CN102977350B - Preparation method of modified carboxyl-terminated hyperbranched polyester resin and coating containing resin - Google Patents
- ️Wed Aug 27 2014
Detailed Description
The following are non-limiting examples of the technical solutions of the present invention.
Example 1:
1) preparation of modified carboxyl-terminated hyperbranched polyester resin
a) Consists of the following components:
a dihydric alcohol: neopentyl glycol 104g (1 mol);
tribasic acid: 1,3, 5-benzenetricarboxylic acid 210g (1 mmol)
Silanol: KR220L 5.2.2 g from Xin Yuan company
Xylene: 2.08g
Silicone oligomer: CRS 150156 g
Epoxy resin: 10g of dicyclopentadiene dioxide;
crosslinking catalyst: 1.04g of tetrabutyl titanate;
organic solvent: 300g of propylene glycol methyl ether acetate;
b) the synthesis steps are as follows:
uniformly mixing dihydric alcohol and tribasic acid, heating to 70 ℃, and adding silanol and xylene; heating at 180 deg.C for 1h, heating to 240 deg.C, and heating for 1 h; cooling to 90 ℃, and adding an organic solvent, an organic silicon oligomer, epoxy resin and a crosslinking catalyst which are 1.0 time of the weight of the trihydric alcohol; heating to 110 ℃, and heating for 2 h; cooling to 90 deg.C, and adding the rest organic solvent.
c) Modified carboxyl-terminated hyperbranched polyester resin performance
Comprehensive performance of modified carboxyl-terminated hyperbranched polyester resin
Solvent resistance 1: at 25 ℃, the wipe was rubbed back and forth 100 times with butanone.
Heat resistance: baking the test piece at 180 ℃ for 2h, putting the test piece into a constant temperature box type electric furnace checked by a potential difference meter, raising the temperature by 5 ℃/min, beginning timing along with the temperature of the furnace to the temperature required by the experiment, taking out the test piece after the test piece is continuously heated to room temperature (25 ℃), and observing the surface condition of the coating by using a magnifying glass, wherein if the test piece has no cracking or falling phenomena, the heat resistance of the coating is proved to be good.
2) Coating material
a) Composition of
Modified carboxyl-terminated hyperbranched polyester resin: 100g of the modified carboxyl-terminated hyperbranched polyester resin prepared in the above way;
filling: 40g of titanium dioxide;
organosilicon auxiliary agent: silicone oil/350cst 8g；
High boiling point solvent: dibasic ester mixture (DBE) 5 g.
b) Preparation process
Uniformly mixing the filler, the modified carboxyl-terminated hyperbranched polyester resin, the organic silicon assistant and the high-boiling-point solvent, and adding the mixture into a grinding machine to grind the mixture to the required particle size to obtain the modified carboxyl-terminated hyperbranched polyester resin.
c) Performance of
Performance index of paint
Example 2:
1) preparation of modified carboxyl-terminated hyperbranched polyester resin
a) Consists of the following components:
a dihydric alcohol: neopentyl glycol 62.4g (0.6 mol); 36g (0.4 mol) of 2-methyl-1, 3-propanediol;
tribasic acid: 210g (1.0 mol) of 1,2, 4-benzenetricarboxylic acid, 105g (0.5 mol) of 1,3, 5-benzenetricarboxylic acid silanol: heptapoly (cyclopentyl) silsesquioxane trisilicol 4.84g, heptaisobutylsilsesquioxane trisilicol 5.0g xylene: 9.84g
Silicone oligomer: CRF 150100 g CRF KR21247.6g from shin-Etsu Co
Epoxy resin: trimethylolpropane glycidyl ether 49.2 g;
crosslinking catalyst: tetrabutyl titanate 4.9g
Organic solvent: propylene glycol methyl ether acetate 147g butanol 23g
b) The synthesis steps are as follows:
uniformly mixing dihydric alcohol and tribasic acid, heating to 90 ℃, and adding silanol and xylene; heating at 200 deg.C for 3 hr, heating to 220 deg.C, and heating for 2 hr; cooling to 90 ℃, and adding propylene glycol methyl ether acetate, organic silicon oligomer, epoxy resin and a crosslinking catalyst; heating to 115 deg.C for 3 h; the temperature is reduced to 90 ℃, and finally butanol is added.
c) Modified carboxyl-terminated hyperbranched polyester resin performance
Comprehensive performance of modified carboxyl-terminated hyperbranched polyester resin
2) Coating material
a) Composition of
Modified carboxyl-terminated hyperbranched polyester resin: 160g of modified carboxyl-terminated hyperbranched polyester resin prepared in the step 1;
filling: titanium dioxide 20g, silicon dioxide 8g
Organosilicon auxiliary agent: silicone oil/350cst 1g。
High boiling point solvent: dibasic ester mixture (DBE) 5 g; ethylene glycol ethyl ether acetate (CAC): 5g of the total weight.
