CN108164650B - 端烯基非离子型水性聚氨酯改性丙烯酸酯乳液及其制备方法 - Google Patents
端烯基非离子型水性聚氨酯改性丙烯酸酯乳液及其制备方法 Download PDFInfo
- Publication number
- CN108164650B CN108164650B CN201711433220.3A CN201711433220A CN108164650B CN 108164650 B CN108164650 B CN 108164650B CN 201711433220 A CN201711433220 A CN 201711433220A CN 108164650 B CN108164650 B CN 108164650B
- Authority
- CN
- China
- Prior art keywords
- polyglycol ether
- emulsion
- terminal alkenyl
- waterborne polyurethane
- alkenyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000004814 polyurethane Substances 0.000 title claims abstract description 89
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 89
- 239000000839 emulsion Substances 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 150000001252 acrylic acid derivatives Chemical class 0.000 title claims abstract description 18
- 238000004945 emulsification Methods 0.000 title description 2
- 239000000178 monomer Substances 0.000 claims abstract description 66
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 58
- 229920000151 polyglycol Polymers 0.000 claims abstract description 54
- 239000010695 polyglycol Substances 0.000 claims abstract description 54
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 24
- -1 carboxylate ions Chemical class 0.000 claims abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 12
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 9
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 60
- 238000006243 chemical reaction Methods 0.000 claims description 38
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 32
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 24
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 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 17
- 125000005394 methallyl group Chemical group 0.000 claims description 15
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 14
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 14
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 14
- 238000004321 preservation Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 150000003384 small molecules Chemical class 0.000 claims description 10
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 9
