CN103772631A - Method of modifying surface hydrophobicity of gel coat resin by triblock fluorine-containing copolymer - Google Patents
Method of modifying surface hydrophobicity of gel coat resin by triblock fluorine-containing copolymer Download PDFInfo
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- CN103772631A CN103772631A CN201410026615.1A CN201410026615A CN103772631A CN 103772631 A CN103772631 A CN 103772631A CN 201410026615 A CN201410026615 A CN 201410026615A CN 103772631 A CN103772631 A CN 103772631A
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- fluorine
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- macromole evocating
- coating resin
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 78
- 239000011737 fluorine Substances 0.000 title claims abstract description 78
- 229920005989 resin Polymers 0.000 title claims abstract description 54
- 239000011347 resin Substances 0.000 title claims abstract description 54
- 229920001577 copolymer Polymers 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 168
- 239000003795 chemical substances by application Substances 0.000 claims description 120
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 84
- 239000011248 coating agent Substances 0.000 claims description 48
- 238000000576 coating method Methods 0.000 claims description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 42
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 42
- 239000002904 solvent Substances 0.000 claims description 42
- 239000000178 monomer Substances 0.000 claims description 33
- 239000000853 adhesive Substances 0.000 claims description 29
- 230000001070 adhesive effect Effects 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 29
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 21
- 239000000706 filtrate Substances 0.000 claims description 21
- 230000007935 neutral effect Effects 0.000 claims description 21
- 238000001556 precipitation Methods 0.000 claims description 21
- 238000002360 preparation method Methods 0.000 claims description 15
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 14
- 238000010790 dilution Methods 0.000 claims description 14
- 239000012895 dilution Substances 0.000 claims description 14
- 229960004756 ethanol Drugs 0.000 claims description 14
- 238000012869 ethanol precipitation Methods 0.000 claims description 14
- 239000003999 initiator Substances 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 claims description 7
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 claims description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 7
- ARFLASKVLJTEJD-UHFFFAOYSA-N ethyl 2-bromopropanoate Chemical compound CCOC(=O)C(C)Br ARFLASKVLJTEJD-UHFFFAOYSA-N 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- 238000002390 rotary evaporation Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 238000009423 ventilation Methods 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 6
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical group C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 claims description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 2
- SJQITXILEOCXGI-UHFFFAOYSA-N 3,3,6,6-tetramethyl-1,2,4,5-tetraoxane Chemical compound CC1(C)OOC(C)(C)OO1 SJQITXILEOCXGI-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical group CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 7
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 18
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- YJKHMSPWWGBKTN-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)F YJKHMSPWWGBKTN-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- QTKPMCIBUROOGY-UHFFFAOYSA-N 2,2,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)F QTKPMCIBUROOGY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 229920002313 fluoropolymer Polymers 0.000 description 2
- 239000004811 fluoropolymer Substances 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 1
- -1 Hexafluorobutyl Chemical group 0.000 description 1
- 101500021084 Locusta migratoria 5 kDa peptide Proteins 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 239000006121 base glass Substances 0.000 description 1
- ZENDLNWEHXPRPL-UHFFFAOYSA-N benzene 2,2-dimethylpropane-1,3-diol Chemical group OCC(C)(CO)C.C1=CC=CC=C1 ZENDLNWEHXPRPL-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000011151 fibre-reinforced plastic Substances 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Graft Or Block Polymers (AREA)
Abstract
本发明一种以三嵌段含氟共聚物改性胶衣树脂表面疏水性的方法，属于高分子聚合领域。按照下述步骤进行：先制备三嵌段含氟共聚物；再制备改性胶衣树脂，本发明以原子转移自由基聚合的方法合成三嵌段含氟共聚物，结构和分子量都可以控制；采用胶衣树脂和三嵌段含氟共聚物共混方法，易于在生产过程中实施；利用三嵌段含氟共聚物改性的胶衣树脂固化后具有独特的表面性能，接触角能达到109.5°。The invention discloses a method for modifying the surface hydrophobicity of a gel coat resin with a three-block fluorine-containing copolymer, which belongs to the field of polymer polymerization. Follow the steps below: firstly prepare a three-block fluorine-containing copolymer; then prepare a modified gel coat resin. The present invention synthesizes a three-block fluorine-containing copolymer by atom transfer radical polymerization, and the structure and molecular weight can be controlled; The blending method of gel coat resin and tri-block fluorine-containing copolymer is easy to implement in the production process; the gel coat resin modified by tri-block fluorine-containing copolymer has unique surface properties after curing, and the contact angle can reach 109.5 °.
Description
Technical field
The invention belongs to high molecular polymerization field, relate in particular to the preparation method who utilizes three block fluorinated copolymer modified adhesive coating resin surface hydrophobicitys.