b) Preparation process
Uniformly mixing the filler, the modified carboxyl-terminated hyperbranched polyester resin, the high-boiling-point solvent and the auxiliary agent, and adding the mixture into a grinding machine to grind the mixture to the required particle size to obtain the modified carboxyl-terminated hyperbranched polyester resin.
c) Performance of
Performance index of paint
Example 3:
1) preparation of hydroxy silicone oil
a) Formulation of
Octamethylcyclotetrasiloxane: 200g
Tetramethyl ammonium hydroxide: 0.02g
Water: 7.4g
DMF：60g
b) Preparation process
Adding octamethylcyclotetrasiloxane, tetramethylammonium hydroxide and DMF (dimethyl formamide) in a reactor provided with a condenser tube, a thermometer, a dropping funnel and a stirrer in sequence according to a ratio, starting stirring and heating up, heating up to 90 ℃, keeping the temperature constant, dropwise adding distilled water under stirring, after dropwise adding, reacting at constant temperature for 9.5 hours, heating up to 150 ℃, reacting for 1 hour, cooling to 80 ℃, starting reduced pressure distillation, controlling the pressure at 0.06MPa, evaporating off small molecules generated in the reaction process, cooling to room temperature, and adjusting the solid content to 60% to obtain 157g of hydroxyl silicone oil.
c) Performance of
The weight average molecular weight of the hydroxyl silicone oil is detected by adopting gel permeation chromatography, and the result is 504; the hydroxyl content of the hydroxyl silicone oil was measured by an acetic anhydride method, and found to be 8.2 w%.
2) Preparation of Silicone oligomers
a) Composition of
Monomethyltrimethoxysilane: 42.0g (0.28 mol)
Dimethyl dimethoxy silane: 18.7g (0.14 mol)
Mono-phenyltrimethoxysilane: 123.0g (0.58 mol),
b) preparation process
Siloxane and 4.5mmol of hydrochloric acid are sequentially added into a reactor provided with a condenser tube, a thermometer, a dropping funnel and a stirrer according to the proportion, stirring and heating are started, the temperature is kept constant after the temperature is raised to 60 ℃, 31.7g of distilled water is dropwise added under stirring, after the dropwise addition is finished, constant temperature reaction is carried out for 3 hours, reduced pressure distillation is started, the pressure is controlled to be 0.06MPa, small molecules generated in the reaction process are evaporated, the temperature is cooled to room temperature, the solid content is adjusted to be 60%, and 290g of organic silicon oligomer is obtained.
c) Performance of
The weight average molecular weight of the organic silicon oligomer is detected by adopting gel permeation chromatography, and the result is 802; the hydroxyl content of the organic silicon oligomer is measured by an acetic anhydride method, and the result is 10.6 w%; the methoxy content of the organosilicon oligomer is determined by an acetyl perchlorate method, and the result is 7.4 w%; R/Si = 1.14; ph/Me = 1.04.
3) Preparation of modified carboxyl-terminated hyperbranched polyester resin
a) Consists of the following components:
a dihydric alcohol: neopentyl glycol 52g (0.5 mol); 27g (0.3 mol) of 2-methyl-1, 3-propanediol and 23.2 (0.2 mol) of 1, 4-cyclohexanediol
Silanol: 5g of hydroxy silicone oil prepared in step 1 and 3.2g of heptaphenyl silsesquioxane trisilicol
Tribasic acid: 252g (1.2 mmol) of 1,2, 4-benzenetricarboxylic acid
Xylene: 7.3g
Silicone oligomer: 120g of the silicone oligomer prepared in step 2, 24987.4 g of Dow Corning Co
Epoxy resin: 4g of bis ((3, 4-epoxycyclohexyl) methyl) adipate; 8g of bisphenol S epoxy resin;
crosslinking catalyst: 2.9g of tetraisobutyl titanate and 2.0g of tetrabutyl titanate
Organic solvent: dipropylene glycol methyl ether acetate 158g, dipropylene glycol butyl ether acetate 90g
b) The synthesis steps are as follows:
uniformly mixing dihydric alcohol and tribasic acid, heating to 85 ℃, and adding silanol and xylene; heating at 210 deg.C for 2.5h, heating to 235 deg.C, and heating for 3 h; cooling to 90 ℃, and adding dipropylene glycol methyl ether acetate, organic silicon oligomer, epoxy resin and a crosslinking catalyst; heating to 120 deg.C for 2.5 h; cooling to 90 deg.C, and adding dipropylene glycol butyl ether acetate.
c) Modified carboxyl-terminated hyperbranched polyester resin performance
Comprehensive performance of modified carboxyl-terminated hyperbranched polyester resin
4) Coating material
a) Composition of
Modified carboxyl-terminated hyperbranched polyester resin: 100g of modified carboxyl-terminated hyperbranched polyester resin prepared in the step 3;
filling: 20g of silicon dioxide; titanium dioxide 10g, silicon carbide 10g
Organosilicon auxiliary agent: CoatOSil 70014 g; silicone oil/350cst 6g；
High boiling point solvent: 5g of diethylene glycol butyl ether acetate; and 5g of butyl acetate.
