CN109337057A - A kind of Organic fluoride boron and the hydrophobic flame-retarded unsaturated polyester resin of epoxy-modified high adhesion force - Google Patents
A kind of Organic fluoride boron and the hydrophobic flame-retarded unsaturated polyester resin of epoxy-modified high adhesion force Download PDFInfo
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- CN109337057A CN109337057A CN201811134943.8A CN201811134943A CN109337057A CN 109337057 A CN109337057 A CN 109337057A CN 201811134943 A CN201811134943 A CN 201811134943A CN 109337057 A CN109337057 A CN 109337057A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/698—Polyesters containing atoms other than carbon, hydrogen and oxygen containing boron
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- 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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
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- 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
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
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- 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
- C09D5/18—Fireproof paints including high temperature resistant paints
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The present invention relates to a kind of Organic fluoride boron and the hydrophobic flame-retarded unsaturated polyester resin of epoxy-modified high adhesion force, it is characterized in that, the unsaturated polyester resin participates in the esterification of polyester resin using fluorine-containing polyacid, borate biological, epoxy-modified monomer, make the boron oxygen key in the unsaturated polyester resin molecular structure containing the good epoxy group of the preferable fluorin radical of hydrophobicity, adhesive force and with fire-retardant synergy of fluorine atom, hydrophobicity, adhesive force, the flame retardant property of resin are greatly improved；The unsaturated polyester (UP) uses the last evacuated recycling of solvent method preparation, and the method is more environmentally-friendly, and the molecular weight and performance of resin are more uniform, and it is 100% that the theory of resin effectively contains admittedly；The present invention have many advantages, such as adhesive force is good, hydrophobicity is good, stain resistant is good, from anti-flammability.
Description
Technical field
The present invention relates to unsaturated polyester resin more particularly to a kind of Organic fluoride boron and epoxy-modified high adhesion force are hydrophobic
Flame-retarded unsaturated polyester resin belongs to resin modified technical field.
Technical background
China is the big producer of world's timber and wood-based product, and global furniture (mainly wooden woodenware man at present
Tool) the first big country of outlet, all consuming a large amount of coatings for furniture every year, (wherein, wooden Wooden furniture paint is commonly referred to as " wood use
Coating " or " woodcare paint ").Current domestic most commonly used coatings for furniture kind be mainly polyurethane paint, nitrate paint, alkyd paint,
Unsaturated polyester varnish etc..
Unsaturated polyester resin is most common one kind in thermosetting resin, it is by monounsaturated dicarboxylic acid, unsaturated binary
Line polymer made of acid and dihydric alcohol polycondensation, diluted by cross-linking monomer or active solvent to be formed with certain viscosity
Resin solution.The woodcare paint made of unsaturated polyester (UP) has good appearance, hardness and high solid, less pollution, and
It has excellent performance, improves the sagging phenomenon of vertical plane coating, but unsaturated polyester resin is cured as free radicals copolymerization reaction, this
Kind copolyreaction can be inhibited in the presence of aerobic, therefore be applied with the unsaturated polyester varnish that unsaturated polyester resin is prepared
Working hour does not overcome always needs the traditional constructions technique such as polish, polish.So-called air-drying property is not by the oxygen inhibition in air
And reaching film surface drying, air-dried unsaturated polyester resin makes PE furniture lacquer eliminate traditional construction technique in construction technology
Polishing, polishing, cost saved cost.
Chinese patent CN201710345754.4 discloses a kind of 100% unsaturated polyester resin of solid content and preparation method thereof,
The low VOC ordor removing PE varnish, including following component: 100% unsaturated polyester resin of solid content, low Odor-active monomer, food-grade
Antioxidant, levelling agent, defoaming agent, resist sagging auxiliary agent.The PE varnish of the invention has low voc and very friendly construction link
Smell, and have traditional unsaturated polyester varnish one-pass molding thicker paint film, bridging is good, richness is high, wear-resisting, high glaze etc.
Advantage.But invention the disadvantages of there are traditional furniture paint generally existing poor adhesive forces.
Summary of the invention
It is in order to overcome the shortcomings of the prior art and insufficient, the present invention is intended to provide a kind of Organic fluoride boron and epoxy-modified height are attached
Put forth effort hydrophobic flame-retarded unsaturated polyester resin.
