CN103421288B - A kind of method containing fluorine graft copolymer modified unsaturated polyester resin - Google Patents
A kind of method containing fluorine graft copolymer modified unsaturated polyester resin Download PDFInfo
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- CN103421288B CN103421288B CN201310328277.2A CN201310328277A CN103421288B CN 103421288 B CN103421288 B CN 103421288B CN 201310328277 A CN201310328277 A CN 201310328277A CN 103421288 B CN103421288 B CN 103421288B
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Abstract
A kind of method containing fluorine graft copolymer modified unsaturated polyester resin of the present invention, belongs to field of macromolecule polymerization.With the synthesis of the method for living polymerization containing fluorine graft copolymer, structure and molecular weight can control; Adopt unsaturated polyester resin in the production phase with containing fluorine graft copolymer blend method, be easy to implement in process of production; Due to use high thermal stability, high unreactiveness and low surface energy containing fluorine graft copolymer, reduce the volatility of unsaturated polyester resin solvent, the health of enabling environment protection and protection workmen; After unsaturated polyester resin being solidified containing fluorine graft copolymer, there is unique surface property.The occasion of industry, agricultural, traffic and some special applications can be widely used in.
Description
technical field:
The invention belongs to field of macromolecule polymerization, particularly relate to the preparation method utilized containing fluorine graft copolymer modified unsaturated polyester resin.
background technology:
Unsaturated polyester resin (UPR) is generated through polycondensation by unsaturated dibasic acid (maleic anhydride), saturated diprotic acid, dibasic alcohol, owing to containing unsaturated double-bond in molecular resin chain, therefore can with double bond containing monomer, generate 3-D solid structure as copolyreaction occurs for vinylbenzene, vinyl toluene etc., form insoluble not molten thermosetting resin.It is an important kind in plastics industry in modern age, is widely used in industry, agricultural, traffic, building and national defense industry.Because unsaturated polyester generally also exists poor toughness, the shortcomings such as intensity is not high, easily burns, and shrinking percentage is large, thus limit its range of application.In order to expand unsaturated polyester resin range of application, particularly in order to meet the requirement of some special dimensions, need to carry out modification to unsaturated polyester, to improve the performance of UPR.
Bond energy due to C-F key in fluoropolymer is larger, more stable, F atom is not only combined firmly with C atom, and it is very tight in the arrangement of carbon chain backbone skin, effectively prevent the exposure of C atom and C chain, therefore fluoropolymer shows remarkable chemical stability, the characteristic such as corrosion-resistant, anti-oxidant.Due to general fluorine-containing homopolymer can not solvability poor, and easily move to surface in solidification process.Therefore adopt the method synthesising graft copolymer of a certain proportion of fluorochemical monomer and vinyl monomer active free radical polymerization, obtained then can be dissolved in unsaturated polyester resin system containing fluorine graft copolymer.Have the characteristics such as the high thermal stability of fluoropolymer, high unreactiveness and low surface energy containing fluorine graft copolymer concurrently, the volatility of unsaturated polyester resin solvent can be reduced, and the surface property of final curing system is improved.
Summary of the invention
Its concrete steps are as follows:
The object of this invention is to provide a kind of method being modifier modification unsaturated polyester resin containing fluorine graft copolymer with the synthesis of the method for copolymerization.
Containing a method for fluorine graft copolymer modified unsaturated polyester resin, carry out according to following step:
One, containing the preparation of fluorine graft copolymer:
(1) by a certain proportion of vinyl monomer, halogen-containing vinyl monomer, initiator and solvent, be placed in 80 DEG C of constant temperature oil baths under magnetic stirring and react 24h; After reaction terminates, obtain pure macromole evocating agent;
(2) by reaction flask in advance through baking-vacuum outgas 3 times, applying argon gas cooling after, add a certain proportion of organic halogen catalyzer, part and macromole evocating agent and vacuumize applying argon gas again, 3 times repeatedly; Then add solvent and fluorochemical monomer, be placed in 110 DEG C of oil baths and react; After reaction terminates, be cooled to room temperature;
(3) product obtained, except desolventizing and catalyzer, obtains containing fluorine graft copolymer;
Two, the preparation of unsaturated polyester resin prepolymer:
Unsaturated dibasic acid, monounsaturated dicarboxylic acid and dibasic alcohol are adopted melt-polycondensation under the effect of catalyzer, dibasic alcohol and diprotic acid direct melt polycondensation, logical nitrogen 180 DEG C of condensation polymerizations 3 hours, vacuum hydro-extraction when later stage viscosity increases, treats that acid number is for subsequent use to 20-60mgKOH/g cooling.
