CN102504671A - Anticorrosion energy-saving type curing agent for rapidly curing epoxy powder coating at low temperature and preparation method thereof - Google Patents
Anticorrosion energy-saving type curing agent for rapidly curing epoxy powder coating at low temperature and preparation method thereof Download PDFInfo
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- CN102504671A CN102504671A CN2011103328654A CN201110332865A CN102504671A CN 102504671 A CN102504671 A CN 102504671A CN 2011103328654 A CN2011103328654 A CN 2011103328654A CN 201110332865 A CN201110332865 A CN 201110332865A CN 102504671 A CN102504671 A CN 102504671A
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Abstract
The invention relates to an anticorrosion energy-saving type curing agent for rapidly curing epoxy powder coating at low temperature and a preparation method thereof. The anticorrosion energy-saving type curing agent for rapidly curing the epoxy powder coating at the low temperature is characterized by including that: weight ratio of low molecular weight epoxy resin and bisphenol epoxy resin is 60 to 80 : 90 to 110, a catalyst occupies 0.1% to 0.5% of total weight of reactant, dosage of an imidazole-cyanate ester compound is 0.7% to 1% of weight of epoxy rein in the powder coating, the catalyst is a mixed catalyst which is composed of quaternary ammonium salt and quaternary phosphonium salt according to proportion of 1:1, and weight ratio of imidazole and cyanate ester in the imidazole-cyanate ester compound is 70 to 80 : 80 to 90. The anticorrosion energy-saving type curing agent for rapidly curing the epoxy powder coating at the low temperature and the preparation method thereof substantially improve anticorrosion performance of a coating, meet requirements of low-temperature curing, enable the cured coating to have good adhesion and mechanical properties, lead the epoxy powder coating to be cured rapidly at one and a half minutes at 180 DEG C, and can meet construction requirements of a pipeline in bending, hoisting, penetrating and installing processes.
Description
Technical field
The present invention relates to a kind of solidifying agent that is used for the cured epoxy powder coating; Relate to a kind of anticorrosion, energy-saving low temperature fast curable epoxy used for powder coating solidifying agent; Comprise arborescens phenols curing agent and imidazoles-isocyanate compound and preparation method; The special addition agent that belongs to macromolecular material is the anticorrosion energy-saving low temperature fast curable epoxy used for powder coating solidifying agent that epoxide powder coating is used.
Background technology
At present because energy-conservation needs, national regulation steel pipe anti-corrosion spray with the solidification value of powder coating from before 200 ℃, curing in 1 minute becomes 180 ℃, 1 fen semicure.Therefore, former curing system is difficult to meet the demands under new curing system.Press for the new curing system of development, to satisfy new curing process.The anticorrosion epoxy powder coating that state uses now, solidifying agent commonly used mainly is resol and phenols curing agent.And with the epoxy powder coating of resol as solidifying agent, good heat resistance, mechanical property is high, wide material sources, and low price.But owing to contain a large amount of phenyl ring in the structure, film performance is more crisp, and especially under-30 ℃ of low temperature, toughness is relatively poor, and a large amount of rimose disadvantages are arranged when-30 ℃ of clod washes.Existing phenols curing agent need be under the catalysis of imidazoles promotor, at ability completion of cure more than 200 ℃.Existing solidifying agent does not still have and a kind ofly can possess simultaneously: mechanical property is high, and sticking power is excellent, and-30 ℃ of cold-bending properties are good, and can make epoxide powder coating at 180 ℃, 1 minute half quick-setting characteristic.
Summary of the invention
The technical problem that solves
For fear of the weak point of prior art, the present invention proposes a kind of anticorrosion energy-saving low temperature fast curable epoxy used for powder coating solidifying agent and preparation method thereof,
Technical scheme
A kind of anticorrosion energy-saving low temperature fast curable epoxy used for powder coating solidifying agent; It is characterized in that component is: the weight part of low-molecular-weight epoxy resin and bisphenol resin is 60～80: 90～110; Catalyzer is 0.1～0.5% of a reaction-ure mixture; Imidazoles-cyanate esters, consumption be in the powder coating weight epoxy 0.7～1%; Said catalyzer is quaternary ammonium salt and quaternary alkylphosphonium salt with the mixed catalyst of forming at 1: 1.The weight part of imidazoles and vulcabond is 70～80: 80～90 in said imidazoles-cyanate esters.
