WO2022183604A1 - Method for completely continuously preparing waterborne polyurethane by means of prepolymerization-emulsification - Google Patents
Method for completely continuously preparing waterborne polyurethane by means of prepolymerization-emulsification Download PDFInfo
- Publication number
- WO2022183604A1 WO2022183604A1 PCT/CN2021/095919 CN2021095919W WO2022183604A1 WO 2022183604 A1 WO2022183604 A1 WO 2022183604A1 CN 2021095919 W CN2021095919 W CN 2021095919W WO 2022183604 A1 WO2022183604 A1 WO 2022183604A1
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- WO
- WIPO (PCT)
- Prior art keywords
- parts
- stage
- emulsification
- chain extender
- reaction
- Prior art date
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- 238000004945 emulsification Methods 0.000 title claims abstract description 32
- 239000004814 polyurethane Substances 0.000 title claims abstract description 28
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 239000000463 material Substances 0.000 claims abstract description 30
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 6
- 230000003068 static effect Effects 0.000 claims abstract description 6
- 239000004970 Chain extender Substances 0.000 claims description 36
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 230000035484 reaction time Effects 0.000 claims description 23
- 238000009210 therapy by ultrasound Methods 0.000 claims description 12
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 10
- -1 polybutylene adipate Polymers 0.000 claims description 10
- 150000003384 small molecules Chemical group 0.000 claims description 10
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 125000005442 diisocyanate group Chemical group 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 150000002009 diols Chemical class 0.000 claims description 6
- 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 description 6
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 5
- 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 claims description 5
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 5
- 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 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-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
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 229960002887 deanol Drugs 0.000 claims description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 4
- 239000012972 dimethylethanolamine Substances 0.000 claims description 4
- 235000019253 formic acid Nutrition 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
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 4
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 3
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 3
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 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 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 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
- 150000001875 compounds Chemical class 0.000 claims description 2
- 125000003010 ionic group Chemical group 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000921 polyethylene adipate Polymers 0.000 claims description 2
- 229920000379 polypropylene carbonate Polymers 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- KCLIFOXATBWLMW-UHFFFAOYSA-M sodium;ethane-1,2-diamine;ethanesulfonate Chemical compound [Na+].NCCN.CCS([O-])(=O)=O KCLIFOXATBWLMW-UHFFFAOYSA-M 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- 230000009257 reactivity Effects 0.000 abstract description 5
- 239000003960 organic solvent Substances 0.000 abstract description 4
- 238000007086 side reaction Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000004132 cross linking Methods 0.000 abstract description 2
- 238000006386 neutralization reaction Methods 0.000 abstract description 2
- 230000015556 catabolic process Effects 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 14
- 238000010923 batch production Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- 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
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G18/3275—Hydroxyamines containing two hydroxy groups
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- 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
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- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
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- 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
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- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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- 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
- C08G18/6655—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 with compounds of group C08G18/3271
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G18/6633—Compounds of group C08G18/42
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- 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
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- 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
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Definitions
- the invention relates to a method for preparing water-based polyurethane by prepolymerization and emulsification, and belongs to the field of polymer materials.
- Waterborne polyurethane was introduced in the 1960s, and it is a new type of polyurethane system that uses water instead of organic solvents as the dispersion medium. Compared with traditional solvent-based polyurethane, water-based polyurethane only volatilizes water into the atmosphere during use, which is environmentally friendly and meets the requirements of modern green chemical processes; at the same time, because the dispersion medium is water, water-based polyurethane is also non-toxic, non-flammable, and difficult It can replace traditional solvent-based polyurethane and is widely used in leather, synthetic leather, biomedical, furniture, automobile and aerospace and other fields. It is a new material developed by the country.
- the most commonly used production process of water-based polyurethane is batch production, that is, a polyurethane prepolymer with a hydrophilic group in the main chain is first synthesized in a prepolymerization reactor, and then the material is transferred to a dispersion tank and emulsified with water.
- This production process mainly has the following shortcomings: (1) the reaction time is long (6-8 hours), the production efficiency is low, and the production cost is high; (2) the production relies too much on labor, and the degree of automation is low; (3) the product quality is unstable, There is a large gap between batches; (4) In order to facilitate emulsification, a low-boiling organic solvent must be added to the prepolymer to reduce the viscosity, and after emulsification, the solvent is removed by vacuum distillation, resulting in increased energy consumption and waste of resources; (5) The product is solid The low content results in high drying and shipping costs.
- Patents CN202011253943.7, CN201310255840.8, CN201711045576.X, CN201711049518.4, CN201210116805.3 all use twin-screw extruder as the reactor for water-based polyurethane synthesis, which can realize continuous production of water-based polyurethane. Since the twin-screw extruder is characterized by high production efficiency and short action time, the above patent can only shorten the reaction time by increasing the reaction temperature (the reaction temperature even exceeds 200°C).
- the temperature of the polyurethane reaction is generally in the range of 70-90 °C, especially in the later stage of the reaction, if the temperature exceeds 90 °C, side reactions such as branching and cross-linking will be triggered, the ratio of raw materials will be destroyed, and the product structure will be out of control. Emulsification also affects product quality.
- the present invention provides a method for preparing water-based polyurethane by pre-polymerization-emulsification, characterized in that the process steps and conditions of the method are as follows, and the parts of materials used are all parts by weight number:
- the material enters the second stage ultrasonic treatment zone, the ultrasonic intensity is 200-300W/cm 2 , the frequency is 25-30kHz, the reaction temperature is controlled at 70-80 °C, and the reaction time is 3-6min;
- the material enters the sixth-stage tubular emulsifier, the circulating flow rate is 200-400r/min, the number of cycles is 30-50 times, and the emulsification time is 20-40min, and water-based polyurethane is obtained after emulsification;
- the ratio of the length L to the diameter D of the twin-screw reactor screw is 15 ⁇ L/D ⁇ 30, and the rotational speed is 200-300rmp;
- the diisocyanate described in step (1) is one of isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated toluene diisocyanate, hydrogenated diphenylmethane diisocyanate and hexamethylene diisocyanate. one or more;
- the dihydric alcohol described in step (1) is polybutylene adipate diol, polyethylene adipate diol, polypropylene glycol, polyethylene glycol, polycarbonate with a number-average molecular weight of 500-8000 One or more of ethylene glycol and polypropylene carbonate glycol;
- the small molecule chain extender described in step (1) is one or more of 1,4-butanediol, 1,3-propanediol, ethylene glycol, ethylenediamine, and 1,4-butanediamine;
- the hydrophilic chain extender described in step (1) is dimethylol propionic acid, dimethylol butyric acid, methyldiethanolamine, sodium ethylenediaminoethanesulfonate, 1,4-butanediol-2 - one or more of sodium sulfonate;
- the catalyst described in step (1) is one or more of dibutyltin dilaurate, bismuth isooctanoate, bismuth laurate, and bismuth neodecanoate;
- the neutralizing agent described in the step (4) refers to a compound that neutralizes the hydrophilic group in the hydrophilic chain extender into an ionic group;
- Chain agent, neutralizer is one or more of triethylamine, dimethylethanolamine, for methyldiethanolamine hydrophilic chain extender, neutralizer is one or more of formic acid, acetic acid, for Sodium ethylenediamine ethanesulfonate, 1,4-butanediol-2-sodium sulfonate hydrophilic chain extender, no neutralizer is needed;
- the post-chain extender described in step (5) is one or more of ethylenediamine, hexamethylenediamine, hydrazine hydrate, and p-phenylenediamine.