Described unsaturated dibasic acid or acid anhydrides are MALEIC ANHYDRIDE, FUMARIC ACID TECH GRADE etc. with the organic compound containing double bond of two carboxyl or polymkeric substance; Monounsaturated dicarboxylic acid is Tetra hydro Phthalic anhydride, m-phthalic acid etc.; Dibasic alcohol is organic compound or polymkeric substance containing two hydroxyl such as ethylene glycol, propylene glycol, butyleneglycol; Catalyzer is organotin, as dibutyltin dilaurate, stannous octoate, two (dodecyl sulphur) dibutyl tin, dibutyltin diacetate etc.; Diprotic acid: dibasic alcohol: the mol ratio of catalyzer is 1:1.01-1.10:0.001-0.05; In diprotic acid, monounsaturated dicarboxylic acid and unsaturated dibasic acid mol ratio are 1:0-10.
Three, the preparation of modified unsaturated polyester resin:
What the unsaturated polyester resin prepolymer of synthesis is added total mass 1-5% contains fluorine graft copolymer, 50-80 DEG C of low rate mixing mixing, finally adds thinner vinylbenzene, methyl methacrylate etc.; Finally prepare modified unsaturated polyester resin.
Vinyl monomer wherein in step one described in (1) is vinylbenzene, methyl methacrylate etc.; Halogen-containing vinyl monomer is p-chloromethyl styrene etc.; Initiator is organo-peroxide, as dibenzoyl peroxide, and the benzoyl peroxide tert-butyl ester etc., or be azo-compound Diisopropyl azodicarboxylate etc.; Or oxidation-reduction system, as dibenzoyl peroxide and DMA etc.; Mentioned solvent is toluene, dimethylbenzene etc., and solvent load is 1-2 times by volume of monomer consumption; Vinyl monomer: halogen-containing vinyl monomer: initiator mol ratio is 1-10:1:0.001-0.01.
Organic halogen catalyzer wherein described in step one (2) is low-valent metal halogenide, as cuprous bromide; Part is 2,2 '-bipyridine (bpy); Fluorochemical monomer is containing double bond C=C and-F functional group, as: vinylformic acid hexafluoro butyl ester (G01), Hexafluorobutyl mathacrylate (G02), trifluoroethyl methacrylate (G03), methacrylic acid 12 heptyl ester (G04) etc.; Described solvent is toluene, pimelinketone; Wherein (2) described fluorochemical monomer: macromole evocating agent=10 ~ 220:1(mol ratio), organic halogen catalyzer: fluorochemical monomer=1 ~ 2:100 (mol ratio), low-valent metal halide catalyst: part=1:3 (mol ratio), 20% ~ 35% of solvent load=system quality; Described solvent is toluene, pimelinketone.
The invention has the advantages that 1: with the synthesis of the method for living polymerization containing fluorine graft copolymer, structure and molecular weight can control; 2: adopt unsaturated polyester resin in the production phase with containing fluorine graft copolymer blend method, be easy to implement in process of production; 3: due to use high thermal stability, high unreactiveness and low surface energy containing fluorine graft copolymer, reduce the volatility of unsaturated polyester resin solvent, the health of enabling environment protection and protection workmen; 4: after unsaturated polyester resin being solidified containing fluorine graft copolymer, there is unique surface property.The occasion of industry, agricultural, traffic and some special applications can be widely used in.