Background technology
Gel coating resin is the visual appearance for improving glass fiber reinforced unsaturated polyester resin base glass fiber reinforced plastics product and protects the material of structural sheet not developed by external environment erosion medium resistance, therefore the Main Function of gel coating resin is the surface decoration to glass fiber reinforced plastics product and the protection to structural sheet.The gel coating resin of domestic production at present can be divided into adjacent benzene type, adjacent benzene-neopentyl glycol type, metaphenylene, isophthalic-neopentyl glycol type and vinyl ester type etc. by the type of matrix resin; Can be divided into again goods gel coat, mould gel coat, fire-retardant gel coat, gel coat peculiar to vessel, snappiness gel coat, food grade gel coat etc. by function and purposes.The continuous lifting of gel coating resin in kind and performance, constantly expands the Application Areas of gel coating resin, is all widely used at present in many industries such as sanitary ware, transportation, construction industry, entertainment industryes.
The surface property that fluorinated copolymer is good, the ordered structure mainly forming in surperficial enrichment with on surface from fluoro-containing group.In fluoropolymer because the bond energy of C-F key is larger, more stable, F atom is not only combined firmly with C atom, and very tight in the outer arrangement of carbochain skeleton, effectively prevent the exposure of C atom and C chain, therefore fluoropolymer shows remarkable chemical stability, the characteristic such as corrosion-resistant, anti-oxidant.Utilize atom transfer radical polymerization (ATRP) to synthesize three block fluorinated copolymers, in multipolymer, introduce C-F key and Si (OCH
3)
3group, utilizes C-F key to improve the surface property of material on the one hand, utilizes on the other hand Si (OCH
3)
3the silicon dioxde reaction of group and gel coating resin the inside improves silica sphere, further improves the surface property of material.
Summary of the invention
The object of this invention is to provide the method for the synthetic three block fluorinated copolymers of a kind of method take atom transfer radical polymerization (ATRP) as modifier modification gel coating resin surface hydrophobicity.
With a method for three block fluorinated copolymer modified adhesive coating resin surface hydrophobicitys, carry out according to following step:
The preparation of (1) three block fluorinated copolymer:
(a) fluorine-containing macromole evocating agent is synthetic: be aggregated in 500 mL there-necked flasks and carry out, oxygen and the moisture in reaction unit is removed in roasting bottle ventilation for three times, then at N
2under protection, add successively Catalysts Cu Br, fluorochemical monomer, solvent toluene, coordination agent pentamethyl-diethyl triamine (PMDETA), the initiator 2 bromopropionic acid ethyl ester of metering, stir and be warming up to 70 ℃, in constant temperature oil bath, react 6 h.Reaction finishes to dilute with tetrahydrofuran (THF) afterwards, cross post through neutral alumina and separate mantoquita, filtrate is removed most of solvent through rotary evaporation, precipitates with dehydrated alcohol, through tetrahydrofuran (THF) and anhydrous alcohol solution, precipitation for several times after purifying, polymkeric substance through 40 ℃ of vacuum-dryings to constant weight.
(b) the fluorine-containing macromole evocating agent of diblock is synthetic: first roasting bottle is taken a breath after three times, at N
2under protection, fluorine-containing macromole evocating agent is added in 250 mL there-necked flasks, bake bottle three times more at a lower temperature subsequently, add CuBr, then take a breath twice, add solvent toluene.Below after fluorine-containing macromole evocating agent dissolves completely, finally add styrene monomer at 40 ℃, add successively coordination agent PMDETA with syringe, react 24 h at 80 ℃ of constant temperature oil baths.Wherein the weight ratio of fluorine-containing macromole evocating agent/catalyzer/coordination agent/monomer is l～3:l～3:2～5:10～80.The product obtaining is the fluorine-containing macromole evocating agent of diblock.After finishing, reaction add the rear neutral alumina column of crossing of tetrahydrofuran (THF) dilution to remove mantoquita.Gained filtrate is removed most of solvent through revolving to steam, by ethanol precipitation, uses after tetrahydrofuran (THF) and dissolve with ethanol, precipitation several purifying, and dry under 40 ℃ of vacuum, obtain the fluorine-containing macromole evocating agent of two blocks.
(c) three block fluorinated copolymers is synthetic: first roasting bottle is taken a breath after three times, at N
2under protection, fluorine-containing diblock macromole evocating agent is added in 100mL there-necked flask, roasting bottle three times at a lower temperature subsequently, adds CuBr, then takes a breath twice, adds successively coordination agent PMDETA with syringe, adds solvent phenylfluoroform.Below after the fluorine-containing macromole evocating agent of diblock dissolves completely, finally add silane coupling agent at 40 ℃, react 10 h at 110 ℃ of constant temperature oil baths.The weight ratio of the fluorine-containing macromole evocating agent/catalyzer/coordination agent/monomer of diblock is 1～3:1～3:2～5:10～80, adds the rear neutral alumina column of crossing of tetrahydrofuran (THF) dilution to remove mantoquita after reaction finishes.Gained filtrate is removed most of solvent through revolving to steam, by ethanol precipitation, uses after tetrahydrofuran (THF) and dissolve with ethanol, precipitation several purifying, and dry under 40 ℃ of vacuum, obtain three block fluorinated copolymers.