- the reaction degree of the water-based polyurethane is about 15-20% after the pre-reaction for 2-4 minutes under the conditions of step (1) in the claims (100-150° C.), although the temperature is relatively high in this stage. , but with few side effects.
- step (1) the conditions of step (1) in the claims (100-150° C.)
- step (2) under the cavitation of ultrasonic, the reactivity of isocyanate group with hydroxyl and amino groups in the material will be greatly improved;
- the whole reaction can be completed by reacting in the twin-screw reactor for 5-8min. Since the reaction temperature in the later stage is the same as that of the traditional batch process, the problems of increased by-products and uncontrolled product structure caused by high temperature in the later stage are avoided.
- the addition timing and conditions of the ultrasonic treatment zone must be strictly limited.
- the reaction activity of the material is not improved enough, and the low temperature of the third stage at 70-80 °C cannot promote the reaction to 100% in a short time; if the second stage ultrasonic treatment is too late, the material If the reactivity is increased excessively, a large number of side reactions will occur in the third stage, the viscosity of the product will increase sharply, and even normal emulsification will not be possible.
- the time, intensity, frequency and temperature of the second ultrasonic treatment must also be strictly limited to the conditions described in step (2) of the claims, otherwise the improvement of the reactivity of the material will be insufficient or excessive.
- the process method involved in the present invention does not use any organic solvent, has no selectivity to raw materials, and is suitable for the synthesis of any type of water-based polyurethane.
- hydrophilic chain extender methyldiethanolamine
- the material enters the second-stage ultrasonic treatment zone, the ultrasonic intensity is 200W/cm 2 , the frequency is 25kHz, the reaction temperature is controlled at 70°C, and the reaction time is 6min;
- the material enters the sixth-stage tubular emulsifier, the circulating flow rate is 200r/min, the number of cycles is 35 times, and the emulsification time is 40min, and water-based polyurethane is obtained after emulsification;
- hydrophilic chain extender dimethylol propionic acid
- post-chain extender hydrazine hydrate
- the material enters the second-stage ultrasonic treatment zone, the ultrasonic intensity is 300W/cm 2 , the frequency is 30kHz, the reaction temperature is controlled at 72°C, and the reaction time is 4min;
- the material enters the sixth-stage tubular emulsifier, the circulating flow rate is 300r/min, the number of cycles is 40 times, and the emulsification time is 30min, and water-based polyurethane is obtained after emulsification;
- hydrophilic chain extender sodium 1,4-butanediol-2-sulfonate
- the material enters the second-stage ultrasonic treatment zone, the ultrasonic intensity is 250W/cm 2 , the frequency is 25kHz, the reaction temperature is controlled at 78°C, and the reaction time is 3min;
- reaction products 400 parts of reaction products, 400 parts of deionized water, 2 parts of post-chain extender (p-phenylenediamine) are simultaneously injected into the fifth-stage static mixer for pre-emulsification;
- post-chain extender p-phenylenediamine
- the material enters the sixth-stage tubular emulsifier, the circulating flow rate is 400r/min, the number of cycles is 40 times, and the emulsification time is 35min, and water-based polyurethane is obtained after emulsification;
- Example Example 1 Example 2 Example 3 solid content 31% 45% 56% Emulsion viscosity (20°C) 245cP 420cP 580cP Modulus at 100% stretch 1.3 1.9 4.2 Tensile strength (MPa) 9 26 38 Elongation at break 840 930 1150
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
Disclosed is a process method for completely continuously preparing a waterborne polyurethane by means of prepolymerization-emulsification. In the method, a sonochemically enhanced double-screw extruder is used as a waterborne polyurethane prepolymerization and neutralization reactor, and a static mixer and a tubular emulgator are used as a prepolymer emulsification device for prepolymerization and emulsification in a completely continuous manner. The production efficiency is high, the cost is low, and the product quality is stable. The method is particularly suitable for producing a high-solid-content waterborne polyurethane. More importantly, additionally installing a specialized ultrasonic generator in a specific area of the double-screw extruder for a sonochemical treatment on a prepolymerization intermediate can significantly improve the reactivity of materials, such that a prepolymerization reaction can be rapidly completed at a low temperature of 70-80°C in a later stage. The production process is energy-saving and environmentally friendly, side reactions such as branching, crosslinking and degradation caused by high temperatures in the later stage are also avoided, and the obtained waterborne polyurethane is controllable in structure and stable in quality. The process method does not involve the use of any organic solvents, has no selectivity for raw materials, and is suitable for the synthesis of any type of waterborne polyurethane.
Description
本发明涉及一种预聚-乳化全连续制备水性聚氨酯的方法，属于高分子材料领域。The invention relates to a method for preparing water-based polyurethane by prepolymerization and emulsification, and belongs to the field of polymer materials.
水性聚氨酯于上世纪60年代问世，是以水代替有机溶剂作为分散介质的新型聚氨酯体系。与传统溶剂型聚氨酯相比，水性聚氨酯在使用过程中仅有水挥发进入大气，环境友好，满足现代绿色化工过程要求；同时，由于分散介质为水，水性聚氨酯还具有无毒、不易燃、不易爆等特性，可取代传统溶剂型聚氨酯，广泛应用于皮革、合成革、生物医疗、家具、汽车及航空航天等领域，属国家重点发展的新材料。Waterborne polyurethane was introduced in the 1960s, and it is a new type of polyurethane system that uses water instead of organic solvents as the dispersion medium. Compared with traditional solvent-based polyurethane, water-based polyurethane only volatilizes water into the atmosphere during use, which is environmentally friendly and meets the requirements of modern green chemical processes; at the same time, because the dispersion medium is water, water-based polyurethane is also non-toxic, non-flammable, and difficult It can replace traditional solvent-based polyurethane and is widely used in leather, synthetic leather, biomedical, furniture, automobile and aerospace and other fields. It is a new material developed by the country.
