CN107722687A - 水性可剥离树脂及其制备方法 - Google Patents
水性可剥离树脂及其制备方法 Download PDFInfo
- Publication number
- CN107722687A CN107722687A CN201710845199.1A CN201710845199A CN107722687A CN 107722687 A CN107722687 A CN 107722687A CN 201710845199 A CN201710845199 A CN 201710845199A CN 107722687 A CN107722687 A CN 107722687A
- Authority
- CN
- China
- Prior art keywords
- water
- parts
- peelable resin
- based peelable
- propionic acid
- 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.)
- Granted
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000011347 resin Substances 0.000 title claims abstract description 64
- 229920005989 resin Polymers 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims description 12
- -1 hydroxy silicate Chemical compound 0.000 claims abstract description 43
- 229920000570 polyether Polymers 0.000 claims abstract description 37
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 32
- 150000002334 glycols Chemical class 0.000 claims abstract description 32
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 15
- 229920002635 polyurethane Polymers 0.000 claims abstract description 15
- 239000004814 polyurethane Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 10
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 10
- 239000010703 silicon Substances 0.000 claims abstract description 10
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 128
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 78
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 42
- 235000019260 propionic acid Nutrition 0.000 claims description 39
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 39
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 30
- 229910052961 molybdenite Inorganic materials 0.000 claims description 23
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 23
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 18
- MYRTYDVEIRVNKP-UHFFFAOYSA-N divinylbenzene Substances C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 15
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 14
- 238000004132 cross linking Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 239000012948 isocyanate Substances 0.000 claims description 7
- 239000003085 diluting agent Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229920005749 polyurethane resin Polymers 0.000 claims description 6
