CN103601872B - A kind ofly reduce the catalyzer that end group is the saturated polyester resin solidification value of carboxyl - Google Patents
A kind ofly reduce the catalyzer that end group is the saturated polyester resin solidification value of carboxyl Download PDFInfo
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- CN103601872B CN103601872B CN201310593777.9A CN201310593777A CN103601872B CN 103601872 B CN103601872 B CN 103601872B CN 201310593777 A CN201310593777 A CN 201310593777A CN 103601872 B CN103601872 B CN 103601872B
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Abstract
The present invention relates to and a kind ofly reduce the catalyzer that end group is the saturated polyester resin solidification value of carboxyl, its raw material form component and parts by weight as follows: low-viscosity polyester resin 70-95 part; Can phase-transfer catalyst 5-20 part of catalysis carboxyl; Catalyzer 1-10 part of epoxide group open loop can be impelled; Antioxidant 5-20 part.Catalyzer of the present invention reduces the solidification value of polyester/epoxy or pure polyester powdery paints, shorten set time, powder coating can be impelled to react at a lower temperature, play energy-conservation effect, the ornamental and functional of powder coating can not be affected, and the color generation xanthochromia of powder coating can not be made, can use in white or light powder, simultaneously, this method for preparing catalyst is simple, easy to operate, respond national energy-saving and reduced discharging call, reduced production cost, improve the economic benefit of enterprise.
Description
Technical field
The invention belongs to catalyst technical field, relate to catalyzer, especially a kind ofly reduce the Catalysts and its preparation method that end group is the saturated polyester resin solidification value of carboxyl.
Background technology
Powder coating and coating technology are new technologies of exploitation in mid-term in 20th century, novel process, owing to having without the need to discharging organism in air, reduce environmental pollution, technique and simply, easily realize the features such as industrial automation, coating performance be excellent, cause the attention of countries in the world coating industry.Powder coating itself be a kind of novel, not containing solvent, 100% solid powdery coating, although pollution-free, under needing the storing temperature more than 180 DEG C, melting and solidification, just can reach service requirements, country and society all require energy-saving and emission-reducing now, focus on environmental protection, so when ensure powder coating ornamental and other functional constant, reduce storing temperature and just become the matter of utmost importance that will solve in industry.Solve the low-temperature curing problem of powder coating, will start with from solidifying agent or catalyzer, just need to consider catalyzer after selecting suitable solidifying agent, the catalyzer of present routine is also the most obvious catalyzer of effect is exactly imidazoles, promote epoxy resin open loop, epoxide powder coating can be made or epoxy/polyester powder coating is minimum is reduced to 120 DEG C of solidifications, but, the decorative function on its surface is just basic to disappear, so simple imidazoles catalyzer is not also ideal catalyst that powder coating realizes low-temperature curing, this just needs a kind of cosmetic requirement of can taking into account of exploitation also can reach the constant low temperature catalyst of its performance of low-temperature curing.
Meanwhile, there is the shortcoming easily causing the ornamental difference of powder coating, easily occur the discolourations such as true hole bubble, contaminative, color generation xanthochromia in simple imidazoles catalyzer.
By retrieval, find patent publication us as relevant to patent application of the present invention in next chapter:
1, for the epoxy-imidazole catalyst (200980112915.9) of powder coating application, the method comprises: imidazoles, amine are contacted under the condition that there is not the solvent added with one or more epoxy resin, to form solids epoxy-imidazole catalyst.In other respects, embodiment disclosed herein relates to epoxy-imidazole catalyst, and curable compositions, method for the formation of curable compositions, and be used in there is not the solvent added condition under epoxy-imidazole catalyst of being formed form the method for thermosetting resin.
Being contrasted by technical characteristic, there are the different of essence in above-mentioned patent document and present patent application.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art part, there is provided one that powder coating can be impelled to react at a lower temperature, play energy-conservation effect, but the ornamental and functional of powder coating can not be affected, and the color generation xanthochromia of powder coating can not be made, the catalyzer of the saturated polyester resin solidification value that the reduced end group that can use in white or light powder is carboxyl, this method for preparing catalyst is simple, easy to operate.
The technical solution adopted for the present invention to solve the technical problems is:
Reduce the catalyzer that end group is the saturated polyester resin solidification value of carboxyl, its raw material form component and parts by weight as follows:
And described low-viscosity polyester resin, the range of viscosities of this resin 175 DEG C time is 60 ~ 65Po, and softening temperature is at 90 ~ 100 DEG C.