To overcome shortcoming and defect of the existing technology, the present invention provides technical solution: a kind of Organic fluoride boron and
The hydrophobic flame-retarded unsaturated polyester resin of epoxy-modified high adhesion force, which is characterized in that the unsaturated polyester resin uses
Fluorine-containing polyacid, borate biological, epoxy-modified monomer participate in the esterification of polyester resin, make the unsaturated polyester (UP) tree
In rouge molecular structure containing the good epoxy group of the preferable fluorin radical of hydrophobicity, adhesive force and with fire-retardant synergy of fluorine atom
Boron oxygen key, hydrophobicity, adhesive force, the flame retardant property of resin be greatly improved；The unsaturated polyester (UP) uses solvent
Method prepares last evacuated recycling, and the method is more environmentally-friendly, and the molecular weight and performance of resin are more uniform, and the theory of resin has
It is 100% that effect contains admittedly.
The Organic fluoride boron and the epoxy-modified hydrophobic flame-retarded unsaturated polyester resin of high adhesion force, with parts by weight
Meter, preparation method are as follows:
Under logical condition of nitrogen gas, in equipped with division box, reflux unit, temperature control device reactor, 8-15 parts of gas is sequentially added
Stemness monomer, 8-15 parts of epoxy-modified monomers, 20-30 parts of dihydric alcohol, 6-10 parts of polyalcohol, 3-5 parts of boronic acid derivatives,
12-18 parts of fluorine-containing polyacids, 20-30 parts of maleic anhydrides, 6-10 parts of fumaric acid, 0.3-0.8 parts of anti-yellowing agents, 0.1-0.4
Part polymerization inhibitor, 5-10 parts of toluene, are warming up to 100 DEG C and start stirring, be then to slowly warm up to 160 DEG C of heat preservation 2h with 10 DEG C/h, after
It is continuous to be to slowly warm up to 195 DEG C with 10 DEG C/h, then 195 ± 5 DEG C of heat preservations, until system acid value≤45mgKOH/g, stops logical nitrogen at this time
Gas is cooled to 160 DEG C, and heat preservation is lower to pump solvent and unreacted small molecule using vacuum pump, until system acid value≤25mgKOH/g,
Gains are filtered to recycle through condenser；Then cooling body is to 0.3-0.5 parts of polymerization inhibitors of 100 DEG C or less additions, 0.5-1 parts of yellowing-resistants
Agent, 18-25 parts of styrene are cooled to 70 DEG C after mixing evenly with bottom discharge, as Organic fluoride boron and epoxy-modified high attachment
The hydrophobic flame-retarded unsaturated polyester resin of power.
The air-drying property monomer is dicyclopentadiene, allyl glycidyl ether, benzyl glycidyl ether, allyl are poly-
At least one of ethylene oxide ether.
The epoxy-modified monomer is bisphenol F epoxy resin, 3,4- epoxycyclohexyl formic acid -3', 4'- epoxycyclohexyl
At least one of methyl esters, trihydroxymethylpropanyltri diglycidyl ether, two (3,4- epoxycyclohexyl-methyl) adipate esters.
The dihydric alcohol is at least one of ethylene glycol, propylene glycol, neopentyl glycol, diethylene glycol (DEG), triethylene glycol.
The polyalcohol is at least one of glycerol, trimethylolpropane, pentaerythrite.
The boronic acid derivatives are phenylboric acid, vinyl boronic acids, isopropyl ylboronic acid, cyclopropylboronic acid, isobutyl group boron
At least kind in acid.
The fluorine-containing polyacid is the fluoro- succinic acid of 2- hydroxyl -3,3- two, the fluoro- 1,3,5- penta of 3- hydroxyl -2,2,4,4- four
At least one of three acid, ptfe phthalic anhydride, four toluene fluoride dioctyl phthalate, tetrafluoro terephthalic acid (TPA).
The anti-yellowing agent be hypophosphorous acid, triphenyl phosphite, Trimethyl phosphite, in triethyl phosphite at least
It is a kind of.
The polymerization inhibitor is hydroquinone, in tert-butyl catechol, Pyrogentisinic Acid's monobutyl ether, methylnaphthohydroquinone, 1,4-benzoquinone
At least one.
The present invention have many advantages, such as adhesive force is good, hydrophobicity is good, stain resistant is good, from anti-flammability.