目前，水性聚氨酯最常用的生产工艺为间歇式生产，即先在预聚反应釜中合成主链含亲水基团的聚氨酯预聚体，再将物料转移到分散釜中和并加水乳化。这种生产工艺主要存在如下缺点：(1)反应时间长(6-8小时)，生产效率低，生产成本高；(2)生产过度依赖人工，自动化程度低；(3)产品质量不稳定，各批次间差距较大；(4)为便于乳化，预聚体中须添加低沸点有机溶剂降低粘度，乳化后再减压蒸馏去除溶剂，造成能耗增加与资源浪费；(5)产品固含量低，导致干燥和运输费用成本高。At present, the most commonly used production process of water-based polyurethane is batch production, that is, a polyurethane prepolymer with a hydrophilic group in the main chain is first synthesized in a prepolymerization reactor, and then the material is transferred to a dispersion tank and emulsified with water. This production process mainly has the following shortcomings: (1) the reaction time is long (6-8 hours), the production efficiency is low, and the production cost is high; (2) the production relies too much on labor, and the degree of automation is low; (3) the product quality is unstable, There is a large gap between batches; (4) In order to facilitate emulsification, a low-boiling organic solvent must be added to the prepolymer to reduce the viscosity, and after emulsification, the solvent is removed by vacuum distillation, resulting in increased energy consumption and waste of resources; (5) The product is solid The low content results in high drying and shipping costs.
连续化生产可解决传统间歇式生产存在的瓶颈问题。专利 CN202011253943.7、CN201310255840.8、CN201711045576.X、CN201711049518.4、CN201210116805.3均采用双螺杆挤出机作为水性聚氨酯合成的反应器，可实现水性聚氨酯连续化生产。由于双螺杆挤出机的特点是生产效率高、作用时间短，上述专利只能通过提高反应温度(反应温度甚至超过了200℃)缩短反应时间。然而，聚氨酯反应的温度一般在70-90℃范围内，尤其是在反应后期，如温度超过90℃，会引发支化、交联等副反应，破坏原料配比，导致产品结构失控，既难于乳化，也影响产品品质。Continuous production can solve the bottleneck problem of traditional batch production. Patents CN202011253943.7, CN201310255840.8, CN201711045576.X, CN201711049518.4, CN201210116805.3 all use twin-screw extruder as the reactor for water-based polyurethane synthesis, which can realize continuous production of water-based polyurethane. Since the twin-screw extruder is characterized by high production efficiency and short action time, the above patent can only shorten the reaction time by increasing the reaction temperature (the reaction temperature even exceeds 200°C). However, the temperature of the polyurethane reaction is generally in the range of 70-90 °C, especially in the later stage of the reaction, if the temperature exceeds 90 °C, side reactions such as branching and cross-linking will be triggered, the ratio of raw materials will be destroyed, and the product structure will be out of control. Emulsification also affects product quality.
发明内容SUMMARY OF THE INVENTION
本发明是为了克服现有技术存在的缺点和不足，提供一种预聚-乳化全连续制备水性聚氨酯的方法，其特征在于该方法的工艺步骤和条件如下，所用物料的份数均为重量份数：In order to overcome the shortcomings and deficiencies of the prior art, the present invention provides a method for preparing water-based polyurethane by pre-polymerization-emulsification, characterized in that the process steps and conditions of the method are as follows, and the parts of materials used are all parts by weight number:
(1)将二异氰酸酯50-180份、二元醇80-300份、小分子扩链剂1-10份、亲水扩链剂5-20份、催化剂0.055-0.24份混合均匀，再预热至100-150℃，连续注入第一段双螺杆反应器，反应温度控制在100-150℃，反应时间2-4min；(1) Mix 50-180 parts of diisocyanate, 80-300 parts of diol, 1-10 parts of small molecule chain extender, 5-20 parts of hydrophilic chain extender, and 0.055-0.24 part of catalyst, and then preheat To 100-150 ℃, continuously injected into the first-stage twin-screw reactor, the reaction temperature was controlled at 100-150 ℃, and the reaction time was 2-4min;
(2)第一段反应完毕后，物料进入第二段超声处理区，超声强度为200-300W/cm
2，频率为25-30kHz，反应温度控制在70-80℃，反应时间3-6min；
(2) after the first stage reaction is completed, the material enters the second stage ultrasonic treatment zone, the ultrasonic intensity is 200-300W/cm 2 , the frequency is 25-30kHz, the reaction temperature is controlled at 70-80 ℃, and the reaction time is 3-6min;
(3)第二段反应完毕后，物料进入第三段双螺杆反应器，反应温度控制在70-80℃，反应时间5-8min；(3) After the second-stage reaction is completed, the material enters the third-stage twin-screw reactor, and the reaction temperature is controlled at 70-80°C, and the reaction time is 5-8min;
(4)第三段反应完毕后，物料与中和剂0-15份进入第四段双螺杆反 应器，反应温度控制在30-40℃，反应时间1-2min，获得中和产物；(4) after the third section of reaction is completed, 0-15 parts of material and neutralizer enter the fourth section of twin-screw reactor, temperature of reaction is controlled at 30-40 ℃, and the reaction times 1-2min obtains neutralization product;
(5)将中和产物、去离子水300-1100份、后扩链剂0-3份同时注入第五段静态混合器进行预乳化；(5) 300-1100 parts of neutralized product, deionized water, and 0-3 parts of post-chain extender are simultaneously injected into the fifth-stage static mixer for pre-emulsification;
(6)预乳化完毕后，物料进入第六段管式乳化器，循环流速为200-400r/min，循环次数为30-50次，乳化时间为20-40min，乳化后得到水性聚氨酯；(6) After the pre-emulsification is completed, the material enters the sixth-stage tubular emulsifier, the circulating flow rate is 200-400r/min, the number of cycles is 30-50 times, and the emulsification time is 20-40min, and water-based polyurethane is obtained after emulsification;