b) Preparation process
Uniformly mixing the filler, the modified carboxyl-terminated hyperbranched polyester resin, the organic silicon assistant and the high-boiling-point solvent, and adding the mixture into a grinding machine to grind the mixture to the required particle size to obtain the modified carboxyl-terminated hyperbranched polyester resin.
c) Coating performance
Performance index of paint
Example 4:
1) preparation of modified carboxyl-terminated hyperbranched polyester resin
a) Consists of the following components:
a dihydric alcohol: 2-methyl-1, 3-propanediol 63g (0.7 mol), 1, 4-cyclohexanediol 81.2g (0.3 mol)
Silanol: heptapoly (cyclopentyl) silsesquioxane trissilanol 10g
Tribasic acid: 252g (1.2 mmol) of 1,2, 4-benzenetricarboxylic acid
Xylene: 5.76g
Silicone oligomer: 307450g from Dow Corning, 303750g from Dow Corning, KR921860g from Xinyue, KR21740g from Xinyue
Epoxy resin: bis ((3, 4-epoxycyclohexyl) methyl) adipate 9 g; 12g of 3, 4-epoxidized 3 ', 4 ' -epoxidized cyclohexanemethyl 3,4 ' -cyclohexanecarboxylate; dicyclopentadiene dioxide 22 g;
crosslinking catalyst: tetrabutyl titanate 4.32g
Organic solvent: 72.8g of propylene glycol methyl ether acetate, 100g of butanol, 30g of dipropylene glycol methyl ether acetate and 20g of dipropylene glycol butyl ether acetate
b) The synthesis steps are as follows:
uniformly mixing dihydric alcohol and tribasic acid, heating to 80 ℃, and adding silanol and xylene; heating at 220 deg.C for 2.5h, heating to 230 deg.C, and heating for 2.5 h; cooling to 90 ℃, and adding propylene glycol methyl ether acetate, butanol, organic silicon oligomer, epoxy resin and a crosslinking catalyst; heating to 110 deg.C for 3 h; cooling to 70 deg.C, and adding dipropylene glycol methyl ether acetate and dipropylene glycol butyl ether acetate.
c) Modified carboxyl-terminated hyperbranched polyester resin performance
Comprehensive performance of modified carboxyl-terminated hyperbranched polyester resin
2) Coating material
a) Composition of
Modified carboxyl-terminated hyperbranched polyester resin: 120g of modified carboxyl-terminated hyperbranched polyester resin prepared in the step 1;
filling: 10g of silicon carbide; 10g of silicon dioxide;
organosilicon auxiliary agent: CoatOSil 35004 g; silicone oil/350cst 4g；
High boiling point solvent: 10g of 3-Ethyl Ether Propionate (EEP); dibasic ester mixture (DBE) 10 g.
b) Preparation process
Uniformly mixing the filler, the modified carboxyl-terminated hyperbranched polyester resin, the organic silicon assistant and the high-boiling-point solvent, and adding the mixture into a grinding machine to grind the mixture to the required particle size to obtain the modified carboxyl-terminated hyperbranched polyester resin.
c) Performance of
Performance index of paint
Example 5
1) Preparation of hydroxy silicone oil
a) Formulation of
Octamethylcyclotetrasiloxane: 200g
Tetramethyl ammonium hydroxide: 0.02g
Water: 3.6g
DMF：50g
b) Preparation process
Adding octamethylcyclotetrasiloxane, tetramethylammonium hydroxide and DMF (dimethyl formamide) in a reactor provided with a condenser tube, a thermometer, a dropping funnel and a stirrer in sequence according to a ratio, starting stirring and heating up, heating up to 80 ℃, keeping the temperature constant, dropwise adding distilled water under stirring, after dropwise adding, reacting at constant temperature for 8 hours, heating up to 150 ℃ for reacting for 1 hour, cooling to 80 ℃, starting reduced pressure distillation, controlling the pressure to be 0.06MPa, evaporating off small molecules generated in the reaction process, and cooling to room temperature to obtain 176g of hydroxyl silicone oil.
c) Performance of
The weight average molecular weight of the hydroxyl silicone oil is detected by adopting gel permeation chromatography, and the result is 1103; the hydroxyl content of the hydroxyl silicone oil was measured by an acetic anhydride method, and was 2.9 w%.