- QVDTXNVYSHVCGW-ONEGZZNKSA-N isopentenol Chemical compound CC(C)\C=C\O QVDTXNVYSHVCGW-ONEGZZNKSA-N 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 8
- 239000003995 emulsifying agent Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 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
- 239000004615 ingredient Substances 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 claims 2
- 239000002131 composite material Substances 0.000 abstract description 10
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 3
- 238000010559 graft polymerization reaction Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 7
- 238000004090 dissolution Methods 0.000 description 6
- 238000011049 filling Methods 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 5
- 238000000576 coating method Methods 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 2
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 2
- 229920002593 Polyethylene Glycol 800 Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 2
- 229940085675 polyethylene glycol 800 Drugs 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011527 polyurethane coating Substances 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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920003009 polyurethane dispersion Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000001932 seasonal effect Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 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 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
-
- 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
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
- C08G18/3278—Hydroxyamines containing at least three hydroxy groups
- C08G18/3281—Hydroxyamines containing at least three hydroxy groups containing three 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
- C08G18/4833—Polyethers containing oxyethylene units
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—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
- C08G18/6688—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 C08G18/3271
-
- 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/6795—Unsaturated polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—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
- C08G18/75—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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Paints Or Removers (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
一种端烯基非离子型水性聚氨酯改性丙烯酸酯乳液及其制备方法,首先利用端烯基聚乙二醇醚、二异氰酸酯、小分子二元醇和小分子三元醇为原料制备含双键的非离子型水性聚氨酯单体,然后将丙烯酸酯类单体和所制备的端烯基非离子型水性聚氨酯单体通过乳液聚合方法,得到水性聚氨酯改性丙烯酸酯乳液;本发明相比常规水性聚氨酯,制备工艺简单快速,能耗较低,不需要溶剂,环境友好,且非离子型水性聚氨酯中不含有羧酸根离子,吸水率大大降低,而且将丙烯酸酯和端烯基非离子型水性聚氨酯进行接枝聚合得到的复合乳液成膜之后,力学性能、耐候性、耐水性及综合性能均得到明显的改善。
Description
技术领域
本发明涉及一种端烯基非离子型水性聚氨酯改性丙烯酸酯乳液及其制备方法,尤其是合成了端烯基非离子型水性聚氨酯,操作加工方便,节能环保,减少羧基含量,提高水性聚氨酯-丙烯酸酯复合乳液的耐水性。
背景技术
水性聚氨酯涂料是近年来迅速发展的一类水性涂料,不仅具有传统聚氨酯涂料所具有的优良耐磨性、高强度等优异性能,同时安全环保,对环境无污染,与日益强化的环境友好的时代特征相适应,成为高性能现代涂料品种的研发热点。丙烯酸酯与其他合成高分子树脂相比,具有很多突出的优点,如优异的耐光性、户外暴晒耐久性,即紫外光照射不易黄变,能保持原来的光泽和色泽,有较强的耐腐蚀性,优异的柔韧性和低的颜料反应性。因此在家电、汽车、建筑、纺织、涂料等行业有很广泛的应用。但是丙烯酸酯一般为链状线性结构,属于热塑性高分子材料,对于温度极为敏感,涂层经不起季节的变化。聚氨酯/丙烯酸酯复合乳液是同时兼有聚氨酯和聚丙烯酸酯两者优点的一类高分子聚合物 PUA)被誉为“第三代水性聚氨酯”,PUA乳液在家具漆、电泳漆、电沉积涂料、建筑涂料、汽车底漆,皮革加工中都有广泛的应用,成为了近年来国内外的研究热点。丙烯酸酯和聚氨酯两类聚合物在微观状态下制备的聚氨酯-丙烯酸酯杂化水分散体,可以弥补单一聚氨酯分散体自增稠差、固含低,乳胶膜的耐水性差和单一丙烯酸酯水分散体热黏冷脆,柔韧性差,不耐溶剂的缺点,可以进行优势互补。水性聚氨酯-丙烯酸酯复合乳液可以将聚氨酯较高的拉伸强度和冲击强度、优异的耐磨性、与丙烯酸酯良好的附着力、耐候性、耐酸碱,较低的成本有机的结合在一起。然而目前工业中所制备的水性聚氨酯大多都含有羧酸根离子,与丙烯酸酯结合后,耐水性仍然不是很理想,而且制备工艺复杂,能耗较高,不利于工业化生产。
中国专利 CN103739818 A公开了一种“水性聚氨酯-丙烯酸乳液及其制备方法和应用”该发明将异氰酸酯单体、聚醚型多元醇、亲水扩链剂及有机硅按照比例进行逐步聚合,制备预聚物,经自乳化法合成出阴离子水性聚氨酯乳液,加入丙烯酸酯类单体继续聚合,制备双改性的水性聚氨酯乳液。该发明的乳液涂饰成膜后,具有良好的表面性能,综合性能优异。但其所制备的水性聚氨酯中含有大量的羧酸根离子,使得成膜之后耐水性较差。
中国专利CN 105461863 A提供了“一种丙烯酸酯改性水性聚氨酯乳液及其制备方法”利用丙烯酸酯参与反应将双键引入到聚氨酯主链,随后引发丙烯酸单体的聚合,能够形成复杂的网状结构,相比较传统水性聚氨酯来说,耐水性、耐热性、力学性能有了明显的提高。但其制备水性聚氨酯过程中需要大量的丙酮作溶剂,危害人体污染环境。
中国专利CN 106117451 A公开了“一种丙烯酸酯接枝改性水性聚氨酯树脂的制备方法”利用聚酯多元醇、甲苯二异氰酸酯、二羟甲基丙酸、甲基丙二醇、丙烯酸羟乙酯等原料制备出聚氨酯预聚体,然后与丙烯酸酯类单体进行聚合,兼顾了水性聚氨酯和丙烯酸的综合性能。但是,其中水性聚氨酯中的羧酸根离子仍然会导致复合乳液的耐水性不够理想。
发明内容
基于上述现有技术,本发明的目的是改变常规离子型水性聚氨酯制备方法复杂吸水率高的缺点,利用具有亲水性的端烯基聚乙二醇醚中一端的羟基与异氰酸酯反应生成具有亲水性的短链聚氨酯,制备工艺简单,能耗较低;而且其高活性的端烯键能够顺利的与丙烯酸酯类单体聚合。
为了实现上述目的,本发明引入一种新的端烯基非离子型水性聚氨酯,并提供一种端烯基非离子型水性聚氨酯改性丙烯酸酯乳液及其制备方法,其中所述端烯基非离子型水性聚氨酯的原料组成及其摩尔比配比是:端烯基聚乙二醇醚、二异氰酸酯、小分子二元醇或分子量小于1000的聚乙二醇及小分子三元醇等于2.0∶1.0-2.0∶0-1.0∶0-0.66mol;
所述水性聚氨酯改性丙烯酸酯乳液的聚合阶段的原料组成及其配比按重量计是:端烯基非离子型水性聚氨酯6-60份;丙烯酸酯单体60-114份,其中硬单体与软单体的比例为0.7-1.5∶1;引发剂过硫酸铵APS:0.3-1.0份;乳化剂十二烷基硫酸钠SDS:2.0-6.0份,按固含量为40%配料;其余为去离子水。