Embodiment
Below in conjunction with example, the present invention is described in further detail.
Embodiment 1
Polymerization procedure is as follows:
1, containing the preparation of fluorine graft copolymer
(1) in the there-necked flask with mechanical stirrer and prolong, 20g vinylbenzene, 10g p-chloromethyl styrene, 0.1g dibenzoyl peroxide and 50g toluene is added, pass into 30min nitrogen, be placed in 80 DEG C of constant temperature oil baths under magnetic stirring and react 24h.After reaction terminates, namely 45 DEG C of vacuum-dryings obtain pure macromole evocating agent.
(2) by reaction flask in advance through baking-vacuum outgas 3 times, after applying argon gas cooling, add a certain proportion of cuprous bromide (CuBr) 1g, 2,2 '-bipyridine (bpy) 3g and macromole evocating agent 1g vacuumizes applying argon gas again, 3 times repeatedly.Then add toluene and dodecafluoroheptyl methacrylate 100g, be placed in 110 DEG C of oil baths and react.After reaction terminates, be cooled to room temperature, the multipolymer of synthesis take hexanaphthene as solvent, and with Soxhlet extractor extracting 48h respectively, to remove the macromole evocating agent having neither part nor lot in reaction, 60 DEG C of vacuum-dryings are to constant weight.Obtain containing fluorine graft copolymer.
2, the preparation of unsaturated polyester resin prepolymer
Propylene glycol, 167.4g; MALEIC ANHYDRIDE 98g; Tetra hydro Phthalic anhydride 148g leads to nitrogen 180 DEG C of condensation polymerizations 3 hours, vacuum hydro-extraction when later stage viscosity increases, and treats that acid number is for subsequent use to 40mgKOH/g cooling.
3, the preparation of modified unsaturated polyester resin
What the unsaturated polyester resin prepolymer 100g of synthesis is added total amount 3g contains fluorine graft copolymer, and at 50 DEG C of temperature, low rate mixing mixing, finally adds thinner 60g vinylbenzene.The unsaturated polyester resin of final preparation modification.
Embodiment 2
Polymerization procedure is as follows:
1, containing the preparation of fluorine graft copolymer
(1) in the there-necked flask with mechanical stirrer and prolong, 20g vinylbenzene, 20g p-chloromethyl styrene, 0.1g dibenzoyl peroxide and 50g toluene is added, pass into 30min nitrogen, be placed in 80 DEG C of constant temperature oil baths under magnetic stirring and react 24h.After reaction terminates, namely 45 DEG C of vacuum-dryings obtain pure macromole evocating agent.
(2) by reaction flask in advance through baking-vacuum outgas 3 times, after applying argon gas cooling, add a certain proportion of cuprous bromide (CuBr) 1g, 2,2 '-bipyridine (bpy) 3g and macromole evocating agent 1g vacuumizes applying argon gas again, 3 times repeatedly.Then add toluene and dodecafluoroheptyl methacrylate 20g, be placed in 110 DEG C of oil baths and react.After reaction terminates, be cooled to room temperature, the multipolymer of synthesis take hexanaphthene as solvent, and with Soxhlet extractor extracting 48h respectively, to remove the macromole evocating agent having neither part nor lot in reaction, 60 DEG C of vacuum-dryings are to constant weight.Obtain containing fluorine graft copolymer.
2, the preparation of unsaturated polyester resin prepolymer
Propylene glycol, 146g; Glycol ether 28.6g; MALEIC ANHYDRIDE 98g; Phthalate anhydride 148g leads to nitrogen 180 DEG C of condensation polymerizations 3 hours, vacuum hydro-extraction when later stage viscosity increases, and treats that acid number is for subsequent use to 45mgKOH/g cooling.
3, the preparation of modified unsaturated polyester resin
What the unsaturated polyester resin prepolymer 100g of synthesis is added total amount 2g contains fluorine graft copolymer, and at 50 DEG C of temperature, low rate mixing mixing, finally adds thinner vinylbenzene and each 40g of methyl methacrylate that mass ratio is 1:1.Finally prepare modified unsaturated polyester resin.