Specific embodiment
Below with reference to embodiment to a kind of Organic fluoride boron of the invention and the hydrophobic fire-retardant insatiable hunger of epoxy-modified high adhesion force
It is further described with polyester resin.It is understood that specific embodiment described herein is used only for explaining correlation
Invention, rather than the restriction to the invention.
Embodiment 1
A kind of Organic fluoride boron and the hydrophobic flame-retarded unsaturated polyester resin of epoxy-modified high adhesion force, based on parts by weight, system
Preparation Method is as follows:
Under logical condition of nitrogen gas, in equipped with division box, reflux unit, temperature control device reactor, 15 parts of allyl is sequentially added
Base polyoxyethylene ether, 8 parts of 3,4- epoxycyclohexyl formic acid -3', 4'- epoxycyclohexanecarboxylates, 30 parts of ethylene glycol, 6 parts of season
Penta tetrol, 5 parts of isobutaneboronic acids, 12 parts of ptfe phthalic anhydrides, 30 parts of maleic anhydrides, 6 parts of fumaric acid, 0.8 part time
Phosphoric acid, 0.1 part of butyl-catechol, 10 parts of toluene, are warming up to 100 DEG C and start stirring, be then to slowly warm up to 160 with 10 DEG C/h
DEG C heat preservation 2h, continues with 10 DEG C/h to be to slowly warm up to 195 DEG C, then 195 ± 5 DEG C of heat preservations, until system acid value≤45mgKOH/g,
Stop logical nitrogen at this time, be cooled to 160 DEG C, heat preservation is lower to pump solvent and unreacted small molecule using vacuum pump, until system acid value
≤ 25mgKOH/g filters gains and recycles through condenser；Then cooling body is to 100 DEG C or less additions, 0.3 part of butyl neighbour benzene two
Phenol, 1 part of hypophosphorous acid, 18 parts of styrene, are cooled to 70 DEG C after mixing evenly with bottom discharge, as Organic fluoride boron and epoxy-modified
The hydrophobic flame-retarded unsaturated polyester resin of high adhesion force.
Embodiment 2
A kind of Organic fluoride boron and the hydrophobic flame-retarded unsaturated polyester resin of epoxy-modified high adhesion force, based on parts by weight, system
Preparation Method is as follows:
Under logical condition of nitrogen gas, in equipped with division box, reflux unit, temperature control device reactor, 8 parts of benzyl contracting is sequentially added
Water glycerin ether, 15 parts of bisphenol F epoxy resins, 20 parts of neopentyl glycol, 10 parts of neopentyl glycol, 3 parts of vinyl boronic acids, 18 parts of 2-
The fluoro- succinic acid of hydroxyl -3,3- two, 20 parts of maleic anhydrides, 10 parts of fumaric acid, 0.3 portion of triphenyl phosphite, 0.4 part of methyl
Quinhydrones, 5 parts of toluene, are warming up to 100 DEG C and start stirring, are then to slowly warm up to 160 DEG C of heat preservation 2h with 10 DEG C/h, continue with 10
DEG C/h is to slowly warm up to 195 DEG C, then 195 ± 5 DEG C of heat preservations, until system acid value≤45mgKOH/g, stops logical nitrogen, drop at this time
Temperature is to 160 DEG C, and heat preservation is lower to pump solvent and unreacted small molecule using vacuum pump, until system acid value≤25mgKOH/g, filters institute
Object is obtained to recycle through condenser；Then cooling body is to 100 DEG C or less additions 0.5 part of methylnaphthohydroquinone, 0.5 part of triphenyl phosphite, 25
Part styrene, is cooled to 70 DEG C after mixing evenly with bottom discharge, as Organic fluoride boron and the hydrophobic resistance of epoxy-modified high adhesion force
Retardant unsaturated polyester resin.