2) Preparation of modified carboxyl-terminated hyperbranched polyester resin
a) Consists of the following components:
a dihydric alcohol: neopentyl glycol 83.2g (0.8 mol); 2-methyl-1, 3-propanediol 18g (0.2 mol)
Silanol: 4g of hydroxy silicone oil prepared in step 1
Tribasic acid: 231g (1.1 mmol) of 1,3, 5-benzenetricarboxylic acid
Xylene: 7g of
Silicone oligomer: 23321.3 g of Dow Corning, 24920 g of Dow Corning, Z-610820g of Dow Corning, IC 83620 g of Wake, KR 21310 g of Xinyue, KR 921820 g of Xinyue, KR 21720 g of Xinyue
Epoxy resin: 14g of bis (2, 3-epoxycyclopentyl) ether; 12g of 3, 4-epoxidized 3 ', 4 ' -epoxidized cyclohexanemethyl 3,4 ' -cyclohexanecarboxylate;
crosslinking catalyst: tetrabutyl titanate 3.1g
Organic solvent: propylene glycol methyl ether acetate 151g, butanol 34g
b) The synthesis steps are as follows:
uniformly mixing dihydric alcohol and tribasic acid, heating to 80 ℃, and adding silanol and xylene; heating at 190 deg.C for 3h, heating to 220 deg.C, and heating for 2 h; cooling to 90 ℃, and adding propylene glycol methyl ether acetate, organic silicon oligomer, epoxy resin and a crosslinking catalyst; heating to 115 deg.C for 3 h; the temperature is reduced to 90 ℃, and finally butanol is added.
c) Modified carboxyl-terminated hyperbranched polyester resin performance
Comprehensive performance of modified carboxyl-terminated hyperbranched polyester resin
3) Coating material
a) Composition of
Modified carboxyl-terminated hyperbranched polyester resin: 140g of modified carboxyl-terminated hyperbranched polyester resin prepared in the step 2;
filling: 25g of silicon dioxide; 10g of titanium dioxide;
pigment: 10g of carbon black;
organosilicon auxiliary agent: CoatOSil 35004 g; 76502g CoatOSil;
high boiling point solvent: 2g of methyl isoamyl ketone (MIAK); isobutyl isobutyrate 4 g.
b) Preparation process
The pigment, the filler, the modified carboxyl-terminated hyperbranched polyester resin, the organic silicon assistant and the high-boiling point solvent are uniformly mixed and added into a grinding machine to be ground to the required particle size, and the modified carboxyl-terminated hyperbranched polyester resin is obtained.
c) Performance of
Performance index of paint
Example 6
1) Preparation of hydroxy silicone oil
a) Formulation of
Octamethylcyclotetrasiloxane: 200g
Tetramethyl ammonium hydroxide: 0.02g
Water: 4g
DMF：60g
b) Preparation process
Adding octamethylcyclotetrasiloxane, tetramethylammonium hydroxide and DMF (dimethyl formamide) in a reactor provided with a condenser tube, a thermometer, a dropping funnel and a stirrer in sequence according to a ratio, starting stirring and heating up, heating to 85 ℃, keeping the temperature constant, dropwise adding distilled water under stirring, after dropwise adding, reacting at constant temperature for 10h, heating to 150 ℃ for reacting for 1h, cooling to 80 ℃, starting reduced pressure distillation, controlling the pressure to be 0.06MPa, evaporating off small molecules generated in the reaction process, and cooling to room temperature to obtain 143g of hydroxyl silicone oil.
c) Performance of
The weight average molecular weight of the hydroxyl silicone oil is detected by adopting a gel permeation chromatography, and the result is 997; the hydroxyl content of the hydroxyl silicone oil was measured by an acetic anhydride method, and the result was 3.02 w%.
2) Preparation of modified carboxyl-terminated hyperbranched polyester resin
a) Consists of the following components:
a dihydric alcohol: neopentyl glycol 104g (1.0 mol);
silanol: 3.36g of hydroxy silicone oil prepared in step 1, KR220L 6g of Xinyue company
Tribasic acid: 252g (1.2 mol) of 1,2, 4-benzenetricarboxylic acid
Xylene: 4.12g
Silicone oligomer: CRS 15027 g, CRS 21130 g, CRS 21240 g, CRS 21460 g, and CRS 21640 g
Epoxy resin: dicyclopentadiene dioxide 32 g;
crosslinking catalyst: tetrabutyl titanate 2.8g
Organic solvent: 135g of propylene glycol methyl ether acetate, 20g of dipropylene glycol methyl ether acetate and 10g of dipropylene glycol butyl ether acetate
b) Preparation process
Uniformly mixing dihydric alcohol and tribasic acid, heating to 70 ℃, and adding silanol and xylene; heating at 210 deg.C for 1h, heating to 220 deg.C, and heating for 3 h; cooling to 90 ℃, and adding propylene glycol methyl ether acetate, organic silicon oligomer, epoxy resin and a crosslinking catalyst; heating to 120 deg.C for 3 h; finally adding dipropylene glycol methyl ether acetate and dipropylene glycol butyl ether acetate.
c) Modified carboxyl-terminated hyperbranched polyester resin performance
Comprehensive performance of modified carboxyl-terminated hyperbranched polyester resin
3) Coating material
a) Composition of
Modified carboxyl-terminated hyperbranched polyester resin: 120g of modified carboxyl-terminated hyperbranched polyester resin prepared in the step 2;
filling: 25g of silicon dioxide; 5g of titanium dioxide;
pigment: 5g of iron oxide red;
organosilicon auxiliary agent: CoatOSil 35004 g; CoatOSil 75102 g; silicone oil/350cst4g；
High boiling point solvent: dibasic ester mixture (DBE) 12 g.
