecular chains, greatly reduces the water resistance of the formed polyurethane film, and greatly hinders the industrial application of the waterborne polyurethane. In addition, because the chain extender is usually introduced into the polyurethane molecular chain in a hard segment manner, the proportion of the hard segment content in the polyurethane molecular chain is usually increased when the aqueous polyurethane is synthesized by the chain extender reported above, a polyurethane material with high toughness is difficult to obtain, and the practical application of the aqueous polyurethane in the fields of leather and high-toughness film products is greatly restricted.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: how to realize the improvement of the toughness of the polyurethane on the basis of improving the emulsibility and the water resistance of the polyurethane by the chain extender.
In order to solve the technical problems, the invention provides a flexible sulfonic acid type hydrophilic chain extender and a preparation method and application thereof.
A flexible sulfonic acid type hydrophilic chain extender is disclosed, wherein the molecular structure general formula of the flexible sulfonic acid type hydrophilic chain extender is shown as I:
wherein R is H or CH3(ii) a m is 1 or 2; n is any integer of 1-20; x is 1 or 2.
Further, the flexible sulfonic acid type hydrophilic chain extender is prepared by reacting aldehyde containing sulfonic acid ion groups with ether diamine under an acid catalyst to generate an aldimine intermediate product, and then reducing the aldimine intermediate product by using a reducing agent.
The invention also provides a preparation method of the flexible sulfonic acid type hydrophilic chain extender, which comprises the following steps of reacting aldehyde containing sulfonic acid ion groups with ether diamine under the action of an acid catalyst to generate an aldimine intermediate product, and reducing the aldimine intermediate product by using a reducing agent to prepare the flexible sulfonic acid type hydrophilic chain extender, wherein the reaction formula is as follows:
wherein R is H or CH3(ii) a m is 1 or 2; n is any integer of 1-20; x is 1 or 2.
Further, the molar ratio of the aldehyde containing a sulfonic acid ionic group to the ether diamine is 2-2.2: 1.
Further, the adding mass of the acidic catalyst is 1-2 wt% of the using amount of the ether diamine.
Further, the addition amount of the reducing agent is 3-3.2 times of the molar amount of the ether diamine.
Further, the acid catalyst is one or two of p-toluenesulfonic acid and sulfuric acid; and/or the reducing agent is one or more of sodium borohydride, sodium cyanoborohydride, sodium triacetoxyborohydride and lithium aluminum hydride.
In addition, the invention also provides an application of the flexible sulfonic acid type hydrophilic chain extender or the flexible sulfonic acid type hydrophilic chain extender prepared by the preparation method in the synthesis of the aqueous polyurethane dispersion.
Further, the above applications include:
mixing polymer polyol with isocyanate, and reacting at 50-80 ℃ to obtain a polyurethane prepolymer;
and mixing the polyurethane prepolymer with the flexible sulfonic acid type hydrophilic chain extender, reacting at 50-80 ℃, and dispersing in water to obtain the aqueous polyurethane dispersion.
Further, mixing the polyurethane prepolymer and the flexible sulfonic acid type hydrophilic chain extender according to the mass usage of the flexible sulfonic acid type hydrophilic chain extender being 3-15 wt% of the polyurethane prepolymer.
Compared with the prior art, the invention has the advantages that: the flexible sulfonic acid type hydrophilic chain extender provided by the invention takes a flexible ether chain as a skeleton, contains a plurality of sulfonic acid ion groups and has secondary amino groups which can participate in polyurethane chain extension reaction, and in the later-stage volatilization film-forming process of the aqueous polyurethane dispersion prepared by the chain extender, the skeleton structure of the flexible ether chain can weaken the risk of reducing the flexibility of a polyurethane molecular chain caused by the formation of urea bonds on the one hand, and can effectively avoid the problem that the toughness of a polyurethane material is reduced because the proportion of hard segments in the polyurethane molecular chain is increased by adopting a chain extension means in the prior art; on the other hand, the micro-phase separation degree of the soft and hard sections of the waterborne polyurethane in the film volatilization process can be reduced, and a waterborne polyurethane material with high toughness can be obtained. In addition, 2 or 4 sulfonic acid ion hydrophilic groups can endow more hydrophilic groups on a polyurethane molecular chain under the condition of lower chain extender consumption, so that the emulsifying property and the long-term stability of polyurethane are ensured, the water resistance of a polyurethane film formed by the aqueous polyurethane dispersion is improved, and the industrial application of the aqueous polyurethane in the fields of leather and high-toughness film products is facilitated.
