CN102134417A - Amine-blocked sulfonic acid catalyst - Google Patents
Amine-blocked sulfonic acid catalyst Download PDFInfo
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- CN102134417A CN102134417A CN2010101126583A CN201010112658A CN102134417A CN 102134417 A CN102134417 A CN 102134417A CN 2010101126583 A CN2010101126583 A CN 2010101126583A CN 201010112658 A CN201010112658 A CN 201010112658A CN 102134417 A CN102134417 A CN 102134417A
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Abstract
The invention relates to a catalyst applied to thermosetting powder coatings, which is used for catalyzing the powder coating with polyester resin end-capped by hydroxyl with low hydroxyl value and 1,3,4,6-tetrakis(methoxymethyl) glycoluril as main base materials so that the coating generates the surface effects including wrinkle, reticulate pattern, moire, spot pattern and the like, and the thermosetting powder coating has superior outdoor weatherability and outstanding decorative property. If the amine-blocked sulfonic acid catalyst, as an indispensible ingredient of the wrinkle thermosetting powder coating, is not used, the coating does not have appearances, such as wrinkle, reticulate pattern, moire, spot pattern and other effects.
Description
[applied technical field]
The present invention relates to be applied to a class catalyzer of thermosetting powder coating(s), being used for catalysis is the powder coating of main base-material with the hydroxy-end capped vibrin and the tetramethyl oxygen methyl glycoluril of low hydroxyl value, making films form have wrinkle, the surface effect of reticulate pattern, moire, some flower etc., this type of thermosetting powder coating(s) has excellent outdoor weatherability and splendid ornamental.
[background technology]
In the thermosetting powder coating(s) triturating, a kind of crimping powder coating that is applied to the open air need adopt amine sealing sulfonic acid could form needed surface effect as catalyzer.This type of thermosetting powder coating(s) prescription is that hydroxy-end capped saturated polyester resin, tetramethyl oxygen methyl glycoluril, sealing or the non-blocked isocyanate, the amine that adopt low hydroxyl value seal raw materials compositions such as sulfonic acid catalyst, pigment (comprising pigment extender), flow agent, defoamer.Amine sealing sulfonic acid catalyst is the neccessary composition of this class thermosetting powder coating(s), if the appearance of film of effects such as not having amine sealing sulfonic acid catalyst just can't form has wrinkle, reticulate pattern, moire, some flower.But this type of amine sealing sulfonic acid catalyst is still blank at home, and at present main dependence on import similar catalyst is developed has this type of effect thermosetting powder coating(s).
Amine sealing sulfonic acid catalyst from external import, because this series products is in the monopoly position of foreign enterprise technical know-how and production marketing, cause domestic this type of catalyzer selling price high, limited exploitation, producing and selling and the application of domestic this type of powder coating undoubtedly.
[summary of the invention]
In order to satisfy development of domestic powder coating enterprise product and the needs of using, break this class amine sealing sulfonic acid catalyst and can only rely on history from external import.Through long term studies and development, developed this amine sealing sulfonic acid catalyst, and through the test of how tame foreign capital affiliate, affirmation can be satisfied the development and the application of this type of powder coating product.