b) Preparation process
The pigment, the filler, the modified carboxyl-terminated hyperbranched polyester resin, the organic silicon assistant and the high-boiling point solvent are uniformly mixed and added into a grinding machine to be ground to the required particle size, and the modified carboxyl-terminated hyperbranched polyester resin is obtained.
c) Performance of
Performance index of paint
Example 7
1) Preparation of hydroxy silicone oil
a) Formulation of
Octamethylcyclotetrasiloxane: 200g
Tetramethyl ammonium hydroxide: 0.02g
Water: 4.8g
DMF：60g
b) Preparation process
Adding octamethylcyclotetrasiloxane, tetramethylammonium hydroxide and DMF (dimethyl formamide) in a reactor provided with a condenser tube, a thermometer, a dropping funnel and a stirrer in sequence according to a ratio, starting stirring and heating up, heating up to 80 ℃, keeping the temperature constant, dropwise adding distilled water under stirring, after dropwise adding, reacting at constant temperature for 10h, heating up to 150 ℃ for reacting for 1h, cooling to 80 ℃, starting reduced pressure distillation, controlling the pressure to be 0.06MPa, evaporating off small molecules generated in the reaction process, and cooling to room temperature to obtain 166g of hydroxyl silicone oil.
c) Performance of
The weight average molecular weight of the hydroxyl silicone oil is detected by adopting a gel permeation chromatography, and the result is 806; the hydroxyl content of the hydroxyl silicone oil was measured by an acetic anhydride method, and the result was 4.6 w%.
2) Preparation of modified carboxyl-terminated hyperbranched polyester resin
a) Consists of the following components:
a dihydric alcohol: neopentyl glycol 104g (1.0 mol);
silanol: 7.3g of hydroxy silicone oil prepared in step 1
Tribasic acid: 294g (1.4 mol) of 1,2, 4-benzenetricarboxylic acid
Xylene: 6.4g
Silicone oligomer: CRS 150160 g, IC 836100 g of Wacker
Epoxy resin: trimethylolpropane glycidyl ether 11 g; 13g of 3, 4-epoxidized 3 ', 4' -epoxidized cyclohexanemethyl cyclohexanecarboxylate; 10g of bisphenol S epoxy resin;
crosslinking catalyst: tetrabutyl titanate 2.12g, dioctylzinc oxide 1.0g
Organic solvent: propylene glycol methyl ether acetate 156g butanol 25g
b) The synthesis steps are as follows:
uniformly mixing dihydric alcohol and tribasic acid, heating to 75 ℃, and adding silanol and xylene; heating at 180 deg.C for 1h, heating to 240 deg.C, and heating for 1 h; cooling to 90 ℃, and adding propylene glycol methyl ether acetate, organic silicon oligomer, epoxy resin and a crosslinking catalyst; heating to 110 ℃, and heating for 2 h; finally butanol is added.
c) Modified carboxyl-terminated hyperbranched polyester resin performance
Comprehensive performance of modified carboxyl-terminated hyperbranched polyester resin
3) Coating material
a) Composition of
Modified carboxyl-terminated hyperbranched polyester resin: 110g of modified carboxyl-terminated hyperbranched polyester resin prepared in the step 2;
filling: 15g of silicon dioxide; 5g of titanium dioxide;
pigment: phthalocyanine blue 8 g;
high boiling point solvent: dibasic ester mixture (DBE) 40 g; isobutyl isobutyrate 20 g.
b) Preparation process
The pigment, the filler, the modified carboxyl-terminated hyperbranched polyester resin, the organic silicon assistant and the high-boiling point solvent are uniformly mixed and added into a grinding machine to be ground to the required particle size, and the modified carboxyl-terminated hyperbranched polyester resin is obtained.
c) Performance of
Performance index of paint
Example 8
1) Preparation of hydroxy silicone oil
a) Formulation of
Octamethylcyclotetrasiloxane: 200g
Tetramethyl ammonium hydroxide: 0.02g
Water: 5.8g
N, N' -Dimethylformamide (DMF): 60g of
b) Preparation process
Adding octamethylcyclotetrasiloxane, tetramethylammonium hydroxide and DMF (dimethyl formamide) in a reactor provided with a condenser tube, a thermometer, a dropping funnel and a stirrer in sequence according to a ratio, starting stirring and heating up, heating up to 85 ℃, keeping the temperature constant, dropwise adding distilled water under stirring, after dropwise adding, reacting at constant temperature for 8 hours, heating up to 150 ℃, reacting for 1 hour, cooling to 80 ℃, starting reduced pressure distillation, controlling the pressure to be 0.06MPa, evaporating off small molecules generated in the reaction process, and cooling to room temperature to obtain the hydroxyl silicone oil.
c) Performance of
The weight average molecular weight of the hydroxyl silicone oil is detected by adopting gel permeation chromatography, and the result is 516; the hydroxyl content of the hydroxyl silicone oil is measured by an acetic anhydride method, and the result is 8.03 w%.
