CN103073711B - A kind of TGIC heat resistant powder coating organic-silicon-modified terminal carboxyl polyester resin and preparation method thereof - Google Patents
A kind of TGIC heat resistant powder coating organic-silicon-modified terminal carboxyl polyester resin and preparation method thereof Download PDFInfo
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Abstract
The invention discloses the organic-silicon-modified terminal carboxyl polyester resin of a kind of heat resistant powder coating, obtained through melt polycondensation reaction by the component of following weight content: organosilicon 5 ~ 25%, polyvalent alcohol 25% ~ 45%, aromatic polycarboxylic acid 35 ~ 65%, aliphatic polyol acid 0% ~ 5%, acidolysis agent 4% ~ 15%, esterifying catalyst 0.01 ~ 0.15%.The invention also discloses the preparation method of organic-silicon-modified polyester resin for powder coating.Vibrin prepared by the present invention has suitable second-order transition temperature, softening temperature, package stability, and the powder coating of preparation has excellent thermotolerance, is especially applicable to the powder coating being used in polyester/TGIC curing system.
Description
Technical field
The present invention relates to the organic-silicon-modified terminal carboxyl polyester resin of a kind of TGIC heat resistant powder coating, the invention still further relates to the preparation method of this organic-silicon-modified terminal carboxyl polyester resin.
Background technology
Powder coating and application thereof due to low stain, saving resource, labour productivity is high and be convenient to carry out the features such as automatic production, since the seventies and eighties, obtained and developed rapidly.Along with the development of coatings industry, be widely used in the application of powder coating on metal substrate, in recent years, the development & application of the functional products such as antimicrobial form, high wearable, heat resistant type becomes the developing direction of powder coating.Thermotolerance powder coating refers to and stands more than 200 DEG C temperature for a long time, and film is good, and can make the powder coating that object of protection normally plays a role in hot environment.From polymer stabilisation mechanism, the thermotolerance of polymkeric substance depends primarily on its molecular structure.Vibrin is because backbone structure is mainly based on C-O key; thermotolerance is poor; easily aging after using under the condition of certain high temperature; the powder coating made has the scene such as efflorescence, loss of gloss in coating after high bake; lose the provide protection as coating, so need through certain modification to improve thermotolerance.
Silicone resin be with Si-O key be main chain, its bond energy for 452kJ/mol, exceed 96kJ/mol than the 356kJ/mol of C-C key, this is the major cause that silicone resin has high-temperature stability.Meanwhile, the hydroxyl in silicone resin has highly cross-linked property by the Si-O-Si key generated after thermooxidizing, makes it more stable, at the Si-O chain that skin is formed, plays a protective role to superpolymer inside.Because Si-O polarity is large, therefore, it is possible to effectively prevent the oxygenizement of connected oh group.The main chain of silicone resin is linked by Si-O and forms, and side chain is then other various organic group, therefore, both containing organic group in silicone resin, again containing inorganic structure, makes it have characteristic that is organic and inorganics simultaneously.Therefore silicone resin has the advantages such as excellent thermotolerance, weathering resistance, electrical insulating property, chemical proofing and combustion-supporting property.But simple organosilicon coating in the market product is little, and price is more expensive, organosilicon due to polarity low, the face that the surface tension low sticking power to ground deficiency is difficult to be used alone or use is too narrow.
