CN103421287A - Preparation method of unsaturated polyester resin modified by polyester-polysiloxane - Google Patents
Preparation method of unsaturated polyester resin modified by polyester-polysiloxane Download PDFInfo
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- CN103421287A CN103421287A CN2013103278175A CN201310327817A CN103421287A CN 103421287 A CN103421287 A CN 103421287A CN 2013103278175 A CN2013103278175 A CN 2013103278175A CN 201310327817 A CN201310327817 A CN 201310327817A CN 103421287 A CN103421287 A CN 103421287A
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Abstract
The invention provides a preparation method of unsaturated polyester resin modified by polyester-polysiloxane and belongs to the field of macromolecule aggregation. The preparation method comprises the following steps: unsaturated polyester resin with functional groups is prepared by adopting such method that polyester resin alcohol or acid is excess; alcohol or acid with vinyl is adopted to seal the matrix of prepared unsaturated polyester resin, and polyester macromolecules with vinyl groups are prepared; polyester modified polysiloxane is compounded by adopting hydrosilylation method to polysiloxane containing hydrogen and vinyl polyester macromolecules. According to the invention, because the polyester modified polysiloxane with high thermal stability, high chemical inertness and low surface energy is added, the volatility of an unsaturated polyester resin solvent is reduced, which is beneficial to environmental protection and can protect the health of constructors, and the polyester modified polysiloxane enables the unsaturated polyester resin to have unique surface properties after solidification, and to meet requirements of high temperature resistance, low temperature and viscosity resistance, low electrical conductivity on the surface and the like in a special usage occasion.
Description
Technical field:
The invention belongs to the high molecular polymerization field, relate in particular to the preparation method who utilizes the polyester-polysiloxane modified unsaturated polyester resin.
Background technology:
Unsaturated polyester resin (UPR) is to be generated through polycondensation by unsaturated dibasic acid (maleic anhydride), saturated diprotic acid, dibasic alcohol, owing in the molecular resin chain, containing unsaturated double-bond, therefore can with double bond containing monomer, as copolyreaction generating three-dimensional three-dimensional arrangement occurs for vinylbenzene, vinyl toluene etc., form insoluble not molten thermosetting resin.It is an important kind in the plastics industry in modern age.The shortcomings such as because unsaturated polyester generally exists poor toughness, intensity is not high, easily burns, and shrinking percentage is large, thus limited its range of application.In order to enlarge the 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.
Hydrogen containing siloxane refers to the polysiloxane by the active hydrogen end-blocking.It,, as producing organic-silicon-modified block or the crucial starting raw material of graft copolymer and important silicone intermediate, is subject to the attention of each large organosilicon company of the world and research institution, always many about its research report.Utilize the Si-H key on its end group, by hydrosilation reaction, can on the polysiloxane molecule chain, introduce various organic groups; So hydrogen containing siloxane is at plastics, resin modified, in silicon oil modified, the linking agent of liquid silastic, extraordinary organic silicon surfactant and branch-shape polymer synthetic, important purposes is arranged.
Therefore vibrin that can terminal hydroxy group and carry out esterification synthesis of vinyl macromole with the vinyl monomer of carboxyl, or with the vibrin of end carboxyl and hydroxyl vinyl monomer esterification synthesis of vinyl macromole; Then carry out the addition of silicon hydrogen under certain condition with hydrogen containing siloxane, reaction obtains polyester-polysiloxane.The silicone-modified unsaturated polyester resin made can be dissolved in the unsaturated polyester resin system.Can reduce the volatility of unsaturated polyester resin solvent, and the thermotolerance of final curing system, anti-low temperature viscosity, low electric conductivity and surface property are improved.
Summary of the invention
The purpose of this invention is to provide the method for utilizing the polyester-polysiloxane modified unsaturated polyester resin.