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N dimethylmethane Natural products CCC ATUOYWHBWRKTHZ-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
- 238000002454 metastable transfer emission spectrometry Methods 0.000 claims description 4
- 239000001294 propane Substances 0.000 claims description 4
- 125000003944 tolyl group Chemical group 0.000 claims description 4
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical group CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 125000002496 methyl group Chemical class [H]C([H])([H])* 0.000 claims description 3
- 125000005474 octanoate group Chemical group 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 239000007983 Tris buffer Substances 0.000 claims description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 150000002009 diols Chemical class 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 2
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 claims 1
- 239000004743 Polypropylene Substances 0.000 claims 1
- ZXPDYFSTVHQQOI-UHFFFAOYSA-N diethoxysilane Chemical compound CCO[SiH2]OCC ZXPDYFSTVHQQOI-UHFFFAOYSA-N 0.000 claims 1
- 150000002513 isocyanates Chemical class 0.000 claims 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 1
- 229920001155 polypropylene Polymers 0.000 claims 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 claims 1
- 239000003973 paint Substances 0.000 abstract description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 6
- 229920001296 polysiloxane Polymers 0.000 abstract description 5
- 229920001971 elastomer Polymers 0.000 abstract description 3
- 239000000806 elastomer Substances 0.000 abstract description 3
- 239000000377 silicon dioxide Substances 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 8
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 description 6
- 150000002576 ketones Chemical class 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- GAURFLBIDLSLQU-UHFFFAOYSA-N diethoxy(methyl)silicon Chemical compound CCO[Si](C)OCC GAURFLBIDLSLQU-UHFFFAOYSA-N 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- WVICRWJHVDRYSU-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;methyl prop-2-enoate Chemical compound COC(=O)C=C.C=CC1=CC=CC=C1C=C WVICRWJHVDRYSU-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000000016 photochemical curing Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- SSYDTHANSGMJTP-ZXZARUISSA-N (3s,4r)-oxolane-3,4-diol Chemical compound O[C@H]1COC[C@H]1O SSYDTHANSGMJTP-ZXZARUISSA-N 0.000 description 1