上述技术方案中,进一步地,所述端烯基聚乙二醇醚是烯丙基聚乙二醇醚-600,烯丙基聚乙二醇醚-800,烯丙基聚乙二醇醚-1000,烯丙基聚乙二醇醚-2000,烯丙基聚乙二醇醚-3000,甲基烯丙基聚乙二醇醚-600,甲基烯丙基聚乙二醇醚-800,甲基烯丙基聚乙二醇醚-1000,甲基烯丙基聚乙二醇醚-2000,甲基烯丙基聚乙二醇醚-2400,甲基烯丙基聚乙二醇醚-3100,甲基烯丙基聚乙二醇醚-4000,甲基烯丙基聚乙二醇醚-5000,异戊烯醇聚氧乙烯醚-1000,异戊烯醇聚氧乙烯醚-2400,异戊烯醇聚氧乙烯醚-3000,异戊烯醇聚氧乙烯醚-5000中的一种或几种单体的混合物或其它分子量在600~6000的端烯基聚氧乙烯醚。
上述技术方案中,进一步地,所述二异氰酸酯是六亚甲基二异氰酸酯HDI,异佛尔酮二异氰酸酯IPDI和二环己基甲烷二异氰酸酯HMDI中的一种。
上述技术方案中,进一步地,所述小分子二元醇是1,4-丁二醇、乙二醇、三乙二醇和分子量低于1000的聚乙二醇中的一种。
上述技术方案中,进一步地,所述小分子三元醇是丙三醇、三乙醇胺、三羟甲基丙烷和三异丙醇胺中的一种。
上述技术方案中,进一步地,所述硬单体是甲基丙烯酸甲酯、苯乙烯和丙烯腈中的一种或几种单体的混合。
上述技术方案中,进一步地,所述软单体是丙烯酸丁酯、丙烯酸乙酯、丙烯酸-2-乙基已酯和丙烯酸异辛酯中的一种或几种单体的混合。
本发明引入一种新的端烯基非离子型水性聚氨酯,还提供一种端烯基非离子型水性聚氨酯改性丙烯酸酯乳液的制备方法,其特征在于:所述制备方法是按下列步骤进行的:
(1)制备端烯基非离子型水性聚氨酯,其原料组成及其配比按摩尔比为:端烯基聚乙二醇醚、二异氰酸酯、小分子二元醇或分子量小于1000的聚乙二醇和小分子三元醇等于2.0∶1.0-2.0∶0-1.0∶0-0.66 mol;
具体制备方法是:
先将端烯基聚乙二醇醚升温至100~120℃,在-0.09Mpa下脱水2h,脱水结束后降至40℃以下,并加入少量磷酸来中和残留在端烯基聚乙二醇醚中的碱性催化剂以防止其影响端烯基聚乙二醇醚和二异氰酸酯的反应,备用;
在装有搅拌器、温度计的四口烧瓶中,按配比首先加入计算量的二异氰酸酯,接着分批次加入脱水的端烯基聚乙二醇醚,搅拌反应30min,然后升温至60-80℃反应2h;
最后加入计算量的小分子二元醇或分子量小于1000的聚乙二醇或小分子三元醇或者几种小分子二元醇、三元醇的混合物,于50-80℃搅拌反应0.5-2h,获得端烯基非离子型水性聚氨酯;
(2)通过乳液聚合获得水性聚氨酯改性的丙烯酸酯乳液,其原料组成及其按重量计配比为:端烯基非离子型水性聚氨酯6-60份;丙烯酸酯单体60-114份,其中硬单体与软单体的比例为0.7-1.5∶1;引发剂过硫酸铵APS:0.3-1.0份;乳化剂:2.0-6.0份,按固含量为40%配料,其余为去离子水;
具体制备方法如下:
首先将部分去离子水,部分乳化剂和部分引发剂先混合于装有搅拌器的四口烧瓶中,搅拌溶解;其次将丙烯酸酯单体滴加到上述四口烧瓶中,高速搅拌30min得到混合单体的预乳化液,取一定量的混合单体预乳化液于装有搅拌器、温度计、回流冷凝管的四口烧瓶中,剩余的混合单体预乳化液装入恒压滴定管中;然后将计量的水性聚氨酯单体、剩余的乳化剂和引发剂以及剩余的去离子水加入四口烧瓶中,缓慢升温至75℃左右,保温反应30min,接着开始滴加剩余的混合单体预乳化液,2h滴加完毕之后继续在此温度保温反应1h,反应结束后降至室温,过滤出料,制得所述丙烯酸酯乳液。
实现本发明上述所提供的一种端烯基非离子型水性聚氨酯改性丙烯酸酯乳液及其制备方法的技术方案,与现有技术相比,本发明以端烯基聚乙二醇醚,二异氰酸酯,小分子二元醇或分子量小于1000的聚乙二醇和小分子三元醇制备得到端烯基非离子型水性聚氨酯,在制备过程中,利用具有亲水性的端烯基聚乙二醇醚中一端的羟基可以与异氰酸酯很容易反应生成具有亲水性的短链聚氨酯,制备工艺简单,能耗较低。而且其高活性的端烯键,能够顺利的与丙烯酸酯类单体聚合,从而合成水性聚氨酯-丙烯酸酯复合乳液。
具体实施方式
实施本发明所提供的一种端烯基非离子型水性聚氨酯改性丙烯酸酯乳液及其制备方法,其主要特征是制备了端烯基非离子型水性聚氨酯,其结构可表达如下:
以端烯基聚乙二醇醚,异佛尔酮二异氰酸酯IPDI,1,4-丁二醇,丙三醇为原料合成的结构如下:
无扩链无交联
式中,R代表:端烯基聚乙二醇醚
有扩链无交联
式中,R代表:端烯基聚乙二醇醚
交联型
式中,R代表:端烯基聚乙二醇醚
实施例1
以烯丙基聚乙二醇醚-1000(APEG-1000)、异佛尔酮二异氰酸酯(IPDI)为原料,按摩尔配比2.0∶1.0,制备无扩链无交联的端烯基非离子型水性聚氨酯;具体制备方法如下:
第一步:在装有搅拌器、温度计的四口烧瓶中,首先加入计算的49.95g(0.225mol)IPDI,接着分批次加入450.0g(0.45mol)脱过水的APEG-1000,先在室温反应30min,然后升温至70℃反应2h,即可得到设计的端烯基非离子型水性聚氨酯。
第二步:通过乳液聚合得到水性聚氨酯改性的丙烯酸酯乳液,按固含量40%配料,其中端烯基非离子型水性聚氨酯、甲基丙烯酸甲酯、丙烯酸丁酯、十二烷基硫酸钠(SDS)、过硫酸铵(APS)配比为(按重量计):24份∶48份∶48份∶2.8份∶0.5份。
具体制备方法如下:
首先将80g去离子水,2.2g SDS,0.4g APS先混合于装有搅拌器的四口烧瓶中,搅拌溶解;其次将48g甲基丙烯酸甲酯和48g丙烯酸丁酯同时滴加到上述四口烧瓶中,高速搅拌30min得到混合单体的预乳化液;取25g混合单体预乳化液于装有搅拌器、温度计、回流冷凝管的四口烧瓶中,将剩余混合单体预乳化液装于恒压滴定管中;然后将24g第一步所述水性聚氨酯,0.6g SDS,0.1g APS和100g去离子水加入四口烧瓶中,缓慢升温至75℃,保温反应30min,接着开始滴加剩余的混合单体预乳化液,2h滴加完毕之后继续在此温度保温反应1h,反应结束后降至室温,过滤出料,即可得到所发明的产品。
实施例2
以甲基烯丙基聚乙二醇醚-5000(HPEG-5000)、异佛尔酮二异氰酸酯(IPDI)、1,4-丁二醇为原料,按摩尔配比2∶ 2∶1,制备有扩链无交联的端烯基非离子型水性聚氨酯。具体制备方法如下:
第一步:在装有搅拌器、温度计的四口烧瓶中,首先加入计算的29.97g(0.135mol)IPDI,接着分批次加入675g(0.135mol)脱过水的HPEG-5000,先在室温反应30min,然后升温至70℃反应2h,接着加入6.075g(0.0675mol) 1,4-丁二醇在50℃下反应0.5h,即可得到设计的端烯基非离子型水性聚氨酯。
第二步:通过乳液聚合得到水性聚氨酯改性的丙烯酸酯乳液,按固含量40%配料,其中端烯基非离子型水性聚氨酯、甲基丙烯酸甲酯、丙烯酸丁酯、十二烷基硫酸钠(SDS)、过硫酸铵(APS)配比为(按重量计):12份∶61份∶47份∶2.6份∶0.7份。
具体制备方法如下:
首先将80g去离子水,2.2g SDS,0.5g APS先混合于装有搅拌器的四口烧瓶中,搅拌溶解;其次将61g甲基丙烯酸甲酯和47g丙烯酸丁酯同时滴加到上述四口烧瓶中,高速搅拌30min得到混合单体的预乳化液;取15g混合单体预乳化液于装有搅拌器、温度计、回流冷凝管的四口烧瓶中,将剩余混合单体预乳化液装于恒压滴定管中;然后将12g第一步所述水性聚氨酯,0.4g SDS,0.2g APS和100g去离子水加入四口烧瓶中,缓慢升温至75℃,保温反应30min,接着开始滴加剩余的混合单体预乳化液,2h滴加完毕之后继续在此温度保温反应1h,反应结束后降至室温,过滤出料,即可得到所发明的产品。
实施例3
以甲基烯丙基聚乙二醇醚-2400(HPEG-2400)、异佛尔酮二异氰酸酯(IPDI)、丙三醇为原料,按摩尔配比1.5∶1∶ 0.16,制备含有交联的端烯基非离子型水性聚氨酯;具体制备方法如下:
第一步:首先在装有搅拌器、温度计的四口烧瓶中,首先加入计算的49.95g(0.225mol)IPDI,接着分批次加入810.0g(0.3375mol)脱过水的HPEG-2400,先在室温反应30min;其次升温至70℃反应2h,接着加入3.5g (0.0375mol)丙三醇在50℃下反应0.5h,即可得到设计的端烯基非离子型水性聚氨酯。
第二步:通过乳液聚合得到水性聚氨酯改性的丙烯酸酯乳液,按固含量40%配料,其中端烯基非离子型水性聚氨酯、甲基丙烯酸甲酯、丙烯酸丁酯、十二烷基硫酸钠(SDS)、过硫酸铵(APS)配比为(按重量计):6份∶50份∶64份∶2.4份∶0.4份;具体制备方法如下:
首先将80g去离子水,2.0g SDS,0.3g APS先混合于装有搅拌器的四口烧瓶中,搅拌溶解;其次将50g甲基丙烯酸甲酯和64g丙烯酸丁酯同时滴加到上述四口烧瓶中,高速搅拌30min得到混合单体的预乳化液;取 12g混合单体预乳化液于装有搅拌器、温度计、回流冷凝管的四口烧瓶中,将剩余混合单体预乳化液装于恒压滴定管中;然后将6g第一步所述水性聚氨酯,0.4g SDS,0.1g APS和100g去离子水加入四口烧瓶中,缓慢升温至75℃,保温反应30min,接着开始滴加剩余的混合单体预乳化液,2h滴加完毕之后继续在此温度保温反应1h,反应结束后降至室温,过滤出料,即可得到所发明的产品。
实施例4
以异戊烯醇聚氧乙烯醚-3000(TPEG-3000或IPEG-3000)、异佛尔酮二异氰酸酯(IPDI)、1,4-丁二醇,丙三醇为原料,按摩尔配比2: 2: 0.5: 0.33,制备既有扩链又有交联的端烯基非离子型水性聚氨酯;具体操作过程如下:
第一步:在装有搅拌器、温度计的四口烧瓶中,首先加入计算的49.95g(0.225mol)IPDI,接着分批次加入675.0g(0.225mol)脱过水的TPEG-3000,先在室温反应30min,然后升温至70℃反应2h,接着加入5.07g(0.056mol) 1,4-丁二醇和3.43g(0.037mol)丙三醇在50℃下反应0.5h,即可得到设计的端烯基非离子型水性聚氨酯。
第二步:通过乳液聚合得到水性聚氨酯改性的丙烯酸酯乳液,按固含量40%配料,其中端烯基非离子型水性聚氨酯、甲基丙烯酸甲酯、丙烯酸丁酯、十二烷基硫酸钠(SDS)、过硫酸铵(APS)配比为(按重量计):36份∶42份∶42份∶2.8份∶0.8份;具体制备方法如下:
首先将80g去离子水,2.2g SDS,0.6g APS先混合于装有搅拌器的四口烧瓶中,搅拌溶解;其次将42g甲基丙烯酸甲酯和42g丙烯酸丁酯同时滴加到上述四口烧瓶中,高速搅拌30min得到混合单体的预乳化液;取35g混合单体预乳化液于装有搅拌器、温度计、回流冷凝管的四口烧瓶中,将剩余混合单体预乳化液装于恒压滴定管中;然后将36g第一步所述水性聚氨酯,0.6g SDS,0.2g APS和100g去离子水加入四口烧瓶中,缓慢升温至75℃,保温反应30min,接着开始滴加剩余的混合单体预乳化液,2h滴加完毕之后继续在此温度保温反应1h,反应结束后降至室温,过滤出料,即可得到所发明的产品。