The method of polyester-polysiloxane modified unsaturated polyester resin, according to following step, carry out:
(1) preparation of the vibrin prepolymer of end of tape group:
Diprotic acid and dibasic alcohol are adopted to melt-polycondensation under the effect of catalyzer, dibasic alcohol and diprotic acid direct melt polycondensation, logical nitrogen 180-250 ℃ condensation polymerization 3 hours, use vacuum hydro-extraction when later stage viscosity increases, and treats that acid number is cooling standby to 20-60mgKOH/g;
(2) synthetic with the esterification of the polyester macromolecule of vinyl groups:
End of tape hydroxyl prepared by step (1) or the polyester prepolyer of carboxyl add the equimolar vinyl carboxylic acid of appropriate solvent, catalyzer, stopper and polyester prepolyer or vinyl alcohol esterification monomer, carry out esterification at the temperature of 100-250 ℃, the synthesis of vinyl polyester macromolecule.
(3) preparation of polyester-polysiloxane:
Hydrogeneous based polysiloxane, vinyl polyester macromolecule, solvent and catalyzer. pass into nitrogen, stir, be warming up to 150-220 ℃ of temperature, reaction certain hour 5-10 hour, obtain the water white transparency viscous liquid. carry out underpressure distillation at the temperature of 55-80 ℃, steam solvent and finally prepare polyester-polysiloxane;
(4) polyester-polysiloxane modified unsaturated polyester resin:
To prepare polyester-polysiloxane and add in unsaturated polyester resin, obtain the unsaturated polyester resin of modification.
Wherein the described diprotic acid of step (1) is compound or the polymkeric substance that terephthalic acid, m-phthalic acid, FUMARIC ACID TECH GRADE, oxalic acid, propanedioic acid, succinic acid, hexanodioic acid or sebacic acid etc. contain two carboxyls or acid anhydrides; Wherein said diprotic acid or replace with acid anhydrides, described acid anhydrides is Tetra hydro Phthalic anhydride, MALEIC ANHYDRIDE;
Described dibasic alcohol is organic compound or polymkeric substance that contains two hydroxyls such as ethylene glycol, propylene glycol, butyleneglycol;
Described catalyzer is organotin, as dibutyltin dilaurate, stannous octoate, two (dodecyl sulphur) dibutyl tin, dibutyltin diacetate etc.;
Described diprotic acid: dibasic alcohol: the mol ratio of catalyzer is 1:1.01-1.10:0.001-0.05 or is 1:0.90-1.00:0.001-0.05.
The vinyl alcohol described in step (2) wherein
The esterification monomerFor the hydroxyl vinyl compound of simple function group, as 2-vinyl-4-hydroxyl quinazoline, alpha-brominated isopropylformic acid hydroxy butyl ester, 4-hydroxybutyl vinyl ether etc.; Or the carboxy vinyl compound is as vinylformic acid, methacrylic acid etc.; Solvent is toluene, dimethylbenzene, tetrahydrofuran (THF), benzene etc.; Catalyzer is the vitriol oil, concentrated hydrochloric acid, p-methyl benzenesulfonic acid, sulfur oxychloride etc.; Stopper is Resorcinol, para benzoquinone, phenothiazine, beta-phenyl naphthylamines, p-ten.-butylcatechol, methylene blue, 1, the bitter hydrazine of 1-phenylbenzene-2-etc.; Polyester prepolyer: vinyl carboxylic acid or vinyl alcohol: solvent: stopper: the mol ratio of catalyzer is 1:1:0-1:0.001-0.010:0.001-0.10.
Wherein in step (3), solvent is dimethylbenzene, toluene, ethylbenzene etc.; Hydrogen containing siloxane is hydrogen-containing siloxane (comprising single-ended hydrogen radical siloxane, both-end hydrogen radical siloxane), containing hydrogen silicone oil (comprising single-ended hydrogen base silicone oil, both-end hydrogen base silicone oil) etc.; Solvent is dimethylbenzene, toluene, ethylbenzene etc.; Catalyzer is H
2PtCl
66H
2O, (phCN)
2PdCl
2, (Ph
3P)
4Pd, (Ph
3P)
3RhCl, (Ph
3P)
2CORhCl, Co
2(CO)
8, Ni (CO)
4, Cr (CO)
6, (Ph are phenyl) such as Pd/C, Pt.Catalyzer solvent commonly used is Virahol, tetrahydrofuran (THF), pimelinketone, glycol dimethyl ether and dimethyl phthalate etc.; Hydrogeneous based polysiloxane: vinyl polyester macromolecule: solvent: the mol ratio of catalyzer is 1:1-5:0-2:0.001 ‰-1 ‰.