- DBXBTMSZEOQQDU-UHFFFAOYSA-N 3-hydroxyisobutyric acid Chemical class OCC(C)C(O)=O DBXBTMSZEOQQDU-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008236 heating water Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000548 poly(silane) polymer Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—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
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
-
- 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
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/20—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for coatings strippable as coherent films, e.g. temporary coatings strippable as coherent films
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3009—Sulfides
Abstract
提供一种水性可剥离树脂,其包含按照质量份数计的,20‑40份的聚醚二元醇、30‑50份的二异氰酸酯和5‑20份的柔性端羟基有机硅低聚物。本发明将有机硅单体首先合成柔性端羟基有机硅低聚物,有机硅低聚物接枝到聚醚二元醇,进一步参与聚氨酯的合成反应,形成硅氧聚醚混合软段的弹性体,提升了漆膜的拉伸强度,降低漆膜脆性,实现漆膜整片剥离。
Description
技术领域
本发明通常涉及涂料领域,且特别地,涉及水性可剥离树脂及其制备方法。
背景技术
可剥离树脂作为可剥离涂料的成膜物质,要求树脂具有一定的可剥离性。树脂的内聚力要足够大,以满足漆膜在剥离过程中不容易断裂并且在基材上无残留;树脂与基材附着力适中,既可以保证涂膜对基材的粘附,同时在需要剥离时又能轻易剥离,此外,成膜树脂还必须具有一定的弹性,能够减缓外界对基材的冲击。目前,市场上的水性可剥离树脂制得的漆膜脆性大、漆膜强度低,不易整片剥离,并且漆膜经过高低温循环后易开裂,使得水性可剥离树脂没有被广泛应用。
因此,研发一种漆膜脆性小、漆膜强度高,易整片剥离的水性可剥离树脂是本领域技术人员亟待解决的技术问题。
发明内容
本发明提供一种水性可剥离树脂及其制备方法,将有机硅单体首先合成柔性端羟基有机硅低聚物,有机硅低聚物接枝到聚醚二元醇中,进一步参与聚氨酯的合成反应,形成硅氧聚醚混合软段的弹性体,提升了漆膜的拉伸强度,降低漆膜脆性,实现漆膜整片剥离。
本发明提供一种水性可剥离树脂,其包含按照质量份数计的,20-40份的聚醚二元醇、30-50份的二异氰酸酯和5-20份的柔性端羟基有机硅低聚物。
在某些实施方式中,所述的水性可剥离树脂中,其还包括5-15份的二羟甲基丙酸和2-8份的二甘醇;其中,所述二羟甲基丙酸与所述柔性端羟基有机硅低聚物质量之比为0.9-1.5:1。
在某些实施方式中,所述的水性可剥离树脂中-NCO:-OH的摩尔比在1.5-2的范围内。
在某些实施方式中,所述的水性可剥离树脂中,聚醚二元醇的分子量大于2000;
所述二异氰酸酯为甲苯二异氰酸酯(TDI)、二苯基甲烷二异氰酸酯(MDI)、3-异氰酸酯基亚甲基-3,5,5-三甲基环己基异氰酸酯(IPDI)中的一种或多种;
合成所述柔性端羟基有机硅低聚物所用到的有机硅单体为甲基三乙氧基硅烷、二甲基二乙氧基硅烷、苯基三乙氧基硅烷中的两种或三种。
在某些实施方式中,所述的水性可剥离树脂中,其还包括20-30份的三羟甲基丙烷三丙烯酸酯,所述三羟甲基丙烷三丙烯酸酯的官能度为3。
在某些实施方式中,所述的水性可剥离树脂中,其还包括1-5份交联度为40%的聚丙烯酸甲酯-二乙烯苯。
在某些实施方式中,所述的水性可剥离树脂中,其还包括3-10份的纳米MoS2/TiO2;
其中所述纳米MoS2/TiO2与所述聚丙烯酸甲酯-二乙烯苯按照质量比1:1.5-2.5混合。
在某些实施方式中,所述的水性可剥离树脂中,所述聚醚二元醇选自由聚乙二醇、聚丙二醇、混合聚乙二醇/丙二醇和聚四氢呋喃二醇组成的组中的至少一种。
本发明另一方面提供一种水性可剥离树脂的制备方法,其包括如下步骤:
(1)在装有氮气保护装置的四口瓶中加入二异氰酸酯,200-400r/min的转速下搅拌并依次滴加端羟基有机硅低聚物和聚醚二元醇,缓慢升温至70-80℃,反应1-2h;
(2)加入二羟甲基丙酸和丙酮,50℃-70℃保温2-3h后,加入二甘醇和催化剂辛酸亚锡,保温3-4h,反应期间视粘度变化加入稀释剂丙酮;
(3)反应期间控制NCO:OH摩尔比在1.5-2范围内,然后降温至40℃以下,加入与所述二羟甲基丙酸等物质的量的三乙胺,反应20-30min,得到亲水性聚氨酯溶液;