(2) preparation of modified adhesive coating resin
In gel coating resin, add three block fluorinated copolymers of total amount (mass percent) 1%～15%, at suitable temperature, low rate mixing mixes, and it is fully mixed, and finally prepares modified adhesive coating resin.Get a certain amount of modified adhesive coating resin, add and account for the solidifying agent of gel coating resin consumption (mass percent) 1%～2% and the promotor of (mass percent) 0.5%～1%, be uniformly mixed rear self-vulcanizing.
Wherein said step (1) (a) the wherein fluorochemical monomer described in (a) described fluorochemical monomer be the fluorochemical monomer that (methyl) vinylformic acid hexafluoro butyl ester, (methyl) vinylformic acid trifluoro ethyl ester, (methyl) dodecafluorhe-ptylacrylate, (methyl) vinylformic acid ten trifluoro monooctyl esters etc. contain C=C key.Wherein (a) described initiator/catalyst/coordination agent/monomer is l～3:1～3:2～5:100～250.
Wherein said step (1) (b) wherein (b) described vinyl monomer is vinylbenzene (St), methyl methacrylate (MMA), hydroxyethyl methylacrylate (HEMA) etc.Wherein (b) described fluorine-containing macromole evocating agent/catalyzer/coordination agent/monomer is 1～3:1～3:2～5:10～80.
Wherein said step (1) (c) wherein (c) described silane coupling agent is 3-glycidyl ether oxygen base propyl trimethoxy silicane (KH-560), γ-methacryloxypropyl trimethoxy silane (KH-570), vinyltriethoxysilane (A-151), vinyltrimethoxy silane (A-171) etc.Wherein (c) described fluorine-containing macromole evocating agent/catalyzer/coordination agent/monomer of diblock is 1～3:1～3:2～5:10～80.
The wherein said described consumption that adds three block fluorinated copolymers of step (2) is 1～15%; Wherein said solidifying agent is cyclohexanone peroxide, methylethyl ketone peroxide, diacetone peroxide, the first and second base diperoxy hydrogen etc., and consumption is 1%～2%; Wherein said promotor is cobalt naphthenate, cobalt iso-octoate solution etc., and consumption is 0.5%～1%.
The present invention has advantages of as follows: 1,, with the synthetic three block fluorinated copolymers of method of atom transfer radical polymerization, structure and molecular weight can be controlled; 2, adopt gel coating resin and three block fluorinated copolymer blend methods, be easy to implement in process of production; 3, utilize three block fluorinated copolymer modifications gel coating resin solidify after there is unique surface property, contact angle can reach 109.5 °.
Embodiment
Below in conjunction with example, the present invention is described in further detail.
Embodiment 1
Polymerization procedure is as follows:
1, the preparation of three block fluorinated copolymers:
(a) fluorine-containing macromole evocating agent is synthetic: be aggregated in 500 mL there-necked flasks and carry out, oxygen and the moisture in reaction unit is removed in roasting bottle ventilation for three times, then at N
2under protection, add successively the Catalysts Cu Br(0.1g of metering), dodecafluoroheptyl methacrylate (G04) (10g), solvent toluene (10.4g), coordination agent pentamethyl-diethyl triamine (PMDETA) (0.2g), initiator 2 bromopropionic acid ethyl ester (0.1g) (weight ratio of initiator/catalyst/coordination agent/monomer is l:1:2:100); stirring is warming up to 70 ℃, reacts 6 h in constant temperature oil bath.Reaction finishes to dilute with tetrahydrofuran (THF) afterwards, cross post through neutral alumina and separate mantoquita, filtrate is removed most of solvent through rotary evaporation, precipitates with dehydrated alcohol, through tetrahydrofuran (THF) and anhydrous alcohol solution, precipitation for several times after purifying, polymkeric substance through 40 ℃ of vacuum-dryings to constant weight.
(b) the fluorine-containing macromole evocating agent of diblock is synthetic: first roasting bottle is taken a breath after three times, at N
2under protection, fluorine-containing macromole evocating agent (1g) is added in 250 mL there-necked flasks, bake bottle three times more at a lower temperature subsequently, add CuBr (1g), then take a breath twice, add solvent toluene (14g).Below after fluorine-containing macromole evocating agent dissolves completely, finally add vinylbenzene (10g) at 40 ℃, add successively coordination agent PMDETA (2g) with syringe, react 24 h at 80 ℃ of constant temperature oil baths.Wherein fluorine-containing macromole evocating agent/catalyzer/coordination agent/monomer is l:l:2:10, and the product of acquisition is the fluorine-containing macromole evocating agent of diblock.After finishing, reaction add the rear neutral alumina column of crossing of tetrahydrofuran (THF) dilution to remove mantoquita.Gained filtrate is removed most of solvent through revolving to steam, by ethanol precipitation, uses after tetrahydrofuran (THF) and dissolve with ethanol, precipitation several purifying, and dry under 40 ℃ of vacuum, obtain the fluorine-containing macromole evocating agent of two blocks.