Wherein the middle polyester-polysiloxane addition of step (4) is generally the 1-5% of modified unsaturated polyester resin amount
The invention has the advantages that 1: the method with vibrin alcohol or excessive acid prepares the unsaturated polyester resin that contains functional group; 2: adopt with alcohol or the acid of vinyl and carry out unsaturated polyester resin envelope base prepared by (1), the polyester macromolecule that preparation contains vinyl group; 3: adopt the method for hydrogeneous radical siloxane and the addition of vinyl polyester macromolecule silicon hydrogen to synthesize polyester-modified polysiloxanes.4: due to the polyester-modified polysiloxanes that has added high thermal stability, high unreactiveness and low surface energy, reduced the volatility of unsaturated polyester resin solvent, enabling environment protection and protection workmen's health; 5: polyester-modified polysiloxanes has unique surface property after unsaturated polyester resin is solidified, and meets the Special use occasions such as service requirements high temperature resistance, anti-low temperature viscosity and surperficial low electric conductivity.
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 the vibrin prepolymer of terminal hydroxyl
Propylene glycol, 180g; Phthalate anhydride 296g; Antimonous oxide 0.3g, logical 180 ℃ of condensation polymerizations of nitrogen 3 hours, use vacuum hydro-extraction when later stage viscosity increases, and treats that acid number is cooling standby to 20mgKOH/g.
2, the polyester macromolecule of vinyl groups is synthetic
The preparation of vinyl polyester macromolecule adds vibrin prepolymer 100g, vinylformic acid 10g, Resorcinol (stopper) 0.2g, the zeolite 10g of end of tape hydroxyl in the 250mL there-necked flask of water trap and reflux exchanger is housed, toluene 50g, p-methyl benzenesulfonic acid (catalyzer) 1g, stirring is warming up to catalyzer and dissolves fully, regularly measure esterification yield, stop heating when almost constant to esterification yield, go out the vinyl polyester macromolecule with rotary film evaporator rectifying after being cooled to 70 ℃.
3, the preparation of polyester-polysiloxane
In the dry there-necked flask of being furnished with agitator, spherical condensation tube, nitrogen airway, add the tetrahydrofuran solution (1 ‰ volumetric molar concentration) of hydrogen containing siloxane 100g, vinyl polyester macromolecule 150g, solvent toluene 200g and 0.02g Platinic chloride to pass into nitrogen, stir, be warming up to 190 ℃ of temperature of temperature, 10 hours reaction times, obtain the water white transparency viscous liquid. carry out underpressure distillation under 55 ℃, steam solvent toluene.Obtain polyester-polysiloxane.
4, polyester-polysiloxane modified unsaturated polyester resin
The polyester-polysiloxane that unsaturated polyester resin 100g is added to 3g, at 50 ℃ of temperature, low rate mixing mixes, and prepares modified unsaturated polyester resin.
Embodiment 2
Polymerization procedure is as follows:
1, the preparation of the vibrin prepolymer of terminal carboxyl(group)
Propylene glycol, 160g; Phthalate anhydride 320g; Antimony glycol 0.3g, logical 180 ℃ of condensation polymerizations of nitrogen 3 hours, use vacuum hydro-extraction when later stage viscosity increases, and treats that acid number is cooling standby to 80mgKOH/g.
2, the polyester macromolecule of vinyl groups is synthetic
The preparation of vinyl polyester macromolecule adds vibrin prepolymer 100g, 2-vinyl-4-hydroxyl quinazoline 10g, Resorcinol (stopper) 0.2g, the zeolite 10g of end of tape carboxyl in the 250mL there-necked flask of water trap and reflux exchanger is housed, toluene 50g, p-methyl benzenesulfonic acid (catalyzer) 1g, stirring is warming up to catalyzer and dissolves fully, regularly measure esterification yield, stop heating when almost constant to esterification yield, go out the vinyl polyester macromolecule with rotary film evaporator rectifying after being cooled to 70 ℃.