步骤(1)、(3)、(4)中所述双螺杆反应器螺杆的长度L与直径D比为15≤L/D≤30，转速200-300rmp；In steps (1), (3) and (4), the ratio of the length L to the diameter D of the twin-screw reactor screw is 15≤L/D≤30, and the rotational speed is 200-300rmp;
步骤(1)中所述二异氰酸酯为异佛尔酮二异氰酸酯、甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、氢化甲苯二异氰酸酯、氢化二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯中的一种或多种；The diisocyanate described in step (1) is one of isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated toluene diisocyanate, hydrogenated diphenylmethane diisocyanate and hexamethylene diisocyanate. one or more;
步骤(1)中所述二元醇为数均分子量在500-8000的聚己二酸丁二醇酯二醇、聚己二酸乙二醇酯二醇、聚丙二醇、聚乙二醇、聚碳酸亚乙酯二醇、聚碳酸亚丙酯二醇中的一种或多种；The dihydric alcohol described in step (1) is polybutylene adipate diol, polyethylene adipate diol, polypropylene glycol, polyethylene glycol, polycarbonate with a number-average molecular weight of 500-8000 One or more of ethylene glycol and polypropylene carbonate glycol;
步骤(1)中所述小分子扩链剂为1,4-丁二醇、1,3-丙二醇、乙二醇、乙二胺、1,4-丁二胺中的一种或多种；The small molecule chain extender described in step (1) is one or more of 1,4-butanediol, 1,3-propanediol, ethylene glycol, ethylenediamine, and 1,4-butanediamine;
步骤(1)中所述亲水扩链剂为二羟甲基丙酸、二羟甲基丁酸、甲基二乙醇胺、乙二胺基乙磺酸钠、1,4-丁二醇-2-磺酸钠中一种或多种；The hydrophilic chain extender described in step (1) is dimethylol propionic acid, dimethylol butyric acid, methyldiethanolamine, sodium ethylenediaminoethanesulfonate, 1,4-butanediol-2 - one or more of sodium sulfonate;
步骤(1)中所述催化剂为二月桂酸二丁基锡、异辛酸铋、月桂酸铋、新癸酸铋中的一种或多种；The catalyst described in step (1) is one or more of dibutyltin dilaurate, bismuth isooctanoate, bismuth laurate, and bismuth neodecanoate;
步骤(4)中所述中和剂是指将亲水扩链剂中的亲水基团中和成 离子基团的化合物；对于二羟甲基丙酸、二羟甲基丁酸亲水扩链剂，中和剂为三乙胺、二甲基乙醇胺中的一种或多种，对于甲基二乙醇胺亲水扩链剂，中和剂为甲酸、乙酸中的一种或多种，对于乙二胺基乙磺酸钠、1,4-丁二醇-2-磺酸钠亲水扩链剂，则无需中和剂；The neutralizing agent described in the step (4) refers to a compound that neutralizes the hydrophilic group in the hydrophilic chain extender into an ionic group; Chain agent, neutralizer is one or more of triethylamine, dimethylethanolamine, for methyldiethanolamine hydrophilic chain extender, neutralizer is one or more of formic acid, acetic acid, for Sodium ethylenediamine ethanesulfonate, 1,4-butanediol-2-sodium sulfonate hydrophilic chain extender, no neutralizer is needed;
步骤(5)中所述后扩链剂为乙二胺、己二胺、水合肼、对苯二胺中的一种或多种。The post-chain extender described in step (5) is one or more of ethylenediamine, hexamethylenediamine, hydrazine hydrate, and p-phenylenediamine.
本发明所涉及的方法的原理是：The principle of the method involved in the present invention is:
本发明经过大量实验后发现，在权力要求书步骤(1)条件(100-150℃)下预反应2-4min后，水性聚氨酯的反应程度约为15-20％，这一阶段虽温度较高，但副反应很少。在这一阶段后，如物料经过步骤(2)所述超声处理，在超声的空化作用下，物料中异氰酸酯基团与羟基、氨基的反应活性将大幅提升；后期只需在70-80℃的双螺杆反应器中反应5-8min，就可以完成全部反应。由于后期反应温度与传统间歇式工艺无异，避免了后期高温导致的副产物增多、产品结构失控问题。After a large number of experiments in the present invention, it is found that the reaction degree of the water-based polyurethane is about 15-20% after the pre-reaction for 2-4 minutes under the conditions of step (1) in the claims (100-150° C.), although the temperature is relatively high in this stage. , but with few side effects. After this stage, if the material is subjected to ultrasonic treatment as described in step (2), under the cavitation of ultrasonic, the reactivity of isocyanate group with hydroxyl and amino groups in the material will be greatly improved; The whole reaction can be completed by reacting in the twin-screw reactor for 5-8min. Since the reaction temperature in the later stage is the same as that of the traditional batch process, the problems of increased by-products and uncontrolled product structure caused by high temperature in the later stage are avoided.
需要指出的是，超声处理区的添加时机和条件须严格限制。实验发现，如第二段超声处理过早，对物料反应活性提升不够，第三段70-80℃低温无法在短时间内将反应推进至100％；如第二段超声处理过晚，对物料反应活性提升过度，在第三段会出现大量副反应，产物粘度暴增，甚至无法正常乳化。与此同时，第二段超声处理的时间、强度、频率、温度也须严格限定为权力要求书步骤(2)中所述条件，否者对物料反应活性的提升也会出现不足或过度。It should be pointed out that the addition timing and conditions of the ultrasonic treatment zone must be strictly limited. Experiments have found that if the second stage ultrasonic treatment is too early, the reaction activity of the material is not improved enough, and the low temperature of the third stage at 70-80 ℃ cannot promote the reaction to 100% in a short time; if the second stage ultrasonic treatment is too late, the material If the reactivity is increased excessively, a large number of side reactions will occur in the third stage, the viscosity of the product will increase sharply, and even normal emulsification will not be possible. At the same time, the time, intensity, frequency and temperature of the second ultrasonic treatment must also be strictly limited to the conditions described in step (2) of the claims, otherwise the improvement of the reactivity of the material will be insufficient or excessive.