Powder coating mainly comprises mixed type, TGIC curing and the pure polyester type of Primid, what wherein maximum, the consumption in market was maximum surely belongs to TGIC curing, because TGIC curing compares the advantage that mixed powder coating has weathering resistance, compare Primid type and there is the apparent advantage in plate face, therefore organosilicon is combined the added value that further can expand the type polyester with TGIC type vibrin, the market requirement is also guaranteed simultaneously.TGIC heat resistant powder coating organic silicon polyester resin and TGIC polyester resin for powder coating basic condition similar, all that the TGIC of use is as solidifying agent, but compare common TGIC type powder coating, it has higher added value, not only can use as general T GIC type powder coating, and due to the advantage of himself thermotolerance, the workpiece surface of some needs compared with elevated operating temperature can be coated in, this is not available for general TGIC type powder coating, compares solid rocket motor simultaneously, pure organosilicon coating has again advantage on cost.Although the performance advantage price advantage of this type vibrin largely can expand its range of application of its market, but the copolymerization owing to being organosilicon and vibrin should be seen, that is on its segment also containing more C-O key and C-C key, and this heat labile main cause that is polymer is so the temperature capability in fact promoted has the limit.
Summary of the invention
An object of the present invention is to provide the organic-silicon-modified terminal carboxyl polyester resin of a kind of TGIC heat resistant powder coating, this vibrin has suitable second-order transition temperature, softening temperature, package stability, the powder coating of preparation has excellent thermotolerance, is especially applicable to the powder coating being used in polyester/TGIC curing system.
Two of object of the present invention is to provide the preparation method of above-mentioned organic-silicon-modified terminal carboxyl polyester resin.
First object of the present invention is realized by following technical measures: the organic-silicon-modified terminal carboxyl polyester resin of a kind of TGIC heat resistant powder coating, acid number is 30 ~ 36mgKOH/g, hydroxyl value is all less than l0mgKOH/g, second-order transition temperature is 50 ~ 65 DEG C, melt viscosity is 3000 ~ 7000mPa.s, number-average molecular weight is 3000 ~ 8000, and its raw material cocondensation primarily of following weight percent forms:
Organosilicon 5 ~ 25%
Polyvalent alcohol 25% ~ 45%
Aromatic polycarboxylic acid 35 ~ 65%
Aliphatic polyol acid 0% ~ 5%
Acidolysis agent 4% ~ 15%
Esterifying catalyst 0.01 ~ 0.15%.
Organosilicon of the present invention can for the silicone intermediate (oligopolymer) containing alkoxyl group (Si-OR ＇), comprise DOW CORNING product as RSN-3074, RSN-3037 and Wacker 368, for the silicone intermediate (oligopolymer) containing silicone hydroxyl (Si-OH), RSN-6018 and Wacker 604 of DOW CORNING product can also be comprised.
Polyvalent alcohol of the present invention is neopentyl glycol, 2-methyl isophthalic acid, one or more mixtures in ammediol, 1,2-PD.
Aromatic polycarboxylic acid of the present invention is one or both the mixture in terephthaldehyde and m-phthalic acid.
Aliphatic polyol acid of the present invention is one or both mixtures in hexanodioic acid and 1,4 cyclohexanedicarboxylic acid.
Acidolysis agent of the present invention comprises one or more mixtures in m-phthalic acid, hexanodioic acid, 1,4 cyclohexanedicarboxylic acid and trimellitic acid 1,2-anhydride.
Esterifying catalyst of the present invention is tin compound or Titanium series catalyst.Described tin compound is tin oxalate or dibutyl tin laurate, and described Titanium series catalyst is tetrabutyl titanate or titanium isopropylate.
Second object of the present invention is achieved through the following technical solutions: the preparation method of the organic-silicon-modified terminal carboxyl polyester resin of a kind of TGIC heat resistant powder coating, and its concrete steps are:
(1) get organosilicon and the polyvalent alcohol of proportional quantity, be heated to material and melt, then add the aromatic polycarboxylic acid of proportional quantity, the sour and esterifying catalyst of aliphatic polyol, logical nitrogen continues temperature reaction, starts to generate to 180 DEG C of esterification water and distillates; Then be warming up to 250 DEG C gradually, after the little esterification water up to 95% of coreaction 5 ~ 10 is discharged, acid number reaches 9 ~ 15mgKOH/g;
(2) the acidolysis agent of getting proportional quantity adds reaction kettle for reaction 3 ~ 5 hours, acid number reaches 38 ~ 48mgKOH/g, vacuumize polycondensation 1 ~ 5 hour, acid number reaches 30 ~ 36mgKOH/g, melt viscosity is 3000 ~ 7000mPa.s and stopped reaction, and depolymerization obtains the organic-silicon-modified terminal carboxyl polyester resin of TGIC heat resistant powder coating of molecular weight uniform distribution.