Embodiment 3
Polymerization procedure is as follows:
1, containing the preparation of fluorine graft copolymer
(1) in the there-necked flask with mechanical stirrer and prolong, 20g vinylbenzene, 10g p-chloromethyl styrene, 0.1g Diisopropyl azodicarboxylate and 50g toluene is added, pass into 30min nitrogen, be placed in 50 DEG C of constant temperature oil baths under magnetic stirring and react 24h.After reaction terminates, namely 45 DEG C of vacuum-dryings obtain pure macromole evocating agent.
(2) by reaction flask in advance through baking-vacuum outgas 3 times, after applying argon gas cooling, add a certain proportion of cuprous bromide (CuBr) 1g, 2,2 '-bipyridine (bpy) 3g and macromole evocating agent 1g vacuumizes applying argon gas again, 3 times repeatedly.Then add toluene and dodecafluoroheptyl methacrylate 100g, be placed in 110 DEG C of oil baths and react.After reaction terminates, be cooled to room temperature, the multipolymer of synthesis take hexanaphthene as solvent, and with Soxhlet extractor extracting 48h respectively, to remove the macromole evocating agent having neither part nor lot in reaction, 60 DEG C of vacuum-dryings are to constant weight.Obtain containing fluorine graft copolymer.
2, the preparation of unsaturated polyester resin prepolymer
Propylene glycol, 170g; Glycol ether 291.7g; MALEIC ANHYDRIDE 343.2g; Phthalate anhydride 111g, hexanodioic acid 109.6g.Logical nitrogen 180 DEG C of condensation polymerizations 3 hours, vacuum hydro-extraction when later stage viscosity increases, treats that acid number is for subsequent use to 55mgKOH/g cooling.
3, the preparation of modified unsaturated polyester resin
What the unsaturated polyester resin prepolymer 100g of synthesis is added total amount 5g contains fluorine graft copolymer, and at 50 DEG C of temperature, low rate mixing mixing, finally adds thinner vinylbenzene 80g.Finally prepare modified unsaturated polyester resin.
Embodiment 4
Polymerization procedure is as follows:
1, containing the preparation of fluorine graft copolymer
(1) in the there-necked flask with mechanical stirrer and prolong, 40g vinylbenzene, 20g p-chloromethyl styrene, 0.1g dibenzoyl peroxide and 0.05gN is added, accelerine and 50g toluene, pass into 30min nitrogen, be placed in 40 DEG C of constant temperature oil baths under magnetic stirring and react 24h.After reaction terminates, namely 40 DEG C of vacuum-dryings obtain pure macromole evocating agent.
(2) by reaction flask in advance through baking-vacuum outgas 3 times, after applying argon gas cooling, add a certain proportion of cuprous bromide (CuBr) 1g, 2,2 '-bipyridine (bpy) 3g and macromole evocating agent 1g vacuumizes applying argon gas again, 3 times repeatedly.Then add toluene and Hexafluorobutyl mathacrylate 50g, be placed in 110 DEG C of oil baths and react.After reaction terminates, be cooled to room temperature, the multipolymer of synthesis take hexanaphthene as solvent, and with Soxhlet extractor extracting 48h respectively, to remove the macromole evocating agent having neither part nor lot in reaction, 60 DEG C of vacuum-dryings are to constant weight.Obtain containing fluorine graft copolymer.
2, the preparation of unsaturated polyester resin prepolymer
Propylene glycol, 76g; Glycol ether 106g; MALEIC ANHYDRIDE 103g; Phthalate anhydride 80g, tetrabromophthalic anhydride 111g.Logical nitrogen 180 DEG C of condensation polymerizations 3 hours, vacuum hydro-extraction when later stage viscosity increases, treats that acid number is for subsequent use to 43mgKOH/g cooling.