(4)在30-40℃,1000-1500r/min的转速下搅拌所述聚氨酯溶液,减压蒸馏除去丙酮,得到水性可剥离聚氨酯树脂。
在某些实施方式中,所述的水性可剥离树脂的制备方法中,还包括:
在所述步骤(1)中还包括,在滴加聚醚二元醇后,加入官能度为3的三羟甲基丙烷三丙烯酸酯;
在所述步骤(2)中还包括,在加入二羟甲基丙酸和丙酮后,加入交联度为40%的聚丙烯酸甲酯-二乙烯苯和纳米MoS2/TiO2。
具体实施方式
现详细说明本发明的多种示例性实施方式,该详细说明不应认为是对本发明的限制,而应理解为是对本发明的某些方面、特性和实施方案的更详细的描述。
应理解本发明中所述的术语仅仅是为描述特别的实施方式,并非用于限制本发明。另外,对于本发明中的数值范围,应理解为还具体公开了该范围的上限和下限之间的每个中间值。在任何陈述值或陈述范围内的中间值以及任何其他陈述值或在所述范围内的中间值之间的每个较小的范围也包括在本发明内。这些较小范围的上限和下限可独立地包括或排除在范围内。
除非另有说明,否则本文使用的所有技术和科学术语具有本发明所述领域的常规技术人员通常理解的相同含义。虽然本发明仅描述了优选的方法和材料,但是在本发明的实施或测试中也可以使用与本文所述相似或等同的任何方法和材料。本说明书中提到的所有文献通过引用并入,用以公开和描述与所述文献相关的方法和:或材料。在与任何并入的文献冲突时,以本说明书的内容为准。
在不背离本发明的范围或精神的情况下,可对本发明说明书的具体实施方式做多种改进和变化,这对本领域技术人员而言是显而易见的。由本发明的说明书得到的其他实施方式对技术人员而言是显而易见得的。本申请说明书和实施例仅是示例性的。
关于本文中所使用的“包含”、“包括”、“具有”、“含有”等等,均为开放性的用语,即意指包含但不限于。
本发明中所述的“份”如无特别说明,均按质量计。
本发明中所述的水性可剥离树脂中,包含按照质量份数计的,20-40份的聚醚二元醇、30-50份的二异氰酸酯和5-20份的柔性端羟基有机硅低聚物。将有机硅单体首先合成柔性端羟基有机硅低聚物,有机硅低聚物接枝到聚醚二元醇上,并进一步参与聚氨酯的合成反应,形成硅氧聚醚混合软段的弹性体,提升了漆膜的拉伸强度,缓冲外界对基材的冲击,避免外界环境引起的漆膜开裂现象的发生。其中,合成所述柔性端羟基有机硅低聚物至少包括如下步骤:将有机硅单体加入四口瓶中,搅拌状态下水浴加热升温至68-72℃,将加有浓盐的去离子水缓慢滴加到四口瓶中,使其在0.5~lh内滴加完毕,待去离子水滴加完毕后,保持温度65-70℃反应4h;将温度升温至80℃蒸出产物乙醇,得到柔性端羟基有机硅低聚物。
在某些实施方式中,所述的水性可剥离树脂中还包括5-15份的二羟甲基丙酸、2-8份的二甘醇和辛酸亚锡,且所述二羟甲基丙酸与所述柔性端羟基有机硅低聚物质量之比为0.9-1.5:1。
在所述水性可剥离树脂中,二羟甲基丙酸和二甘醇作为扩链剂,辛酸亚锡作为催化剂。所述二羟甲基丙酸与所述柔性端羟基有机硅低聚物质量之比0.9-1.5:1时,水性可剥离树脂表现出良好的水溶性,当二羟甲基丙酸与所述柔性端羟基有机硅低聚物质量之比低于0.9:1时,水性可剥离树脂的水溶性差,当二羟甲基丙酸与所述柔性端羟基有机硅低聚物质量之比高于1.5:1时,随着二羟甲基丙酸用量增加,端羟基的聚硅烷基和双羟基甲基丙酸中羟基同时与异氰酸根基团反应,生成一些分子量低的副产物,降低水性剥离树脂的身材效率。优选的,所述二羟甲基丙酸与所述柔性端羟基有机硅低聚物质量之比为0.9-1.2:1,更优选地,所述二羟甲基丙酸与所述柔性端羟基有机硅低聚物质量之比为0.9-1:1,例如。所述二羟甲基丙酸与所述柔性端羟基有机硅低聚物质量之比为0.9:1或是1:1。
在某些实施方式中,所述的水性可剥离树脂中-NCO/-OH的摩尔比在1.5-2的范围内。优选地,所述的水性可剥离树脂中-NCO/-OH的摩尔比在1.6-2的范围内。例如,所述的水性可剥离树脂中-NCO/-OH的摩尔比为1.6、1.7、1.8、1.9或2。
在某些实施方式中,所述的水性可剥离树脂中还包括20-30份的三羟甲基丙烷三丙烯酸酯,所述三羟甲基丙烷三丙烯酸酯的官能度为3。
三羟甲基丙烷三丙烯酸酯是紫外光固化材料,用于溶解和稀释低聚物,起到调节体系的粘度的作用,参与整个光固化反应。三羟甲基丙烷三丙烯酸酯在分子结构中含有具有光活性的碳碳双键或环氧基。官能度为3的三羟甲基丙烷三丙烯酸酯是三维网状的高分子聚合物,使得水性可剥离树脂具有固化速度快、交联度高、硬度增加、热稳定性好,耐化学性好的特点,并争强所述水性可剥离树脂的光固化反应的活性。
在某些实施方式中,所述的水性可剥离树脂中还包括包括1-5份交联度为40%的聚丙烯酸甲酯-二乙烯苯和3-10份的纳米MoS2/TiO2,其中,所述纳米MoS2/TiO2与所述聚丙烯酸甲酯-二乙烯苯按照质量比1.5-2.5:1混合。例如,所述纳米MoS2/TiO2与所述聚丙烯酸甲酯-二乙烯苯按照质量比1.5:1、2:1或2.5:1
纳米MoS2/TiO2作为一种复合催化剂,其以纳米TiO2是提供载体,纳米MoS2作为活性组分,MoS2在复合催化剂的表面形成长约10-30nm,厚约8nm的纳米片。单层纳米MoS2在c轴方向上堆积随性很高,所述的水性可剥离树脂中的阳离子和聚丙烯酸甲酯-二乙烯苯在单层MoS2纳米片沿c轴方向上重堆积,形成MoS2夹层化合物,且形成的夹层化合物仍维持了一定的单分子层特性。在所述水性可剥离树脂中形成MoS2夹层化合物,使得水性可剥离树脂具有片层结构,使得水性可剥离树脂形成的漆膜具有整体可剥离的特性。