And described can the phase-transfer catalyst of catalysis carboxyl be salt.
And described salt is triethyl benzyl ammonia chloride, triphenyl ethyl phosphonium bromide phosphorus, choline chloride 60, triphenyl phosphorus or Triphenylphospine oxide.
And the described catalyzer of epoxide group open loop that impels is imidazoles or modified imidazole.
And described imidazoles or modified imidazole are 2-methyl-imidazoles or Diphenylimidazolines.
And described antioxidant is Hinered phenols antioxidant.
And described Hinered phenols antioxidant is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester.
Can reduce the preparation method that end group is the catalyzer of the saturated polyester resin solidification value of carboxyl as above, step is as follows:
Various material is added to high speed mixer, extrude through forcing machine after dry blending, one district's temperature is 80-90 DEG C, two district's temperature are 100-120 DEG C, carry out melting, mixing, extrude, cool, compressing tablet, become the Off-white solid of sheet, obtain and can reduce the catalyzer that end group is the saturated polyester resin solidification value of carboxyl.
Can reduce the preparation method that end group is the catalyzer of the saturated polyester resin solidification value of carboxyl as above, step is as follows:
Be that the saturated polyester resin of carboxyl puts into reactor by end group low for viscosity, make its melting at the temperature of 170-180 DEG C, stirring, then can catalysis carboxyl phase-transfer catalyst, the catalyzer of epoxide group open loop, antioxidant can be impelled to join in the vibrin of melting respectively, carry out stirring 20 minutes, cooling compressing tablet, finally form milky solid, obtain and can reduce the catalyzer that end group is the saturated polyester resin solidification value of carboxyl
Advantage of the present invention and positively effect are:
1, catalyzer of the present invention reduces the solidification value of polyester/epoxy or pure polyester powdery paints, shorten set time, powder coating can be impelled to react at a lower temperature, play energy-conservation effect, the ornamental and functional of powder coating can not be affected, and the color generation xanthochromia of powder coating can not be made, can use in white or light powder, simultaneously, this method for preparing catalyst is simple, easy to operate, respond national energy-saving and reduced discharging call, reduced production cost, improve the economic benefit of enterprise.
2, catalyzer of the present invention have employed viscosity and the lower end group of softening temperature is the saturated polyester resin of carboxyl, not only contribute to the dispersion of each effective constituent in vibrin of catalyzer, the melt viscosity of this catalyzer can also be reduced, thus reduce the melt viscosity of powder coating, facilitate levelling, reach decorative effect comparatively attractive in appearance.
3, have employed can the phase-transfer catalyst of catalysis carboxyl for catalyzer of the present invention, such as triethyl benzyl ammonia chloride, triphenyl ethyl phosphonium bromide phosphorus, choline chloride 60, triphenyl phosphorus, Triphenylphospine oxides etc., can make the carboxyl generation phase transition of saturated polyester resin in powder coating, accelerate the speed of reaction of the carboxyl of vibrin and the epoxide group of epoxy resin, make powder coating just can reach complete quick-setting requirement at a lower temperature.
4, catalyzer of the present invention have employed the catalyzer that can impel epoxide group open loop, such as imidazoles or modified imidazole class, the first catalyzed epoxies open loop of such catalyzer, make system at a lower temperature with regard to energy fast setting, but simple imidazoles can make the serious xanthochromia of system, and make film coated surface produce bubble, so employ the imidazoles of modification, such as diphenyl-imidazole quinoline class, significantly improve the shortcoming of coating xanthochromia, and this catalyzer can be used in white or light powder coating.
5, the antioxidant that catalyzer of the present invention adopts is polynary hindered phenol type antioxidant, and abandoned arylamine kind antioxidant, phenolic antioxidant does not have contaminative, can be used for colourless or light color systems, expands the use range of powder coating, improves the economic benefit of enterprise.
Embodiment
Below by specific embodiment, the invention will be further described, and following examples are descriptive, is not determinate, can not limit protection scope of the present invention with this.
The method used in the present invention, if no special requirements, is ordinary method; The reagent used in the present invention, if no special requirements, is commercially available prod.
