CN115612053A - Preparation method of zero-VOC high-solid-content soft waterborne polyurethane emulsion - Google Patents
Preparation method of zero-VOC high-solid-content soft waterborne polyurethane emulsion Download PDFInfo
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- CN115612053A CN115612053A CN202211054140.8A CN202211054140A CN115612053A CN 115612053 A CN115612053 A CN 115612053A CN 202211054140 A CN202211054140 A CN 202211054140A CN 115612053 A CN115612053 A CN 115612053A
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- solid
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- polyol
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- chain extender
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- 239000000839 emulsion Substances 0.000 title claims abstract description 43
- 239000004814 polyurethane Substances 0.000 title claims abstract description 40
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229920005862 polyol Polymers 0.000 claims abstract description 27
- 150000003077 polyols Chemical class 0.000 claims abstract description 27
- 238000003756 stirring Methods 0.000 claims abstract description 27
- 239000004970 Chain extender Substances 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000008367 deionised water Substances 0.000 claims abstract description 19
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000012948 isocyanate Substances 0.000 claims abstract description 13
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000007599 discharging Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 32
- -1 polyethylene adipate Polymers 0.000 claims description 32
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 14
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 14
- 229910052797 bismuth Inorganic materials 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical group OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 10
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 9
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- 150000002009 diols Chemical class 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 229920001451 polypropylene glycol Polymers 0.000 claims description 8
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 8
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 4
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 claims description 2
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- UQOQXWZPXFPRBR-UHFFFAOYSA-K bismuth dodecanoate Chemical compound [Bi+3].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O UQOQXWZPXFPRBR-UHFFFAOYSA-K 0.000 claims description 2
- NSPSPMKCKIPQBH-UHFFFAOYSA-K bismuth;7,7-dimethyloctanoate Chemical compound [Bi+3].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O NSPSPMKCKIPQBH-UHFFFAOYSA-K 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 2
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 229920001610 polycaprolactone Polymers 0.000 claims description 2
- 239000004632 polycaprolactone Substances 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 229920000921 polyethylene adipate Polymers 0.000 claims description 2
- 229960001124 trientine Drugs 0.000 claims description 2
- 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 claims 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims 1
- 239000007787 solid Substances 0.000 abstract description 14
- 239000002649 leather substitute Substances 0.000 abstract description 5
- 238000005187 foaming Methods 0.000 abstract description 4
- 230000007062 hydrolysis Effects 0.000 abstract description 4
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 239000010985 leather Substances 0.000 abstract 1
- 239000004753 textile Substances 0.000 abstract 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000005485 electric heating Methods 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000007865 diluting Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 1
- BEGBSFPALGFMJI-UHFFFAOYSA-N ethene;sodium Chemical group [Na].C=C BEGBSFPALGFMJI-UHFFFAOYSA-N 0.000 description 1
- 125000003916 ethylene diamine group Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- BCDGQXUMWHRQCB-UHFFFAOYSA-N glycine methyl ketone Natural products CC(=O)CN BCDGQXUMWHRQCB-UHFFFAOYSA-N 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- KCLIFOXATBWLMW-UHFFFAOYSA-M sodium;ethane-1,2-diamine;ethanesulfonate Chemical compound [Na+].NCCN.CCS([O-])(=O)=O KCLIFOXATBWLMW-UHFFFAOYSA-M 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000004758 synthetic textile 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
- C08G18/65—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
-
- 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
- C08G18/30—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
- 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
- C08G18/4825—Polyethers containing two hydroxy groups
-
- 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
- C08G2101/00—Manufacture of cellular products
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a preparation method of a zero-VOC high-solid content soft waterborne polyurethane emulsion, which comprises the steps of adding polyol, a hydrophilic auxiliary agent and isocyanate into a reaction container, and reacting for 2-4h at 80-90 ℃; adding a chain extender and a catalyst into a reaction container, and reacting for 2-4h at 60-80 ℃; cooling to 30-50 deg.C, stirring, adding deionized water into the reaction vessel, stirring at high speed for 15min, adding the chain extender into the reaction vessel, stirring for 15min, filtering, and discharging. The waterborne polyurethane emulsion prepared by the invention does not contain VOC, has a solid content of 60%, can be used as a foaming material, has excellent softness, strength and hydrolysis resistance, and is suitable for synthetic leather, leather and textile industries.