与现有技术相比，本发明所涉及的方法的有益效果为：Compared with the prior art, the beneficial effects of the method involved in the present invention are:
(1)在第一、三段双螺杆反应器之间添加一超声处理区，严格限制超声处理的时间、强度、温度、频率，可显著提升水性聚氨酯预聚中间体的反应活性，使反应后期可在70-80℃低温条件下进行，同时反应时间不会大幅延长，保持了双螺杆挤出反应的高效性，生产方法节能环保，反应副反应少，产品结构可控；(1) Add an ultrasonic treatment zone between the first and third-stage twin-screw reactors, and strictly limit the time, intensity, temperature and frequency of ultrasonic treatment, which can significantly improve the reactivity of the water-based polyurethane prepolymer intermediate, and make the reaction later stage. It can be carried out at a low temperature of 70-80 ℃, and the reaction time will not be greatly prolonged, and the high efficiency of the twin-screw extrusion reaction is maintained, the production method is energy-saving and environmentally friendly, the reaction side reactions are few, and the product structure is controllable;
(2)本发明的整个预聚、乳化过程全连续进行，生产效率高，自动化程度高，生产成本低，产品质量稳定，尤其适用于高固含水性聚氨酯生产；(2) the entire prepolymerization and emulsification process of the present invention is carried out continuously, with high production efficiency, high degree of automation, low production cost and stable product quality, and is especially suitable for the production of high-solid water-containing polyurethane;
(3)本发明涉及的工艺方法不使用任何有机溶剂，对原料无选择性，适用于任何类型水性聚氨酯的合成。(3) The process method involved in the present invention does not use any organic solvent, has no selectivity to raw materials, and is suitable for the synthesis of any type of water-based polyurethane.
下面通过实施例对本发明进行具体的描述，只用于对本发明进行进一步说明，不能理解为对本发明保护范围的限定，该领域的技术工程师可根据上述发明的内容对本发明作出一些非本质的改进和调整。The present invention will be specifically described below through examples, which are only used to further illustrate the present invention, and should not be construed as limiting the scope of protection of the present invention. Technical engineers in this field can make some non-essential improvements and Adjustment.
实施例1：Example 1:
配方：(重量份数)Recipe: (weight parts)
80份聚合物二元醇：聚碳酸亚乙酯二醇(Mn＝3000)80 parts of polymer glycol: polyethylene carbonate glycol (Mn=3000)
50份二异氰酸酯：异佛尔酮二异氰酸酯50 parts diisocyanate: isophorone diisocyanate
2份小分子扩链剂：1,3-丙二醇2 parts small molecule chain extender: 1,3-propanediol
5份亲水扩链剂：甲基二乙醇胺5 parts hydrophilic chain extender: methyldiethanolamine
0.055份催化剂：二月桂酸二丁基锡0.055 parts Catalyst: Dibutyltin dilaurate
300份去离子水300 parts deionized water
1.93份中和剂：甲酸1.93 parts neutralizer: formic acid
2份后扩链剂：乙二胺2 parts post-chain extender: ethylenediamine
制备方法：Preparation:
(1)将异佛尔酮二异氰酸酯50份、聚碳酸亚乙酯二醇(Mn＝3000)80份、小分子扩链剂(1,3-丙二醇)2份、亲水扩链剂(甲基二乙醇胺)5份、催化剂(二月桂酸二丁基锡)0.055份混合均匀，再预热至100℃，连续注入第一段双螺杆反应器，反应温度控制在120℃，反应时间3min；(1) 50 parts of isophorone diisocyanate, 80 parts of polyethylene carbonate glycol (Mn=3000), 2 parts of small molecule chain extender (1,3-propylene glycol), hydrophilic chain extender (methyl benzene) 5 parts of base diethanolamine) and 0.055 part of catalyst (dibutyltin dilaurate) were mixed evenly, preheated to 100°C, and continuously injected into the first-stage twin-screw reactor, the reaction temperature was controlled at 120°C, and the reaction time was 3min;
(2)第一段反应完毕后，物料进入第二段超声处理区，超声强度为200W/cm
2，频率为25kHz，反应温度控制在70℃，反应时间6min；
(2) after the first-stage reaction is completed, the material enters the second-stage ultrasonic treatment zone, the ultrasonic intensity is 200W/cm 2 , the frequency is 25kHz, the reaction temperature is controlled at 70°C, and the reaction time is 6min;
(3)第二段反应完毕后，物料进入第三段双螺杆反应器，反应温度控制在70℃，反应时间8min；(3) after the second-stage reaction is completed, the material enters the third-stage twin-screw reactor, and the reaction temperature is controlled at 70°C, and the reaction time is 8min;
(4)第三段反应完毕后，物料与1.93份中和剂(甲酸)进入第四段双螺杆反应器，反应温度控制在30℃，反应时间2min，获得中和产物；(4) after the third stage reaction is completed, the material and 1.93 parts of neutralizer (formic acid) enter the fourth stage twin-screw reactor, and the reaction temperature is controlled at 30 ° C, and the reaction time is 2min to obtain a neutralized product;
(5)将中和产物、去离子水300份、后扩链剂(乙二胺)2份同时注入第五段静态混合器进行预乳化；(5) 300 parts of neutralized product, deionized water, and 2 parts of post-chain extender (ethylenediamine) are simultaneously injected into the fifth-stage static mixer for pre-emulsification;
(6)预乳化完毕后，物料进入第六段管式乳化器，循环流速为200r/min，循环次数为35次，乳化时间为40min，乳化后得到水性聚氨酯；(6) After the pre-emulsification is completed, the material enters the sixth-stage tubular emulsifier, the circulating flow rate is 200r/min, the number of cycles is 35 times, and the emulsification time is 40min, and water-based polyurethane is obtained after emulsification;
步骤(1)、(3)、(4)中所述双螺杆反应器螺杆的长度L与直径D比为L/D＝20，转速200rmp。In steps (1), (3) and (4), the ratio of the length L to the diameter D of the screw of the twin-screw reactor is L/D=20, and the rotational speed is 200 rmp.