The raw material that is adopted: tosic acid or tosic acid hydrate (PTSA), trifluoromethanesulfonic acid (TFMSA), N, N-dimethylethanolamine (DMEA), N, N-dimethyl propanol amine (DMAMP), diethylamine (DEA), aerosil.These raw materials are technical grade, purified grade or SILVER REAGENT (chemical pure) raw material, and the basic materialization performance is as follows:
Tosic acid (PTSA) tosic acid hydrate (PTSA) trifluoromethanesulfonic acid (TFMSA)
Molecular formula: C
7H
8O
3S molecular formula: C
7H
8O
3SH
2O molecular formula: CF
3SO
3H
Relative molecular weight: 172.2 molecular weight: 190.22 molecular weight: 150.07
Fusing point: 106-107 ℃ fusing point: 103～106 ℃ of fusing points :-40 ℃
Outward appearance: the external sight of white crystals: the external sight of white crystals: colourless transparent liquid
N, N-dimethylethanolamine (DMEA) N, N-dimethyl propanol amine (DMAMP) diethylamine (DEA)
Molecular formula: C
4H
11NO molecular formula: C
5H
13NO molecular formula: C4H11N
Molecular weight is 89.14 molecular weight: 103.2 molecular weight: 73.14
Fusing point :-59.0 ℃ of fusing points:＜-20 ℃ of fusing points :-38.9 ℃
Outward appearance: colourless or little yellow liquid outward appearance: clear amber in color liquid appearance: colourless liquid
The synthesis process of amine sealing sulfonic acid:
One, at room temperature, a certain amount of DMEA is placed among the container, the ratio that is quinaldine acid basicity (can little meta-alkalescence) in acid-base neutralisation slowly adds PTSA among the DMEA then, in adition process, adopt and carry out while adding the mode that stirs, treat the whole solubilizing reactions of PTSA after, leave standstill or whipped state under carry out more than 20 minutes, promptly finish the closing process process of DMEA, make colourless transparent liquid product to light yellow DMEA sealing PTSA to PTSA.Building-up process is an exothermic process, and whole technological process does not need heating process, does not also need process for cooling.
They are two years old, at room temperature, a certain amount of DMAMP is placed among the container, the ratio that is quinaldine acid basicity (can little meta-alkalescence) in acid-base neutralisation slowly adds PTSA among the DMAMP then, in adition process, adopt and carry out while adding the mode that stirs, treat the whole solubilizing reactions of PTSA after, leave standstill or whipped state under carry out more than 20 minutes, promptly finish the closing process process of DMAMP, make colourless transparent liquid product to light yellow DMAMP sealing PTSA to PTSA.Building-up process is an exothermic process, and whole technological process does not need heating process, does not also need process for cooling.
Three, at room temperature, a certain amount of DEA is placed among the container, the ratio that is quinaldine acid basicity (can little meta-alkalescence) in acid-base neutralisation slowly adds TFMSA among the DEA then, in adition process, adopt and carry out while stirring the mode that adds, after treating the whole hybrid reactions of TFMSA, leave standstill or whipped state under carry out more than 20 minutes, promptly finish the closing process process of DEA to TFMSA, make the light yellow transparent liquid product of DEA sealing TFMSA.Building-up process is an exothermic process, and whole technological process does not need heating process, does not also need process for cooling.
More than three technological processs respectively synthetic amine sealing sulphur be: N, N-dimethylethanolamine sealing tosic acid (DMEA/PTSA), N, N-dimethyl propanol amine sealing tosic acid (DMAMP/PTSA), quadrol sealing trifluoromethanesulfonic acid (DEA/TFMSA).These three kinds of amine sealing sulfonic acid are colourless to light yellow transparent liquid, also inconvenient when therefore being applied to the thermosetting powder coating(s) product, also be not easy to transportation, handle and need to adopt aerosil respectively this liquid amine sealing sulfonic acid to be adsorbed powder shaped.Promptly adopting aerosil is carrier, mix to stir forming loose white powder or particulate thing respectively with these three kinds of liquid amine sealing sulfonic acid, containing amine sealing sulfonic acid in every kind of mix products is 60.0%～80.0% (optimum content is 72.0 ± 3.0%).Final synthetic three kinds is the amine sealing sulfonic acid of carrier with the aerosil, and product appearance is free-pouring loose white powder or particulate thing, and the product of powder shaped is convenient to transportation and is used.And the amine of this body powder shaped sealing sulfonic acid is used for effective active composition among the powder coating and is adopting three kinds of liquid amine sealing sulfonic acid before the aerosil mixing and absorption.
The amine of powder shaped sealing sulfonic acid promptly can be applicable to thermosetting powder coating(s), is that 72 ± 3% powder shaped amine sealing sulfonic acid is that example is introduced its application in powder coating with effective component content below.Adopting aerosil is the amine sealing sulfonic acid catalyst of carrier, and the consumption of recommending in the powder coating prescription is 0.4%～1.5%, and the high more coating film gloss of consumption is low more, decorative pattern is more little, and opposite gloss is high more, decorative pattern is big more.The prescription that three kinds of amine sealing sulfonic acid is applied in the powder coating sees Table l.