(c) three block fluorinated copolymers is synthetic: first roasting bottle is taken a breath after three times, at N
2under protection, fluorine-containing diblock macromole evocating agent (1g) is added in 100mL there-necked flask; bake bottle three times at a lower temperature subsequently; add CuBr (1g); then take a breath twice; add successively coordination agent PMDETA (2g) with syringe, add solvent phenylfluoroform (14g).Below after the fluorine-containing macromole evocating agent of diblock dissolves completely, finally add γ-methacryloxypropyl trimethoxy silane (KH-570) (10g) at 40 ℃, react 10 h at 110 ℃ of constant temperature oil baths.The weight ratio of the fluorine-containing macromole evocating agent/catalyzer/coordination agent/monomer of diblock is 1:1:2:10, adds the rear neutral alumina column of crossing of tetrahydrofuran (THF) dilution to remove mantoquita after reaction finishes.Gained filtrate is removed most of solvent through revolving to steam, by ethanol precipitation, uses after tetrahydrofuran (THF) and dissolve with ethanol, precipitation several purifying, and dry under 40 ℃ of vacuum, obtain three block fluorinated copolymers.
2, the preparation of modified adhesive coating resin
In 100g gel coating resin, add the three block fluorinated copolymers of total amount 1g, at suitable temperature, low rate mixing mixes, and it is fully mixed, and finally prepares modified adhesive coating resin.Get a certain amount of modified adhesive coating resin, add the cobalt iso-octoate of 1g methylethyl ketone peroxide and 0.5g, be uniformly mixed rear self-vulcanizing.
Embodiment 2
Polymerization procedure is as follows:
1, the preparation of three block fluorinated copolymers:
(a) fluorine-containing macromole evocating agent is synthetic: be aggregated in 500 mL there-necked flasks and carry out, oxygen and the moisture in reaction unit is removed in roasting bottle ventilation for three times, then at N
2under protection, add successively the Catalysts Cu Br(0.3g of metering), dodecafluoroheptyl methacrylate (G04) (25g), solvent toluene (26.1g), coordination agent pentamethyl-diethyl triamine (PMDETA) (0.5g), initiator 2 bromopropionic acid ethyl ester (0.3g) (weight ratio of initiator/catalyst/coordination agent/monomer is 3:3:5:250); stirring is warming up to 70 ℃, reacts 6 h in constant temperature oil bath.Reaction finishes to dilute with tetrahydrofuran (THF) afterwards, cross post through neutral alumina and separate mantoquita, filtrate is removed most of solvent through rotary evaporation, precipitates with dehydrated alcohol, through tetrahydrofuran (THF) and anhydrous alcohol solution, precipitation for several times after purifying, polymkeric substance through 40 ℃ of vacuum-dryings to constant weight.
(b) the fluorine-containing macromole evocating agent of diblock is synthetic: first roasting bottle is taken a breath after three times, at N
2under protection, fluorine-containing macromole evocating agent (1g) is added in 250 mL there-necked flasks, bake bottle three times more at a lower temperature subsequently, add CuBr (1g), then take a breath twice, add solvent toluene (30.33g).Below after fluorine-containing macromole evocating agent dissolves completely, finally add vinylbenzene (26.67g) at 40 ℃, add successively coordination agent PMDETA (1.67g) with syringe, react 24 h at 80 ℃ of constant temperature oil baths.Wherein the weight ratio of fluorine-containing macromole evocating agent/catalyzer/coordination agent/monomer is 3:3:5:80, and the product of acquisition is the fluorine-containing macromole evocating agent of diblock.After finishing, reaction add the rear neutral alumina column of crossing of tetrahydrofuran (THF) dilution to remove mantoquita.Gained filtrate is removed most of solvent through revolving to steam, by ethanol precipitation, uses after tetrahydrofuran (THF) and dissolve with ethanol, precipitation several purifying, and dry under 40 ℃ of vacuum, obtain the fluorine-containing macromole evocating agent of two blocks.
(c) three block fluorinated copolymers is synthetic: first roasting bottle is taken a breath after three times, at N
2under protection, fluorine-containing diblock macromole evocating agent (1g) is added in 100mL there-necked flask; bake bottle three times at a lower temperature subsequently; add CuBr (1g); then take a breath twice; add successively coordination agent PMDETA (1.67g) with syringe, add solvent phenylfluoroform (30.33g).Below after the fluorine-containing macromole evocating agent of diblock dissolves completely, finally add γ-methacryloxypropyl trimethoxy silane (KH-570) (26.67g) at 40 ℃, react 10 h at 110 ℃ of constant temperature oil baths.The weight ratio of the fluorine-containing macromole evocating agent/catalyzer/coordination agent/monomer of diblock is 3:3:5:80, adds the rear neutral alumina column of crossing of tetrahydrofuran (THF) dilution to remove mantoquita after reaction finishes.Gained filtrate is removed most of solvent through revolving to steam, by ethanol precipitation, uses after tetrahydrofuran (THF) and dissolve with ethanol, precipitation several purifying, and dry under 40 ℃ of vacuum, obtain three block fluorinated copolymers.