Description
Technical Field
The invention belongs to the field of synthetic leather, and particularly relates to a preparation method of a zero-VOC high-solid-content soft type aqueous polyurethane emulsion.
Background
Aqueous polyurethane resins play an important role in the field of synthetic leather and the like, and although aqueous polyurethane uses water as a solvent, evaporation of water requires a large amount of heat of evaporation, resulting in high energy consumption, so that high-solid-content aqueous polyurethane will be the mainstream.
The traditional synthesis method of the waterborne polyurethane is generally divided into two methods, the first method is a prepolymer method, a large amount of triethylamine is added in the synthesis process for neutralization, so that VOC still exists in the product, and in addition, the prepolymer synthesized by the method is high in viscosity and high in production difficulty, and the solid content is difficult to achieve more than 50%. And the waterborne polyurethane synthesized by the prepolymer method has high modulus and hard hand feeling, cannot achieve soft and full hand feeling, and is difficult to be used in synthetic leather in large quantities. In the other method, a large amount of solvent is needed in the synthesis process by adopting an acetone method, so that the safety is poor and the economical efficiency is low.
CN113136160A discloses a water-based polyurethane adhesive and a preparation method thereof, wherein the traditional sulfamate (aqueous solution of ethylenediamine ethanesulfonic acid sodium salt) and polyethylene glycol monomethyl ether are used as hydrophilic groups, and the adhesive synthesized by the method has the characteristics of excellent hydrolysis resistance, good initial adhesion, high peel strength and the like. However, in the preparation process, the sodium ethylene diamine ethyl sulfonate is used in the form of aqueous solution, a large amount of isocyanate groups are consumed by water, a large amount of acetone is required to be added to reduce the viscosity of the prepolymer, a large amount of energy consumption is required for production to remove the prepolymer, the acetone remaining in the emulsion has the problems of VOC emission and the like, in addition, the organotin is used as a catalyst in the patent, the environment-friendly requirement is not met, and the solid content of the prepared waterborne polyurethane is up to 51.2%.
When the traditional solvent-free method is used for synthesizing the waterborne polyurethane, other effective measures are needed to reduce the viscosity of the polyurethane prepolymer to smoothly disperse due to the lack of the dilution effect of the solvent. In order to obtain prepolymer viscosity as low as possible, the molecular weight of the polyurethane prepolymer needs to be as low as possible, and in the synthesis of the existing polyurethane prepolymer, a large amount of isocyanate is often required to be added to reduce the molecular weight of the polyurethane due to the existence of chain extenders with the function of increasing the molecular weight. This results in excessively large hard segment content and high resin modulus in the finally produced polyurethane. In addition, carboxylic acid belongs to weak acid, the hydrophilic effect is not good, when high-solid-content waterborne polyurethane is synthesized, the particle size of the emulsion is unstable, layering is easy to occur, and the stable emulsion with the content of 50% or more is generally difficult to synthesize.
Therefore, in the prior art, a preparation technology of a soft aqueous polyurethane resin with no VOC emission and high solid content is lacking, which is a problem to be solved urgently.
Disclosure of Invention
The invention aims to provide a preparation method of a zero-VOC high-solid-content soft type aqueous polyurethane emulsion aiming at the technical problems in the prior art. The waterborne polyurethane emulsion prepared by the invention does not contain VOC, has solid content of 60 percent, has good emulsion stability, and has excellent softness, strength and hydrolysis resistance when being used as a foaming material.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a zero-VOC high-solid content soft type aqueous polyurethane emulsion comprises the following steps:
(1) Taking the following raw materials in parts by weight: 10-50 parts of isocyanate, 10-60 parts of polyol, 5-20 parts of hydrophilic auxiliary agent, 0.5-15 parts of chain extender, 0.01-0.12 part of catalyst, 0.1-0.8 part of rear chain extender and 30-33 parts of deionized water; the hydrophilic assistant is hydroxysulfonate and polyethylene glycol monomethyl ether with the number average molecular weight of 400-2500;
(2) Adding polyol, hydrophilic auxiliary agent and isocyanate into a reaction vessel, and reacting for 2-4h at 80-90 ℃;
(3) Adding a chain extender and a catalyst into a reaction vessel, and reacting for 2-4h at 60-80 ℃;
(4) Cooling to 30-50 ℃, uniformly stirring, adding deionized water into a reaction container, stirring at a high speed for 15min, adding a rear chain extender into the reaction container, continuing stirring for 15min, filtering and discharging to obtain the zero-VOC high-solid-content soft waterborne polyurethane emulsion.