Vibrin acid number prepared by the present invention is 30 ~ 36mgKOH/g, and hydroxyl value is all less than l0mgKOH/g, and second-order transition temperature is 50 ~ 65 DEG C, and melt viscosity is 3000 ~ 7000mPa.s(200 DEG C/ICI), number-average molecular weight is 3000 ~ 8000.Vibrin of the present invention has suitable second-order transition temperature, softening temperature, package stability, and the powder coating of preparation has excellent thermotolerance, is especially applicable to the powder coating being used in polyester/TGIC curing system.Organic-silicon-modified terminal carboxyl polyester resin is obtained in the present invention by the organic resin cocondensation of organosilicon and polyvalent alcohol or hydroxyl, have the advantage of both vibrin and silicone resin concurrently, mutually cover the shortage, obtain good modified effect, greatly improve the performance of resin, expand its use range, also reduce costs.
The preparation process being applicable to powder coating of the present invention is that the vibrin of synthesis is weighed up rear mixing in proportion with TGIC, color stuffing and other auxiliary agent respectively, melt extrudes, cools fragmentation, pulverizes and sieves and make powder coating.The powder coating made has excellent thermotolerance.
Embodiment
Organosilicon in following synthetic example can for the silicone intermediate (oligopolymer) containing alkoxyl group (Si-OR ＇), comprise DOW CORNING product as RSN-3074, RSN-3037 and Wacker 368, for the silicone intermediate (oligopolymer) containing silicone hydroxyl (Si-OH), RSN-6018 and Wacker 604 of DOW CORNING product can also be comprised.
Synthetic example 1: the synthesis of silicone modified polyester resin A
Heating jacket is being housed, agitator, thermometer, in the 1L four-hole boiling flask of distillation column and prolong, add neopentyl glycol 215g, be warming up to 140 DEG C to silicone intermediate organosilicon (RSN-6018) 60g added after neopentyl glycol is melted completely containing silicone hydroxyl (Si-OH), be warmed up to 170 DEG C, insulation 1h, then terephthalic acid 321.5g and tetrabutyl titanate 0.6g is added successively, logical nitrogen temperature to 180 DEG C starts esterification and produces esterification water to distillate, distillation column temperature is controlled not higher than 100 DEG C in reaction process, then 250 DEG C are warming up to gradually, after the little esterification water up to 95% of coreaction 5 ~ 10 is discharged, acid number reaches 12 ~ 15mgKOH/g, then add 45g acidolysis agent m-phthalic acid reaction 3 ~ 5 hours, acid number reaches 40 ~ 48mgKOH/g, and vacuumize polycondensation 1 ~ 5 hour, acid number reaches 30 ~ 33mgKOH/g, and melt viscosity is 4000 ~ 6500mPa.s and stopped reaction.
Synthetic example 2: the synthesis of silicone modified polyester resin B
Heating jacket is being housed, agitator, thermometer, in the 1L four-hole boiling flask of distillation column and prolong, add neopentyl glycol 210g, be warming up to 140 DEG C to silicone intermediate organosilicon (Silres 604) 60g added after neopentyl glycol is melted completely containing silicone hydroxyl (Si-OH), be warmed up to 170 DEG C, insulation 1h, then terephthalic acid 321.5g and tin class catalyzer 0.5g is added successively, logical nitrogen temperature to 180 DEG C starts esterification and produces esterification water to distillate, distillation column temperature is controlled not higher than 100 DEG C in reaction process, then 250 DEG C are warming up to gradually, after the little esterification water up to 95% of coreaction 5 ~ 10 is discharged, acid number reaches 9 ~ 12mgKOH/g, then add 45g acidolysis agent m-phthalic acid reaction 3 ~ 5 hours, acid number reaches 38 ~ 46mgKOH/g, and vacuumize polycondensation 1 ~ 5 hour, acid number reaches 30 ~ 33mgKOH/g, and melt viscosity is 5000 ~ 7000mPa.s and stopped reaction.