实施例5
以烯丙基聚乙二醇醚-600(APEG-600)、异佛尔酮二异氰酸酯(IPDI)、聚乙二醇-400为原料,按摩尔配比2∶ 2∶ 1,制备有扩链无交联的端烯基非离子型水性聚氨酯;具体制备方法如下:
第一步:在装有搅拌器、温度计的四口烧瓶中,首先加入计算的49.95g(0.225mol)IPDI,接着分批次加入450.0g(0.225mol)脱水的APEG-2000,先在室温反应30min,然后升温至70℃反应2h,接着加入44.8g(0.112mol) 聚乙二醇-400在50℃下反应1.0h,即可得到设计的端烯基非离子型水性聚氨酯。
第二步:通过乳液聚合得到水性聚氨酯改性的丙烯酸酯乳液,按固含量40%配料,其中端烯基非离子型水性聚氨酯、甲基丙烯酸甲酯、丙烯酸丁酯、十二烷基硫酸钠(SDS)、过硫酸铵(APS)配比为(按重量计):60份∶33份∶27份∶2.6份∶0.6份;具体制备方法如下:
首先将80g去离子水,2.2g SDS,0.5g APS先混合于装有搅拌器的四口烧瓶中,搅拌溶解;其次将33g甲基丙烯酸甲酯和27g丙烯酸丁酯同时滴加到上述四口烧瓶中,高速搅拌30min得到混合单体的预乳化液;取46g混合单体预乳化液于装有搅拌器、温度计、回流冷凝管的四口烧瓶中,将剩余混合单体预乳化液装于恒压滴定管中;然后将60g第一步所述水性聚氨酯,0.4g SDS,0.1g APS和100g去离子水加入四口烧瓶中,缓慢升温至75℃,保温反应30min,接着开始滴加剩余的混合单体预乳化液,2h滴加完毕之后继续在此温度保温反应1h,反应结束后降至室温,过滤出料,即可得到所发明的产品。
实施例6
以烯丙基聚乙二醇醚-600(APEG-600)、异佛尔酮二异氰酸酯(IPDI)、聚乙二醇-800,三乙醇胺为原料,按摩尔配比2∶2∶ 0.5∶ 0.33,制备既有扩链又有交联的端烯基非离子型水性聚氨酯;具体制备方法如下:
第一步:在装有搅拌器、温度计的四口烧瓶中,首先加入计算的49.95g(0.225mol)IPDI,接着分批次加入135.0g(0.225mol)脱水的APEG-600,先在室温反应30min,然后升温至70℃反应2h,接着加入44.8g(0.056mol) 聚乙二醇-800和5.52g(0.037mol)三乙醇胺在50℃下反应0.5h,即可得到设计的端烯基非离子型水性聚氨酯。
第二步:通过乳液聚合得到水性聚氨酯改性的丙烯酸酯乳液,按固含量40%配料,其中端烯基非离子型水性聚氨酯、甲基丙烯酸甲酯、丙烯酸丁酯、十二烷基硫酸钠(SDS)、过硫酸铵(APS)配比为(按重量计):30份:41份:49份:3.2份:0.3份;具体制备方法如下:
首先将80g去离子水,2.4g SDS,0.2g APS先混合于装有搅拌器的四口烧瓶中,搅拌溶解;其次将41g甲基丙烯酸甲酯和49g丙烯酸丁酯同时滴加到上述四口烧瓶中,高速搅拌30min得到混合单体的预乳化液;取30g混合单体预乳化液于装有搅拌器、温度计、回流冷凝管的四口烧瓶中,将剩余混合单体预乳化液装于恒压滴定管中;然后将30g第一步所述水性聚氨酯,0.8g SDS,0.1g APS和100g去离子水加入四口烧瓶中,缓慢升温至75℃,保温反应30min,接着开始滴加剩余的混合单体预乳化液,2h滴加完毕之后继续在此温度保温反应1h,反应结束后降至室温,过滤出料,即可得到所发明的产品。
对比实施例1
选取购自某公司的水性聚氨酯-丙烯酸酯分散乳液,固含量约为40%。
乳胶膜的制备及性能测试:将本发明的复合乳液及对比实施例1乳液涂覆于聚四氟乙烯板上,30℃干燥一周,得到厚度约为0.6mm的薄膜样品,对其进行吸水率、拉伸强度、断裂伸长率性能的测试,见表1。
表1 不同复合乳液的性能
由表1可以看出,本发明所述的水性聚氨酯-丙烯酸酯复合乳液与常规复合乳液相比,吸水率显著减低,力学性能优异。
Claims (7)
1.一种端烯基非离子型水性聚氨酯改性丙烯酸酯乳液,其特征在于:
所述端烯基非离子型水性聚氨酯的原料组成及其摩尔比配比是:端烯基聚乙二醇醚、二异氰酸酯、小分子二元醇或分子量小于1000的聚乙二醇及小分子三元醇等于2.0∶1.0-2.0∶0-1.0∶0-0.66;
所述水性聚氨酯改性丙烯酸酯乳液的聚合阶段的原料组成及其配比按重量计是:端烯基非离子型水性聚氨酯6-60份;丙烯酸酯单体60-114份,其中硬单体与软单体的比例为0.7-1.5∶1;引发剂过硫酸铵APS:0.3-1.0份;乳化剂十二烷基硫酸钠SDS:2.0-6.0份,按固含量为40%配料;其余为去离子水;
具体制备方法是按下列步骤进行的:
(1)制备端烯基非离子型水性聚氨酯,其原料组成及其摩尔比配比为:端烯基聚乙二醇醚、二异氰酸酯、小分子二元醇或分子量小于1000的聚乙二醇和小分子三元醇等于2.0∶1.0-2.0∶0-1.0∶0-0.66 ;
具体制备方法是:
先将端烯基聚乙二醇醚升温至100~120℃,在-0.09Mpa下脱水2h,脱水结束后降至40℃以下,并加入少量磷酸来中和残留在端烯基聚乙二醇醚中的碱性催化剂以防止其影响端烯基聚乙二醇醚和二异氰酸酯的反应,备用;