The low-viscosity polyester resin used in the present invention is the certain resin of index parameter, and when 175 DEG C, range of viscosities is 60 ~ 65Po, and softening temperature requires at 90 ~ 100 DEG C, 2820 vibrin of such as Ao Puer, 6055 of Zhongfa Chemistry Co., Ltd., Hangzhou.
Embodiment 1:
Reduce the catalyzer that end group is the saturated polyester resin solidification value of carboxyl, its raw material form component and weight as follows:
The step of the preparation method of above-mentioned catalyzer is as follows:
Vibrin 6055 is put into reactor, make its melting at the temperature of 170-180 DEG C, stirring, then triphenyl ethyl phosphonium bromide phosphorus, 2-phenylimidazole and antioxidant 1010 (order arbitrarily) are joined in the vibrin of melting respectively, carry out stirring 20 minutes, cooling compressing tablet, finally form milky solid, obtain and can reduce the catalyst A that end group is the saturated polyester resin solidification value of carboxyl.
Using method: the catalyst A obtained can according to the needs of powder coating solidification temperature, and the addition being 0.1%-5% by massfraction joins in the formula of powder coating.
Embodiment 2:
Reduce the catalyzer that end group is the saturated polyester resin solidification value of carboxyl, its raw material form component and weight as follows:
The step of the preparation method of above-mentioned catalyzer is as follows:
Various material is added to high speed mixer, extrude through forcing machine after dry blending, one district's temperature is 80-90 DEG C, two district's temperature are 100-120 DEG C, carry out melting, mixing, extrude, cool, compressing tablet, become the Off-white solid of sheet, obtain and can reduce the catalyst B that end group is the saturated polyester resin solidification value of carboxyl.
Using method: the catalyst B obtained can according to the needs of powder coating solidification temperature, and the addition being 0.1%-5% by massfraction joins in the formula of powder coating.
Embodiment 3:
Reduce the catalyzer that end group is the saturated polyester resin solidification value of carboxyl, its raw material form component and weight as follows:
The preparation method of above-mentioned catalyzer, with embodiment 1, obtains and can reduce the catalyzer C that end group is the saturated polyester resin solidification value of carboxyl.
Using method: the catalyzer C obtained can according to the needs of powder coating solidification temperature, and the addition being 0.1%-5% by massfraction joins in the formula of powder coating.
The practical application effect of powder coating of the present invention and test situation:
For checking the practical application effect of catalyzer of the present invention, concrete operations are as follows: catalyst A embodiment obtained, B and C join in the formula of powder coating by a certain amount of respectively, in table 1, the project such as solidification value, horizontal flow, impact, hardness of coating is tested contrast.
Concrete correlation detection Indexs measure is undertaken by following standard:
Film adhesive is undertaken by GB/T9286-1998 regulation;
Film shock-resistance is undertaken by GB/T1732-1993 regulation;
Coating film gloss degree, by the regulation of GB/T9754, is tested with 60 ° of angles;
Hardness of film carries out according to GB/T6739-1996 regulation;
Coating alkali resistance is undertaken by first method (infusion method) in GB/T9274-1988, model is immersed 5%(mass percent) in sodium hydroxide (chemical pure) solution to specific time, take out model, visual observation film immediately after rinsing lightly with flowing water.Not occurring as there being two pieces in three pieces of models bubbling, ftractureing, peel off, dry linting, the defects of film coating phenomenon such as obviously variable color, obviously loss of gloss, be then chosen as " without exception ".
Coating acid resistance is undertaken by first method (infusion method) in GB/T9274-1988.Model is immersed to specific time in 3% (mass percent) hydrochloric acid (chemical pure) solution, take out model, visual observation film immediately after rinsing lightly with flowing water.Not occurring as there being two pieces in three pieces of models bubbling, ftractureing, peel off, dry linting, the defects of film coating phenomenon such as obviously variable color, obviously loss of gloss, be then chosen as " without exception ".
The correlation detection repertory of table 1 catalyzer of the present invention
As can be seen from Table 1, utilize the synthesis of this inventive method two kinds of diverse ways catalyzer obviously can both reduce solidification value, and effect is more or less the same, by regulating the ratio of each effective constituent, the solidification value of combining powder coating and decorative effect, can find preferably catalyst proportion and powder coating formulation, in all immovable situation of the various performance of powder coating, at least can reduce by the solidification value of 20 DEG C, save the energy of 10%.