Detailed Description
The specific embodiment provides a flexible sulfonic acid type hydrophilic chain extender, wherein the molecular structure general formula of the flexible sulfonic acid type hydrophilic chain extender is shown as I:
wherein R is H or CH3(ii) a m is 1 or 2; n is any integer of 1-20; x is 1 or 2.
Further, the flexible sulfonic acid type hydrophilic chain extender is prepared by reacting aldehyde containing sulfonic acid ion groups with ether diamine under an acid catalyst to generate an aldimine intermediate product, and then reducing the aldimine intermediate product by using a reducing agent.
The specific embodiment also provides a preparation method of the flexible sulfonic acid type hydrophilic chain extender, which comprises the steps of reacting aldehyde containing sulfonic acid ion groups with ether diamine under the action of an acid catalyst for 5-6 hours to generate an aldimine intermediate product, and reducing the aldimine intermediate product by a reducing agent for 5-6 hours to obtain the flexible sulfonic acid type hydrophilic chain extender, wherein the molar ratio of the aldehyde containing sulfonic acid ion groups to the ether diamine is 2-2.2: 1; the adding mass of the acidic catalyst is 1-2 wt% of the using amount of the ether diamine; the addition amount of the reducing agent is 3-3.2 times of the molar amount of the ether diamine; the reaction formula is as follows:
wherein R is H or CH3(ii) a m is 1 or 2; n is any integer of 1-20; x is 1 or 2.
Further, the acid catalyst is one or two of p-toluenesulfonic acid and sulfuric acid; and/or the reducing agent is one or more of sodium borohydride, sodium cyanoborohydride, sodium triacetoxyborohydride and lithium aluminum hydride.
In addition, the specific embodiment also provides an application of the flexible sulfonic acid type hydrophilic chain extender or the flexible sulfonic acid type hydrophilic chain extender prepared by the preparation method in the synthesis of the aqueous polyurethane dispersion.
Further, the application includes:
mixing the dehydrated polymer polyol with the molecular weight of 200-10000 and isocyanate in a reactor, and then reacting for 4-10 hours at 50-80 ℃ to obtain a polyurethane prepolymer;
according to the mass usage of the flexible sulfonic acid type hydrophilic chain extender being 3-15 wt% of the polyurethane prepolymer, the polyurethane prepolymer is cooled, then the flexible sulfonic acid type hydrophilic chain extender is added, then the reaction is carried out for 4-6 hours at 50-80 ℃, and then the reaction is carried out for 4-6 hours at room temperature under high-speed shearing and then the aqueous polyurethane dispersion is obtained after the reaction is dispersed in water.
Further, the polymer polyol is polyether polyol and/or polyester polyol; the polyether polyol is one or more of polyethylene glycol, polypropylene glycol and polytetrahydrofuran glycol, and the polyester polyol is one or more of polyhexamethylene adipate glycol, polybutylene adipate glycol, polyethylene adipate glycol, polycaprolactone glycol or polycarbonate glycol; the isocyanate is one or more of toluene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, naphthalene diisocyanate, xylylene diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate.
Further, in the above application, the molar ratio of the sum of hydroxyl groups and secondary amino groups to isocyanate groups is 1: 1.
The following detailed description of the preferred embodiments of the invention, which is to be taken in an illustrative rather than a limiting sense, illustrates the principles of the invention.
Example 1
Adding 18.1 g of ether diamine a, 22.9g of sodium benzaldehyde-2-sulfonate, 0.1g of p-toluenesulfonic acid and 50mL of dimethyl sulfoxide into a reaction bottle, and reacting at room temperature for 5 hours under stirring; adding 6.1g of sodium borohydride, and reacting at room temperature for 5 hours; and precipitating the reaction mixed system in acetone for 2 times, washing the obtained solid with a large amount of acetone, and drying in vacuum to obtain the chain extender I-126.5 g.