2) Preparation of Silicone oligomers
a) Composition of
Monomethyltriethoxysilane: 44.5g (0.25 mol)
Dimethyl diethoxysilane: 50.3g (0.34 mol)
Mono-phenyltriethoxysilane: 98.4g (0.41 mol),
b) preparation process
Siloxane and 7.0mmol of hydrochloric acid are sequentially added into a reactor provided with a condenser tube, a thermometer, a dropping funnel and a stirrer according to the proportion, stirring and heating are started, the temperature is kept constant after the temperature is raised to 70 ℃, 43.1g of distilled water is dropwise added under stirring, after the dropwise addition is finished, constant temperature reaction is carried out for 3 hours, reduced pressure distillation is started, the pressure is controlled to be 0.06MPa, small molecules generated in the reaction process are evaporated, the temperature is cooled to room temperature, the solid content is adjusted to 80%, and 230g of organic silicon oligomer is obtained.
c) Performance of
The weight average molecular weight of the organic silicon oligomer is detected by adopting a gel permeation chromatography, and the result is 1986; the hydroxyl content of the organic silicon oligomer is determined by an acetic anhydride method, and the result is 15 w%; the ethoxy content of the organic silicon oligomer is determined by an acetyl perchlorate method, and the result is 3 w%; R/Si = 1.34; ph/Me = 0.44.
3) Preparation of modified carboxyl-terminated hyperbranched polyester resin
a) Consists of the following components:
a dihydric alcohol: neopentyl glycol 104g (1.0 mol);
silanol: 4.2g of polyhydroxy silicone oil prepared in step 1
Tribasic acid: 1,2, 4-benzenetricarboxylic acid 210g (1 mmol)
Xylene: 3.64g
Silicone oligomer: step 2 preparation of Silicone oligomer 239
Epoxy resin: 10.4g of dicyclopentadiene dioxide;
crosslinking catalyst: 1.5g of tetrabutyl titanate, 0.5g of dioctyltin oxide, 0.5g of tetra-n-butyl titanate, 0.5g of dioctylzinc oxide and 0.5g of diisooctylzinc oxide;
organic solvent: propylene glycol methyl ether acetate 250g
b) The synthesis steps are as follows:
uniformly mixing dihydric alcohol and tribasic acid, heating to 90 ℃, and adding silanol and xylene; heating at 180 deg.C for 1h, heating to 240 deg.C, and heating for 1 h; cooling to 90 ℃, and adding an organic solvent, an organic silicon oligomer, epoxy resin and a crosslinking catalyst which are 1.0 time of the weight of the trihydric alcohol; heating to 110 ℃, and heating for 2 h; and finally adding the residual organic solvent.
c) Modified carboxyl-terminated hyperbranched polyester resin performance
Comprehensive performance of modified carboxyl-terminated hyperbranched polyester resin
4) Coating material
a) Composition of
Modified carboxyl-terminated hyperbranched polyester resin: 150g of modified carboxyl-terminated hyperbranched polyester resin prepared in the step 3;
filling: 15g of silicon dioxide; 5g of titanium dioxide;
organosilicon auxiliary agent: CoatOSil 35005 g; silicone oil/350cst 5g；
High boiling point solvent: dibasic ester mixture (DBE) 10 g.
b) Preparation process
Uniformly mixing the filler, the modified carboxyl-terminated hyperbranched polyester resin, the organic silicon assistant and the high-boiling-point solvent, and adding the mixture into a grinding machine to grind the mixture to the required particle size to obtain the modified carboxyl-terminated hyperbranched polyester resin.
c) Performance of
Performance index of paint
Example 9
1) Silicone oligomers
a) Composition of
Monomethyltriethoxysilane: 69.1g (0.36 mol)
Dimethyl diethoxysilane: 34.0g (0.21 mol)
Mono-phenyltriethoxysilane: 109.24g (0.43 mol),
b) preparation process
Siloxane and 5.5mmol of hydrochloric acid are sequentially added into a reactor provided with a condenser tube, a thermometer, a dropping funnel and a stirrer according to the proportion, stirring and heating are started, the temperature is kept constant after the temperature is raised to 70 ℃, 42.7g of distilled water is dropwise added under stirring, after the dropwise addition is finished, constant temperature reaction is carried out for 3 hours, reduced pressure distillation is started, the pressure is controlled to be 0.06MPa, small molecules generated in the reaction process are evaporated, the temperature is cooled to room temperature, the solid content is adjusted to be 60%, and 322g of organic silicon oligomer is obtained.
c) Performance of
The weight average molecular weight of the silicone oligomer is detected by gel permeation chromatography, and the result is 1808; the hydroxyl content of the organic silicon oligomer is determined by an acetic anhydride method, and the result is 20 w%; the ethoxy content of the organic silicon oligomer is determined by an acetyl perchlorate method, and the result is 2.5 w%; R/Si = 1.21; ph/Me = 0.55.