Tin compound is tin oxalate or dibutyl tin laurate.
Synthetic example 3: the synthesis of silicone modified polyester resin C
Heating jacket is being housed, agitator, thermometer, in the 1L four-hole boiling flask of distillation column and prolong, add neopentyl glycol 241.8g, be warming up to 140 DEG C to silicone intermediate organosilicon (RSN-3074) 38.75g added after neopentyl glycol is melted completely containing methoxyl group (Si-OR '), tetrabutyl titanate 0.5g, logical nitrogen temperature is to 190 DEG C, insulation 3h, then add terephthalic acid 332g to start esterification and produce esterification water to distillate, distillation column temperature is controlled not higher than 100 DEG C in reaction process, then 250 DEG C are warming up to gradually, after the little esterification water up to 95% of coreaction 5 ~ 10 is discharged, acid number reaches 10 ~ 13mgKOH/g, then add 55.5g acidolysis agent m-phthalic acid reaction 3 ~ 5 hours, acid number reaches 42 ~ 46mgKOH/g, and vacuumize polycondensation 1 ~ 5 hour, acid number reaches 31 ~ 35mgKOH/g, and melt viscosity is 4500 ~ 6500mPa.s and stopped reaction.
Synthetic example 4: the synthesis of silicone modified polyester resin D
Heating jacket is being housed, agitator, thermometer, in the 1L four-hole boiling flask of distillation column and prolong, add neopentyl glycol 245.16g, be warming up to 140 DEG C to silicone intermediate organosilicon (RSN-3074) 54.25g added after neopentyl glycol is melted completely containing methoxyl group (Si-OR '), tetrabutyl titanate 0.5g, logical nitrogen temperature is to 190 DEG C, insulation 3h, then add terephthalic acid 332g to start esterification and produce esterification water to distillate, distillation column temperature is controlled not higher than 100 DEG C in reaction process, then 250 DEG C are warming up to gradually, after the little esterification water up to 95% of coreaction 5 ~ 10 is discharged, acid number reaches 9 ~ 13mgKOH/g, then add 57.6g acidolysis agent m-phthalic acid reaction 3 ~ 5 hours, acid number reaches 40 ~ 48mgKOH/g, and vacuumize polycondensation 1 ~ 5 hour, acid number reaches 30 ~ 33mgKOH/g, and melt viscosity is 4000 ~ 7000mPa.s and stopped reaction.
Synthetic example 5: the synthesis of silicone modified polyester resin E
Heating jacket is being housed, agitator, thermometer, in the 1L four-hole boiling flask of distillation column and prolong, add neopentyl glycol 253.56g, be warming up to 140 DEG C to silicone intermediate organosilicon (RSN-3074) 80.35g added after neopentyl glycol is melted completely containing methoxyl group (Si-OR '), tetrabutyl titanate 0.5g, logical nitrogen temperature is to 190 DEG C, insulation 3h, then add terephthalic acid 332g to start esterification and produce esterification water to distillate, distillation column temperature is controlled not higher than 100 DEG C in reaction process, then 250 DEG C are warming up to gradually, after the little esterification water up to 95% of coreaction 5 ~ 10 is discharged, acid number reaches 11 ~ 15mgKOH/g, then add 60.1g acidolysis agent m-phthalic acid reaction 3 ~ 5 hours, acid number reaches 38 ~ 48mgKOH/g, and vacuumize polycondensation 1 ~ 5 hour, acid number reaches 32 ~ 36mgKOH/g, and melt viscosity is 5000 ~ 7000mPa.s and stopped reaction.