Preferably, in the step (1), the raw materials are taken according to the following parts by weight: 20-50 parts of isocyanate, 20-40 parts of polyol, 5-15 parts of hydrophilic auxiliary agent, 1-10 parts of chain extender, 0.02-0.08 part of catalyst, 0.2-0.8 part of rear chain extender and 30-33 parts of deionized water.
Preferably, in the step (1), the isocyanate is selected from one or more of isophorone diisocyanate, hexamethylene diisocyanate and dicyclohexylmethane diisocyanate;
the polyol is selected from one or more of polypropylene oxide polyol, polyethylene oxide polyol, polytetrahydrofuran ether glycol, polycaprolactone diol, polycarbonate polyol, polyethylene adipate diol, polyethylene adipate 1,4-butanediol diol, polyethylene adipate 1,6-hexanediol diol, polyethylene adipate neopentyl glycol ester diol or polyethylene adipate neopentyl glycol ester 1,6-hexanediol diol, and the number average molecular weight of the polyol is 1000-3000;
the chain extender is selected from one or more of ethylene glycol, diethylene glycol, methyl propylene glycol, 1,4-butanediol, 1,6-hexanediol, trimethylolpropane, pentaerythritol or neopentyl glycol;
the catalyst is selected from one or more of bismuth laurate, bismuth isooctanoate, bismuth carboxylate, bismuth neodecanoate, bismuth naphthenate and bismuth nitrate;
the rear chain extender is selected from one or more of ethylenediamine, hydrazine hydrate, isophorone diamine, hydroxyethyl diethylamine, diethylenetriamine, triethylene tetramine, gamma-aminopropyl triethoxysilane or N-beta-aminoethyl-gamma-aminopropyl methyl dimethoxysilane.
Preferably, the isocyanate is one or more of isophorone diisocyanate, hexamethylene diisocyanate, or dicyclohexylmethane diisocyanate.
Preferably, the polyol is a polyoxypropylene polyol and/or a polytetrahydrofuran ether glycol, and the number average molecular weight of the polyol is 1000-3000.
Preferably, the chain extender is methyl propylene glycol and/or 1,4-butanediol.
Preferably, the catalyst is bismuth carboxylate.
Preferably, the post-chain extender is one or more of ethylenediamine, diethylenetriamine or isophoronediamine.