The reaction formula is as follows:
example 2
Adding ether diamine a-211.1 g, benzaldehyde-4-sodium sulfonate 21.8g, p-toluenesulfonic acid 0.11g and dimethyl sulfoxide 50mL into a reaction bottle, and reacting at room temperature for 5h under stirring; adding 5.9g of sodium borohydride, and reacting at room temperature for 5 hours; and precipitating the reaction mixed system in acetone for 2 times, washing the obtained solid with a large amount of acetone, and drying in vacuum to obtain chain extender I-229.2 g.
The reaction formula is as follows:
example 3
Adding ether diamine a-328.0 g, benzaldehyde-4-sodium sulfonate 2.08g, p-toluenesulfonic acid 0.56g and dimethyl sulfoxide 80mL into a reaction bottle, and reacting at room temperature for 5h under stirring; adding 1.0g of sodium cyanoborohydride, and reacting at room temperature for 5 h; and precipitating the reaction mixed system in acetone for 2 times, washing the obtained solid with a large amount of acetone, and drying in vacuum to obtain the chain extender I-327.2 g.
The reaction formula is as follows:
example 4
Adding ether diamine a-410.2 g, benzaldehyde-2-sodium sulfonate 20.8g, p-toluenesulfonic acid 0.1g and dimethyl sulfoxide 70mL into a reaction bottle, and reacting at room temperature for 5h under stirring; adding 5.7g of sodium borohydride, and reacting at room temperature for 5 hours; and precipitating the reaction mixed system in acetone for 2 times, washing the obtained solid with a large amount of acetone, and drying in vacuum to obtain chain extender I-428.5 g.
The reaction formula is as follows:
example 5
Adding ether diamine a-513.1 g, benzaldehyde-4-disulfonic acid sodium 4.2g, p-toluenesulfonic acid 0.15g and dimethyl sulfoxide 40mL into a reaction bottle, and reacting at room temperature for 5h under stirring; adding 1.2g of sodium borohydride, and reacting at room temperature for 5 hours; and precipitating the reaction mixed system in acetone for 2 times, washing the obtained solid with a large amount of acetone, and drying in vacuum to obtain chain extender I-515.6 g.
The reaction formula is as follows:
example 6
Adding ether diamine a-211.1 g, benzaldehyde-2, 4-disulfonic acid sodium 30.9g, p-toluenesulfonic acid 0.11g and dimethyl sulfoxide 80mL into a reaction bottle, and reacting at room temperature for 5h under stirring; adding 5.7g of sodium borohydride, and reacting at room temperature for 5 hours; and precipitating the reaction mixed system in acetone for 2 times, washing the obtained solid with a large amount of acetone, and drying in vacuum to obtain chain extender I-638.4 g.
The reaction formula is as follows:
example 7
Adding ether diamine a-328.0 g, benzaldehyde-3, 5-disulfonic acid sodium 31.0g, p-toluenesulfonic acid 0.30g and dimethyl sulfoxide 80mL into a reaction bottle, and reacting at room temperature for 5h under stirring; adding 0.6g of sodium borohydride, and reacting for 5 hours at room temperature; and precipitating the reaction mixed system in acetone for 2 times, washing the obtained solid with a large amount of acetone, and drying in vacuum to obtain chain extender I-753.1 g.
The reaction formula is as follows:
example 8
Adding ether diamine a-624.7 g, benzaldehyde-2, 4-disulfonic acid sodium 30.9g, p-toluenesulfonic acid 0.25g and dimethyl sulfoxide 80mL into a reaction bottle, and reacting at room temperature for 5h under stirring; adding 5.7g of sodium borohydride, and reacting for 5 hours at room temperature; and precipitating the reaction mixed system in acetone for 2 times, washing the obtained solid with a large amount of acetone, and drying in vacuum to obtain chain extender I-850.8 g.
The reaction formula is as follows:
application example 1
10g of polyethylene glycol (molecular weight is 1000) is added into a reaction kettle, 1.85g of toluene diisocyanate is added after dehydration, and the reaction is carried out for 4 hours at 50 ℃. And (2) cooling to 40 ℃, adding 0.36g of chain extender of the I-1 polysulfonic acid ionic group, reacting for 6 hours at 50 ℃, cooling to room temperature, and dispersing in water under high-speed shearing to obtain the aqueous polyurethane dispersion, wherein the aqueous polyurethane dispersion is emulsion-shaped, and the solid content can reach 61%.