Claims (1)
1. can reduce the catalyzer that end group is the saturated polyester resin solidification value of carboxyl, it is characterized in that: its raw material form component and parts by weight as follows:
Described low-viscosity polyester resin, the range of viscosities of this resin 175 DEG C time is 60 ~ 65Po, and softening temperature is at 90 ~ 100 DEG C;
Described can the phase-transfer catalyst of catalysis carboxyl be salt;
Described salt is triethyl benzyl ammonia chloride, choline chloride 60, triphenylphosphine or triphenylphosphine oxide;
The described catalyzer of epoxide group open loop that impels is imidazoles or modified imidazole;
Described imidazoles or modified imidazole are 2-methyl-imidazoles or Diphenylimidazolines;
Described antioxidant is Hinered phenols antioxidant;
Described Hinered phenols antioxidant is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester;
Described reduced end group is the preparation method of the catalyzer of the saturated polyester resin solidification value of carboxyl, and step is as follows:
Various material is added to high speed mixer, extrude through forcing machine after dry blending, one district's temperature is 80-90 DEG C, two district's temperature are 100-120 DEG C, carry out melting, mixing, extrude, cool, compressing tablet, become the Off-white solid of sheet, obtain and can reduce the catalyzer that end group is the saturated polyester resin solidification value of carboxyl;
Or described reduced end group is the preparation method of the catalyzer of the saturated polyester resin solidification value of carboxyl, and step is as follows:
Be that the saturated polyester resin of carboxyl puts into reactor by end group low for viscosity, make its melting at the temperature of 170-180 DEG C, stirring, then can catalysis carboxyl phase-transfer catalyst, the catalyzer of epoxide group open loop, antioxidant can be impelled to join in the vibrin of melting respectively, carry out stirring 20 minutes, cooling compressing tablet, finally form milky solid, obtain and can reduce the catalyzer that end group is the saturated polyester resin solidification value of carboxyl.
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| CN201310593777.9A CN103601872B (en) | 2013-11-21 | 2013-11-21 | A kind ofly reduce the catalyzer that end group is the saturated polyester resin solidification value of carboxyl |
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| CN201310593777.9A CN103601872B (en) | 2013-11-21 | 2013-11-21 | A kind ofly reduce the catalyzer that end group is the saturated polyester resin solidification value of carboxyl |
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| CN103601872B true CN103601872B (en) | 2015-07-29 |
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| CN104861829A (en) * | 2015-05-05 | 2015-08-26 | 天津翔盛粉末涂料有限公司 | Boiling-resistant epoxy polyester type powder paint and preparation method and application |
| TWI814925B (en) * | 2018-10-29 | 2023-09-11 | 美商湛新美國股份有限公司 | Low bake powder coating resins and process for coating substrates |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86100991A (en) * | 1985-02-08 | 1986-08-20 | 采煤化学公司 | With Resins, epoxy and carboxy(l)polyester is the preparation method of the powder coating of main component |
| CN102643595A (en) * | 2012-04-27 | 2012-08-22 | 天津翔盛粉末涂料有限公司 | Fired epoxy powder coating special for hot rolling coating of large-caliber steel pipes |
| CN103396724A (en) * | 2013-06-26 | 2013-11-20 | 浙江中法新材料有限公司 | Preparation method of polyester resin master batch for regulating and controlling solidification speed of powdery coating, and application of polyester resin master batch |
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2013
- 2013-11-21 CN CN201310593777.9A patent/CN103601872B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86100991A (en) * | 1985-02-08 | 1986-08-20 | 采煤化学公司 | With Resins, epoxy and carboxy(l)polyester is the preparation method of the powder coating of main component |
| CN102643595A (en) * | 2012-04-27 | 2012-08-22 | 天津翔盛粉末涂料有限公司 | Fired epoxy powder coating special for hot rolling coating of large-caliber steel pipes |
| CN103396724A (en) * | 2013-06-26 | 2013-11-20 | 浙江中法新材料有限公司 | Preparation method of polyester resin master batch for regulating and controlling solidification speed of powdery coating, and application of polyester resin master batch |
Non-Patent Citations (2)
| Title |
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| 周祥兴.抗氧剂.《中外塑料改性助剂速查手册》.机械工业出版社,2009,第172页. * |
| 陈平等.环氧树脂的固化反应,固化剂和促进剂.《环氧树脂及其应用》.化学工业出版社,2011,第42-62页. * |
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