Synthesis comparative example 1: the synthesis of reference vibrin F
In the 1L four-hole boiling flask that heating jacket, agitator, thermometer, distillation column and prolong are housed, add neopentyl glycol 280g, be warming up to 140 DEG C and add terephthalic acid 406g, organotin catalysts 0.5g after neopentyl glycol is melted completely, logical nitrogen temperature to 180 DEG C starts esterification and produces esterification water to distillate, distillation column temperature is controlled not higher than 100 DEG C in reaction process, then 250 DEG C are warming up to gradually, after the little esterification water up to 95% of coreaction 5 ~ 10 is discharged, acid number reaches 11 ~ 15mgKOH/g; Then add 66g acidolysis agent m-phthalic acid reaction 3 ~ 5 hours, acid number reaches 42 ~ 48mgKOH/g, and vacuumize polycondensation 1 ~ 5 hour, acid number reaches 32 ~ 36mgKOH/g, and melt viscosity is 3000 ~ 5000mPa.s and stopped reaction.
The performance of the organic-silicon-modified terminal carboxyl polyester resin of the present invention's synthesis embodies by the performance being prepared into powder coating.The vibrin that above-described embodiment A ~ E, comparative example F synthesize is weighed up rear mixing with TGIC, flow agent, titanium dioxide, barium sulfate, st-yrax, optical brightener etc. in the ratio in table 2 respectively, with screw extrusion press melting extrude respectively, compressing tablet, fragmentation, then sheet stock is pulverized and sieved and makes powder coating.
Powder coating prepared by embodiment 1-6 adopts electrostatic gun to be sprayed on the metal sheet of surface treatment (phosphatization), solidify through 200 DEG C/10min, then resistance toheat sign is carried out, after 250 DEG C of baking ovens toast, test glossiness and aberration according to the standard of GB 1735-79, the performance test results is as shown in table 3:
Known according to table 3, organosilicon kind is different but content difference is little embodiment 1,2 and 3 is close at final coating heat resistance, and comparing embodiment 3,4 and 5 and comparative example 1, the thermotolerance of the final resin of the visible change along with silicone content presents certain difference, guarantor's light rate of embodiment 5 resin of higher silicone content is less with chromatic aberration, and the resin of high silicone content embodies the advantage of superior heat resistance.In the outward appearance of plate face, there is comparatively serious loss of gloss, superficial degradation and pulverization situation in comparative example 1 plate face after being heated, then superficial degradation situation is better to add organosilyl embodiment 1 ~ 5.
Claims (2)
1. the organic-silicon-modified terminal carboxyl polyester resin of TGIC heat resistant powder coating, it is characterized in that, its acid number is 30 ~ 36mgKOH/g, hydroxyl value is less than l0mgKOH/g, second-order transition temperature is 50 ~ 65 DEG C, melt viscosity is 3000 ~ 7000mPa s, and number-average molecular weight is 3000 ~ 8000, and its raw material cocondensation primarily of following weight percent forms:
Organosilicon 7.8 ~ 25%
Polyvalent alcohol 25% ~ 45%
Aromatic polycarboxylic acid 35 ~ 65%
Aliphatic polyol acid 0% ~ 5%
Acidolysis agent 4% ~ 15%
Esterifying catalyst 0.01 ~ 0.15%;
Described organosilicon is the silicone intermediate containing alkoxyl group or the silicone intermediate containing silicone hydroxyl; Described polyvalent alcohol is neopentyl glycol, 2-methyl isophthalic acid, one or more mixtures in ammediol, 1,2-PD; Described aromatic polycarboxylic acid is one or both the mixture in terephthalic acid and m-phthalic acid, and described aliphatic polyol acid is one or both mixtures in hexanodioic acid and 1,4 cyclohexanedicarboxylic acid; Described acidolysis agent is one or more mixtures in m-phthalic acid, hexanodioic acid, 1,4 cyclohexanedicarboxylic acid and trimellitic acid 1,2-anhydride;
Described method of condensing is:
(1) get organosilicon and the polyvalent alcohol of proportional quantity, be heated to material and melt, then add the aromatic polycarboxylic acid of proportional quantity, the sour and esterifying catalyst of aliphatic polyol, logical nitrogen continues temperature reaction, starts to generate to 180 DEG C of esterification water and distillates; Then be warming up to 250 DEG C gradually, after the little esterification water up to 95% of coreaction 5 ~ 10 is discharged, acid number reaches 9 ~ 15mgKOH/g;
(2) the acidolysis agent of getting proportional quantity adds reaction kettle for reaction 3 ~ 5 hours, acid number reaches 38 ~ 48mgKOH/g, vacuumize polycondensation 1 ~ 5 hour, acid number reaches 30 ~ 36mgKOH/g, melt viscosity is 3000 ~ 7000mPa.s and stopped reaction, and depolymerization obtains the organic-silicon-modified terminal carboxyl polyester resin of TGIC heat resistant powder coating of molecular weight uniform distribution.