3, the preparation of modified unsaturated polyester resin
What the unsaturated polyester resin prepolymer 100g of synthesis is added total amount 5% contains fluorine graft copolymer, and at 50 DEG C of temperature, low rate mixing mixing, finally adds thinner vinylbenzene 100g.Finally prepare modified unsaturated polyester resin.
Embodiment 5
Polymerization procedure is as follows:
1, containing the preparation of fluorine graft copolymer
(1) in the there-necked flask with mechanical stirrer and prolong, 20g vinylbenzene, 20g is added to chloroethyl vinylbenzene, 0.1g dibenzoyl peroxide and 50g toluene, pass into 30min nitrogen, be placed in 80 DEG C of constant temperature oil baths under magnetic stirring and react 24h.After reaction terminates, namely 40 DEG C of vacuum-dryings obtain pure macromole evocating agent.
(2) by reaction flask in advance through baking-vacuum outgas 3 times, after applying argon gas cooling, add a certain proportion of cuprous bromide (CuBr) 1g, 2,2 '-bipyridine (bpy) 3g and macromole evocating agent 1g vacuumizes applying argon gas again, 3 times repeatedly.Then add toluene and Hexafluorobutyl mathacrylate 100g, be placed in 110 DEG C of oil baths and react.After reaction terminates, be cooled to room temperature, the multipolymer of synthesis take hexanaphthene as solvent, and with Soxhlet extractor extracting 48h respectively, to remove the macromole evocating agent having neither part nor lot in reaction, 60 DEG C of vacuum-dryings are to constant weight.Obtain containing fluorine graft copolymer.
2, the preparation of unsaturated polyester resin prepolymer
Propylene glycol, 76g; Glycol ether 106g; MALEIC ANHYDRIDE 103g; Phthalate anhydride 80g, tetrabromophthalic anhydride 111g.Logical nitrogen 180 DEG C of condensation polymerizations 3 hours, vacuum hydro-extraction when later stage viscosity increases, treats that acid number is for subsequent use to 43mgKOH/g cooling.
3, the preparation of modified unsaturated polyester resin
What the unsaturated polyester resin prepolymer 100g of synthesis is added total amount 5g contains fluorine graft copolymer, and at 50 DEG C of temperature, low rate mixing mixing, finally adds thinner methylpropanoic acid methyl esters 100g.Finally prepare modified unsaturated polyester resin.
The surface property experimental data of curing system:
By above-mentioned preparation do not add containing fluorine graft copolymer unsaturated polyester resin and add and add spin-coating film after solidifying agent containing fluorine graft copolymer and unsaturated polyester resin, test its water contact angle and gauging surface tension data with contact angle tester, result is as follows:
Water contact angle and surface tension data (25 DEG C)
From table can obviously find out, modified unsaturated polyester resin hydrophobic properties of the surface be improved significantly.
Claims (1)
1., containing a method for fluorine graft copolymer modified unsaturated polyester resin, it is characterized in that carrying out according to following step:
One, containing the preparation of fluorine graft copolymer:
(1) by a certain proportion of vinyl monomer, halogen-containing vinyl monomer, initiator and solvent, be placed in 80 DEG C of constant temperature oil baths under magnetic stirring and react 24h; After reaction terminates, obtain pure macromole evocating agent;
(2) by reaction flask in advance through baking-vacuum outgas 3 times, applying argon gas cooling after, add a certain proportion of organic halogen catalyzer, part and macromole evocating agent and vacuumize applying argon gas again, 3 times repeatedly; Then add solvent and fluorochemical monomer, be placed in 110 DEG C of oil baths and react; After reaction terminates, be cooled to room temperature;
(3) product obtained, except desolventizing and catalyzer, obtains containing fluorine graft copolymer;