The invention has the beneficial effects that:
the preparation method provided by the invention is a novel anionic and nonionic preparation method, by introducing the hydroxy sulfonate and the polyethylene glycol monomethyl ether as hydrophilic soft segments, no chain extender is arranged in the prepolymer molecule, the isocyanate dosage is small under the condition of the same polyurethane molecular weight, and the product has better softness and rebound resilience. In addition, sulfonate belongs to strong acid salt, the hydrophilic effect is good, and a very small amount of hydroxyl sulfonate can be matched with nonionic groups to synthesize stable high-solid-content emulsion. The method solves the difficulty of synthesizing the waterborne polyurethane with high solid content and low modulus by a solvent-free method, does not need acetone and triethylamine in the synthesis process, and fundamentally solves the VOC problem. In addition, a negative non-ionic system is adopted to synthesize the high-solid-content (60%) aqueous polyurethane emulsion, so that the evaporation heat of water in use is greatly reduced, and the characteristics of greenness, environmental protection, low carbon and the like are really achieved. The product of the invention has high stability, the preparation method is simple, the continuous production can be realized, and the prepared waterborne polyurethane emulsion has excellent softness, strength and hydrolysis resistance when being used as a foaming material, and is suitable for the industries of synthetic leather, textile and the like.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely a few embodiments of the invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
Example 1
Adding 300g of polytetrahydrofuran ether diol PTMEG-2000, 10g of polyethylene glycol monomethyl ether MPEG-1000, 50g of hydroxy sulfonate BY-3305 and 120g of isophorone diisocyanate (IPDI) into a 1000ml four-neck flask provided with a stirrer, a condensation reflux pipe and an electric heating sleeve, reacting for 2h at 80 ℃, titrating NCO to 6.15% BY an n-butylamine method, adding 8g of 1, 4-butanediol and 0.1g of a bismuth carboxylate catalyst, continuing to react for 2-3h at 60-70 ℃, titrating NCO to 4.52% BY the n-butylamine method, cooling to 50 ℃, uniformly stirring, quickly adding 310g of deionized water, stirring at 1000rpm for 15min at high speed, diluting 8g of ethylenediamine with 20g of deionized water, adding into the emulsion, continuing to stir for 15min, and filtering BY a 300-mesh filter screen to obtain the zero-VOC high-solid-content flexible waterborne polyurethane emulsion with the solid content of 60%.
Example 2
150g of polytetrahydrofuran ether diol PTMEG-2000, 150g of polyoxypropylene polyol PPG-2000, 8g of polyethylene glycol monomethyl ether MPEG-1000, 50g of hydroxysulfonate BY-3305 and 120g of isophorone diisocyanate (IPDI) are added into a 1000ml four-neck flask provided with a stirrer, a reflux condenser and an electric heating sleeve, the mixture reacts for 2 hours at 80 ℃, NCO is titrated to 6.20% BY an n-butylamine method, 8g of 1, 4-butanediol and 0.1g of bismuth carboxylate catalyst are added, the reaction continues for 2 to 3 hours at 60 to 70 ℃, NCO is titrated to 4.56% BY the n-butylamine method, the temperature is reduced to 50 ℃, stirring is carried out uniformly, 284g of deionized water is added rapidly, stirring is carried out at 1000rpm for 15 minutes, 8.2g of ethylenediamine is diluted BY 20g of deionized water and then added into the emulsion, stirring is carried out for 15 minutes continuously, and filtering is carried out BY a 300-mesh filter screen, so as to obtain the high-solid-content flexible polyurethane emulsion with zero VOC and 60% of solid content.
Example 3
200g of polypropylene oxide polyol PPG-2000, 100g of polypropylene oxide polyol PPG-1000, 8g of polyethylene glycol monomethyl ether MPEG-1000, 48g of hydroxyl sulfonate BY-3305 and 120g of isophorone diisocyanate (IPDI) are added into a 1000ml four-neck flask provided with a stirrer, a reflux condenser and an electric heating sleeve, the mixture reacts for 2h at 80 ℃, NCO is titrated to 5.36% BY an n-butylamine method, 2g1, 4-butanediol and 0.1g of bismuth carboxylate catalyst are added, the reaction is continued for 2-3h at 60-70 ℃, NCO is titrated to 4.95% BY the n-butylamine method, the temperature is reduced to 50 ℃, stirring is uniformly carried out, 284g of deionized water is rapidly added, stirring is carried out at 1000rpm for 15min, 8.2g of ethylenediamine is diluted BY 15g of deionized water and then added into the emulsion, stirring is continued for 15min, and filtering is carried out BY a 300-mesh filter screen, so as to obtain the high-solid-content soft waterborne polyurethane emulsion with zero VOC and 60% solid content.
