Method for preparing hyperbranched polyester modified organic silicon resin

A technology of polyester modification and silicone, which is applied in the direction of coating, etc., can solve the problems of unsatisfactory heat resistance, acid resistance and salt spray resistance, etc., and achieve excellent salt spray resistance, water and solvent resistance, and high The effect of heat resistance

Active Publication Date: 2012-06-20

HANGZHOU JIHUA POLYMER MATERIAL CO LTD

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AI-Extracted Technical Summary

Problems solved by technology

However, the heat resistance, acid resistance and salt spra...

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Abstract

The invention relates to organic silicon resin, in particular to a method for preparing hydroxyl-terminated hyperbranched polyester modified organic silicon resin. The method comprises the following steps of: adding 40 to 60 weight percent of hydroxyl-terminated hyperbranched polyester, 40 to 60 weight percent of organic silicon resin and a cross linking catalyst into a reactor; after heating the mixture for 1 to 3 hours at the temperature of 110 to 120 DEG C, warming to the temperature of 150 to 180 DEG C and heating for 1 to 3 hours; and finally, reducing the temperature to the room temperature and adding an organic solvent to regulate the solid content to the range of 60 to 70 percent so as to obtain the hydroxyl-terminated hyperbranched polyester modified organic silicon resin. The method combines the advantages of the hydroxyl-terminated hyperbranched polyester with the organic silicon resin and excellent heat resistance, low surface energy, excellent boiling resistance and excellent salt fog resistance are obtained. The resin prepared by the method disclosed by the invention can be used for preparing a coating with high temperature resistance and low surface energy.

Application Domain

Coatings

Technology Topic

Surface energyTemperature resistance +10

Image

Examples

Experimental program(10)

Example Embodiment

[0039] Example 1:

[0040] 1) Hydroxy-terminated hyperbranched polyester

[0041] a) Composition:

[0042] Triol: Trimethylolethane 96g (0.8mol); 1,3,5-benzenetriol 25.2g (0.2mol);

[0043] Dibasic acid: terephthalic acid 132.8g (0.8mol); succinic acid 23.6g (0.2mol);

[0044] b) Synthesis steps:

[0045] Add the triol and dibasic acid to a reactor equipped with heating, condensation and nitrogen protection. Under the protection of nitrogen, the temperature is increased to 110°C for 2h; at a heating rate of 20°C per hour to 240°C, the temperature is kept at 1.33kPa for 4h ; Finally, cool to room temperature to obtain 235 g of hydroxyl-terminated hyperbranched polyester.

[0046] c) Performance of hydroxyl-terminated hyperbranched polyester

[0047] The weight average molecular weight of the hydroxyl-terminated hyperbranched polyester was detected by gel permeation chromatography and the result was 3998.

[0048] The hydroxyl value was tested according to the method described in GB/T7193.2-1987, and the result was 241mgKOH/g.

[0049] 2) Hydroxy-terminated hyperbranched polyester modified silicone

[0050] a) Composition:

[0051] Hydroxyl-terminated hyperbranched polyester: 60g of hydroxyl-terminated hyperbranched polyester prepared in step 1;

[0052] Silicone resin: Shin-Etsu silicone resin KR216 40g;

[0053] Tin dioctyl oxide: 1g.

[0054] b) Preparation process:

[0055] Add the hydroxyl-terminated hyperbranched polyester and silicone resin prepared in step 1 to a reactor equipped with heating, condensation and nitrogen protection devices, add a catalyst, heat up to 120°C for 2 hours, and heat up to 160°C for 2 hours, and finally After cooling to room temperature, propylene glycol methyl ether acetate was added to adjust the solid content to 70% to obtain 132 g of hydroxyl-terminated hyperbranched polyester modified silicone resin.

[0056] c) Performance of hydroxyl-terminated hyperbranched polyester modified silicone

[0057] Comprehensive properties of hydroxyl-terminated hyperbranched polyester modified silicone

[0058]

[0059] Heat resistance: After baking the test piece at 180°C for 2h, put it in a constant temperature box-type electric furnace checked by a potentiometer, increase the temperature at 5°C/min, and start timing when the furnace temperature reaches the required temperature of the experiment. After the high temperature continues, take it out and cool to room temperature (25°C). Use a magnifying glass to observe the surface condition of the coating. If there is no cracking or falling off, the coating has good heat resistance.

[0060] 3) Paint

[0061] a) Composition

[0062] Hydroxyl-terminated hyperbranched polyester modified silicone resin: 100g of the hydroxyl-terminated hyperbranched polyester modified silicone resin prepared in step 2;

[0063] Pigment filler: carbon black 40g; titanium dioxide 20g;

[0064] Silicone additives: silicone oil 8g;

[0065] High boiling point solvent: Dibasic acid ester mixture (DBE) 5g.