实施例2：Example 2:
配方：(重量份数)Recipe: (weight parts)
200份聚合物二元醇：聚碳酸亚乙酯二醇(Mn＝2000)200 parts of polymer glycol: polyethylene carbonate glycol (Mn=2000)
100份二异氰酸酯：甲苯二异氰酸酯100 parts diisocyanate: toluene diisocyanate
6份小分子扩链剂：1,4-丁二醇6 parts small molecule chain extender: 1,4-butanediol
15份亲水扩链剂：二羟甲基丙酸15 parts hydrophilic chain extender: dimethylol propionic acid
0.15份催化剂：异辛酸铋0.15 parts catalyst: bismuth isooctanoate
400份去离子水400 parts deionized water
10份中和剂：二甲基乙醇胺10 parts Neutralizer: Dimethylethanolamine
2.5份后扩链剂：水合肼2.5 parts post-chain extender: hydrazine hydrate
制备方法：Preparation:
(1)将甲苯二异氰酸酯100份、聚碳酸亚乙酯二醇(Mn＝2000)200份、小分子扩链剂(1,4-丁二醇)6份、亲水扩链剂(二羟甲基丙酸)15份、催化剂(异辛酸铋)0.15份混合均匀，再预热至120℃，连续注入第一段双螺杆反应器，反应温度控制在130℃，反应时间3min；(1) 100 parts of toluene diisocyanate, 200 parts of polyethylene carbonate glycol (Mn=2000), 6 parts of small molecule chain extender (1,4-butanediol), hydrophilic chain extender (dihydroxy 15 parts of methylpropionic acid) and 0.15 part of catalyst (bismuth isooctanoate) were mixed evenly, then preheated to 120°C, and continuously injected into the first-stage twin-screw reactor, the reaction temperature was controlled at 130°C, and the reaction time was 3min;
(2)第一段反应完毕后，物料进入第二段超声处理区，超声强度为300W/cm
2，频率为30kHz，反应温度控制在72℃，反应时间4min；
(2) after the first-stage reaction is completed, the material enters the second-stage ultrasonic treatment zone, the ultrasonic intensity is 300W/cm 2 , the frequency is 30kHz, the reaction temperature is controlled at 72°C, and the reaction time is 4min;
(3)第二段反应完毕后，物料进入第三段双螺杆反应器，反应温度控制在75℃，反应时间6min；(3) after the second-stage reaction is completed, the material enters the third-stage twin-screw reactor, the reaction temperature is controlled at 75°C, and the reaction time is 6min;
(4)第三段反应完毕后，物料与10份中和剂(二甲基乙醇胺)进入第四段双螺杆反应器，反应温度控制在35℃，反应时间1.5min，获得中和产物；(4) after the third stage reaction is completed, the material and 10 parts of neutralizer (dimethylethanolamine) enter the fourth stage twin-screw reactor, and the reaction temperature is controlled at 35 ° C, and the reaction time is 1.5min to obtain a neutralized product;
(5)将中和产物、去离子水400份、后扩链剂(水合肼)2.5份同时注入第五段静态混合器进行预乳化；(5) 400 parts of neutralized product, deionized water, and 2.5 parts of post-chain extender (hydrazine hydrate) are simultaneously injected into the fifth-stage static mixer for pre-emulsification;
(6)预乳化完毕后，物料进入第六段管式乳化器，循环流速为300r/min，循环次数为40次，乳化时间为30min，乳化后得到水性聚氨酯；(6) After the pre-emulsification is completed, the material enters the sixth-stage tubular emulsifier, the circulating flow rate is 300r/min, the number of cycles is 40 times, and the emulsification time is 30min, and water-based polyurethane is obtained after emulsification;
步骤(1)、(3)、(4)中所述双螺杆反应器螺杆的长度L与直径D比为L/D＝25，转速250rmp。In steps (1), (3) and (4), the ratio of the length L to the diameter D of the twin-screw reactor screw is L/D=25, and the rotational speed is 250 rmp.
实施例3：Example 3:
配方：(重量份数)Recipe: (weight parts)
300份聚合物二元醇：聚乙二醇(Mn＝2000)300 parts of polymer glycol: polyethylene glycol (Mn=2000)
180份二异氰酸酯：六亚甲基二异氰酸酯180 parts diisocyanate: hexamethylene diisocyanate
8份小分子扩链剂：乙二醇8 parts small molecule chain extender: ethylene glycol
20份亲水扩链剂：1,4-丁二醇-2-磺酸钠20 parts of hydrophilic chain extender: sodium 1,4-butanediol-2-sulfonate
0.22份催化剂：月桂酸铋0.22 parts catalyst: bismuth laurate
400份去离子水400 parts deionized water
2份后扩链剂：对苯二胺2 parts post-chain extender: p-phenylenediamine
(1)将六亚甲基二异氰酸酯180份、聚乙二醇(Mn＝2000)300份、小分子扩链剂(乙二醇)8份、亲水扩链剂(1,4-丁二醇-2-磺酸钠)20份、催化剂(月桂酸铋)0.22份混合均匀，再预热至120℃，连续注入第一段双螺杆反应器，反应温度控制在140℃，反应时间2min；(1) 180 parts of hexamethylene diisocyanate, 300 parts of polyethylene glycol (Mn=2000), 8 parts of small molecule chain extender (ethylene glycol), hydrophilic chain extender (1,4-butanediol) 20 parts of alcohol-2-sodium sulfonate) and 0.22 part of catalyst (bismuth laurate) were mixed evenly, preheated to 120°C, and continuously injected into the first-stage twin-screw reactor, the reaction temperature was controlled at 140°C, and the reaction time was 2min;
(2)第一段反应完毕后，物料进入第二段超声处理区，超声强度为250W/cm
2，频率为25kHz，反应温度控制在78℃，反应时间3min；
(2) after the first-stage reaction is completed, the material enters the second-stage ultrasonic treatment zone, the ultrasonic intensity is 250W/cm 2 , the frequency is 25kHz, the reaction temperature is controlled at 78°C, and the reaction time is 3min;
(3)第二段反应完毕后，物料进入第三段双螺杆反应器，反应温度控制在80℃，反应时间5min；(3) after the second-stage reaction is completed, the material enters the third-stage twin-screw reactor, and the reaction temperature is controlled at 80°C, and the reaction time is 5min;
(4)第三段反应完毕后，物料直接进入第四段双螺杆反应器，反应温度控制在40℃，反应时间1min，获得反应产物；(4) After the third-stage reaction is completed, the material directly enters the fourth-stage twin-screw reactor, the reaction temperature is controlled at 40 ° C, and the reaction time is 1 min to obtain the reaction product;
(5)将反应产物、去离子水400份、后扩链剂(对苯二胺)2份同时注入第五段静态混合器进行预乳化；(5) 400 parts of reaction products, 400 parts of deionized water, 2 parts of post-chain extender (p-phenylenediamine) are simultaneously injected into the fifth-stage static mixer for pre-emulsification;
(6)预乳化完毕后，物料进入第六段管式乳化器，循环流速为400r/min，循环次数为40次，乳化时间为35min，乳化后得到水性聚氨酯；(6) After the pre-emulsification is completed, the material enters the sixth-stage tubular emulsifier, the circulating flow rate is 400r/min, the number of cycles is 40 times, and the emulsification time is 35min, and water-based polyurethane is obtained after emulsification;
步骤(1)、(3)、(4)中所述双螺杆反应器螺杆的长度L与直径D比为L/D＝20，转速300rmp。In steps (1), (3) and (4), the ratio of the length L to the diameter D of the screw of the twin-screw reactor is L/D=20, and the rotational speed is 300 rmp.
