CN1498910A - Resinoid phenols solidified agent and preparation method - Google Patents
Resinoid phenols solidified agent and preparation method Download PDFInfo
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- CN1498910A CN1498910A CNA021395101A CN02139510A CN1498910A CN 1498910 A CN1498910 A CN 1498910A CN A021395101 A CNA021395101 A CN A021395101A CN 02139510 A CN02139510 A CN 02139510A CN 1498910 A CN1498910 A CN 1498910A
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Abstract
A resinous phenolic solidifying agent for the powder epoxy paint is prepared from low-molecular epoxy resin and biphenol resin through chain enlarging reaction under the action of catalyst to obtain the product containing phenhydroxy as terminal group. Its advantages are high purity and narrow molecular weight distribution. Its main parameters are 90-95 deg.C for softening point, 70-80 deg.C for vitrification temp and 0.28-0.40 eq/100g for hydroxy number.
Description
Technical field: the present invention relates to a kind of arborescens phenols curing agent and preparation method, belong to the special addition agent of macromolecular material, is the good quick curing agent that epoxide powder coating is used.
Background technology: at present, at bend pipe, lift, pass through with the installation process construction in, be starved of and obtain sticking power and good mechanical property, the solidifying agent of anti--30 ℃ of clod washes simultaneously.And the anticorrosion epoxy powder coating that China uses now, solidifying agent commonly used mainly is a resol.And with the epoxy powder coating of resol as solidifying agent, good heat resistance, mechanical property height, 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 solidifying agent does not still have and a kind ofly can possess simultaneously: the mechanical property height, and the sticking power excellence ,-30 ℃ of cold-bending properties are good, and can make the quick-setting characteristic of epoxide powder coating.
Summary of the invention: for avoiding the deficiencies in the prior art part, the present invention has developed a kind of novel arborescens phenols curing agent, not only sticking power and good mechanical property, anti--30 ℃ of clod washes simultaneously, and can make the epoxide powder coating 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.
Technological thought of the present invention is: by low-molecular-weight epoxy resin and bisphenol resin, carry out chain extension under catalyst, obtain containing the arborescens solidifying agent of phenolic hydroxyl group as end group.Resins, epoxy is lower molecular weight linear structure Resins, epoxy, and good toughness further prolongs chain, makes its two ends contain phenolic hydroxyl group, thus curable epoxy.Because of itself being epoxy resin structural, good therefore as epoxy curing agent with epoxy resin compatibility, and contain great amount of hydroxy group, the sticking power height.Bisphenol, owing to contain phenolic hydroxyl group in the structure, the first step and Resins, epoxy reaction reach the chain extension purpose, the reaction of second step, it is excessive to need, and makes the product two ends of generation contain phenolic hydroxyl group, uses thereby can be used as solidifying agent.Simultaneously, excessive because of add-on, contain unreacted bisphenol in the system, can increase the speed of response of system, reach the fast setting purpose.A large amount of in addition phenolic hydroxyl groups is given the excellent sticking power of filming.
Low-molecular-weight epoxy resin and bisphenol resin are the reactions of 60～100: 20～60 ratios by weight, and mixed catalyst is 0.1～0.5% of a reaction-ure mixture.
Bisphenol can adopt alkyl to replace dihydroxyphenyl propane or halogen to ask for for dihydroxyphenyl propane etc.
Catalyzer can adopt quaternary ammonium salt and quaternary alkylphosphonium salt, and as 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 molecular weight distribution 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 60～100, 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 ℃.
Preparation method of the present invention:
(1) earlier 60～100 weight part low-molecular-weight epoxy resins is thrown in reactor, be warming up to 120 ℃, stir, add 20～60 weight part bisphenols and 0.1～0.5 part of mixed catalyst, be warming up to 150～160 ℃, reacted 1～3 hour, be cooled to 120 ℃, this is product I;
(2) above-mentioned product I again with 60～100 parts of bisphenols and 0.1～0.5 part of mixed catalyst, mix, be warming up to 150～160 ℃, reacted 3～4 hours, discharging, cooling promptly gets arborescens phenols curing agent of the present invention.
Arborescens phenols curing agent available ontologies polymerization of the present invention is produced, and products therefrom is pure.The salient features of arborescens phenols curing agent of the present invention: 90～95 ℃ of softening temperatures, 70～80 ℃ of second-order transition temperatures, hydroxyl value 0.28～0.40eq/100g.This solidifying agent cured coating has more wide Application Areas and bigger using value than phenolic resin curative.
The present invention's advantage compared to existing technology is:
Reasonably prescription and production technique are increasing substantially under the coating flexible situation, have reached the high adhesive force of external anticorrosion special curing agent, and levelling property is splendid to wait key property, and cost reduces greatly.Adopt low-molecular-weight epoxy resin to carry out chain extension, make solidifying agent and epoxy resin compatibility good, cross-linking density reduces, and toughness is splendid, especially low-temperature flexibility.Bisphenol provides the reactive behavior point, gives the solidifying agent hyperergy, has increased the content of phenolic hydroxyl groups of system simultaneously, and sticking power, thermotolerance are increased substantially.And arborescens phenols curing agent of the present invention 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 is an arborescens phenols curing agent preparation method's of the present invention step synoptic diagram
Embodiment:
Embodiment 1:
Earlier 100 weight part low-molecular-weight epoxy resins are thrown in reactor, 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 3 hours, be cooled to 120 ℃, this is product I;
With product I, with 96 parts of bisphenol resins and 0.5 part of mixed catalyst, stir again, be warming up to 150 ℃, reacted 4 hours, discharging, cooling promptly gets arborescens phenols curing agent of the present invention.