[0066] b) Preparation process

[0067] The pigment filler, hydroxyl-terminated hyperbranched polyester modified silicone resin, silicone additives, and high boiling point solvent are mixed uniformly, and then added to a grinder to grind to the required particle size.

[0068] c) performance

[0069] Performance index of coating

[0070]

[0071] 1*Boiling resistance: After baking the test piece at 180°C for 2h, cool it to room temperature, then place the test piece in distilled water at 100°C and heat it until the paint film is damaged, such as blistering, loss of gloss, discoloration, and turtle Phenomenon such as cracking.

[0072] 2*Heat resistance: After baking the test piece at 180℃ for 2h, put it in a constant temperature box-type electric furnace checked by a potentiometer, increase the temperature by 5℃/min, and start timing when the furnace temperature reaches the experimental temperature. After the sample has been subjected to continuous high temperature, take it out and cool it to room temperature (25°C). Use a magnifying glass to observe the surface condition of the coating. If there is no cracking or falling off, the coating has good heat resistance.

[0073] 3*Surface tension: measured by a surface tension measuring instrument at 25°C.

Example Embodiment

[0074] Example 2:

[0075] 1) Hydroxy-terminated hyperbranched polyester

[0076] a) Composition:

[0077] Triols: 168g (1.4mol) of trimethylolethane; 37.8g (0.3mol) of 1,2,4-benzenetriol; 37.8g (0.3mol) of 1,3,5-benzenetriol;

[0078] Dibasic acid: isophthalic acid 66.4g (0.4mol); terephthalic acid 66.4g (0.4mol); adipic acid 29.2g (0.2mol);

[0079] b) Synthesis steps:

[0080] Add the triol and dibasic acid to a reactor equipped with heating, condensation and nitrogen protection. Under the protection of nitrogen, the temperature is raised to 110°C for 2h; at a heating rate of 20°C per hour to 240°C, the temperature is kept at 0.66kPa for 2h ; Finally, cool to room temperature to obtain 364 g of hydroxyl-terminated hyperbranched polyester.

[0081] c) Performance of hydroxyl-terminated hyperbranched polyester

[0082] The weight average molecular weight of the hydroxyl-terminated hyperbranched polyester was detected by gel permeation chromatography and the result was 1990.

[0083] The hydroxyl value was tested according to the method described in GB/T7193.2-1987, and the result was 638mgKOH/g.

[0084] 2) Hydroxy-terminated hyperbranched polyester modified silicone

[0085] a) Composition:

[0086] Hydroxyl-terminated hyperbranched polyester: 40g of hydroxyl-terminated hyperbranched polyester prepared in step 1;

[0087] Silicone resin: Dow Corning 3037 60g;

[0088] Catalyst: 3 g of dioctyl tin oxide.

[0089] b) Preparation process:

[0090] Add the hydroxyl-terminated hyperbranched polyester and silicone resin prepared in step 1 into a reactor equipped with heating, condensation and nitrogen protection devices, add catalyst, heat up to 110°C for 3 hours, and heat up to 180°C for 1 hour, and finally After cooling to room temperature, propylene glycol methyl ether acetate was added to adjust the solid content to 60% to obtain 160 g of hydroxyl-terminated hyperbranched polyester modified silicone resin.

[0091] c) Performance of hydroxyl-terminated hyperbranched polyester modified silicone

[0092] Comprehensive properties of hydroxyl-terminated hyperbranched polyester modified silicone

[0093]

[0094] 3) Paint

[0095] a) Composition

[0096] Hydroxy-terminated hyperbranched polyester modified silicone resin: 160g of the hydroxyl-terminated hyperbranched polyester modified silicone resin prepared in step 2;

[0097] Pigment filler: carbon black 20g;

[0098] High boiling point solvent: Dibasic acid ester mixture (DBE) 5g; Ethylene glycol ethyl ether acetate (CAC): 5g.

[0099] b) Preparation process

[0100] The pigment filler, hydroxyl-terminated hyperbranched polyester modified silicone resin, and high boiling point solvent are mixed uniformly, and then added to a grinder to grind to the required particle size.

[0101] c) performance

[0102] Performance index of coating

[0103]

Example Embodiment

[0104] Example 3:

[0105] 1) Hydroxy-terminated hyperbranched polyester

[0106] a) Composition:

[0107] Triol: 192g (1.6mol) of trimethylolethane;

[0108] Dibasic acid: 157.7g (0.95mol) of isophthalic acid; 7.3g (0.05mol) of adipic acid;

[0109] b) Synthesis steps:

[0110] Put the triol and dibasic acid into a reactor equipped with heating, condensation and nitrogen protection. Under the protection of nitrogen, the temperature is increased to 110℃, and the temperature is kept for 2h; the heating rate is 20℃ per hour to 240℃, and the temperature is 2.5kPa. h; Finally, it is cooled to room temperature to obtain 310 g of hydroxyl-terminated hyperbranched polyester.