2, the preparation of modified adhesive coating resin
In 100g gel coating resin, add the three block fluorinated copolymers of 15g, at 25 ℃ of temperature, low rate mixing mixes, and it is fully mixed, and finally prepares modified adhesive coating resin.Get a certain amount of modified adhesive coating resin, add the cobalt iso-octoate of 2g methylethyl ketone peroxide and 1g, be uniformly mixed rear self-vulcanizing.
Embodiment 3
Polymerization procedure is as follows:
1, the preparation of three block fluorinated copolymers:
(a) fluorine-containing macromole evocating agent is synthetic: be aggregated in 500 mL there-necked flasks and carry out, oxygen and the moisture in reaction unit is removed in roasting bottle ventilation for three times, then at N
2under protection, add successively the Catalysts Cu Br(0.1g of metering), Hexafluorobutyl mathacrylate (G02) (15g), solvent toluene (10.4g), coordination agent pentamethyl-diethyl triamine (PMDETA) (0.3g), initiator 2 bromopropionic acid ethyl ester (0.1g) (weight ratio of initiator/catalyst/coordination agent/monomer is l:1:3:150); stirring is warming up to 70 ℃, reacts 6 h in constant temperature oil bath.Reaction finishes to dilute with tetrahydrofuran (THF) afterwards, cross post through neutral alumina and separate mantoquita, filtrate is removed most of solvent through rotary evaporation, precipitates with dehydrated alcohol, through tetrahydrofuran (THF) and anhydrous alcohol solution, precipitation for several times after purifying, polymkeric substance through 40 ℃ of vacuum-dryings to constant weight.
(b) the fluorine-containing macromole evocating agent of diblock is synthetic: first roasting bottle is taken a breath after three times, at N
2under protection, fluorine-containing macromole evocating agent (1g) is added in 250 mL there-necked flasks, bake bottle three times more at a lower temperature subsequently, add CuBr (1g), then take a breath twice, add solvent toluene (36g).Below after fluorine-containing macromole evocating agent dissolves completely, finally add methyl methacrylate (30g) at 40 ℃, add successively coordination agent PMDETA (4g) with syringe, react 24 h at 80 ℃ of constant temperature oil baths.Wherein the weight ratio of fluorine-containing macromole evocating agent/catalyzer/coordination agent/monomer is l:l:4:30, and the product of acquisition is the fluorine-containing macromole evocating agent of diblock.After finishing, reaction add the rear neutral alumina column of crossing of tetrahydrofuran (THF) dilution to remove mantoquita.Gained filtrate is removed most of solvent through revolving to steam, by ethanol precipitation, uses after tetrahydrofuran (THF) and dissolve with ethanol, precipitation several purifying, and dry under 40 ℃ of vacuum, obtain the fluorine-containing macromole evocating agent of two blocks.
(c) three block fluorinated copolymers is synthetic: first roasting bottle is taken a breath after three times, at N
2under protection, fluorine-containing diblock macromole evocating agent (1g) is added in 100mL there-necked flask; bake bottle three times at a lower temperature subsequently; add CuBr (2g); then take a breath twice; add successively coordination agent PMDETA (3g) with syringe, add solvent phenylfluoroform (16g).Below after the fluorine-containing macromole evocating agent of diblock dissolves completely, finally add vinyltrimethoxy silane (A-171) (10g) at 40 ℃, react 10 h at 110 ℃ of constant temperature oil baths.The weight ratio of the fluorine-containing macromole evocating agent/catalyzer/coordination agent/monomer of diblock is 1:2:3:10, adds the rear neutral alumina column of crossing of tetrahydrofuran (THF) dilution to remove mantoquita after reaction finishes.Gained filtrate is removed most of solvent through revolving to steam, by ethanol precipitation, uses after tetrahydrofuran (THF) and dissolve with ethanol, precipitation several purifying, and dry under 40 ℃ of vacuum, obtain three block fluorinated copolymers.
2, the preparation of modified adhesive coating resin
In 100g gel coating resin, add the three block fluorinated copolymers of total amount 10g, at suitable temperature, low rate mixing mixes, and it is fully mixed, and finally prepares modified adhesive coating resin.Get a certain amount of modified adhesive coating resin, add the cobalt iso-octoate of 1.5g methylethyl ketone peroxide and 0.75g, be uniformly mixed rear self-vulcanizing.
Embodiment 4
Polymerization procedure is as follows:
1, the preparation of three block fluorinated copolymers:
(a) fluorine-containing macromole evocating agent is synthetic: be aggregated in 500 mL there-necked flasks and carry out, oxygen and the moisture in reaction unit is removed in roasting bottle ventilation for three times, then at N
2under protection, add successively the Catalysts Cu Br(0.1g of metering), trifluoroethyl methacrylate (G03) (10g), solvent toluene (10.5g), coordination agent pentamethyl-diethyl triamine (PMDETA) (0.2g), initiator 2 bromopropionic acid ethyl ester (0.2g) (weight ratio of initiator/catalyst/coordination agent/monomer is 2:1:2:100); stirring is warming up to 70 ℃, reacts 6 h in constant temperature oil bath.Reaction finishes to dilute with tetrahydrofuran (THF) afterwards, cross post through neutral alumina and separate mantoquita, filtrate is removed most of solvent through rotary evaporation, precipitates with dehydrated alcohol, through tetrahydrofuran (THF) and anhydrous alcohol solution, precipitation for several times after purifying, polymkeric substance through 40 ℃ of vacuum-dryings to constant weight.