本发明所述的附着力含量通过参考国家标准《GB/T 1720-1979漆膜附着力测定法》来测试。
本发明所述的断裂伸长率和漆膜拉伸强度通过参考国家标准《GB/T 1040.3-2006塑料拉伸性能测定法》来测试。
本发明所述的180°剥离强度通过参考国家标准《GB/T 2790-1995胶黏剂180°剥离强度试验方法》来测试。
本发明所述的人工加速老化性能通过参考国家标准《GB/T 1865-2009色漆和清漆人工气候老化和人工辐射曝露滤过的氙弧辐射》来测试。
本发明所述的可撕性通过如下方法测试,将产品涂覆于带漆的涂层上,厚度约为30μm,将样品在室温下放置一周后将涂层撕去,观察撕后的残留和破坏原漆的情况。
本发明所述的耐水性通过如下方法测试,将产品涂覆于带漆的涂层上,在40℃水中浸泡168h,观察涂层情况。
本发明所述的耐潮湿性通过如下方法测试,将产品涂覆于带漆的涂层上,60℃/95%相对湿度条件下96h,观察涂层情况。
本发明所述的耐高温存放性通过如下方法测试,将产品涂覆于带漆的涂层上,80℃温度环境中存放168h,观察涂层情况。
本发明所述的耐低温存放性通过如下方法测试,将产品涂覆于带漆的涂层上,-40℃温度环境中存放24h,观察涂层情况。
实施例
实施例1
一种水性可剥离树脂,其包含按照质量份数计的,30份的聚醚二元醇、40份的二异氰酸酯、11份的柔性端羟基有机硅低聚物、10份的二羟甲基丙酸、6份的二甘醇、4份的辛酸亚锡和2份的丙酮;
其中,所述二羟甲基丙酸与所述柔性端羟基有机硅低聚物质量之比为0.9:1;控制所述水性可剥离树脂中-NCO:-OH的摩尔比在1.7。
上述方案中,聚醚二元醇的分子量大于2000;所述二异氰酸酯为3-异氰酸酯基亚甲基-3,5,5-三甲基环己基异氰酸酯(IPDI);
合成所述柔性端羟基有机硅低聚物所用到的有机硅单体为苯基三乙氧基硅烷。
上述方案中,所述聚醚二元醇选自由混合聚乙二醇:丙二醇。
制备方法:
(1)在装有氮气保护装置的四口瓶中加入二异氰酸酯,200-400r/min的转速下搅拌并依次滴加端羟基有机硅低聚物和聚醚二元醇,缓慢升温至70-80℃,反应1-2h;
(2)加入二羟甲基丙酸和丙酮,并在600-800r/min的转速下加入,50℃-70℃保温2-3h后,加入二甘醇和催化剂辛酸亚锡,保温3-4h,反应期间视粘度变化加入稀释剂丙酮;
(3)反应期间控制NCO:OH摩尔比为1.7,然后降温至40℃以下,加入与所述二羟甲基丙酸等物质的量的三乙胺,反应20-30min,得到亲水性聚氨酯溶液;
(4)在30-40℃,1000-1500r/min的转速下搅拌所述聚氨酯溶液,减压蒸馏除去丙酮,得到水性可剥离聚氨酯树脂。
实施例2
一种水性可剥离树脂,其包含按照质量份数计的,40份的聚醚二元醇、50份的二异氰酸酯、20份的柔性端羟基有机硅低聚物、15份的二羟甲基丙酸、8份的二甘醇、5份的辛酸亚锡、30份官能度为3的三羟甲基丙烷三丙烯酸酯、5份交联度为40%的聚丙烯酸甲酯-二乙烯苯、10份的纳米MoS2/TiO2和3份丙酮;
其中,所述二羟甲基丙酸与所述柔性端羟基有机硅低聚物质量之比为1.5:1;控制所述水性可剥离树脂中-NCO:-OH的摩尔比为2;所述纳米MoS2/TiO2与所述聚丙烯酸甲酯-二乙烯苯按照质量比2:1混合。
上述方案中,聚醚二元醇的分子量大于2000;所述二异氰酸酯为二苯基甲烷二异氰酸酯(MDI);合成所述柔性端羟基有机硅低聚物所用到的有机硅单体为二甲基二乙氧基硅烷和苯基三乙氧基硅烷。
上述方案中,所述聚醚二元醇为聚丙二醇。
制备方法:
(1)在装有氮气保护装置的四口瓶中加入二异氰酸酯,200-400r/min的转速下搅拌并依次滴加端羟基有机硅低聚物、聚醚二元醇和官能度为3的三羟甲基丙烷三丙烯酸酯,缓慢升温至70-80℃,反应1-2h;
(2)加入二羟甲基丙酸和丙酮,并在600-800r/min的转速下加入交联度为40%的聚丙烯酸甲酯-二乙烯苯和纳米MoS2/TiO2,50℃-70℃保温2-3h后,加入二甘醇和催化剂辛酸亚锡,保温3-4h,反应期间视粘度变化加入稀释剂丙酮;
(3)反应期间控制NCO:OH摩尔比为2.0,然后降温至40℃以下,加入与所述二羟甲基丙酸等物质的量的三乙胺,反应20-30min,得到亲水性聚氨酯溶液;
(4)在30-40℃,1000-1500r/min的转速下搅拌所述聚氨酯溶液,减压蒸馏除去丙酮,得到水性可剥离聚氨酯树脂。
实施例3
一种水性可剥离树脂,其包含按照质量份数计的,20份的聚醚二元醇、30份的二异氰酸酯、5份的柔性端羟基有机硅低聚物、5份的二羟甲基丙酸、2份的二甘醇、1份的辛酸亚锡、20份官能度为3的三羟甲基丙烷三丙烯酸酯、1份交联度为40%的聚丙烯酸甲酯-二乙烯苯、2.5份的纳米MoS2/TiO2和2份丙酮;
其中,所述二羟甲基丙酸与所述柔性端羟基有机硅低聚物质量之比为1:1;控制所述水性可剥离树脂中-NCO:-OH的摩尔比为1.6;所述纳米MoS2/TiO2与所述聚丙烯酸甲酯-二乙烯苯按照质量比2.5:1混合。
上述方案中,聚醚二元醇的分子量大于2000;所述二异氰酸酯为甲苯二异氰酸酯(TDI);合成所述柔性端羟基有机硅低聚物所用到的有机硅单体为甲基三乙氧基硅烷和二甲基二乙氧基硅烷。
上述方案中,所述聚醚二元醇为聚乙二醇。
制备方法:
(1)在装有氮气保护装置的四口瓶中加入二异氰酸酯,200-400r/min的转速下搅拌并依次滴加端羟基有机硅低聚物、聚醚二元醇和官能度为3的三羟甲基丙烷三丙烯酸酯,缓慢升温至70-80℃,反应1-2h;