Example 4
Adding 300g of polyoxypropylene polyol PPG-1000, 8g of polyethylene glycol monomethyl ether MPEG-1000, 45g of hydroxy sulfonate BY-3305 and 130g of isophorone diisocyanate (IPDI) into a 1000ml four-neck flask provided with a stirrer, a reflux condenser and an electric heating sleeve, reacting for 2h at 80 ℃, titrating NCO to 3.65% BY an n-butylamine method, adding 2g1, 4-butanediol and 0.1g of a bismuth carboxylate catalyst, continuously reacting for 2-3h at 60-70 ℃, titrating NCO to 3.24% BY the n-butylamine method, cooling to 50 ℃, uniformly stirring, quickly adding 284g of deionized water, stirring at high speed for 15min, diluting 8.2g of ethylenediamine with 15g of deionized water, adding into the emulsion, continuously stirring for 15min, and filtering BY a 300-mesh filter screen to obtain the zero-solid-content VOC high-content soft type waterborne polyurethane emulsion with the solid content of 60%.
Example 5
The only difference from example 1 is the replacement of ethylenediamine with diethylenetriamine.
Example 6
The only difference from example 2 is the substitution of diethylenetriamine for ethylenediamine.
Example 7
The only difference from example 3 is the substitution of ethylenediamine with diethylenetriamine.
Example 8
The only difference from example 4 is the replacement of ethylenediamine with diethylenetriamine.
Comparative example 1
Adding 300g of polytetrahydrofuran ether diol PTMEG-2000, 80g of hydroxy sulfonate BY-3305 and 120g of isophorone diisocyanate (IPDI) into a 1000ml four-neck flask provided with a stirrer, a condensation reflux pipe and an electric heating sleeve, reacting for 2h at 80 ℃, titrating NCO to 5.65% BY an n-butylamine method, adding 8g of 1, 4-butanediol and 0.1g of bismuth carboxylate catalyst, continuously reacting for 2-3h at 60-70 ℃, titrating NCO to 4.01% BY the n-butylamine method, cooling to 50 ℃, uniformly stirring, rapidly adding 380g of deionized water, stirring at a high speed of 1000rpm for 15min, diluting 8g of ethylenediamine with 20g of deionized water, adding into the emulsion, continuously stirring for 15min, and filtering BY a 300-mesh filter screen to obtain the zero-VOC high-solid-content flexible aqueous polyurethane emulsion with the solid content of 60%.
Comparative example 2
Adding 300g of polytetrahydrofuran ether diol PTMEG-2000, 10g of dimethylolpropionic acid and 120g of isophorone diisocyanate (IPDI) into a 1000ml four-neck flask provided with a stirrer, a condensation reflux pipe and an electric heating sleeve, reacting for 2h at 80 ℃, titrating NCO to 6.16% by an n-butylamine method, adding 8g of 1, 4-butanediol and 0.1g of bismuth carboxylate catalyst, continuously reacting for 2-3h at 60-70 ℃, titrating NCO to 4.34% by the n-butylamine method, cooling to 50 ℃, uniformly stirring, quickly adding 300g of deionized water, stirring at a high speed of 1000rpm for 15min, diluting 8g of ethylenediamine with 20g of deionized water, adding into the emulsion, continuously stirring for 15min, and filtering by a 300-mesh filter screen to obtain the high-solid-content soft waterborne polyurethane emulsion with zero VOC and 60% of solid content.