The powder coating of three kinds of amine sealings of table 1 sulfonic acid catalyst is used prescription
Remarks: (1) "～" expression prescription amount ranges; (2) form of "---" symbol, prescription does not have this component.
In the table 1, the hydroxyl value of the hydroxy-end capped vibrin of low hydroxyl value is 30 ± 5mgKOH/g, the crosslinking curing ratio of itself and dead front type or non-masked isocyanate is 85: 15, the crosslinked ratio of itself and tetramethoxymethylglycoluril is 94: 6, when formulating of recipe, need vibrin and two kinds of linking agents to reach optimum proportion, otherwise prepared performance powder coating does not reach the best in the crosslinking reaction ratio.It should be noted that vibrin content is high more under the certain situation of amine sealing sulfonic acid consumption, the gloss of filming of prepared powder coating is high more, decorative pattern is big more.The employed dead front type of filling a prescription or non-masked isocyanate are as the speed of response conditioning agent of powder coating crosslinking curing, and consumption is relevant with the consumption of tetramethoxy glycoluril and poly-mutual resin.
In the table 1, a kind of in the amine that is respectively among the present invention the to be developed sealing sulfonic acid that is adopted in each prescription, the catalytic performance of every kind of amine sealing sulfonic acid is slightly had any different.But under total situation, the consumption of amine sealing sulfonic acid is big more, and then the coating film gloss of prepared powder coating is low more, decorative pattern is more little.
In the table 1, st-yrax is a defoamer, is also referred to as air release agent sometimes, and its effect is to eliminate powder coating in baking melting and solidification process, the small molecules volatility thing during fusion is filmed.Benzoic optimum amount is 0.2%～0.8%, should select and use st-yrax according to product and customer requirement.
In the table 1, the use of PE, PP, PTFE wax powder or modified waxes is film performances such as the scratch resistance that is used to improve coating, wear resistance, hardness, feel, and optimum amount is 0.6%～1.2%.
In the table 1, tinting pigment refers to the pigment with pigmentation, comprises pigment dyestuff, mineral dye etc.Its consumption is relevant with tinting strength, hiding rare and the designed thickness of filming of pigment itself, advises that usually it is basic standard that its consumption 60～80 μ m are filmed covers in base material fully.
In the table 1, nanometer, precipitation or ultra-fine barium sulfate, with the industrial raw material that is exclusively used in thermosetting powder coating(s), consumption depends on the consumption of other composition in the prescription.
In the table 1, the prescription total amount, the summation that refers to all raw materials quality parts in the prescription is generally 100%.
As can be seen from Table 1, amine sealing sulfonic acid is that a kind of catalyzer as crosslinking curing exists in the prescription, mainly is that the crosslinking reaction to hydroxyl polyester and tetramethyl oxygen methyl plays katalysis.By the use of this type of catalyzer, make product crosslinking curing in the table 1 become very complicated, finally make the film coated surface after the curing form the wrinkle effect.
This class adopts the crimping powder coating of amine sealing sulfonic acid catalyzes, and the manufacture method of common thermosetting powder coating(s) is the same: weighing → Preblend → extrude → cool off fragmentation → fine powder is broken → and sieves.The median size of obtained powder coating is controlled at 40～45 μ m for best.When carrying out application, adopt the high pressure static electricity rifle powder coating to be coated on the metal base of ground connection, through being film forming 200 ℃ (temperature of metal base) with 10～15 minutes baking-curing conditions, so final film coated surface effect is the wrinkle effect.If ultimate demand is reticulate pattern, moire or some flower effect, also need to adjust formula rate, after mix into reticulate pattern agent, moire agent or some flower component.This class powder coating has excellent weathering resistance and ornamental, is widely used in outdoor furniture, five metals, electrical equipment, automobile etc. and requires the ornamental metal of weathering resistance that requires again to cover with paint, lacquer, colour wash, etc.