3, the preparation of polyester-polysiloxane
In the dry there-necked flask of being furnished with agitator, spherical condensation tube, nitrogen airway, add the pimelinketone solution (1 ‰ volumetric molar concentration) of containing hydrogen silicone oil 100g, vinyl polyester macromolecule 150g, solvent toluene 150g and 0.02g Platinic chloride to pass into nitrogen, stir, be warming up to 180 ℃ of temperature of temperature, 10 hours reaction times, obtain the water white transparency viscous liquid. carry out underpressure distillation under 55 ℃, steam solvent toluene.Obtain polyester-polysiloxane.
4, polyester-polysiloxane modified unsaturated polyester resin
The polyester-polysiloxane that unsaturated polyester resin 100g is added to 5g, at 50 ℃ of temperature, low rate mixing mixes, and prepares modified unsaturated polyester resin.
Embodiment 3
Polymerization procedure is as follows:
1, the preparation of the vibrin prepolymer of terminal hydroxyl
Propylene glycol, 180g; Phthalate anhydride 260g; Antimony glycol 0.3g, logical 180 ℃ of condensation polymerizations of nitrogen 3 hours, use vacuum hydro-extraction when later stage viscosity increases, and treats that acid number is cooling standby to 10mgKOH/g.
2, the polyester macromolecule of vinyl groups is synthetic
The preparation of vinyl polyester macromolecule adds vibrin prepolymer 100g, methacrylic acid 10g, Resorcinol (stopper) 0.2g, the zeolite 10g of end of tape carboxyl in the 250mL there-necked flask of water trap and reflux exchanger is housed, toluene 50g, p-methyl benzenesulfonic acid (catalyzer) 1g, stirring is warming up to catalyzer and dissolves fully, regularly measure esterification yield, stop heating when almost constant to esterification yield, go out the vinyl polyester macromolecule with rotary film evaporator rectifying after being cooled to 70 ℃.
3, the preparation of polyester-polysiloxane
(phCN) that adds containing hydrogen silicone oil 100g, vinyl polyester macromolecule 120g, solvent toluene 200g and 0.02g in the dry there-necked flask of being furnished with agitator, spherical condensation tube, nitrogen airway
2PdCl
2The aqueous isopropanol of (catalyzer) (1 ‰ volumetric molar concentration). pass into nitrogen, stir, be warming up to 200 ℃ of temperature of temperature, 9 hours reaction times, obtain the water white transparency viscous liquid, carry out underpressure distillation under 55 ℃, steam solvent toluene.Obtain polyester-polysiloxane.
4, polyester-polysiloxane modified unsaturated polyester resin
The polyester-polysiloxane that unsaturated polyester resin 100g is added to 3g, at 50 ℃ of temperature, low rate mixing mixes, and prepares modified unsaturated polyester resin.
Embodiment 4
Polymerization procedure is as follows:
1, the preparation of the vibrin prepolymer of terminal carboxyl(group)
Propylene glycol, 160g; Phthalate anhydride 310g; Antimonous oxide 0.3g, logical 180 ℃ of condensation polymerizations of nitrogen 3 hours, use vacuum hydro-extraction when later stage viscosity increases, and treats that acid number is cooling standby to 60mgKOH/g.
2, the polyester macromolecule of vinyl groups is synthetic
The preparation of vinyl polyester macromolecule adds vibrin prepolymer 100g, 4-hydroxybutyl vinyl ether 10g, Resorcinol (stopper) 0.2g, the zeolite 10g of end of tape carboxyl in the 250mL there-necked flask of water trap and reflux exchanger is housed, toluene 50g, p-methyl benzenesulfonic acid (catalyzer) 1g, stirring is warming up to catalyzer and dissolves fully, regularly measure esterification yield, stop heating when almost constant to esterification yield, go out the vinyl polyester macromolecule with rotary film evaporator rectifying after being cooled to 70 ℃.
3, the preparation of polyester-polysiloxane
(the Ph that adds containing hydrogen silicone oil 100g, vinyl polyester macromolecule 120g, solvent toluene 200g and 0.02g in the dry there-necked flask of being furnished with agitator, spherical condensation tube, nitrogen airway
3P)
2The ethylene glycol dimethyl ether solution of CORhCl (catalyzer) (1 ‰ volumetric molar concentration). pass into nitrogen, stir, be warming up to 200 ℃ of temperature of temperature, 8 hours reaction times, obtain the water white transparency viscous liquid, carry out underpressure distillation under 55 ℃, steam solvent toluene.Obtain polyester-polysiloxane.