2. the organic-silicon-modified terminal carboxyl polyester resin of TGIC heat resistant powder coating according to claim 1, is characterized in that, described esterifying catalyst is for having tin compound or Titanium series catalyst.
3. the organic-silicon-modified terminal carboxyl polyester resin of TGIC heat resistant powder coating according to claim 2, is characterized in that, described in have tin compound to be tin oxalate or dibutyl tin laurate.
4. the organic-silicon-modified terminal carboxyl polyester resin of TGIC heat resistant powder coating according to claim 2, is characterized in that, described Titanium series catalyst is tetrabutyl titanate or titanium isopropylate.
5. the TGIC heat resistant powder coating preparation method for organic-silicon-modified terminal carboxyl polyester resin described in any one of Claims 1-4, is characterized in that, comprise the following steps:
(1) get organosilicon and the polyvalent alcohol of proportional quantity, be heated to material and melt, then add the aromatic polycarboxylic acid of proportional quantity, the sour and esterifying catalyst of aliphatic polyol, logical nitrogen continues temperature reaction, starts to generate to 180 DEG C of esterification water and distillates; Then be warming up to 250 DEG C gradually, after the little esterification water up to 95% of coreaction 5 ~ 10 is discharged, acid number reaches 9 ~ 15mgKOH/g;
(2) the acidolysis agent of getting proportional quantity adds reaction kettle for reaction 3 ~ 5 hours, acid number reaches 38 ~ 48mgKOH/g, vacuumize polycondensation 1 ~ 5 hour, acid number reaches 30 ~ 36mgKOH/g, melt viscosity is 3000 ~ 7000mPa.s and stopped reaction, and depolymerization obtains the organic-silicon-modified terminal carboxyl polyester resin of TGIC heat resistant powder coating of molecular weight uniform distribution.
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| CN111234192B (en) * | 2020-03-26 | 2023-04-07 | 邦弗特(山东)新材料有限公司 | Preparation method of organic silicon modified saturated polyester resin with high weather resistance |
| CN114907752B (en) * | 2022-06-27 | 2023-07-28 | 江南载福粉末涂料（张家港）有限公司 | Preparation method of carboxyl-terminated saturated polyester resin with low curing temperature |
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| CN1613935A (en) * | 2004-09-29 | 2005-05-11 | 广州擎天实业有限公司 | Subluminous weather-resistant coating powder and preparation thereof |
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Address after: No.5 Lisha East Road, Shatian Town, Dongguan City, Guangdong Province 523000 Patentee after: Qingtian Material Technology Co., Ltd Address before: Shiling Town, Huadu District, Guangzhou City, Guangdong province 510860 Yufeng Road No. 16 Patentee before: GUANGZHOU KINTE INDUSTRIAL Co.,Ltd. |
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