实施例1-3所制得的水性聚氨酯的物性如下：The physical properties of the prepared water-based polyurethane in Examples 1-3 are as follows:
| 实施例Example | 实施例1Example 1 | 实施例2Example 2 | 实施例3Example 3 |
| 固含量solid content | 31％31% | 45％45% | 56％56% |
| 乳液粘度(20℃)Emulsion viscosity (20℃) | 245cP245cP | 420cP420cP | 580cP580cP |
| 拉伸100％时模量Modulus at 100% stretch | 1.31.3 | 1.91.9 | 4.24.2 |
| 拉伸强度(MPa)Tensile strength (MPa) | 99 | 2626 | 3838 |
| 断裂伸长率Elongation at break | 840840 | 930930 | 11501150 |
Claims (1)
- 一种预聚-乳化全连续制备水性聚氨酯的方法，其特征在于该方法的工艺步骤和条件如下，所用物料的份数均为重量份数：A method for the continuous preparation of water-based polyurethane by prepolymerization-emulsification, characterized in that the process steps and conditions of the method are as follows, and the parts of materials used are all parts by weight:(1)将二异氰酸酯50-180份、二元醇80-300份、小分子扩链剂1-10份、亲水扩链剂5-20份、催化剂0.055-0.24份混合均匀，再预热至100-150℃，连续注入第一段双螺杆反应器，反应温度控制在100-150℃，反应时间2-4min；(1) Mix 50-180 parts of diisocyanate, 80-300 parts of diol, 1-10 parts of small molecule chain extender, 5-20 parts of hydrophilic chain extender, and 0.055-0.24 parts of catalyst, and then preheat To 100-150 ℃, continuously injected into the first-stage twin-screw reactor, the reaction temperature was controlled at 100-150 ℃, and the reaction time was 2-4min;(2)第一段反应完毕后，物料进入第二段超声处理区，超声强度为200-300W/cm 2，频率为25-30kHz，反应温度控制在70-80℃，反应时间3-6min； (2) after the first stage reaction is completed, the material enters the second stage ultrasonic treatment zone, the ultrasonic intensity is 200-300W/cm 2 , the frequency is 25-30kHz, the reaction temperature is controlled at 70-80 ℃, and the reaction time is 3-6min;(3)第二段反应完毕后，物料进入第三段双螺杆反应器，反应温度控制在70-80℃，反应时间5-8min；(3) After the second-stage reaction is completed, the material enters the third-stage twin-screw reactor, and the reaction temperature is controlled at 70-80°C, and the reaction time is 5-8min;(4)第三段反应完毕后，物料与中和剂0-15份进入第四段双螺杆反应器，反应温度控制在30-40℃，反应时间1-2min，获得中和产物；(4) After the third stage reaction is completed, 0-15 parts of material and neutralizer enter the fourth stage twin-screw reactor, the reaction temperature is controlled at 30-40 ° C, and the reaction time is 1-2min to obtain a neutralized product;(5)将中和产物、去离子水300-1100份、后扩链剂0-3份同时注入第五段静态混合器进行预乳化；(5) 300-1100 parts of neutralized product, deionized water, and 0-3 parts of post-chain extender are simultaneously injected into the fifth-stage static mixer for pre-emulsification;(6)预乳化完毕后，物料进入第六段管式乳化器，循环流速为200-400r/min，循环次数为30-50次，乳化时间为20-40min，乳化后得到水性聚氨酯；(6) After the pre-emulsification is completed, the material enters the sixth-stage tubular emulsifier, the circulating flow rate is 200-400r/min, the number of cycles is 30-50 times, and the emulsification time is 20-40min, and water-based polyurethane is obtained after emulsification;步骤(1)、(3)、(4)中所述双螺杆反应器螺杆的长度L与直径D比为15≤L/D≤30，转速200-300rmp；In steps (1), (3) and (4), the ratio of the length L to the diameter D of the twin-screw reactor screw is 15≤L/D≤30, and the rotational speed is 200-300rmp;步骤(1)中所述二异氰酸酯为异佛尔酮二异氰酸酯、甲苯二异 氰酸酯、二苯基甲烷二异氰酸酯、氢化甲苯二异氰酸酯、氢化二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯中的一种或多种；The diisocyanate described in step (1) is one of isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated toluene diisocyanate, hydrogenated diphenylmethane diisocyanate and hexamethylene diisocyanate. one or more;步骤(1)中所述二元醇为数均分子量在500-8000的聚己二酸丁二醇酯二醇、聚己二酸乙二醇酯二醇、聚丙二醇、聚乙二醇、聚碳酸亚乙酯二醇、聚碳酸亚丙酯二醇中的一种或多种；The dihydric alcohol described in step (1) is polybutylene adipate diol, polyethylene adipate diol, polypropylene glycol, polyethylene glycol, polycarbonate with a number-average molecular weight of 500-8000 One or more of ethylene glycol and polypropylene carbonate glycol;步骤(1)中所述小分子扩链剂为1,4-丁二醇、1,3-丙二醇、乙二醇、乙二胺、1,4-丁二胺中的一种或多种；The small molecule chain extender described in step (1) is one or more of 1,4-butanediol, 1,3-propanediol, ethylene glycol, ethylenediamine, and 1,4-butanediamine;步骤(1)中所述亲水扩链剂为二羟甲基丙酸、二羟甲基丁酸、甲基二乙醇胺、乙二胺基乙磺酸钠、1,4-丁二醇-2-磺酸钠中一种或多种；The hydrophilic chain extender described in step (1) is dimethylol propionic acid, dimethylol butyric acid, methyldiethanolamine, sodium ethylenediaminoethanesulfonate, 1,4-butanediol-2 - one or more of sodium sulfonate;步骤(1)中所述催化剂为二月桂酸二丁基锡、异辛酸铋、月桂酸铋、新癸酸铋中的一种或多种；The catalyst described in step (1) is one or more of dibutyltin dilaurate, bismuth isooctanoate, bismuth laurate, and bismuth neodecanoate;步骤(4)中所述中和剂是指将亲水扩链剂中的亲水基团中和成离子基团的化合物；对于二羟甲基丙酸、二羟甲基丁酸亲水扩链剂，中和剂为三乙胺、二甲基乙醇胺中的一种或多种，对于甲基二乙醇胺亲水扩链剂，中和剂为甲酸、乙酸中的一种或多种，对于乙二胺基乙磺酸钠、1,4-丁二醇-2-磺酸钠亲水扩链剂，则无需中和剂；The neutralizing agent described in the step (4) refers to a compound that neutralizes the hydrophilic group in the hydrophilic chain extender into an ionic group; Chain agent, neutralizer is one or more of triethylamine, dimethylethanolamine, for methyldiethanolamine hydrophilic chain extender, neutralizer is one or more of formic acid, acetic acid, for Sodium ethylenediamine ethanesulfonate, 1,4-butanediol-2-sodium sulfonate hydrophilic chain extender, no neutralizer is needed;步骤(5)中所述后扩链剂为乙二胺、己二胺、水合肼、对苯二胺中的一种或多种。The post-chain extender described in step (5) is one or more of ethylenediamine, hexamethylenediamine, hydrazine hydrate, and p-phenylenediamine.