2) Preparation of modified carboxyl-terminated hyperbranched polyester resin
a) Consists of the following components:
a dihydric alcohol: neopentyl glycol 104g (1.0 mol);
silanol: heptapoly (cyclopentyl) silsesquioxane trissilanol 4g, shin-Etsu KR220L 4.3.3 g
Tribasic acid: 252g (1.2 mmol) of 1,2, 4-benzenetricarboxylic acid
Xylene: 4.3g
Silicone oligomer: xinyue silicone resin KR 15049 g, Z-6108100 g from Dow Corning, IC 836100 g from Wake Corp
Epoxy resin: 26g of dicyclopentadiene dioxide;
crosslinking catalyst: tetrabutyl titanate 2.0g diisooctyl zinc oxide 1.2g, diisooctyl tin oxide 1.4g
Organic solvent: 156g of propylene glycol methyl ether acetate, 20g of propylene glycol butyl ether acetate and 10g of isobutanol
b) The synthesis steps are as follows:
uniformly mixing dihydric alcohol and tribasic acid, heating to 80 ℃, and adding silanol and xylene; heating at 190 deg.C for 1.5h, heating to 230 deg.C, and heating for 2 h; cooling to 90 ℃, and adding propylene glycol methyl ether acetate, organic silicon oligomer, epoxy resin and a crosslinking catalyst; heating to 120 ℃, and heating for 2 h; cooling to 90 deg.c and adding propylene glycol butyl ether acetate and isobutanol.
c) Modified carboxyl-terminated hyperbranched polyester resin performance
Comprehensive performance of modified carboxyl-terminated hyperbranched polyester resin
3) Coating material
a) Composition of
Modified carboxyl-terminated hyperbranched polyester resin: 150g of modified carboxyl-terminated hyperbranched polyester resin prepared in the step 2;
filling: 40g of titanium dioxide;
organic auxiliary agents: CoatOSil 75108 g;
high boiling to solvent: dibasic ester mixture (DBE) 2 g.
b) Preparation process
Uniformly mixing the filler, the modified carboxyl-terminated hyperbranched polyester resin, the organic silicon assistant and the high-boiling-point solvent, and adding the mixture into a grinding machine to grind the mixture to the required particle size to obtain the modified carboxyl-terminated hyperbranched polyester resin.
c) Performance of
Performance index of paint
Example 10
1) Preparation of hydroxy silicone oil
a) Formulation of
Octamethylcyclotetrasiloxane: 200g
Tetramethyl ammonium hydroxide: 0.02g
Water: 12g of
DMF：60g
b) Preparation process
Adding octamethylcyclotetrasiloxane, tetramethylammonium hydroxide and DMF (dimethyl formamide) in a reactor provided with a condenser tube, a thermometer, a dropping funnel and a stirrer in sequence according to a ratio, starting stirring and heating up, heating up to 90 ℃, keeping the temperature constant, dropwise adding distilled water under stirring, after dropwise adding, reacting at constant temperature for 9.5 hours, heating up to 150 ℃, reacting for 1 hour, cooling to 80 ℃, starting reduced pressure distillation, controlling the pressure at 0.06MPa, evaporating off small molecules generated in the reaction process, cooling to room temperature, and adjusting the solid content to 60% to obtain 157g of hydroxyl silicone oil.
c) Performance of
The weight average molecular weight of the hydroxyl silicone oil is detected by adopting a gel permeation chromatography, and the result is 301; the hydroxyl group content of the hydroxyl silicone oil was measured by an acetic anhydride method, and found to be 10.1 w%.
2) Silicone oligomers
a) Composition of
Monomethyltrimethoxysilane: 42.0g (0.28 mol)
Dimethyl dimethoxy silane: 18.7g (0.14 mol)
Mono-phenyltrimethoxysilane: 123.0g (0.58 mol),
b) preparation process
Siloxane and 4.5mmol of hydrochloric acid are sequentially added into a reactor provided with a condenser tube, a thermometer, a dropping funnel and a stirrer according to the proportion, stirring and heating are started, the temperature is kept constant after the temperature is raised to 60 ℃, 31.7g of distilled water is dropwise added under stirring, after the dropwise addition is finished, constant temperature reaction is carried out for 3 hours, reduced pressure distillation is started, the pressure is controlled to be 0.06MPa, small molecules generated in the reaction process are evaporated, the temperature is cooled to room temperature, the solid content is adjusted to be 60%, and 290g of organic silicon oligomer is obtained.
c) Performance of
The weight average molecular weight of the organic silicon oligomer is detected by adopting gel permeation chromatography, and the result is 802; the hydroxyl content of the organic silicon oligomer is measured by an acetic anhydride method, and the result is 10.6 w%; the methoxy content of the organosilicon oligomer is determined by an acetyl perchlorate method, and the result is 7.4 w%; R/Si = 1.14; ph/Me = 1.04.