在装有搅拌器、温度计的四口烧瓶中,按配比首先加入计算量的二异氰酸酯,接着分批次加入脱水的端烯基聚乙二醇醚,搅拌反应30min,然后升温至60-80℃反应2h;
最后加入计算量的小分子二元醇或分子量小于1000的聚乙二醇或小分子三元醇或者几种小分子二元醇、三元醇的混合物,于50-80℃搅拌反应0.5-2h,获得端烯基非离子型水性聚氨酯;
(2)通过乳液聚合获得水性聚氨酯改性的丙烯酸酯乳液,其原料组成及其质量比配比为:端烯基非离子型水性聚氨酯6-60份;丙烯酸酯单体60-114份,其中硬单体与软单体的比例为0.7-1.5∶1;引发剂过硫酸铵APS:0.3-1.0份;乳化剂:2.0-6.0份,按固含量为40%配料,其余为去离子水;
具体制备方法如下:
首先将部分去离子水,部分乳化剂和部分引发剂先混合于装有搅拌器的四口烧瓶中,搅拌溶解;其次将丙烯酸酯单体滴加到上述四口烧瓶中,高速搅拌30min得到混合单体的预乳化液,取一定量的混合单体预乳化液于装有搅拌器、温度计、回流冷凝管的四口烧瓶中,剩余的混合单体预乳化液装入恒压滴定管中;然后将计量的水性聚氨酯单体、剩余的乳化剂和引发剂以及剩余的去离子水加入四口烧瓶中,缓慢升温至75℃,保温反应30min,接着开始滴加剩余的混合单体预乳化液,2h滴加完毕之后继续在此温度保温反应1h,反应结束后降至室温,过滤出料,制得所述丙烯酸酯乳液。
2.根据权利要求1所述的端烯基非离子型水性聚氨酯改性丙烯酸酯乳液,其特征在于:所述端烯基聚乙二醇醚是烯丙基聚乙二醇醚-600,烯丙基聚乙二醇醚-1000,烯丙基聚乙二醇醚-2000,烯丙基聚乙二醇醚-3000,甲基烯丙基聚乙二醇醚-600,甲基烯丙基聚乙二醇醚-1000,甲基烯丙基聚乙二醇醚-2000,甲基烯丙基聚乙二醇醚-2400,甲基烯丙基聚乙二醇醚-3100,甲基烯丙基聚乙二醇醚-4000,甲基烯丙基聚乙二醇醚-5000,异戊烯醇聚氧乙烯醚-1000,异戊烯醇聚氧乙烯醚-2400,异戊烯醇聚氧乙烯醚-3000,异戊烯醇聚氧乙烯醚-5000中的一种或几种单体的混合物或其它分子量在600~6000的端烯基聚氧乙烯醚。
3.根据权利要求1所述的端烯基非离子型水性聚氨酯改性丙烯酸酯乳液,其特征在于:所述二异氰酸酯是六亚甲基二异氰酸酯HDI,异佛尔酮二异氰酸酯IPDI和二环己基甲烷二异氰酸酯HMDI中的一种。
4.根据权利要求1所述的端烯基非离子型水性聚氨酯改性丙烯酸酯乳液,其特征在于:所述小分子二元醇是1,4-丁二醇、乙二醇和三乙二醇中的一种。
5.根据权利要求1所述的端烯基非离子型水性聚氨酯改性丙烯酸酯乳液,其特征在于:所述小分子三元醇是丙三醇、三乙醇胺、三羟甲基丙烷和三异丙醇胺中的一种。
6.根据权利要求1所述的端烯基非离子型水性聚氨酯改性丙烯酸酯乳液,其特征在于:所述硬单体是甲基丙烯酸甲酯。
7.根据权利要求1所述的端烯基非离子型水性聚氨酯改性丙烯酸酯乳液,其特征在于:所述软单体是丙烯酸丁酯、丙烯酸乙酯和丙烯酸异辛酯中的一种或几种单体的混合。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201711433220.3A CN108164650B (zh) | 2017-12-26 | 2017-12-26 | 端烯基非离子型水性聚氨酯改性丙烯酸酯乳液及其制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201711433220.3A CN108164650B (zh) | 2017-12-26 | 2017-12-26 | 端烯基非离子型水性聚氨酯改性丙烯酸酯乳液及其制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN108164650A CN108164650A (zh) | 2018-06-15 |
CN108164650B true CN108164650B (zh) | 2020-02-21 |
Family
ID=62521077
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201711433220.3A Expired - Fee Related CN108164650B (zh) | 2017-12-26 | 2017-12-26 | 端烯基非离子型水性聚氨酯改性丙烯酸酯乳液及其制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN108164650B (zh) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110790886A (zh) * | 2019-11-13 | 2020-02-14 | 浩力森涂料(上海)有限公司 | 单组份涂料及其成膜树脂和制备方法 |
CN112625232B (zh) * | 2020-11-26 | 2023-05-05 | 山西佳维新材料股份有限公司 | 一种不饱和氨基聚氧乙烯醚和聚羧酸减水剂及其合成方法和应用 |