Application example 2
10g of polypropylene glycol (molecular weight is 200) is added into a reaction kettle, 11.50g of isophorone diisocyanate is added after dehydration, and the reaction lasts for 6h at 60 ℃. And (3) cooling to 40 ℃, adding 3.25g of chain extender of I-5 polysulfonic acid ionic group, reacting for 4h at 80 ℃, cooling to room temperature, and dispersing in water under high-speed shearing to obtain the aqueous polyurethane dispersion, wherein the aqueous polyurethane dispersion is emulsion and has a solid content of 62%.
Application example 3
10g of polypropylene glycol (molecular weight is 10000) is added into a reaction kettle, 0.40g of toluene diisocyanate is added after dehydration, and the reaction lasts 10 hours at 80 ℃. Cooling to 40 ℃, adding 1.0g of chain extender of I-6 polysulfonic acid ionic group, reacting for 5h at 60 ℃, cooling to room temperature, and dispersing in water under high-speed shearing to obtain the aqueous polyurethane dispersion, wherein the aqueous polyurethane dispersion is emulsion-shaped, and the solid content can reach 58%.
Application example 4
10g of polycaprolactone diol (with the molecular weight of 1000) is added into a reaction kettle, 2.43g of isophorone diisocyanate is added after dehydration, and the reaction lasts for 8h at the temperature of 80 ℃. Cooling to 40 ℃, adding 1.0g of chain extender of I-8 polysulfonic acid ionic group, reacting for 6h at 60 ℃, cooling to room temperature, and dispersing in water under high-speed shearing to obtain the aqueous polyurethane dispersion, wherein the aqueous polyurethane dispersion is emulsion-shaped, and the solid content can reach 67%.
Comparative example 1
The difference from application example 2 is that the polysulfonic acid chain extender adopted in the comparative example is a control sample III
The addition amount of the contrast chain extender sample, the types and the use amounts of other raw materials and the synthesis method are the same as those in application example 2, and the synthesized waterborne polyurethane is dispersed in water under high-speed shearing to obtain a waterborne polyurethane dispersion which is emulsion-shaped and has the solid content of 60%.
Comparative example 2
The difference from application example 4 is that the polysulfonic acid chain extender adopted in the comparative example is used as a control sample IV
The addition amount of the control chain extender sample, the kinds and the amounts of other raw materials, and the synthesis method were the same as in application example 4. The synthesized waterborne polyurethane is dispersed in water under high-speed shearing to obtain a waterborne polyurethane dispersion which is emulsion-shaped and has a solid content of 65 percent.
After the prepared polyurethane emulsion is volatilized to form a film, the mechanical properties of the obtained film product are shown in the following table 1.
Table 1 mechanical properties of film products obtained in application examples 1-4, comparative example 1 and comparative example 2
| Sample (I) | Tensile strength/MPa | Elongation at break/% |
| Application example 1 | 11.3 | 975 |
| Application example 2 | 10.1 | 1530 |
| Application example 3 | 9.8 | 1059 |
| Application example 4 | 11.2 | 1650 |
| Comparative example 1 | 12.5 | 482 |
| Comparative example 2 | 10.3 | 491 |
The mechanical property test of the film product shows that the tensile strength of the waterborne polyurethane material prepared by the chain extender taking the flexible ether chain as the skeleton can be equal to that of a reference sample, the elongation at break is far better than that of the waterborne polyurethane material prepared by the reference sample, and the flexible chain extender can effectively improve the toughness of the waterborne polyurethane material.
Other beneficial effects are as follows:
1) the invention is based on secondary amine sulfonate anion chain extender, and increases the ionic strength of hydrophilic ionic group, regulates the aggregation state of ionic charge on the polyurethane molecular chain and reduces the proportion of hydrophilic chain segment in the polyurethane molecular chain by increasing the number of bonding ionic groups on the chain extender and utilizing the increase of charge density caused by the combined action of multiple sulfonate ionic groups. Meanwhile, the flexible ether chain structure of the chain extender is also beneficial to the compatibility among polyurethane molecular chains and the space mobility of hydrophilic groups. The chain extenders have the essential characteristics that more hydrophilic groups can be endowed on a polyurethane molecular chain under the condition of lower chain extender consumption when the waterborne polyurethane is synthesized, the dispersibility and long-term stability of the polyurethane in water are ensured, the water resistance of a polyurethane film formed by the waterborne polyurethane dispersion is improved, and the industrial application of the waterborne polyurethane is facilitated; in addition, the number of sulfonic acid ion groups on the chain extender is increased, so that the surface charge of micelles in the aqueous polyurethane emulsion can be increased to a certain extent, and the solid content of the emulsion can be improved.