Therefore, three kinds of prepared amine sealing sulfonic acid of the present invention are the hydroxy-terminated polyester resin and the crosslinked indispensable a kind of catalyzer of crimping powder coating system of tetramethyl oxygen methyl glycoluril of low hydroxyl value.
[specific implementation method]
The liquid amine sealing sulfonic acid that obtains among the present invention has three kinds of product intermediates, three kinds of the finished product.The product of final powder shaped is intermediates form three kinds of free-pouring powder shaped of energy or particulate after aerosil adsorbs, mixes a product, and these three kinds of products promptly are the amine sealing sulfonic acid catalyst of carrier with the aerosil.Concrete enforcement is as follows:
Test needed pharmaceutical chemicals: aerosil, adopt technical grade water-absorbent aerosil.Tosic acid or tosic acid hydrate (PTSA), SILVER REAGENT (chemical pure).Trifluoromethanesulfonic acid (TFMSA), SILVER REAGENT (chemical pure).N, N-dimethylethanolamine (DMEA), SILVER REAGENT (chemical pure).N, N-dimethyl propanol amine (DMAMP), SILVER REAGENT (chemical pure).Diethylamine (DEA), SILVER REAGENT (chemical pure).
Needed experiment equipment: electronic balance, range 2000g, precision 0.01g, 1.The 400ml flask, 5.Glass stick, 3.The little medicine spoon of stainless steel (the stainless steel spoon that can adopt tableware to use), 2; The PE high-pressure plastic bag of 30cm * 40cm, 10.
DMEA sealing PTSA preparation process.Use electronic balance, in a flask, take by weighing the DMEA of 95.9g, in the another flask, take by weighing the PTSA of 204.1g.With the little medicine spoon of stainless steel PTSA is slowly transferred to from flask among the flask of splendid attire DMEA, in transfer process, stir with glass stick, PTSA all is dissolved among the DMEA while shifting.In transfer and whipping process, PTSA is dissolved among the DMEA very soon, and the acid-base neutralisation chemical reaction takes place, and discharges little heat.This process lasts till that PTSA all is dissolved among the DMEA, and it is static or continue to stir the DMEA sealing PTSA product of the transparent liquid shape that promptly makes 300g more than 20 minutes to be total to molten reactant then.
DMAMP sealing PTSA preparation process.Use electronic balance, in a flask, take by weighing the DMAMP of 105.5g, in the another flask, take by weighing the PTSA of 194.5g.With the little medicine spoon of stainless steel PTSA is slowly transferred to from flask among the flask of splendid attire DMAMP, in transfer process, stir with glass stick, PTSA all is dissolved among the DMAMP while shifting.In transfer and whipping process, PTSA is dissolved among the DMAMP very soon, and the acid-base neutralisation chemical reaction takes place, and discharges little heat.This process is held the PTSA that continues and all is dissolved among the DMAMP, and it is static or continue to stir the liquid DMAMP sealing PTSA product that promptly makes 300g more than 20 minutes to be total to molten reactant then.
DEA sealing TFMSA preparation process.Use electronic balance, in a flask, take by weighing the DEA of 98.3g, in a flask, take by weighing the TFMSA of 201.7g.TFMSA is slowly poured into from flask among the flask of splendid attire DEA, in pouring process into, stir with glass stick, TFMSA all is mixed among the DEA while pour into.Pour into whipping process in, the acid-base neutralisation chemical reaction takes place in TFMSA and DEA, and discharges little heat.This process lasts till that TFMSA is all miscible among DEA, and it is static or continue to stir the liquid DEA sealing TFMSA product that promptly makes 300g more than 20 minutes to be total to molten reactant then.