The physical properties of the emulsion obtained above when used as a foaming material (expansion ratio 1.8 times) were measured as shown in table 1 below:
TABLE 1
From the data, the modulus of the zero-VOC high-solid-content soft waterborne polyurethane emulsion synthesized by the novel synthesis method can be 1.5MPA, and the emulsion is soft and non-sticky. The resin synthesized by using ethylenediamine as a post-chain extension has better bending-resistant flexibility, while the water-based polyurethane emulsion synthesized by using diethylenetriamine can greatly improve the strength, but has poorer breaking elongation and bending-resistant flexibility, so that different post-chain extenders can be selected according to different purposes. As can be seen from the comparative experiment, in comparative example 1, the stability of the emulsion is deteriorated by using pure hydroxy sulfonate as a hydrophilic group; comparative example 2 the emulsion synthesized using the conventional carboxylate solventless process was very poor in stability, high in modulus, and reduced in flex resistance.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily think of the changes or substitutions within the technical scope of the present invention, and shall cover the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (8)
1. A preparation method of a zero-VOC high-solid-content soft waterborne polyurethane emulsion is characterized by comprising the following steps:
(1) Taking the following raw materials in parts by weight: 10-50 parts of isocyanate, 10-60 parts of polyol, 5-20 parts of hydrophilic auxiliary agent, 0.5-15 parts of chain extender, 0.01-0.12 part of catalyst, 0.1-0.8 part of rear chain extender and 30-33 parts of deionized water; the hydrophilic auxiliary agent is hydroxyl sulfonate and polyethylene glycol monomethyl ether with the number average molecular weight of 400-2500;
(2) Adding polyol, hydrophilic auxiliary agent and isocyanate into a reaction vessel, and reacting for 2-4h at 80-90 ℃;
(3) Adding a chain extender and a catalyst into a reaction container, and reacting for 2-4h at 60-80 ℃;
(4) Cooling to 30-50 ℃, uniformly stirring, adding deionized water into the reaction vessel, stirring at a high speed for 15min, adding the chain extender into the reaction vessel, continuing stirring for 15min, filtering and discharging to obtain the zero-VOC high-solid-content soft waterborne polyurethane emulsion.
2. The preparation method of the zero-VOC high-solid-content soft aqueous polyurethane emulsion according to claim 1, wherein in the step (1), the raw materials are taken according to the following weight parts: 20-50 parts of isocyanate, 20-40 parts of polyol, 5-15 parts of hydrophilic auxiliary agent, 1-10 parts of chain extender, 0.02-0.08 part of catalyst, 0.2-0.8 part of rear chain extender and 30-33 parts of deionized water.
3. The method for preparing the zero-VOC high-solid-content soft aqueous polyurethane emulsion according to claim 1 or 2, wherein in the step (1), the isocyanate is selected from one or more of isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, toluene diisocyanate or diphenylmethane diisocyanate;
the polyol is selected from one or more of polypropylene oxide polyol, polyethylene oxide polyol, polytetrahydrofuran ether glycol, polycaprolactone diol, polycarbonate polyol, polyethylene adipate diol, polyethylene adipate 1,4-butanediol diol, polyethylene adipate 1,6-hexanediol diol, polyethylene adipate neopentyl glycol ester diol or polyethylene adipate neopentyl glycol ester 1,6-hexanediol diol, and the number average molecular weight of the polyol is 1000-3000;
the chain extender is selected from one or more of ethylene glycol, diethylene glycol, methyl propylene glycol, 1,4-butanediol, 1,6-hexanediol, trimethylolpropane, pentaerythritol or neopentyl glycol;
the catalyst is selected from one or more of bismuth laurate, bismuth isooctanoate, bismuth carboxylate, bismuth neodecanoate, bismuth naphthenate and bismuth nitrate;
the rear chain extender is selected from one or more of ethylenediamine, hydrazine hydrate, isophorone diamine, hydroxyethyl diethylamine, diethylenetriamine, triethylene tetramine, gamma-aminopropyl triethoxysilane or N-beta-aminoethyl-gamma-aminopropyl methyl dimethoxysilane.
4. The method for preparing the zero-VOC high-solid-content flexible aqueous polyurethane emulsion according to claim 3, wherein the isocyanate is one or more of isophorone diisocyanate, hexamethylene diisocyanate or dicyclohexylmethane diisocyanate.
5. The method for preparing the zero-VOC high-solid-content soft aqueous polyurethane emulsion according to claim 3, wherein the polyol is polyoxypropylene polyol and/or polytetrahydrofuran ether glycol, and the number average molecular weight of the polyol is 1000-3000.
6. The preparation method of the zero-VOC high-solid-content soft aqueous polyurethane emulsion according to claim 3, wherein the chain extender is methyl propylene glycol and/or 1,4-butanediol.
7. The method for preparing the zero-VOC high-solid-content soft aqueous polyurethane emulsion according to claim 3, wherein the catalyst is bismuth carboxylate.
8. The method for preparing the zero-VOC high-solid-content flexible aqueous polyurethane emulsion according to claim 3, wherein the post-chain extender is one or more of ethylenediamine, diethylenetriamine or isophoronediamine.
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