(b) the fluorine-containing macromole evocating agent of diblock is synthetic: first roasting bottle is taken a breath after three times, at N
2under protection, fluorine-containing macromole evocating agent (1g) is added in 250 mL there-necked flasks, bake bottle three times more at a lower temperature subsequently, add CuBr (2g), then take a breath twice, add solvent toluene (15g).Below after fluorine-containing macromole evocating agent dissolves completely, finally add vinylbenzene (10g) at 40 ℃, add successively coordination agent PMDETA (2g) with syringe, react 24 h at 80 ℃ of constant temperature oil baths.Wherein the weight ratio of fluorine-containing macromole evocating agent/catalyzer/coordination agent/monomer is l:2:2:10, and the product of acquisition is the fluorine-containing macromole evocating agent of diblock.After finishing, reaction add the rear neutral alumina column of crossing of tetrahydrofuran (THF) dilution to remove mantoquita.Gained filtrate is removed most of solvent through revolving to steam, by ethanol precipitation, uses after tetrahydrofuran (THF) and dissolve with ethanol, precipitation several purifying, and dry under 40 ℃ of vacuum, obtain the fluorine-containing macromole evocating agent of two blocks.
(c) three block fluorinated copolymers is synthetic: first roasting bottle is taken a breath after three times, at N
2under protection, fluorine-containing diblock macromole evocating agent (1g) is added in 100mL there-necked flask; bake bottle three times at a lower temperature subsequently; add CuBr (1g); then take a breath twice; add successively coordination agent PMDETA (2g) with syringe, add solvent phenylfluoroform (14g).Below after the fluorine-containing macromole evocating agent of diblock dissolves completely, finally add vinyltriethoxysilane (A-151) (10g) at 40 ℃, react 10 h at 110 ℃ of constant temperature oil baths.The weight ratio of the fluorine-containing macromole evocating agent/catalyzer/coordination agent/monomer of diblock is 1:1:2:10, adds the rear neutral alumina column of crossing of tetrahydrofuran (THF) dilution to remove mantoquita after reaction finishes.Gained filtrate is removed most of solvent through revolving to steam, by ethanol precipitation, uses after tetrahydrofuran (THF) and dissolve with ethanol, precipitation several purifying, and dry under 40 ℃ of vacuum, obtain three block fluorinated copolymers.
2, the preparation of modified adhesive coating resin
In 100g gel coating resin, add the three block fluorinated copolymers of total amount 8g, at suitable temperature, low rate mixing mixes, and it is fully mixed, and finally prepares modified adhesive coating resin.Get a certain amount of modified adhesive coating resin, add the cobalt iso-octoate of 1.5g methylethyl ketone peroxide and 0.75g, be uniformly mixed rear self-vulcanizing.
Embodiment 5
Polymerization procedure is as follows:
1, the preparation of three block fluorinated copolymers:
(a) fluorine-containing macromole evocating agent is synthetic: be aggregated in 500 mL there-necked flasks and carry out, oxygen and the moisture in reaction unit is removed in roasting bottle ventilation for three times, then at N
2under protection, add successively the Catalysts Cu Br(0.1g of metering), methacrylic acid ten trifluoro monooctyl esters (G06) (10g), solvent toluene (10.4g), coordination agent pentamethyl-diethyl triamine (PMDETA) (0.2g), initiator 2 bromopropionic acid ethyl ester (0.1g) (weight ratio of initiator/catalyst/coordination agent/monomer is l:1:2:100); stirring is warming up to 70 ℃, reacts 6 h in constant temperature oil bath.Reaction finishes to dilute with tetrahydrofuran (THF) afterwards, cross post through neutral alumina and separate mantoquita, filtrate is removed most of solvent through rotary evaporation, precipitates with dehydrated alcohol, through tetrahydrofuran (THF) and anhydrous alcohol solution, precipitation for several times after purifying, polymkeric substance through 40 ℃ of vacuum-dryings to constant weight.
(b) the fluorine-containing macromole evocating agent of diblock is synthetic: first roasting bottle is taken a breath after three times, at N
2under protection, fluorine-containing macromole evocating agent (1g) is added in 250 mL there-necked flasks, bake bottle three times more at a lower temperature subsequently, add CuBr (1g), then take a breath twice, add solvent toluene (14g).Below after fluorine-containing macromole evocating agent dissolves completely, finally add vinylbenzene (10g) at 40 ℃, add successively coordination agent PMDETA (2g) with syringe, react 24 h at 80 ℃ of constant temperature oil baths.Wherein the weight ratio of fluorine-containing macromole evocating agent/catalyzer/coordination agent/monomer is l:l:2:10, and the product of acquisition is the fluorine-containing macromole evocating agent of diblock.After finishing, reaction add the rear neutral alumina column of crossing of tetrahydrofuran (THF) dilution to remove mantoquita.Gained filtrate is removed most of solvent through revolving to steam, by ethanol precipitation, uses after tetrahydrofuran (THF) and dissolve with ethanol, precipitation several purifying, and dry under 40 ℃ of vacuum, obtain the fluorine-containing macromole evocating agent of two blocks.