Said bisphenol resin adopts alkyl to replace dihydroxyphenyl propane or halogen replaces dihydroxyphenyl propane.
Said quaternary ammonium salt adopts butyl ammonium chloride.
Said quaternary alkylphosphonium salt fourth adopts basic triphenyl phosphorus chloride.
Said imidazoles adopts glyoxal ethyline or 2-ethyl-4-methylimidazole.
Said cyanate adopts isophorone diisocyanate.
A kind of method for preparing above-mentioned anticorrosion energy-saving low temperature fast curable epoxy used for powder coating solidifying agent is characterized in that step is following:
Step 1: 70～80 weight part glyoxal ethylines are joined in the reactor drum, add 80～90 weight part vulcabond again, be heated to 75 ℃, after not having the free cyano acid ester, reaction finishes, and discharging gets imidazoles-diisocyanate cpd;
Step 2: 60～80 weight part low-molecular-weight epoxy resins are thrown in reactor drum, be warming up to 120 ℃, stir; Add 15～25 weight part bisphenol resins and 0.1～0.5 part of mixed catalyst, be warming up to 150～160 ℃, reacted 1～2 hour; Be cooled to 120 ℃, this is product I;
Step 3: above-mentioned product I again with 75～85 parts of bisphenol resins and 0.1～0.5 part of mixed catalyst, mix, be warming up to 150～160 ℃; Reacted 1～2 hour; Preceding 15 minutes of discharging adds the imidazoles-diisocyanate cpd of 1% weight part, stirs; Cooling promptly gets the anticorrosion low temperature quick curing agent of the present invention.
Beneficial effect
A kind of anticorrosion energy-saving low temperature fast curable epoxy used for powder coating solidifying agent that the present invention proposes and preparation method thereof joins imidazoles-isocyanic ester promotor in the solidifying agent in the solidifying agent preparation.Institute's solidified is filmed, not only sticking power and good mechanical property, anti--30 ℃ of clod washes simultaneously; And can make epoxide powder coating at 180 ℃; 1 minute half fast setting, can satisfy pipeline at bend pipe, lift, pass through with installation process in construction requirement, so can adapt to pressing for of anticorrosion market.
Arborescens phenols curing agent of the present invention and imidazoles-diisocyanate cpd available ontologies polymerization is produced, and products therefrom is pure.The salient features of arborescens phenols curing agent of the present invention: 90～95 ℃ of softening temperatures, OH value 0.58～0.65eq/100g.This solidifying agent cured coating has more wide Application Areas and bigger using value than the existing phenols curing agent of phenolic resin curative and market.
The advantage that the present invention compares prior art is:
Reasonably prescription and production technique under the situation that increases substantially the coating antiseptic performance, satisfy the requirement of low-temperature curing, and cost reduces greatly.Adopt low-molecular-weight epoxy resin to carry out chain extension, make solidifying agent and epoxy resin compatibility property good, cross-linking density reduces, and toughness is splendid, especially low-temperature flexibility.Bisphenol resin provides the reactive behavior point, and less molecular weight is given the solidifying agent hyperergy, has increased the content of phenolic hydroxyl groups of system simultaneously, and usage quantity reduces significantly.Contain imidazoles-diisocyanate cpd in the solidifying agent, both reach the mixing of molecular level, have further improved reactive behavior.And arborescens phenols curing agent of the present invention and imidazoles-diisocyanate cpd can be used substance law production, and production technique is simple, and product is pure, and narrow molecular weight distribution all adopts domestic raw materials, and cost is low.
Description of drawings
Fig. 1: the step synoptic diagram that is the anticorrosion energy-saving low temperature fast curable epoxy used for powder coating solidifying agent preparation method of the present invention.
