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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Abstract
The invention relates to a method of modifying surface hydrophobicity of gel coat resin by a triblock fluorine-containing copolymer, belonging to the field of macromoleclar polymerization. The method comprises the following steps: first, preparing the triblock fluorine-containing copolymer; and then, preparing the modified gel coat resin. The triblock fluorine-containing copolymer is synthesized by an atom transfer radical polymerization method, and the structure and molecular weight can be controlled. The blending method of the gel coat resin and the triblock fluorine-containing copolymer is easy to implement in the production process. The cured gel coat resin modified by the triblock fluorine-containing copolymer has a unique surface property, and the contact angle can reach 109.5 degrees.
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 |
|---|---|---|---|---|
| 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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| 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 coating resin and production 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 coating resin and production 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 |
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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 |
| 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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