(2)加入二羟甲基丙酸和丙酮,并在600-800r/min的转速下加入交联度为40%的聚丙烯酸甲酯-二乙烯苯和纳米MoS2/TiO2,50℃-70℃保温2-3h后,加入二甘醇和催化剂辛酸亚锡,保温3-4h,反应期间视粘度变化加入稀释剂丙酮;
(3)反应期间控制NCO:OH摩尔比为1.6,然后降温至40℃以下,加入与所述二羟甲基丙酸等物质的量的三乙胺,反应20-30min,得到亲水性聚氨酯溶液;
(4)在30-40℃,1000-1500r/min的转速下搅拌所述聚氨酯溶液,减压蒸馏除去丙酮,得到水性可剥离聚氨酯树脂。
实施例4
一种水性可剥离树脂,其包含按照质量份数计的,25份的聚醚二元醇、45份的二异氰酸酯、10份的柔性端羟基有机硅低聚物、12份的二羟甲基丙酸、5份的二甘醇、4份的辛酸亚锡、22份官能度为3的三羟甲基丙烷三丙烯酸酯、4份交联度为40%的聚丙烯酸甲酯-二乙烯苯、8份的纳米MoS2/TiO2和3份的丙酮;
其中,所述二羟甲基丙酸与所述柔性端羟基有机硅低聚物质量之比为1.2:1;控制所述水性可剥离树脂中-NCO:-OH的摩尔比为1.8;所述纳米MoS2/TiO2与所述聚丙烯酸甲酯-二乙烯苯按照质量比2.3:1混合。
上述方案中,聚醚二元醇的分子量大于2000;所述二异氰酸酯为甲苯二异氰酸酯(TDI)、二苯基甲烷二异氰酸酯(MDI)和3-异氰酸酯基亚甲基-3,5,5-三甲基环己基异氰酸酯(IPDI)的混合物;
合成所述柔性端羟基有机硅低聚物所用到的有机硅单体为甲基三乙氧基硅烷、二甲基二乙氧基硅烷和苯基三乙氧基硅烷的混合物。
上述方案中,所述聚醚二元醇为聚乙二醇、聚丙二醇、混合聚乙二醇/丙二醇和聚四氢呋喃二醇组成的混合物。
制备方法:
(1)在装有氮气保护装置的四口瓶中加入二异氰酸酯,200-400r/min的转速下搅拌并依次滴加端羟基有机硅低聚物、聚醚二元醇和官能度为3的三羟甲基丙烷三丙烯酸酯,缓慢升温至70-80℃,反应1-2h;
(2)加入二羟甲基丙酸和丙酮,并在600-800r/min的转速下加入交联度为40%的聚丙烯酸甲酯-二乙烯苯和纳米MoS2/TiO2,50℃-70℃保温2-3h后,加入二甘醇和催化剂辛酸亚锡,保温3-4h,反应期间视粘度变化加入稀释剂丙酮;
(3)反映期间控制NCO:OH摩尔比为1.8,然后降温至40℃以下,加入与所述二羟甲基丙酸等物质的量的三乙胺,反应20-30min,得到亲水性聚氨酯溶液;
(4)在30-40℃,1000-1500r/min的转速下搅拌所述聚氨酯溶液,减压蒸馏除去丙酮,得到水性可剥离聚氨酯树脂。
对比例1
一种水性可剥离树脂,其包含按照质量份数计的,40份的聚醚二元醇、40份的二异氰酸酯、10份的二羟甲基丙酸和5份的二甘醇。
对比例2
一种水性可剥离树脂,其包含按照质量份数计的,30份的聚醚二元醇、30份的二异氰酸酯、5份的柔性端羟基有机硅低聚物、5份的二羟甲基丙酸、2份的二甘醇、20份官能度为3的三羟甲基丙烷三丙烯酸酯和2份的丙酮;
其中,反应期间控制所述水性可剥离树脂中-NCO:-OH的摩尔比为1.6。
对比例3
一种水性可剥离树脂,其包含按照质量份数计的,25份的聚醚二元醇、45份的二异氰酸酯、1份的柔性端羟基有机硅低聚物、12份的二羟甲基丙酸、5份的二甘醇、22份官能度为3的三羟甲基丙烷三丙烯酸酯、1份交联度为40%的聚丙烯酸甲酯-二乙烯苯、8份的纳米MoS2/TiO2和2份的丙酮;
其中,反应期间控制所述水性可剥离树脂中-NCO:-OH的摩尔比为0.5;所述纳米MoS2/TiO2与所述聚丙烯酸甲酯-二乙烯苯按照质量比8:1混合。
上述实施例1-4和对比例1、2中制备得到的水性可剥离树脂的表征测试结果如表1所示,可以看出,本发明所述的水性可剥离树脂在具有较好的附着力的基础上,拉伸强度高、可整片剥离、耐水性好,同时,在潮湿、高温、低温和潮湿的环境中,漆膜稳定性好,且当环境因素恢复至正常状态时,漆膜性能良好,且可实现整体剥离。
表1
在不背离本发明的范围或精神的情况下,可对本发明说明书的具体实施方式做多种改进和变化,这对本领域技术人员而言是显而易见的。由本发明的说明书得到的其他实施方式对技术人员而言是显而易见得的。本申请说明书和实施例仅是示例性的。
Claims (10)
1.一种水性可剥离树脂,其包含按照质量份数计,20-40份的聚醚二元醇、30-50份的二异氰酸酯和5-20份的柔性端羟基有机硅低聚物。
2.根据权利要求1所述的水性可剥离树脂,其还包括5-15份的二羟甲基丙酸和2-8份的二甘醇;其中,所述二羟甲基丙酸与所述柔性端羟基有机硅低聚物质量之比为0.9-1.5:1。
3.根据权利要求2所述的水性可剥离树脂,其中,所述水性可剥离树脂中的-NCO:-OH摩尔比在1.5-2的范围内。
4.根据权利要求1所述的水性可剥离树脂,其中聚醚二元醇的分子量大于2000;
所述二异氰酸酯为甲苯二异氰酸酯(TDI)、二苯基甲烷二异氰酸酯(MDI)、3-异氰酸酯基亚甲基-3,5,5-三甲基环己基异氰酸酯(IPDI)中的一种或多种;
合成所述柔性端羟基有机硅低聚物所用到的有机硅单体为甲基三乙氧基硅烷、二甲基二乙氧基硅烷、苯基三乙氧基硅烷中的两种或三种。
5.根据权利要求1所述的水性可剥离树脂,其还包括20-30份的三羟甲基丙烷三丙烯酸酯,所述三羟甲基丙烷三丙烯酸酯的官能度为3。
6.根据权利要求1所述的水性可剥离树脂,其还包括1-5份交联度为40%的聚丙烯酸甲酯-二乙烯苯。
7.根据权利要求6所述的水性可剥离树脂,其还包括3-10份的纳米MoS2/TiO2;其中所述纳米MoS2/TiO2与所述聚丙烯酸甲酯-二乙烯苯按照质量比1.5-2.5:1混合。