Embodiment 3
A kind of Organic fluoride boron and the hydrophobic flame-retarded unsaturated polyester resin of epoxy-modified high adhesion force, based on parts by weight, system
Preparation Method is as follows:
Under logical condition of nitrogen gas, in equipped with division box, reflux unit, temperature control device reactor, 10 parts of allyl is sequentially added
Base glycidol ether, 12 part of two (3,4- epoxycyclohexyl-methyl) adipate ester, 24 parts of triethylene glycol, 8 parts of pentaerythrite, 4
Part phenylboric acid, 14 parts of fluoro- penta 3 acid of 1,3,5- of 3- hydroxyl -2,2,4,4- four, 22 parts of maleic anhydrides, 7 parts of fumaric acid,
0.6 part of triethyl phosphite, 0.2 part of hydroquinone, 6 parts of toluene, are warming up to 100 DEG C and start stirring, then slow with 10 DEG C/h
160 DEG C of heat preservation 2h are warming up to, continue to be to slowly warm up to 195 DEG C with 10 DEG C/h, then 195 ± 5 DEG C of heat preservations, until system acid value≤
45mgKOH/g stops logical nitrogen at this time, is cooled to 160 DEG C, and heat preservation is lower to pump solvent and unreacted small molecule using vacuum pump,
To system acid value≤25mgKOH/g, filters gains and recycled through condenser；Then cooling body is right to 100 DEG C or less 0.4 part of additions
Benzenediol, 0.9 part of triethyl phosphite, 20 parts of styrene are cooled to 70 DEG C after mixing evenly with bottom discharge, as Organic fluoride boron
With the epoxy-modified hydrophobic flame-retarded unsaturated polyester resin of high adhesion force.
Take the Organic fluoride boron and the epoxy-modified hydrophobic flame-retarded unsaturated polyester resin of high adhesion force, 18 parts of 82 parts of embodiments
Styrene, 3g fume colloidal silica 800r/min are uniformly dispersed, and 2 parts of blue water are then added, 2 parts of plain boiled waters, are added, stir evenly spray
In nanmu surface, repeats to spray after surface drying, spray three times altogether, about 150 microns of paint film overall thickness, test the performance such as following table of paint film
1, as can be seen from Table 1 the present invention have many advantages, such as adhesive force is good, hydrophobicity is good, stain resistant is good, from anti-flammability.
The performance of 1 embodiment 1-3 paint film of table
| Embodiment | Embodiment 2 | Embodiment 3 | |
| Adhesive force | 0 grade | 0 grade | 0 grade |
| Pencil hardness | 4H | 4H | 4H |
| The contact angle of film and water | 132° | 126° | 129° |
| Bending strength GB/T6742-1986 | 3 | 4 | 4 |
| Resistance to greasy dirt and oiliness board pen ink are staining | Easily erasing | Easily erasing | Easily erasing |
| Resistance to combustion time GB12441-2005(>=15min) | 15min14s | 16 min26s | 16 min30s |
| Flame propagation ratio GB12441-2005(≤25) | 23.1 | 22.6 | 21.8 |
| Mass loss GB12441-2005(≤5.0g) | 4.45g | 4.32g | 4.16g |
| Be carbonized volume GB12441-2005(≤25cm3) | 24cm3 | 23cm3 | 23cm3 |
Claims (9)
1. a kind of Organic fluoride boron and the hydrophobic flame-retarded unsaturated polyester resin of epoxy-modified high adhesion force, which is characterized in that described
Unsaturated polyester resin using fluorine-containing polyacid, borate biological, epoxy-modified monomer participate in polyester resin esterification,
Make in the unsaturated polyester resin molecular structure containing the good epoxy group of the preferable fluorin radical of hydrophobicity, adhesive force and with
The boron oxygen key of fire-retardant synergy of fluorine atom；The unsaturated polyester (UP) prepares last evacuated recycling using solvent method,
It is 100% that the theory of resin effectively contains admittedly；Based on parts by weight, the unsaturated polyester resin the preparation method is as follows:
Under logical condition of nitrogen gas, in equipped with division box, reflux unit, temperature control device reactor, 8-15 parts of gas is sequentially added
Stemness monomer, 8-15 parts of epoxy-modified monomers, 20-30 parts of dihydric alcohol, 6-10 parts of polyalcohol, 3-5 parts of boronic acid derivatives,
12-18 parts of fluorine-containing polyacids, 20-30 parts of maleic anhydrides, 6-10 parts of fumaric acid, 0.3-0.8 parts of anti-yellowing agents, 0.1-0.4
Part polymerization inhibitor, 5-10 parts of toluene, are warming up to 100 DEG C and start stirring, be then to slowly warm up to 160 DEG C of heat preservation 2h with 10 DEG C/h, after
It is continuous to be to slowly warm up to 195 DEG C with 10 DEG C/h, then 195 ± 5 DEG C of heat preservations, until system acid value≤45mgKOH/g, stops logical nitrogen at this time
Gas is cooled to 160 DEG C, and heat preservation is lower to pump solvent and unreacted small molecule using vacuum pump, until system acid value≤25mgKOH/g；
Then for cooling body to 0.3-0.5 parts of polymerization inhibitors of 100 DEG C or less additions, 0.5-1 parts of anti-yellowing agents, 18-25 parts of styrene, stirring is equal
70 DEG C are cooled to after even with bottom discharge, the as hydrophobic flameproof unsaturated polyester tree of Organic fluoride boron and epoxy-modified high adhesion force
Rouge.