Embodiment
Combine embodiment, accompanying drawing that the present invention is further described at present:
Present embodiment carries out chain extension by low-molecular-weight epoxy resin and bisphenol resin under catalyst, obtain containing the arborescens phenols curing agent of phenolic hydroxyl group as end group.Simultaneously, adopt isocyanic ester sealing imidazoles, process compound, join in the solidifying agent in the solidifying agent synthetic later stage.Epoxy resin is lower molecular weight linear structure epoxy resin, and good toughness further prolongs chain, makes its two ends contain phenolic hydroxyl group, control molecular weight, thereby the reactive behavior of assurance solidifying agent.Because of itself being epoxy resin structural, good therefore as epoxy curing agent with epoxy resin compatibility property, and contain great amount of hydroxy group, sticking power is high.The imidazoles blocked isocyanate can reduce the solidification value of imidazoles, has prolonged the working life of solidifying agent simultaneously.Such affixture can be dissociated into isocyanic ester and imidazolium compounds under 70～110 ℃ of temperature; And regenerated imidazolium compounds and isocyanic ester can react with epoxy resin together: the regenerated imidazolium compounds is at first opened the oxirane ring of epoxy group(ing) and is generated hydroxyl, again and isocyanate reaction.Simultaneously, the solidifying agent molecular weight is little, and content of phenolic hydroxyl groups is high, can increase the speed of response of system, reaches the fast setting purpose.A large amount of in addition phenolic hydroxyl groups, consumption further reduces when the preparation powder coating.
Low-molecular-weight epoxy resin and bisphenol resin are the reactions of 60～80: 90～110 ratios by weight, and quaternary ammonium salt catalyst is 0.1～0.5% of a reaction-ure mixture.
Bisphenol resin can adopt alkyl to replace dihydroxyphenyl propane or halogen replaces dihydroxyphenyl propane etc.
Catalyzer can adopt quaternary ammonium salt and quaternary alkylphosphonium salt, and like butyl ammonium chloride, Butyltriphenylphosphonium chloride etc., this catalyst reaction heat release relaxes, is easy to control, and branching is few in the product, and is not crosslinked, and MWD is more concentrated.In the solidification process of powder coating, has the quick catalysis effect.
Quaternary ammonium salt and quaternary alkylphosphonium salt were formed mixed catalyst with 1: 1, and add-on is 0.1～0.5% of a reaction-ure mixture.
Low-molecular-weight epoxy resin, charging capacity are 60～80, and oxirane value is 0.48～0.52eq/100g, and epoxy equivalent (weight) is 750～950g/eq, and molecular weight is 300～900, and softening temperature is 85～100 ℃.
Imidazoles-cyanate esters is as epoxide powder coating promotor, consumption be in the powder coating weight epoxy 0.7～1%.Imidazoles can adopt glyoxal ethyline, 2-ethyl-4-methylimidazole.Cyanate can adopt isophorone diisocyanate, and the usage ratio of imidazoles and vulcabond is 70～80: 80～90.
The preparation method of present embodiment:
Step 1: earlier 70～80 weight part glyoxal ethylines are joined in the reactor drum, add 80～90 weight part vulcabond again, be heated to 75 ℃, after not having the free cyano acid ester, reaction finishes, and discharging gets imidazoles-diisocyanate cpd;
Step 2: 60～80 weight part low-molecular-weight epoxy resins are thrown in reactor drum, be warming up to 120 ℃, stir; Add 15～25 weight part bisphenol resins and 0.1～0.5 part of mixed catalyst, be warming up to 150～160 ℃, reacted 1～2 hour; Be cooled to 120 ℃, this is product I;
Step 3: product I again with 75～85 parts of bisphenol resins and 0.1～0.5 part of mixed catalyst, mix, be warming up to 150～160 ℃; Reacted 1～2 hour; Preceding 15 minutes of discharging adds the imidazoles-diisocyanate cpd of 1% weight part, stirs; Cooling promptly gets the anticorrosion low temperature quick curing agent of the present invention.