Claims (6)
1, a kind of arborescens phenols curing agent is characterized in that: major ingredient is low-molecular-weight epoxy resin and bisphenol resin, and carries out chain extension under catalyst.
2, arborescens phenols curing agent according to claim 1 is characterized in that: low-molecular-weight epoxy resin and bisphenol resin are the reactions of 60～100: 20～60 ratios by weight, and mixed catalyst is 0.1～0.5% of a reaction-ure mixture.
3, arborescens phenols curing agent according to claim 1 and 2 is characterized in that: bisphenol can adopt alkyl to replace dihydroxyphenyl propane or halogen to ask for for dihydroxyphenyl propane etc.
4, arborescens phenols curing agent according to claim 1, it is characterized in that: mixed catalyst can adopt quaternary ammonium salt and quaternary alkylphosphonium salt, as butyl ammonium chloride, Butyltriphenylphosphonium chloride etc.
5, arborescens phenols curing agent according to claim 1 and 2, it is characterized in that: the oxirane value of low-molecular-weight epoxy resin is 0.48～0.52eq/100g.
6, a kind of preparation method of arborescens phenols curing agent, it is characterized in that: a, low-molecular-weight epoxy resin and bisphenol are mixed by weight 60～100,20～60,0.1～0.5% the mixed catalyst that adds the said mixture gross weight, in 150～160 ℃ of reactions 1～3 hour, be cooled to 120 ℃, this is product I; B, product I is added 60～100 parts of bisphenols and 0.1～0.5 part of mixed catalyst, be warming up to 150～160 ℃, react discharging while hot, cooling, pulverizing 2～4 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021395101A CN1312190C (en) | 2002-11-11 | 2002-11-11 | Resinoid phenols solidified agent and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021395101A CN1312190C (en) | 2002-11-11 | 2002-11-11 | Resinoid phenols solidified agent and preparation method |
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| Publication Number | Publication Date |
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| CN1498910A true CN1498910A (en) | 2004-05-26 |
| CN1312190C CN1312190C (en) | 2007-04-25 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB021395101A Expired - Fee Related CN1312190C (en) | 2002-11-11 | 2002-11-11 | Resinoid phenols solidified agent and preparation method |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504671A (en) * | 2011-10-27 | 2012-06-20 | 西安大禾化工材料有限公司 | Anticorrosion energy-saving type curing agent for rapidly curing epoxy powder coating at low temperature and preparation method thereof |
| CN103589283A (en) * | 2013-11-10 | 2014-02-19 | 湖南至诚涂料有限公司 | Method for preparing thin-coating powder coating and product |
| CN104693420A (en) * | 2013-12-06 | 2015-06-10 | 天津博瀚科技发展有限公司 | Curing agent for solid phenolic epoxy resin powder and one-step preparation method of curing agent |
| CN109207017A (en) * | 2018-08-03 | 2019-01-15 | 天津翔盛新材料有限公司 | A kind of preparation method and application and anti-corrosive powder paint of low-temperature flexibility phenols curing agent |
| 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 |
| CN114585661A (en) * | 2019-11-29 | 2022-06-03 | 国都化学株式会社 | Method for preparing ultra-low temperature fast curing epoxy resin and composition for powder coating containing resin prepared thereby |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2580444B2 (en) * | 1992-07-10 | 1997-02-12 | ソマール株式会社 | Flexible epoxy resin composition |
| EP0646632A1 (en) * | 1993-09-02 | 1995-04-05 | Loctite (Ireland) Limited | A method of manufacturing a liquid crystal display and a composition for use in the method |
| JP3428699B2 (en) * | 1993-09-24 | 2003-07-22 | ジャパンエポキシレジン株式会社 | Epoxy resin composition |
-
2002
- 2002-11-11 CN CNB021395101A patent/CN1312190C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504671A (en) * | 2011-10-27 | 2012-06-20 | 西安大禾化工材料有限公司 | Anticorrosion energy-saving type curing agent for rapidly curing epoxy powder coating at low temperature and preparation method thereof |
| CN103589283A (en) * | 2013-11-10 | 2014-02-19 | 湖南至诚涂料有限公司 | Method for preparing thin-coating powder coating and product |
| CN104693420A (en) * | 2013-12-06 | 2015-06-10 | 天津博瀚科技发展有限公司 | Curing agent for solid phenolic epoxy resin powder and one-step preparation method of curing agent |
| CN109207017A (en) * | 2018-08-03 | 2019-01-15 | 天津翔盛新材料有限公司 | A kind of preparation method and application and anti-corrosive powder paint of low-temperature flexibility phenols curing agent |
| 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 |
| CN114585661A (en) * | 2019-11-29 | 2022-06-03 | 国都化学株式会社 | Method for preparing ultra-low temperature fast curing epoxy resin and composition for powder coating containing resin prepared thereby |
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| Publication number | Publication date |
|---|---|
| CN1312190C (en) | 2007-04-25 |
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Granted publication date: 20070425 Termination date: 20091211 |