2. Organic fluoride boron according to claim 1 and the hydrophobic flame-retarded unsaturated polyester resin of epoxy-modified high adhesion force,
It is characterized by: the air-drying property monomer is dicyclopentadiene, allyl glycidyl ether, benzyl glycidyl ether, allyl
At least one of base polyoxyethylene ether.
3. Organic fluoride boron according to claim 1 and the hydrophobic flame-retarded unsaturated polyester resin of epoxy-modified high adhesion force,
It is characterized by: the epoxy-modified monomer is bisphenol F epoxy resin, 3,4- epoxycyclohexyl formic acid -3', 4'- epoxide ring
At least one of hexyl methyl esters, trihydroxymethylpropanyltri diglycidyl ether, two (3,4- epoxycyclohexyl-methyl) adipate esters.
4. Organic fluoride boron according to claim 1 and the hydrophobic flame-retarded unsaturated polyester resin of epoxy-modified high adhesion force,
It is characterized by: the dihydric alcohol is at least one of ethylene glycol, propylene glycol, neopentyl glycol, diethylene glycol (DEG), triethylene glycol.
5. Organic fluoride boron according to claim 1 and the hydrophobic flame-retarded unsaturated polyester resin of epoxy-modified high adhesion force,
It is characterized by: the polyalcohol is at least one of glycerol, trimethylolpropane, pentaerythrite.
6. Organic fluoride boron according to claim 1 and the hydrophobic flame-retarded unsaturated polyester resin of epoxy-modified high adhesion force,
It is characterized by: the boronic acid derivatives are phenylboric acid, vinyl boronic acids, isopropyl ylboronic acid, cyclopropylboronic acid, isobutyl group
At least one of boric acid.
7. Organic fluoride boron according to claim 1 and the hydrophobic flame-retarded unsaturated polyester resin of epoxy-modified high adhesion force,
It is characterized by: the fluorine-containing polyacid be the fluoro- succinic acid of 2- hydroxyl -3,3- two, 3- hydroxyl -2,2,4,4- four fluoro- 1,3,
At least one of penta 3 acid of 5-, ptfe phthalic anhydride, four toluene fluoride dioctyl phthalate, tetrafluoro terephthalic acid (TPA).
8. Organic fluoride boron according to claim 1 and the hydrophobic flame-retarded unsaturated polyester resin of epoxy-modified high adhesion force,
It is characterized by: the anti-yellowing agent is hypophosphorous acid, in triphenyl phosphite, Trimethyl phosphite, triethyl phosphite
It is at least one.
9. Organic fluoride boron according to claim 1 and the hydrophobic flame-retarded unsaturated polyester resin of epoxy-modified high adhesion force,
It is characterized by: the polymerization inhibitor is hydroquinone, tert-butyl catechol, Pyrogentisinic Acid's monobutyl ether, methylnaphthohydroquinone, 1,4-benzoquinone
At least one of.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811134943.8A CN109337057A (en) | 2018-09-28 | 2018-09-28 | A kind of Organic fluoride boron and the hydrophobic flame-retarded unsaturated polyester resin of epoxy-modified high adhesion force |
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|---|---|---|---|
| CN201811134943.8A CN109337057A (en) | 2018-09-28 | 2018-09-28 | A kind of Organic fluoride boron and the hydrophobic flame-retarded unsaturated polyester resin of epoxy-modified high adhesion force |
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Cited By (1)
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| CN114736390A (en) * | 2022-05-26 | 2022-07-12 | 泉州永悦新材料有限公司 | Synthesis method of block polymerization epoxy modified unsaturated resin |
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