(c) three block fluorinated copolymers is synthetic: first roasting bottle is taken a breath after three times, at N
2under protection, fluorine-containing diblock macromole evocating agent (1g) is added in 100mL there-necked flask; bake bottle three times at a lower temperature subsequently; add CuBr (1g); then take a breath twice; add successively coordination agent PMDETA (2g) with syringe, add solvent phenylfluoroform (14g).Below after the fluorine-containing macromole evocating agent of diblock dissolves completely, finally add 3-glycidyl ether oxygen base propyl trimethoxy silicane (KH-560) (10g) at 40 ℃, react 10 h at 110 ℃ of constant temperature oil baths.The weight ratio of the fluorine-containing macromole evocating agent/catalyzer/coordination agent/monomer of diblock is 1:1:2:10, adds the rear neutral alumina column of crossing of tetrahydrofuran (THF) dilution to remove mantoquita after reaction finishes.Gained filtrate is removed most of solvent through revolving to steam, by ethanol precipitation, uses after tetrahydrofuran (THF) and dissolve with ethanol, precipitation several purifying, and dry under 40 ℃ of vacuum, obtain three block fluorinated copolymers.
2, the preparation of modified adhesive coating resin
In 100g gel coating resin, add the three block fluorinated copolymers of total amount 10g, at suitable temperature, low rate mixing mixes, and it is fully mixed, and finally prepares modified adhesive coating resin.Get a certain amount of modified adhesive coating resin, add the cobalt iso-octoate of 1.5g methylethyl ketone peroxide and 0.75g, be uniformly mixed rear self-vulcanizing.
The contact angle of gel coating resin after modification:
| Embodiment | Before modification | 1 | 2 | 3 | 4 | 5 |
| Contact angle (°) | 63 | 78.3 | 109.5 | 103.4 | 98.2 | 97.7 |
Wherein, solidify rear water contact angle by breathing out the HARRE-SPCA of section contact angle instrument room temperature measuring.
The above-mentioned description to embodiment is can understand and apply the invention for the ease of those skilled in the art.Those skilled in the art obviously can easily make various modifications to these embodiment, and General Principle described herein are applied in other embodiment and needn't pass through performing creative labour.Therefore, the invention is not restricted to the embodiment here, those skilled in the art are according to announcement of the present invention, and the modification of making for the present invention all should be within protection scope of the present invention.
Claims (5)
1. with a method for three block fluorinated copolymer modified adhesive coating resin surface hydrophobicitys, it is characterized in that carrying out according to following step:
The preparation of (1) three block fluorinated copolymer:
(a) fluorine-containing macromole evocating agent is synthetic: be aggregated in flask and carry out, oxygen and the moisture in reaction unit is removed in roasting bottle ventilation for three times, then at N
2under protection, add successively Catalysts Cu Br, fluorochemical monomer, solvent toluene, coordination agent pentamethyl-diethyl triamine (PMDETA), the initiator 2 bromopropionic acid ethyl ester of metering, stir and be warming up to 70 ℃, in constant temperature oil bath, react 6 h; Reaction finishes to dilute with tetrahydrofuran (THF) afterwards, cross post through neutral alumina and separate mantoquita, filtrate is removed most of solvent through rotary evaporation, precipitates with dehydrated alcohol, through tetrahydrofuran (THF) and anhydrous alcohol solution, precipitation for several times after purifying, polymkeric substance through 40 ℃ of vacuum-dryings to constant weight;
(b) the fluorine-containing macromole evocating agent of diblock is synthetic: first roasting bottle is taken a breath after three times, at N
2under protection, fluorine-containing macromole evocating agent is added in flask, bake bottle three times more at a lower temperature subsequently, add CuBr, then take a breath twice, add solvent toluene; Below after fluorine-containing macromole evocating agent dissolves completely, finally add styrene monomer at 40 ℃, add successively coordination agent PMDETA with syringe, react 24 h at 80 ℃ of constant temperature oil baths; The product obtaining is the fluorine-containing macromole evocating agent of diblock; After finishing, reaction add the rear neutral alumina column of crossing of tetrahydrofuran (THF) dilution to remove mantoquita; Gained filtrate is removed most of solvent through revolving to steam, by ethanol precipitation, uses after tetrahydrofuran (THF) and dissolve with ethanol, precipitation several purifying, and dry under 40 ℃ of vacuum, obtain the fluorine-containing macromole evocating agent of two blocks;
(c) three block fluorinated copolymers is synthetic: first roasting bottle is taken a breath after three times, at N
2under protection, fluorine-containing diblock macromole evocating agent is added in flask, roasting bottle three times at a lower temperature subsequently, adds CuBr, then takes a breath twice, adds successively coordination agent PMDETA with syringe, adds solvent phenylfluoroform; Below after the fluorine-containing macromole evocating agent of diblock dissolves completely, finally add silane coupling agent at 40 ℃, react 10 h at 110 ℃ of constant temperature oil baths; After finishing, reaction add the rear neutral alumina column of crossing of tetrahydrofuran (THF) dilution to remove mantoquita; Gained filtrate is removed most of solvent through revolving to steam, by ethanol precipitation, uses after tetrahydrofuran (THF) and dissolve with ethanol, precipitation several purifying, and dry under 40 ℃ of vacuum, obtain three block fluorinated copolymers;
(2) preparation of modified adhesive coating resin
In gel coating resin, add three block fluorinated copolymers of total amount (mass percent) 1%～15%, at suitable temperature, low rate mixing mixes, and it is fully mixed, and finally prepares modified adhesive coating resin;
Get a certain amount of modified adhesive coating resin, add and account for the solidifying agent of gel coating resin consumption (mass percent) 1%～2% and the promotor of (mass percent) 0.5%～1%, be uniformly mixed rear self-vulcanizing.