8.根据权利要求1所述的水性可剥离树脂,其中,所述聚醚二元醇选自由聚乙二醇、聚丙二醇、混合聚乙二醇/丙二醇和聚四氢呋喃二醇组成的组中的至少一种。
9.一种水性可剥离树脂的制备方法,其包括如下步骤:
(1)在装有氮气保护装置的四口瓶中加入二异氰酸酯,200-400r/min的转速下搅拌并依次滴加端羟基有机硅低聚物和聚醚二元醇,缓慢升温至70-80℃,反应1-2h;
(2)加入二羟甲基丙酸和丙酮,50℃-70℃保温2-3h后,加入二甘醇和催化剂辛酸亚锡,保温3-4h,反应期间视粘度变化加入稀释剂丙酮;
(3)反应期间控制-NCO:-OH摩尔比在1.5-2范围内,然后降温至40℃以下,加入与所述二羟甲基丙酸等物质的量的三乙胺,反应20-30min,得到亲水性聚氨酯溶液;
(4)在30-40℃,1000-1500r/min的转速下搅拌所述聚氨酯溶液,减压蒸馏除去丙酮,得到水性可剥离聚氨酯树脂。
10.根据权利要求9所述的水性可剥离树脂的制备方法,其中,
在所述步骤(1)中还包括,在滴加聚醚二元醇后,加入官能度为3的三羟甲基丙烷三丙烯酸酯;
在所述步骤(2)中还包括,在加入二羟甲基丙酸和丙酮后,加入交联度为40%的聚丙烯酸甲酯-二乙烯苯和纳米MoS2/TiO2。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710845199.1A CN107722687B (zh) | 2017-09-19 | 2017-09-19 | 水性可剥离树脂及其制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710845199.1A CN107722687B (zh) | 2017-09-19 | 2017-09-19 | 水性可剥离树脂及其制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN107722687A true CN107722687A (zh) | 2018-02-23 |
CN107722687B CN107722687B (zh) | 2020-02-07 |
Family
ID=61207680
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710845199.1A Active CN107722687B (zh) | 2017-09-19 | 2017-09-19 | 水性可剥离树脂及其制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN107722687B (zh) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112759718A (zh) * | 2020-12-30 | 2021-05-07 | 上海宝庆通用电工有限公司 | 一种可剥离树脂及其制备方法 |
CN114196319A (zh) * | 2021-11-22 | 2022-03-18 | 北京卫星制造厂有限公司 | 一种表面具有微纳多孔结构的有机硅涂层及其制备方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101205365A (zh) * | 2006-12-19 | 2008-06-25 | 琳得科株式会社 | 加成型聚硅氧烷系剥离剂组合物以及剥离薄膜 |
CN104053721A (zh) * | 2012-01-23 | 2014-09-17 | 味之素株式会社 | 树脂组合物 |
CN104448206A (zh) * | 2014-12-25 | 2015-03-25 | 广州冠志新材料科技有限公司 | 一种环保型可剥离水性聚氨酯树脂及其制备方法和应用 |
CN105688942A (zh) * | 2016-03-14 | 2016-06-22 | 西安建筑科技大学 | 一种层状MoS2-Ni纳米复合材料的制备方法 |
CN106977657A (zh) * | 2016-01-19 | 2017-07-25 | 杭州吉华高分子材料股份有限公司 | 一种水性可剥离树脂及其制备方法和应用 |
-
2017
- 2017-09-19 CN CN201710845199.1A patent/CN107722687B/zh active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101205365A (zh) * | 2006-12-19 | 2008-06-25 | 琳得科株式会社 | 加成型聚硅氧烷系剥离剂组合物以及剥离薄膜 |
CN104053721A (zh) * | 2012-01-23 | 2014-09-17 | 味之素株式会社 | 树脂组合物 |
CN104448206A (zh) * | 2014-12-25 | 2015-03-25 | 广州冠志新材料科技有限公司 | 一种环保型可剥离水性聚氨酯树脂及其制备方法和应用 |
CN106977657A (zh) * | 2016-01-19 | 2017-07-25 | 杭州吉华高分子材料股份有限公司 | 一种水性可剥离树脂及其制备方法和应用 |