More than three amine sealing sulfonic acid technological process respectively synthetic amine sealing sulphur be: N, N-dimethylethanolamine sealing tosic acid (DMEA/PTSA), N, N-dimethyl propanol amine sealing tosic acid (DMAMP/PTSA), quadrol sealing trifluoromethanesulfonic acid (DEA/TFMSA).These three kinds of amine sealing sulfonic acid are colourless to light yellow transparent liquid, also inconvenient when therefore being applied to the thermosetting powder coating(s) product, also be not easy to transportation, handle and need to adopt aerosil respectively this liquid amine sealing sulfonic acid to be adsorbed powder shaped.Promptly adopting aerosil is carrier, mix to stir with these three kinds of liquid amine sealing sulfonic acid respectively and form loose white powder or subparticle shape thing, containing amine sealing sulfonic acid in every kind of mix products is 60.0%～80.0%, but optimum content is 72.0 ± 3.0%.The powder treating processes is:
Take by weighing aerosil 100g respectively with three PE high-pressure plastic bags, then prepared three kinds liquid amine sealing sulfonic acid (300g) are all poured into respectively among the PE high-pressure plastic bag of three splendid attire aerosils.Then, with hand the plastics sack is promptly sealed, and make the enough air of maintenance in the plastics bag, mix by hand, till can't see the aerosil that has raw state.Among whipping process, in case of necessity, also can take to rub, method such as extruding, purpose is that liquid amine sealing sulfonic acid is disperseed by aerosil equably.Treat this end of processing, promptly prepared respectively with the aerosil is the N of carrier, N-dimethylethanolamine sealing tosic acid (DMEA/PTSA), N, N-dimethyl propanol amine sealing tosic acid (DMAMP/PTSA), quadrol sealing trifluoromethanesulfonic acid (DEA/TFMSA).Their effective content is 75.0%, and the quality of every kind of experiment product is 400g.Three kinds is that the outward appearance of the amine sealing sulfonic acid of carrier is free-pouring powder or finely ground particles with the aerosil.To the liquid process of carrying out powderization, also can be by adjusting the consumption of aerosil carrier, its content can be between 60.0%～80.0%, but optimum content is 72.0 ± 3.0%.
So far, all finished the preparation process of the amine sealing sulfonic acid of powder shaped, the amine sealing sulfonic acid of prepared powder shaped promptly can be used as the catalyzer of thermosetting powder coating(s), coming the hydroxy-end capped vibrin and the tetramethyl oxygen methyl glycoluril of the low hydroxyl value of catalysis is the powder coating of main base-material, formation has filming of surface effects such as wrinkle, reticulate pattern, moire, some flower, and this type of thermosetting powder coating(s) has excellent outdoor weatherability and splendid ornamental.
Claims (9)
1. be applied to the class amine sealing sulfonic acid catalyst of thermosetting powder coating(s), it is characterized in that being used for catalysis is the powder coating of main base-material with the hydroxy-end capped vibrin and the tetramethyl oxygen methyl glycoluril of low hydroxyl value, film behind the powder coating solidification form have wrinkle, the surface effect of reticulate pattern, moire, some flower etc., this type of thermosetting powder coating(s) has excellent outdoor weatherability and splendid ornamental.Amine sealing sulfonic acid is the neccessary composition of this class wrinkle thermosetting powder coating(s), if the appearance of film of effects such as not having amine sealing sulfonic acid catalyst just can't form has wrinkle, reticulate pattern, moire, some flower.
2. amine sealing sulfonic acid catalyst according to claim 1, it is characterized in that tosic acid or tosic acid hydrate (PTSA) adopt N, N-dimethylethanolamine (DMEA) or N, N-dimethyl propanol amine (DMAMP) seals, and trifluoromethanesulfonic acid (TFMSA) adopts diethylamine (DEA) to seal, and prepares three kinds of liquid amine sealing sulfonic acid.
3. amine sealing sulfonic acid according to claim 1, the outward appearance of the raw material that its feature adopted: toluenesulphonic acids or tosic acid hydrate (PTSA) are solid crystal, and trifluoromethanesulfonic acid (TFMSA), N, N-dimethylethanolamine (DMEA), N, N-dimethyl propanol amine (DMAMP) is transparent liquid with diethylamine (DEA).