2) The chain extender synthesized by the invention takes the flexible ether chain as the skeleton, and when the water-based polyurethane is prepared by using the chain extender, on one hand, the skeleton structure of the flexible ether chain can weaken the risk of reducing the flexibility of a polyurethane molecular chain caused by the formation of a urea bond, and the problem of reducing the toughness of a polyurethane material caused by increasing the proportion of hard segments in the polyurethane molecular chain by adopting a chain extension means in the prior art can be effectively solved; on the other hand, the micro-phase separation degree of the soft and hard sections of the waterborne polyurethane in the volatilization film forming process can be reduced, so that a waterborne polyurethane material with high toughness can be obtained, and the industrial application of the waterborne polyurethane in the fields of leather and high-toughness film products is facilitated.
3) The invention adopts the conventional organic synthesis means to synthesize the chain extender for the waterborne polyurethane with two or four sulfonic acid ion groups; the synthesis method is simple and efficient, and the raw materials and reagents used in the reaction process are cheap and easy to obtain, so that the amplification of the operation process is easy, and the industrial production is realized.
4) The invention takes the number of ionic groups contained in the hydrophilic chain extender for the waterborne polyurethane as a breakthrough, is expected to break through the technical bottleneck that the excellent dispersibility and good water resistance of the current waterborne polyurethane are difficult to balance and unify, and simultaneously provides a new way for synthesizing the waterborne polyurethane material based on the hydrophilic chain extender.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Claims (9)
1. The flexible sulfonic acid type hydrophilic chain extender is characterized in that the molecular structure general formula of the flexible sulfonic acid type hydrophilic chain extender is shown as I:
wherein R is H or CH3(ii) a m is 1 or 2; n is any integer of 1-20; x is 1 or 2;
the flexible sulfonic acid type hydrophilic chain extender is prepared by reacting aldehyde containing sulfonic acid ion groups with ether diamine under an acid catalyst to generate an aldimine intermediate product, and then reducing the aldimine intermediate product by using a reducing agent.
2. A preparation method of the flexible sulfonic acid type hydrophilic chain extender of claim 1, which is characterized in that aldehyde containing sulfonic acid ion groups reacts with ether diamine under the action of an acid catalyst to generate an aldimine intermediate product, and then the aldimine intermediate product is reduced by a reducing agent to prepare the flexible sulfonic acid type hydrophilic chain extender, wherein the reaction formula is as follows:
wherein R is H or CH3(ii) a m is 1 or 2; n is any integer of 1-20; x is 1 or 2.
3. The method according to claim 2, wherein the molar ratio of the aldehyde having a sulfonic acid ion group to the ether diamine is 2 to 2.2: 1.
4. The method according to claim 2, wherein the acidic catalyst is added in an amount of 1 to 2 wt% based on the amount of the etherdiamine.
5. The method according to claim 2, wherein the reducing agent is added in an amount of 3 to 3.2 times the molar amount of the ether diamine.
6. The production method according to claim 2, wherein the acidic catalyst is one or both of p-toluenesulfonic acid and sulfuric acid; and/or the reducing agent is one or more of sodium borohydride, sodium cyanoborohydride, sodium triacetoxyborohydride and lithium aluminum hydride.
7. Use of the flexible sulfonic acid type hydrophilic chain extender of claim 1 or the flexible sulfonic acid type hydrophilic chain extender prepared by the preparation method of any one of claims 2 to 6 in synthetic aqueous polyurethane dispersions.
8. The use according to claim 7, comprising:
mixing polymer polyol with isocyanate, and reacting at 50-80 ℃ to obtain a polyurethane prepolymer;
and mixing the polyurethane prepolymer with the flexible sulfonic acid type hydrophilic chain extender, reacting at 50-80 ℃, and dispersing in water to obtain the aqueous polyurethane dispersion.
9. The application of the polyurethane prepolymer as claimed in claim 8, wherein the polyurethane prepolymer and the flexible sulfonic acid type hydrophilic chain extender are mixed according to the mass usage of the flexible sulfonic acid type hydrophilic chain extender being 3-15 wt% of the polyurethane prepolymer.
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