Embodiment:
Embodiment 1:
Earlier 80 weight part glyoxal ethylines are thrown in reactor drum, added 85 weight part isophorone diisocyanates again, be warming up to 75 ℃, stir, to there not being the free cyanate, discharging gets imidazoles-diisocyanate cpd.
Earlier 70 weight part low-molecular-weight epoxy resins are thrown in reactor drum, be warming up to 120 ℃, stirred 0.5 hour, add 25 weight part bisphenol resins and 0.5 part of mixed catalyst, be warming up to 150 ℃, reacted 1.5 hours, be cooled to 120 ℃, this is product I;
With product I, with 70 parts of bisphenol resins and 0.5 part of mixed catalyst, stir again; Be warming up to 150 ℃, reacted 1.5 hours, coldly be taken to 100 ℃; Imidazoles-the diisocyanate cpd that adds 1 weight part; Stir, discharging after 15 minutes, cooling promptly gets the anticorrosion energy-saving low temperature fast curable epoxy used for powder coating solidifying agent of the present invention.
Embodiment 2:
In the there-necked flask that whisking appliance, TM and cool condenser are housed; Drop into 83 weight parts glyoxal ethyline and 84 weight parts 1; The 6-hexamethylene diisocyanate rises to 75 ℃ with temperature of reaction by room temperature, and reaction proceeds to be confirmed till the no free isocyanic ester; The isocyanic ester that obtains sealing, i.e. imidazoles-isocyanate compound.
Earlier 70 weight part low-molecular-weight epoxy resins are thrown in reactor drum, be warming up to 90 ℃, add 20 weight part bisphenol resins and 0.1 part of mixed catalyst, be warming up to 150 ℃, reacted 1.5 hours, be cooled to 120 ℃, this is product I;
With product I, with 80 parts of bisphenol resins and 0.5 part of mixed catalyst, stir again; Be warming up to 150 ℃, reacted 2 hours, coldly be taken to 100 ℃; Imidazoles-the diisocyanate cpd that adds 2 weight parts; Stir, discharging after 15 minutes, cooling promptly gets the anticorrosion energy-saving low temperature fast curable epoxy used for powder coating solidifying agent of the present invention.
Claims (7)
1. anticorrosion energy-saving low temperature fast curable epoxy used for powder coating solidifying agent and preparation method thereof; It is characterized in that component is: the weight part of low-molecular-weight epoxy resin and bisphenol resin is 60～80: 90～110; Catalyzer is 0.1～0.5% of a reaction-ure mixture; Imidazoles-cyanate esters, consumption be in the powder coating weight epoxy 0.7～1%; Said catalyzer is quaternary ammonium salt and quaternary alkylphosphonium salt with the mixed catalyst of forming at 1: 1.The weight part of imidazoles and vulcabond is 70～80: 80～90 in said imidazoles-cyanate esters.
2. according to said anticorrosion energy-saving low temperature fast curable epoxy used for powder coating solidifying agent of claim 1 and preparation method thereof, it is characterized in that: said bisphenol resin adopts alkyl to replace dihydroxyphenyl propane or halogen replaces dihydroxyphenyl propane.
3. according to said anticorrosion energy-saving low temperature fast curable epoxy used for powder coating solidifying agent of claim 1 and preparation method thereof, it is characterized in that: said quaternary ammonium salt adopts butyl ammonium chloride.
4. according to said anticorrosion energy-saving low temperature fast curable epoxy used for powder coating solidifying agent of claim 1 and preparation method thereof, it is characterized in that: said quaternary alkylphosphonium salt fourth adopts basic triphenyl phosphorus chloride.
5. according to said anticorrosion energy-saving low temperature fast curable epoxy used for powder coating solidifying agent of claim 1 and preparation method thereof, it is characterized in that: said imidazoles adopts glyoxal ethyline or 2-ethyl-4-methylimidazole.
6. according to said anticorrosion energy-saving low temperature fast curable epoxy used for powder coating solidifying agent of claim 1 and preparation method thereof, it is characterized in that: said cyanate adopts isophorone diisocyanate.