2. a kind of method with three block fluorinated copolymer modified adhesive coating resin surface hydrophobicitys according to claim 1, it is characterized in that wherein said step (1) (a) wherein the fluorochemical monomer described in (a) described fluorochemical monomer for (methyl) vinylformic acid hexafluoro butyl ester, (methyl) vinylformic acid trifluoro ethyl ester, (methyl) dodecafluorhe-ptylacrylate, (methyl) vinylformic acid ten trifluoro monooctyl esters etc. are containing the fluorochemical monomer of C=C key; Wherein (a) described initiator/catalyst/coordination agent/monomer is l～3:1～3:2～5:100～250.
3. a kind of method with three block fluorinated copolymer modified adhesive coating resin surface hydrophobicitys according to claim 1, it is characterized in that wherein said step (1) (b) wherein (b) described vinyl monomer be vinylbenzene (St), methyl methacrylate (MMA), hydroxyethyl methylacrylate (HEMA) etc.;
Wherein (b) described fluorine-containing macromole evocating agent/catalyzer/coordination agent/monomer is 1～3:1～3:2～5:10～80.
4. a kind of method with three block fluorinated copolymer modified adhesive coating resin surface hydrophobicitys according to claim 1, it is characterized in that wherein said step (1) (c) wherein (c) described silane coupling agent be 3-glycidyl ether oxygen base propyl trimethoxy silicane (KH-560), γ-methacryloxypropyl trimethoxy silane (KH-570), vinyltriethoxysilane (A-151), vinyltrimethoxy silane (A-171); Wherein (c) described fluorine-containing macromole evocating agent/catalyzer/coordination agent/monomer of diblock is 1～3:1～3:2～5:10～80.
5. a kind of method with three block fluorinated copolymer modified adhesive coating resin surface hydrophobicitys according to claim 1, is characterized in that the described consumption that adds three block fluorinated copolymers of wherein said step (2) is 1～15%; Wherein said solidifying agent is cyclohexanone peroxide, methylethyl ketone peroxide, diacetone peroxide, the first and second base diperoxy hydrogen etc., and consumption is 1%～2%; Wherein said promotor is cobalt naphthenate, cobalt iso-octoate solution etc., and consumption is 0.5%～1%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109135598A (en) * | 2018-08-07 | 2019-01-04 | 阜南县力韦包装材料有限公司 | A kind of copolymer-modified PET adhesive tape |
| CN110003698A (en) * | 2019-04-15 | 2019-07-12 | 哈尔滨哈玻拓普复合材料有限公司 | A kind of preparation method and applications of the hydrophobic gel coating resin of antenna house high durable |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1221013A (en) * | 1997-12-22 | 1999-06-30 | 黎燕 | Gel coating resin for ship |
| CN1712476A (en) * | 2005-08-08 | 2005-12-28 | 常州天马集团有限公司 | Gel coat resin and manufacturing method thereof |
| CN102504484A (en) * | 2011-10-11 | 2012-06-20 | 国电联合动力技术(连云港)有限公司 | Novel gel coat resin and preparation method thereof |
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2014
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1221013A (en) * | 1997-12-22 | 1999-06-30 | 黎燕 | Gel coating resin for ship |
| CN1712476A (en) * | 2005-08-08 | 2005-12-28 | 常州天马集团有限公司 | Gel coat resin and manufacturing method thereof |
| CN102504484A (en) * | 2011-10-11 | 2012-06-20 | 国电联合动力技术(连云港)有限公司 | Novel gel coat resin and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109135598A (en) * | 2018-08-07 | 2019-01-04 | 阜南县力韦包装材料有限公司 | A kind of copolymer-modified PET adhesive tape |
| CN110003698A (en) * | 2019-04-15 | 2019-07-12 | 哈尔滨哈玻拓普复合材料有限公司 | A kind of preparation method and applications of the hydrophobic gel coating resin of antenna house high durable |
| CN110003698B (en) * | 2019-04-15 | 2021-06-18 | 哈尔滨哈玻拓普复合材料有限公司 | Preparation method of high-weather-resistance hydrophobic gel coat resin for antenna housing |
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