4, polyester-polysiloxane modified unsaturated polyester resin
The polyester-polysiloxane that unsaturated polyester resin 100g is added to 5g, at 50 ℃ of temperature, low rate mixing mixes, and prepares modified unsaturated polyester resin.
Claims (5)
1. the method for polyester-polysiloxane modified unsaturated polyester resin is characterized in that carrying out according to following step:
(1) preparation of the vibrin prepolymer of end of tape group:
Diprotic acid and dibasic alcohol are adopted to melt-polycondensation under the effect of catalyzer, and dibasic alcohol and diprotic acid direct melt polycondensation, logical nitrogen 180-250 ℃ condensation polymerization 3 hours, treat that acid number is cooling standby to 20-60mgKOH/g;
(2) synthetic with the esterification of the polyester macromolecule of vinyl groups:
End of tape hydroxyl prepared by step (1) or the polyester prepolyer of carboxyl add the equimolar vinyl carboxylic acid of appropriate solvent, catalyzer, stopper and polyester prepolyer or vinyl alcohol
The esterification monomer, carry out esterification at the temperature of 100-250 ℃, the synthesis of vinyl polyester macromolecule;
(3) preparation of polyester-polysiloxane:
Hydrogeneous based polysiloxane, vinyl polyester macromolecule, solvent and catalyzer. pass into nitrogen, stir, be warming up to 150-220 ℃ of temperature, reaction certain hour 5-10 hour, obtain the water white transparency viscous liquid; Carry out underpressure distillation at the temperature of 55-80 ℃, steam solvent and finally prepare polyester-polysiloxane;
(4) polyester-polysiloxane modified unsaturated polyester resin:
To prepare polyester-polysiloxane and add in unsaturated polyester resin, obtain the unsaturated polyester resin of modification.
2. the method for polyester-polysiloxane modified unsaturated polyester resin according to claim 1, is characterized in that wherein the described diprotic acid of step (1) is terephthalic acid, m-phthalic acid, FUMARIC ACID TECH GRADE, oxalic acid, propanedioic acid, succinic acid, hexanodioic acid or sebacic acid; Wherein said diprotic acid or replace with acid anhydrides, described acid anhydrides is Tetra hydro Phthalic anhydride, MALEIC ANHYDRIDE;
Described dibasic alcohol is ethylene glycol, propylene glycol, butyleneglycol;
Described catalyzer is organotin, as dibutyltin dilaurate, stannous octoate, two (dodecyl sulphur) dibutyl tin, dibutyltin diacetate;
Described diprotic acid: dibasic alcohol: the mol ratio of catalyzer is 1:1.01-1.10:0.001-0.05 or is 1:0.90-1.00:0.001-0.05.
3. the method for polyester-polysiloxane modified unsaturated polyester resin according to claim 1, it is characterized in that the hydroxyl vinyl compound that wherein the vinyl alcohol esterification monomer described in step (2) is simple function group, as 2-vinyl-4-hydroxyl quinazoline, alpha-brominated isopropylformic acid hydroxy butyl ester, 4-hydroxybutyl vinyl ether etc.; Or the carboxy vinyl compound is as vinylformic acid, methacrylic acid etc.; Solvent is toluene, dimethylbenzene, tetrahydrofuran (THF), benzene; Catalyzer is the vitriol oil, concentrated hydrochloric acid, p-methyl benzenesulfonic acid, sulfur oxychloride; Stopper is Resorcinol, para benzoquinone, phenothiazine, beta-phenyl naphthylamines, p-ten.-butylcatechol, methylene blue, 1, the bitter hydrazine of 1-phenylbenzene-2-; Polyester prepolyer: vinyl carboxylic acid or vinyl alcohol: solvent: stopper: the mol ratio of catalyzer is 1:1:0-1:0.001-0.010:0.001-0.10.