CN105688942A (zh) * | 2016-03-14 | 2016-06-22 | 西安建筑科技大学 | 一种层状MoS2-Ni纳米复合材料的制备方法 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112759718A (zh) * | 2020-12-30 | 2021-05-07 | 上海宝庆通用电工有限公司 | 一种可剥离树脂及其制备方法 |
CN114196319A (zh) * | 2021-11-22 | 2022-03-18 | 北京卫星制造厂有限公司 | 一种表面具有微纳多孔结构的有机硅涂层及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
CN107722687B (zh) | 2020-02-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN104144713B (zh) | 粘合剂制品及其制备方法 | |
TWI449719B (zh) | 含塗料黏著添加劑的可固化含矽烷基聚合物組成物 | |
KR20140027214A (ko) | 수분 경화성 조성물 및 이로부터 제조된 낮은 표면 에너지 코팅 조성물 | |
TW201002774A (en) | Coating agent and its producing method | |
JPH05209122A (ja) | 被覆増粘剤 | |
WO2023087854A1 (zh) | 一种防污涂料及其使用方法和应用 | |
DE102009003275A1 (de) | Verzweigte Polydimethylsiloxan-Polyoxyalkylen Copolymere, ein Verfahren zu ihrer Herstellung und ihre Verwendung als Anti-Vernebelungsadditiv in UV-härtenden Silikonen | |
CN109923188A (zh) | 光学透明粘着片、光学透明粘着片的制造方法、层叠体、带触摸屏的显示装置以及光学透明粘着片的贴合方法 | |
CN107722687A (zh) | 水性可剥离树脂及其制备方法 | |
CN111789779A (zh) | 一种高附着力水性指甲油及其制备方法 | |
JP5526882B2 (ja) | 下地調整材組成物 | |
WO2021230371A1 (ja) | 光湿気硬化型樹脂組成物、電子部品用接着剤、硬化体、及び電子部品 | |
CN105745294A (zh) | 表面保护用粘着片及表面保护用粘着片的使用方法 | |
CN109312111A (zh) | 高模量可固化组合物 | |
JP6399336B2 (ja) | 水性プライマー組成物 | |
CN103339215B (zh) | 光学部件用粘合剂组合物、粘合型光学部件及图像显示装置 | |
CN109153239A (zh) | 脱模膜 | |
CN113692430B (zh) | 底漆组合物 | |
WO2013083670A1 (de) | Reaktive polyurethan-haftklebstoffe | |
JP2023170006A (ja) | 接着性樹脂組成物及び接着性樹脂シート | |
JP6237086B2 (ja) | 無機質系多孔質基材用プライマー組成物およびそれを用いたシーリング施工方法 | |
WO2022260053A1 (ja) | 光湿気硬化型樹脂組成物、電子部品用接着剤、硬化体、及び電子部品 | |
CN110088203A (zh) | 具有改善的机械特性和高透明度的可固化组合物 | |
JP6496121B2 (ja) | 塗料組成物および自動車内装部品 | |
WO2023153514A1 (ja) | 光湿気硬化型樹脂組成物、電子部品用接着剤及び表示素子用接着剤 |
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 | ||
PP01 | Preservation of patent right |
Effective date of registration: 20200918 Granted publication date: 20200207 |
|
PP01 | Preservation of patent right | ||
PD01 | Discharge of preservation of patent | ||
PD01 | Discharge of preservation of patent |
Date of cancellation: 20210715 Granted publication date: 20200207 |
|
PP01 | Preservation of patent right | ||
PP01 | Preservation of patent right |
Effective date of registration: 20210715 Granted publication date: 20200207 |
|
PD01 | Discharge of preservation of patent | ||
PD01 | Discharge of preservation of patent |
Date of cancellation: 20210926 Granted publication date: 20200207 |