7. one kind prepares said each anticorrosion energy-saving low temperature fast curable epoxy used for powder coating solidifying agent of claim 1～4 and preparation method thereof, it is characterized in that step is following:
Step 1: 70～80 weight part glyoxal ethylines are joined in the reactor drum, add 80～90 weight part vulcabond again, be heated to 75 ℃, after not having the free cyano acid ester, reaction finishes, and discharging gets imidazoles-diisocyanate cpd;
Step 2: 60～80 weight part low-molecular-weight epoxy resins are thrown in reactor drum, be warming up to 120 ℃, stir; Add 15～25 weight part bisphenol resins and 0.1～0.5 part of mixed catalyst, be warming up to 150～160 ℃, reacted 1～2 hour; Be cooled to 120 ℃, this is product I;
Step 3: above-mentioned product I again with 75～85 parts of bisphenol resins and 0.1～0.5 part of mixed catalyst, mix, be warming up to 150～160 ℃; Reacted 1～2 hour; Preceding 15 minutes of discharging adds the imidazoles-diisocyanate cpd of 1% weight part, stirs; Cooling promptly gets the anticorrosion low temperature quick curing agent of the present invention.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107674540A (en) * | 2017-09-18 | 2018-02-09 | 江苏锐康新材料科技有限公司 | A kind of low temperature curing type powdery paints and its preparation method and application |
| CN108774445A (en) * | 2018-05-24 | 2018-11-09 | 天津翔盛新材料有限公司 | A kind of Steel Pipe Heat roller coating is without rear special heavy corrosion protection epoxy powder coating of solidification and preparation method thereof |
| CN109627427A (en) * | 2018-11-19 | 2019-04-16 | 天津翔盛新材料有限公司 | A kind of preparation method of low viscosity epoxy resin and super levelling powdery paints |
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| US4335228A (en) * | 1978-02-27 | 1982-06-15 | Air Products And Chemicals, Inc. | Isocyanate blocked imidazoles and imidazolines for epoxy powder coating |
| CN1498910A (en) * | 2002-11-11 | 2004-05-26 | 西北工业大学 | Resinoid phenols solidified agent and preparation method |
| CN101402720A (en) * | 2008-11-14 | 2009-04-08 | 天津大学 | Process for producing cold curing watersoluble solidifying agent of epoxy resin |
| CN101503592A (en) * | 2008-12-19 | 2009-08-12 | 东莞理工学院 | Organic carbamide low temperature curing agent, synthesizing method thereof and epoxy powder coating composition using the low temperature curing agent |
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2011
- 2011-10-27 CN CN2011103328654A patent/CN102504671A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4335228A (en) * | 1978-02-27 | 1982-06-15 | Air Products And Chemicals, Inc. | Isocyanate blocked imidazoles and imidazolines for epoxy powder coating |
| CN1498910A (en) * | 2002-11-11 | 2004-05-26 | 西北工业大学 | Resinoid phenols solidified agent and preparation method |
| CN101402720A (en) * | 2008-11-14 | 2009-04-08 | 天津大学 | Process for producing cold curing watersoluble solidifying agent of epoxy resin |
| CN101503592A (en) * | 2008-12-19 | 2009-08-12 | 东莞理工学院 | Organic carbamide low temperature curing agent, synthesizing method thereof and epoxy powder coating composition using the low temperature curing agent |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107674540A (en) * | 2017-09-18 | 2018-02-09 | 江苏锐康新材料科技有限公司 | A kind of low temperature curing type powdery paints and its preparation method and application |
| CN107674540B (en) * | 2017-09-18 | 2020-03-31 | 江苏锐康新材料科技有限公司 | Low-temperature curing powder coating and preparation method and application thereof |
| CN108774445A (en) * | 2018-05-24 | 2018-11-09 | 天津翔盛新材料有限公司 | A kind of Steel Pipe Heat roller coating is without rear special heavy corrosion protection epoxy powder coating of solidification and preparation method thereof |
| CN109627427A (en) * | 2018-11-19 | 2019-04-16 | 天津翔盛新材料有限公司 | A kind of preparation method of low viscosity epoxy resin and super levelling powdery paints |
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Application publication date: 20120620 |