4. the method for polyester-polysiloxane modified unsaturated polyester resin according to claim 1, is characterized in that wherein the middle solvent of step (3) is dimethylbenzene, toluene, ethylbenzene; Hydrogen containing siloxane is single-ended hydrogen radical siloxane, both-end hydrogen radical siloxane, single-ended hydrogen base silicone oil, both-end hydrogen base silicone oil; Solvent is dimethylbenzene, toluene, ethylbenzene; Catalyzer is H
2PtCl
66H
2O, (phCN)
2PdCl
2, (Ph
3P)
4Pd, (Ph
3P)
3RhCl, (Ph
3P)
2CORhCl, Co
2(CO)
8, Ni (CO)
4, Cr (CO)
6, Pd/C, Pt, wherein Ph is phenyl; The catalyzer solvent is Virahol, tetrahydrofuran (THF), pimelinketone, glycol dimethyl ether or dimethyl phthalate; Hydrogeneous based polysiloxane: vinyl polyester macromolecule: solvent: the mol ratio of catalyzer is 1:1-5:0-2:0.001 ‰-1 ‰.
5. the method for polyester-polysiloxane modified unsaturated polyester resin according to claim 1, is characterized in that polyester-polysiloxane addition in step (4) wherein is generally the 1-5% of modified unsaturated polyester resin amount.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105622910A (en) * | 2016-03-04 | 2016-06-01 | 肇庆福田化学工业有限公司 | Organic silicon-modified high-pollution resistance unsaturated polyester resin and synthesizing method thereof |
| CN107090084A (en) * | 2017-04-21 | 2017-08-25 | 苏州博纳化学科技有限公司 | Defoamer of polyethers scion grafting polysiloxanes and preparation method thereof |
| CN112812543A (en) * | 2021-01-21 | 2021-05-18 | 成都思立可科技有限公司 | Compatibilization method of silicon-based thermoplastic elastomer and silicon-based thermoplastic elastomer obtained by compatibilization method |
| CN113788949A (en) * | 2021-09-16 | 2021-12-14 | 北京化工大学 | Preparation method of polyester plasticizer, product and application thereof |
| CN115651178A (en) * | 2022-09-29 | 2023-01-31 | 新丰见微化工实业有限公司 | Synthesis method of polyester with siloxane side group |
| CN116535760A (en) * | 2023-04-20 | 2023-08-04 | 浙江保禄包装科技股份有限公司 | Aluminum-free composite material for pesticide packaging and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105622910A (en) * | 2016-03-04 | 2016-06-01 | 肇庆福田化学工业有限公司 | Organic silicon-modified high-pollution resistance unsaturated polyester resin and synthesizing method thereof |
| CN105622910B (en) * | 2016-03-04 | 2018-07-10 | 肇庆福田化学工业有限公司 | Organic-silicon-modified high-dirt-resistance unsaturated polyester resin and its synthetic method |
| CN107090084A (en) * | 2017-04-21 | 2017-08-25 | 苏州博纳化学科技有限公司 | Defoamer of polyethers scion grafting polysiloxanes and preparation method thereof |
| CN112812543A (en) * | 2021-01-21 | 2021-05-18 | 成都思立可科技有限公司 | Compatibilization method of silicon-based thermoplastic elastomer and silicon-based thermoplastic elastomer obtained by compatibilization method |
| CN112812543B (en) * | 2021-01-21 | 2022-09-20 | 成都思立可科技有限公司 | Compatibilization method of silicon-based thermoplastic elastomer and silicon-based thermoplastic elastomer obtained by compatibilization method |
| CN113788949A (en) * | 2021-09-16 | 2021-12-14 | 北京化工大学 | Preparation method of polyester plasticizer, product and application thereof |
| CN115651178A (en) * | 2022-09-29 | 2023-01-31 | 新丰见微化工实业有限公司 | Synthesis method of polyester with siloxane side group |
| CN115651178B (en) * | 2022-09-29 | 2024-02-20 | 新丰见微化工实业有限公司 | Synthesis method of polyester with siloxane side group |
| CN116535760A (en) * | 2023-04-20 | 2023-08-04 | 浙江保禄包装科技股份有限公司 | Aluminum-free composite material for pesticide packaging and preparation method thereof |
| CN116535760B (en) * | 2023-04-20 | 2023-12-12 | 浙江保禄包装科技股份有限公司 | Aluminum-free composite material for pesticide packaging and preparation method thereof |
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