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4742095A (en) * | 1985-07-25 | 1988-05-03 | Mobay Corporation | Continuous process for the production of aqueous polyurethane-urea dispersions |
| US4879322A (en) * | 1986-10-21 | 1989-11-07 | Mobay Corporation | Continuous process for the production of aqueous polyurethane urea dispersions |
| DE4219964A1 (en) * | 1992-06-19 | 1993-12-23 | Basf Schwarzheide Gmbh | Stable aq. polyurethane dispersions for coating textiles etc. - contg readily dispersible oligo:urethane-bis:biurets made from di:isocyanate, poly:ol, ionic chain extender and urea |
| EP0384165B1 (en) * | 1989-02-18 | 1994-01-05 | BASF Aktiengesellschaft | Continuous method for making non-self-emulsifying polymer dispersions |
| JP2005232277A (en) * | 2004-02-18 | 2005-09-02 | Mitsui Takeda Chemicals Inc | Aqueous disperse system of polyurethane, its manufacturing method and use |
| CN102633971A (en) * | 2012-04-19 | 2012-08-15 | 王武生 | Double-screw reactor design based continuous production process of aqueous polyurethane dispersion |
| CN106590394A (en) * | 2016-11-25 | 2017-04-26 | 清远市美佳乐环保新材股份有限公司 | Process of preparing waterborne polyurethane optical coating through continuous method |
| CN107903377A (en) * | 2017-10-31 | 2018-04-13 | 上海华峰新材料研发科技有限公司 | Solvent-free sulfonate aqueous polyurethane dispersion of continous way and preparation method thereof |
| CN107903376A (en) * | 2017-10-31 | 2018-04-13 | 上海华峰新材料研发科技有限公司 | Solvent-free aqueous polyurethane dispersion of continous way and its preparation method and application |
| CN108097194A (en) * | 2017-12-28 | 2018-06-01 | 万华化学（宁波）有限公司 | A kind of continuous process system for preparing aqueous polyurethane dispersion, the continuous production processes of aqueous polyurethane dispersion and application |
| CN109734866A (en) * | 2018-12-13 | 2019-05-10 | 华南理工大学 | A kind of high-performance anionic and nonionic type aqueous polyurethane dispersion and preparation method thereof |
| CN112341590A (en) * | 2020-11-11 | 2021-02-09 | 中山大学 | Waterborne polyurethane and continuous preparation process thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103382253B (en) * | 2013-06-25 | 2015-09-09 | 上海华峰新材料研发科技有限公司 | A kind of high-performance water-based polyurethane dispersoid and preparation method thereof |
-
2021
- 2021-03-03 CN CN202110233082.4A patent/CN113024757B/en active Active
- 2021-05-26 WO PCT/CN2021/095919 patent/WO2022183604A1/en active Application Filing
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4742095A (en) * | 1985-07-25 | 1988-05-03 | Mobay Corporation | Continuous process for the production of aqueous polyurethane-urea dispersions |
| US4879322A (en) * | 1986-10-21 | 1989-11-07 | Mobay Corporation | Continuous process for the production of aqueous polyurethane urea dispersions |
| EP0384165B1 (en) * | 1989-02-18 | 1994-01-05 | BASF Aktiengesellschaft | Continuous method for making non-self-emulsifying polymer dispersions |
| DE4219964A1 (en) * | 1992-06-19 | 1993-12-23 | Basf Schwarzheide Gmbh | Stable aq. polyurethane dispersions for coating textiles etc. - contg readily dispersible oligo:urethane-bis:biurets made from di:isocyanate, poly:ol, ionic chain extender and urea |
| JP2005232277A (en) * | 2004-02-18 | 2005-09-02 | Mitsui Takeda Chemicals Inc | Aqueous disperse system of polyurethane, its manufacturing method and use |
| CN102633971A (en) * | 2012-04-19 | 2012-08-15 | 王武生 | Double-screw reactor design based continuous production process of aqueous polyurethane dispersion |
| CN106590394A (en) * | 2016-11-25 | 2017-04-26 | 清远市美佳乐环保新材股份有限公司 | Process of preparing waterborne polyurethane optical coating through continuous method |
| CN107903377A (en) * | 2017-10-31 | 2018-04-13 | 上海华峰新材料研发科技有限公司 | Solvent-free sulfonate aqueous polyurethane dispersion of continous way and preparation method thereof |
| CN107903376A (en) * | 2017-10-31 | 2018-04-13 | 上海华峰新材料研发科技有限公司 | Solvent-free aqueous polyurethane dispersion of continous way and its preparation method and application |
| CN108097194A (en) * | 2017-12-28 | 2018-06-01 | 万华化学（宁波）有限公司 | A kind of continuous process system for preparing aqueous polyurethane dispersion, the continuous production processes of aqueous polyurethane dispersion and application |
| CN109734866A (en) * | 2018-12-13 | 2019-05-10 | 华南理工大学 | A kind of high-performance anionic and nonionic type aqueous polyurethane dispersion and preparation method thereof |
| CN112341590A (en) * | 2020-11-11 | 2021-02-09 | 中山大学 | Waterborne polyurethane and continuous preparation process thereof |
Non-Patent Citations (2)
| Title |
|---|
| KEYVANI M: "IMPROVED POLYURETHANE DISPERSION STABILITY VIA CONTINUOUS PROCESS", ADVANCES IN POLYMER TECHNOLOGY., WILEY AND SONS, HOBOKEN, NJ., US, vol. 22, no. 03, 21 September 2003 (2003-09-21), US , pages 218 - 224, XP001238806, ISSN: 0730-6679, DOI: 10.1002/adv.10050 * |
| LU YING, CUI YANJUN;TANG JINSONG: " A Brief Introduction to Hot Issues of Waterborne Polyurethane Patent Technology", POLYURETHANE INDUSTRY, vol. 34, no. 1, 28 February 2019 (2019-02-28), pages 1 - 4, XP055963946, ISSN: 1005-1902 * |
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