CN112646107B (zh) * | 2020-12-18 | 2022-11-22 | 联泓(江苏)新材料研究院有限公司 | 水性聚氨酯丙烯酸酯树脂及其制备方法和组合物 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60203683A (ja) * | 1984-02-20 | 1985-10-15 | Sumitomo Chem Co Ltd | 接着剤 |
CN103450418A (zh) * | 2013-09-10 | 2013-12-18 | 合肥乐凯科技产业有限公司 | 一种丙烯酸酯-聚氨酯乳液及其制备方法 |
-
2017
- 2017-12-26 CN CN201711433220.3A patent/CN108164650B/zh not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60203683A (ja) * | 1984-02-20 | 1985-10-15 | Sumitomo Chem Co Ltd | 接着剤 |
CN103450418A (zh) * | 2013-09-10 | 2013-12-18 | 合肥乐凯科技产业有限公司 | 一种丙烯酸酯-聚氨酯乳液及其制备方法 |
Non-Patent Citations (1)
Title |
---|
"非离子型聚氨酯-丙烯酸酯复合细乳液的研究";刘楠楠等;《中国涂料》;20101231;第25卷(第01期);第36-40页 * |
Also Published As
Publication number | Publication date |
---|---|
CN108164650A (zh) | 2018-06-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN109734846B (zh) | 一种核壳型水性聚氨酯/丙烯酸酯复合乳液及其制备方法和阻尼涂料 | |
CN108164650B (zh) | 端烯基非离子型水性聚氨酯改性丙烯酸酯乳液及其制备方法 | |
CN109679030A (zh) | 一种水性聚氨酯-聚醋酸乙烯酯树脂及其制备方法和应用 | |
US11976158B2 (en) | Non-ionic water based polyurethane and preparation method and use thereof | |
CN1438257A (zh) | 丙烯酸聚氨酯共聚物乳液及其制备方法和应用 | |
JP2003508600A (ja) | ウルトラハイソリッドアクリル塗料 | |
CN108314770B (zh) | 二氧化碳基水性聚氨酯分散体、制备方法及二氧化碳基水性聚氨酯压敏胶 | |
CN111875769B (zh) | 一种高固含量水性聚氨酯复合乳液及其制备方法 | |
CN110951041B (zh) | 一种水性聚氨酯-丙烯酸酯杂化共聚物及其制备方法 | |
CN104725588B (zh) | 具有ipn结构的无溶剂的阴/非离子型水性聚氨酯‑丙烯酸酯接枝共聚物的制备方法 | |
CN104211878A (zh) | 一种聚氨酯环氧树脂丙烯酸酯三元共聚树脂纳米水分散液的制备方法 | |
CN108467471B (zh) | 一种梳状多支化水性聚氨酯分散体及其制备与应用 | |
CN109575232B (zh) | 一种高抗张强度的无溶剂型水性聚氨酯及其制备方法 | |
CN104629605B (zh) | 一种汽车用单组份水性金属闪光漆及其制备方法 | |
CN101157841A (zh) | 服装人造革用环境友好型水性聚氨酯热溶胶的制备方法 | |
CN105461862A (zh) | 单组份水性阳离子聚氨酯-氟丙烯酸树脂及其制备方法 | |
CN110423323B (zh) | 一种水溶性封闭型聚氨酯固化剂及其制备方法和应用 | |
CN111748072A (zh) | 一种人造或合成革用水性自消光表处剂及制备方法 | |
CN111620984A (zh) | 改性聚氨酯树脂及其制备方法、水性涂料及涂膜制品 | |
AU2020103155A4 (en) | Non-ionic water based polyurethane and preparation method and use thereof | |
CN114409852A (zh) | 丙烯酸改性水性聚氨酯分散体及其制备方法 | |
CN111333802B (zh) | 水性聚氨酯分散体及其制备方法与应用、水性涂料 | |
CN114276498A (zh) | 一种改性聚丙烯酸酯乳液及由其组成的涂料 | |
CN101157843A (zh) | 雨披人造革用环境友好型水性聚氨酯热溶胶的制备方法 | |
CN114316202A (zh) | 一种紫外光固化水性聚氨酯丙烯酸酯乳液及其制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200221 |
|
CF01 | Termination of patent right due to non-payment of annual fee |