[0111] c) Performance of hydroxyl-terminated hyperbranched polyester

[0112] The weight average molecular weight of the hydroxyl-terminated hyperbranched polyester was detected by gel permeation chromatography, and the result was 2611.

[0113] The hydroxyl value was tested according to the method described in GB/T7193.2-1987, and the result was 507mgKOH/g.

[0114] 2) Silicone resin intermediate

[0115] a) Composition

[0116] Monomethyltrimethoxysilane: 42.0g (0.28mol)

[0117] Dimethyldimethoxysilane: 18.7g (0.14mol)

[0118] Monophenyltrimethoxysilane: 123.0g (0.58mol),

[0119] b) Preparation process

[0120] After adding siloxane and 4.5mmol hydrochloric acid in sequence in the reactor equipped with condenser, thermometer, dropping funnel and stirrer according to the ratio, start to stir and raise the temperature, keep the temperature constant after heating to 60℃, add dropwise under stirring 31.7g of distilled water, after the dripping is finished, and after constant temperature reaction for 3 hours, start vacuum distillation, the pressure is controlled at 0.06MPa, the small molecules produced during the reaction are evaporated, cooled to room temperature, and the solid content is adjusted to 60% to obtain organosilicon Resin intermediate 290g.

[0121] c) performance

[0122] The weight average molecular weight of the silicone resin intermediate was determined by gel permeation chromatography, and the result was 802; the hydroxyl content of the silicone resin intermediate was determined by the acetic anhydride method, and the result was 10.6%; the methoxy content of the silicone resin intermediate Measured by perchloric acid acetyl method, the result is 7.4%; R/Si=1.14; ph/Me=1.04.

[0123] 3) Hydroxy-terminated hyperbranched polyester modified silicone

[0124] a) Composition

[0125] Hydroxyl-terminated hyperbranched polyester: 56g of hydroxyl-terminated hyperbranched polyester prepared in step 1;

[0126] Silicone resin: 73.3g of the silicone resin with a solid content of 60% prepared in step 2;

[0127] Catalyst: 2.7 g of tin diisooctyl oxide.

[0128] b) Preparation process

[0129] Add the hydroxyl-terminated hyperbranched polyester and silicone resin prepared in step 1 into a reactor equipped with heating, condensation and nitrogen protection devices, add catalyst, heat up to 115°C for 1.5 hours, and heat up to 175°C for 1.5 hours, and finally After cooling to room temperature, dipropylene glycol methyl ether acetate and dipropylene glycol butyl ether acetate were added to adjust the solid content to 65% to obtain 141 g of hydroxyl-terminated hyperbranched polyester modified silicone resin.

[0130] c) Performance of hydroxyl-terminated hyperbranched polyester modified silicone

[0131] Comprehensive properties of hydroxyl-terminated hyperbranched polyester modified silicone

[0132]

[0133] 4) Paint

[0134] a) Composition

[0135] Hydroxyl-terminated hyperbranched polyester modified silicone resin: 100g of the hydroxyl-terminated hyperbranched polyester modified silicone resin prepared in step 3;

[0136] Pigment filler: phthalocyanine blue 20g; silica 20g;

[0137] Silicone additives: CoatOSil 7001 4g; silicone oil 6g;

[0138] High boiling point solvent: Diethylene glycol butyl ether acetate (DBA) 5g; Ethylene glycol ether acetate (CAC) 5g.

[0139] b) Preparation process

[0140] The pigment filler, hydroxyl-terminated hyperbranched polyester modified silicone resin, silicone additives, and high boiling point solvent are mixed uniformly, and then added to a grinder to grind to the required particle size.

[0141] c) coating performance

[0142] Performance index of coating

[0143]

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PUM

Property	Measurement	Unit
Hydroxyl value	241.0	mgKOH/g
Hydroxyl value	638.0	mgKOH/g
Hydroxyl value	507.0	mgKOH/g
tensile		MPa
Particle size		Pa
strength	10

Description & Claims & Application Information

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the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine

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Classification and recommendation of technical efficacy words

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Method for preparing hyperbranched polyester modified organic silicon resin

AI-Extracted Technical Summary

Problems solved by technology

Abstract

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Examples

Example Embodiment

Example Embodiment

Example Embodiment

PUM

Description & Claims & Application Information

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