4. amine sealing sulfonic acid according to claim 1, the synthesis material of Cai Yonging is tosic acid or tosic acid hydrate and employing N respectively, N-dimethylethanolamine (DMEA), tosic acid or tosic acid hydrate and N, N-dimethyl propanol amine (DMAMP), trifluoromethanesulfonic acid (TFMSA) and diethylamine (DEA).
5. amine sealing sulfonic acid according to claim 1, the employing acid-base neutralisation is the ratio of quinaldine acid basicity when it is characterized in that synthesizing, can little meta-alkalescence.
6. the amine sealing sulfonic acid catalyst of developing according to claim 1 is characterized in that synthesizing at normal temperatures, does not need to adopt the synthesis technique of heating, does not also need the refrigerative synthesis technique.Order of addition(of ingredients) is that sulfonic acid progressively adds in aminated compounds gradually in building-up process, rather than amine adds synthetic in sulfonic acid gradually.
7. the amine of developing according to claim 1 seals sulfonic acid catalyst, and its feature need be finished by stirring technique in the technology of carrying out amine sealing sulfonic acid.
8. the amine of developing according to claim 1 seals sulfonic acid catalyst, the intermediates that it is characterized in that synthetic amine catalyst are: N, N-dimethylethanolamine sealing tosic acid (DMEA/PTSA), N, N-dimethyl propanol amine sealing tosic acid (DMAMP/PTSA), quadrol sealing trifluoromethanesulfonic acid (DEA/TFMSA).These three kinds of amine sealing sulfonic acid are colourless to light yellow transparent liquid,
9. the described amine of claim 1 seals sulfonic acid, it is carrier that the amine sealing sulfonic acid of powderization is characterized in that adopting aerosil, liquid amine sealing sulfonic acid is adsorbed, mixes, final formation has Powdered or finely ground particles, and the content of amine sealing sulfonic acid is between 60.0%～80.0%.Optimum content is 72.0 ± 3.0%.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103289541A (en) * | 2013-05-30 | 2013-09-11 | 漳州市万诚粉体涂料有限公司 | Outdoor powdered cobweb coating and preparation process thereof |
| CN103937397A (en) * | 2014-05-05 | 2014-07-23 | 福建万安实业有限公司 | Dermatoglyph powder coating |
| CN104449258A (en) * | 2014-11-18 | 2015-03-25 | 广州擎天材料科技有限公司 | Crocodile embossed powder coating and preparation method thereof |
| CN106497355A (en) * | 2016-10-28 | 2017-03-15 | 福建万安实业集团有限公司 | A kind of unglazed continuous line type powdery paints |
| CN106519924A (en) * | 2016-10-28 | 2017-03-22 | 福建万安实业集团有限公司 | Turtle shell appearance imitated type powder paint |
| CN106590362A (en) * | 2016-11-11 | 2017-04-26 | 广州擎天材料科技有限公司 | SUV bumper cobweb powder paint excellent in air permeability and preparation method thereof |
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- 2010-01-24 CN CN2010101126583A patent/CN102134417A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103289541A (en) * | 2013-05-30 | 2013-09-11 | 漳州市万诚粉体涂料有限公司 | Outdoor powdered cobweb coating and preparation process thereof |
| CN103937397A (en) * | 2014-05-05 | 2014-07-23 | 福建万安实业有限公司 | Dermatoglyph powder coating |
| CN103937397B (en) * | 2014-05-05 | 2016-02-17 | 福建万安实业有限公司 | A kind of dermatoglyph powder coating |
| CN104449258A (en) * | 2014-11-18 | 2015-03-25 | 广州擎天材料科技有限公司 | Crocodile embossed powder coating and preparation method thereof |
| CN106497355A (en) * | 2016-10-28 | 2017-03-15 | 福建万安实业集团有限公司 | A kind of unglazed continuous line type powdery paints |
| CN106519924A (en) * | 2016-10-28 | 2017-03-22 | 福建万安实业集团有限公司 | Turtle shell appearance imitated type powder paint |
| CN106590362A (en) * | 2016-11-11 | 2017-04-26 | 广州擎天材料科技有限公司 | SUV bumper cobweb powder paint excellent in air permeability and preparation method thereof |
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Application publication date: 20110727 |