Two, the preparation of unsaturated polyester resin prepolymer:
Unsaturated dibasic acid, monounsaturated dicarboxylic acid and dibasic alcohol are adopted melt-polycondensation under the effect of catalyzer, dibasic alcohol and diprotic acid direct melt polycondensation, logical nitrogen 180 DEG C of condensation polymerizations 3 hours, vacuum hydro-extraction when later stage viscosity increases, treats that acid number is for subsequent use to 20-60mgKOH/g cooling;
Three, the preparation of modified unsaturated polyester resin:
What the unsaturated polyester resin prepolymer of synthesis is added total mass 1-5% contains fluorine graft copolymer, 50-80 DEG C of low rate mixing mixing, finally adds thinner vinylbenzene or methyl methacrylate; Finally prepare modified unsaturated polyester resin;
Vinyl monomer wherein in step one described in (1) is vinylbenzene, methyl methacrylate; Halogen-containing vinyl monomer is p-chloromethyl styrene; Initiator is dibenzoyl peroxide, the benzoyl peroxide tert-butyl ester, azo-compound Diisopropyl azodicarboxylate; Dibenzoyl peroxide, DMA; Mentioned solvent is toluene or dimethylbenzene, and solvent load is 1-2 times by volume of monomer consumption; Vinyl monomer: halogen-containing vinyl monomer: initiator mol ratio is 1-10:1:0.001-0.01;
Organic halogen catalyzer wherein described in step one (2) is cuprous bromide; Part is 2,2 '-bipyridine; Fluorochemical monomer is vinylformic acid hexafluoro butyl ester, Hexafluorobutyl mathacrylate, trifluoroethyl methacrylate, methacrylic acid 12 heptyl ester; Described solvent is toluene, pimelinketone; Wherein (2) described fluorochemical monomer: macromole evocating agent with molar ratio computing for 10 ~ 220:1, organic halogen catalyzer: fluorochemical monomer with molar ratio computing for 1 ~ 2:100, low-valent metal halide catalyst: part take molar ratio computing as 1:3, and solvent load is 20% ~ 35% of system quality; Described solvent is toluene, pimelinketone;
Described unsaturated dibasic acid or acid anhydrides are MALEIC ANHYDRIDE or FUMARIC ACID TECH GRADE; Monounsaturated dicarboxylic acid is Tetra hydro Phthalic anhydride or m-phthalic acid; Dibasic alcohol is ethylene glycol, propylene glycol, butyleneglycol; Catalyzer is dibutyltin dilaurate, stannous octoate, two (dodecyl sulphur) dibutyl tin or dibutyltin diacetates; Diprotic acid: dibasic alcohol: the mol ratio of catalyzer is 1:1.01-1.10:0.001-0.05; In diprotic acid, monounsaturated dicarboxylic acid and unsaturated dibasic acid mol ratio are 1:10.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006085695A1 (en) * | 2005-02-14 | 2006-08-17 | Toyota Jidosha Kabushiki Kaisha | Graft copolymer and process for producing the same |
| CN102604029A (en) * | 2012-02-22 | 2012-07-25 | 常州大学 | Fluorine-containing waterborne polyurethane (PU) and preparation method thereof |
| CN102634980A (en) * | 2012-04-19 | 2012-08-15 | 常州大学 | Fluorine-containing waterproofing agent for textiles and method for preparing same |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006085695A1 (en) * | 2005-02-14 | 2006-08-17 | Toyota Jidosha Kabushiki Kaisha | Graft copolymer and process for producing the same |
| CN102604029A (en) * | 2012-02-22 | 2012-07-25 | 常州大学 | Fluorine-containing waterborne polyurethane (PU) and preparation method thereof |
| CN102634980A (en) * | 2012-04-19 | 2012-08-15 | 常州大学 | Fluorine-containing waterproofing agent for textiles and method for preparing same |
Non-Patent Citations (2)
| Title |
|---|
| Synthesis and characterization of a well-defined graft copolymer containing fluorine grafts by living/controlled radical polymerization;Liu, B等;《MACROMOLECULAR CHEMISTRY AND PHYSICS》;20010830;第202卷(第12期);第2504-2508页 * |
| 不饱和聚酯改性研究进展;周艳等;《绝缘材料》;20030830(第04期);41-44 * |
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