3) Preparation of modified carboxyl-terminated hyperbranched polyester resin
a) Consists of the following components:
a dihydric alcohol: 90g (1.0 mol) of 2-methyl-1, 3-propanediol;
silanol: 3.8g of the hydroxysilanol prepared in step 1, KR220L 1.5.5 g from shin-Etsu Co., Ltd., and 1.0g of heptaphenylsilsesquioxane trissilanol
Tribasic acid: 84g (0.4 mol) of 1,2, 4-benzenetricarboxylic acid, 126g (0.6 mmol) of 1,3, 5-benzenetricarboxylic acid
Xylene: 3.2g
Silicone oligomer: KR 212110 g from shin-Etsu corporation, step 2, and prepared silicone intermediate 70g
Epoxy resin: 14g of trimethylolpropane glycidyl ether; 21g of bis (2, 3-epoxycyclopentyl) ether;
crosslinking catalyst: tetrabutyl titanate 1.6g dioctyl Zinc oxide 2.0g
Organic solvent: propylene glycol methyl ether acetate 128g
b) The synthesis steps are as follows:
uniformly mixing dihydric alcohol and tribasic acid, heating to 90 ℃, and adding silanol and xylene; heating at 190 deg.C for 3h, heating to 230 deg.C, and heating for 3 h; cooling to 90 ℃, and adding propylene glycol methyl ether acetate, organic silicon oligomer, epoxy resin and a crosslinking catalyst which are 1.2 times of the weight of the trihydric alcohol; heating to 115 deg.C for 3 h; cooling to 80 deg.C, and adding the rest propylene glycol methyl ether acetate.
c) Modified carboxyl-terminated hyperbranched polyester resin performance
Comprehensive performance of modified carboxyl-terminated hyperbranched polyester resin
4) Coating material
a) Composition of
Modified carboxyl-terminated hyperbranched polyester resin: 120g of modified carboxyl-terminated hyperbranched polyester resin prepared in the step 3;
filling: 20g of titanium dioxide; 40g of silicon dioxide;
organosilicon auxiliary agent: CoatOSil 7510: 2g of the total weight of the mixture;
high boiling point solvent: dibasic ester mixture (DBE): 18 g.
b) Preparation process
Uniformly mixing the filler, the modified carboxyl-terminated hyperbranched polyester resin, the organic silicon assistant and the high-boiling-point solvent, and adding the mixture into a grinding machine to grind the mixture to the required particle size to obtain the modified carboxyl-terminated hyperbranched polyester resin.
c) Performance of
Performance index of paint
Comparative examples
Reference 1 preparation of comparative coating (Ma Yi et al, preparation of amino-terminated silicone oil modified polyester resin, electroplating and coating, 2011, stage 02)
Reference 2 preparation of comparative coating 2 (Lihuagong et al, Synthesis of Silicone-modified hydroxyl-terminated polyesters, synthetic resins and plastics, 2012, 29 (2): 20-23)
Comparative coating 3 reference (CN 102504271A) formulation
Performance of
Performance index of paint
Heat resistance was measured according to method 1; flexibility is detected according to GB/T1731-1993; the cold-heat alternation is detected according to the method GB 9278.
a degradation temperature in thermogravimetric analysis.
The polyester in the comparative coating 1 is prepared by reacting 1, 6-adipic acid, 1, 3-propanediol and hydroxyl silicone oil, the flexibility of the organic silicon modified polyester reaches 4mm, and the cold-hot alternation reaches 35 times, but only a small amount of silicone oil is used for modifying in the process of preparing resin, and an organic silicon intermediate is not used for modifying the polyester, so that the heat resistance of the prepared modified polyester is 280 ℃, and the heat resistance of the modified polyester is far inferior to that of the coating disclosed by the invention.
The resin in the comparative coating 2 is a polyhydroxy polyester resin modified by an organosilicon intermediate, and the resin has good heat resistance, and the heat resistance temperature of the resin reaches 350 ℃. However, the polyhydroxy polyester adopted is not modified by silanol, so that the flexibility is poor, the flexibility is only 6mm, the boiling resistance is only 2.4h, and the cold-heat resistance is 19 times.
The resin in the comparative coating 3 is a polyester resin modified by an organosilicon intermediate, and the resin has good heat resistance, and the heat resistance temperature of the resin reaches 360 ℃. However, only diols such as neopentyl glycol, 2-methyl-1, 3-propanediol and 1, 6-hexanediol are used to react with benzenetricarboxylic acid during the preparation of polyester, and no low molecular weight silicone oil is added, resulting in poor film flexibility of only 6 mm.
The coating prepared by the resin has the heat resistance of 510 ℃ and the flexibility of 3 mm. The heat resistance and flexibility of the paint are far better than those of a comparative paint 1, a comparative paint 2 and a comparative paint 3.