CN1312190C - Resinoid phenols solidified agent and preparation method - Google Patents
Resinoid phenols solidified agent and preparation method Download PDFInfo
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- CN1312190C CN1312190C CNB021395101A CN02139510A CN1312190C CN 1312190 C CN1312190 C CN 1312190C CN B021395101 A CNB021395101 A CN B021395101A CN 02139510 A CN02139510 A CN 02139510A CN 1312190 C CN1312190 C CN 1312190C
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Abstract
The present invention relates to a resinoid phenol curing agent and a preparation method thereof. The curing agent belongs to a special type auxiliary agent of high molecular materials and is a superior fast curing agent for epoxy powder coating materials. The present invention is characterized in that the curing agent is composed of epoxy resin and bisphenol resin with low molecular weight, and under the catalysis of a catalyst, chain extension is carried out to obtain a resinoid curing agent containing phenhydroxy as a terminal group. The resinoid phenol curing agent of the present invention can use the mass polymerization method for production, and obtained products are pure. The resinoid phenol curing agent of the present invention has the main performance of the softening point of 90 to 95 DEG C, the glass transition temperature of 70 to 80 DEG C and the hydroxyl value of 0.28 to 0.40 eq/100g. Coating layers cured by the curing agent have wider application area and higher application value than a phenolic resin curing agent. The resinoid phenol curing agent of the present invention has the advantages of simple production process, pure product, narrow molecular weight distribution, adoption of home-made raw materials and low cost.
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: main raw material is low-molecular-weight epoxy resin and bisphenol resin,, under catalyst, carry out chain extension, obtain containing the arborescens phenols curing 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 resin, 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 resin 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 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 as butyl ammonium chloride and 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) low-molecular-weight epoxy resin and bisphenol resin are mixed by weight 60～100: 20～60, add 0.1～0.5% mixed catalyst of said mixture gross weight, reacted 1～3 hour in 150～160 ℃, be cooled to 120 ℃, this is product I;
(2) product I is added 60～100 parts of bisphenol resins and 0.1～0.5 part of mixed catalyst, be warming up to 150～160 ℃, reacted 2～4 hours, discharging while hot, cooling, pulverizing.
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 resin 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 (5)
1, a kind of arborescens phenols curing agent is characterized in that: main raw material is low-molecular-weight epoxy resin and bisphenol resin, carries out chain extending reaction under catalyst, obtains the arborescens phenols curing agent; Low-molecular-weight epoxy resin and bisphenol resin are 60～100: 20～60 ratios reactions by weight, mixed catalyst be low-molecular-weight epoxy resin and bisphenol resin total amount 0.1～0.5%; Preparation process is: a, with low-molecular-weight epoxy resin and bisphenol resin by weight 60～100: 20～60 mix, 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 bisphenol resins and 0.1～0.5 part of mixed catalyst, be warming up to 150～160 ℃, react discharging while hot, cooling, pulverizing 2～4 hours.
2, arborescens phenols curing agent according to claim 1 is characterized in that: bisphenol resin is to use alkyl to replace dihydroxyphenyl propane or halogen replaces the dihydroxyphenyl propane preparation.
3, arborescens phenols curing agent according to claim 1 is characterized in that: mixed catalyst is quaternary ammonium salt and quaternary alkylphosphonium salt.
4, arborescens phenols curing agent according to claim 3 is characterized in that: mixed catalyst quaternary ammonium salt and quaternary alkylphosphonium salt are butyl ammonium chloride and Butyltriphenylphosphonium chloride.
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.
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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1498910A CN1498910A (en) | 2004-05-26 |
| CN1312190C true 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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Families Citing this family (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 |
| CN103589283B (en) * | 2013-11-10 | 2015-07-15 | 湖南至诚涂料有限公司 | Method for preparing thin-coating powder coating and product |
| CN104693420B (en) * | 2013-12-06 | 2017-09-12 | 天津博瀚科技发展有限公司 | A kind of solid-state phenols epoxy powder curing agent and one one step preparation method |
| 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 |
| EP4067452A4 (en) * | 2019-11-29 | 2023-12-06 | Kukdo Chemical Co., Ltd. | Method for manufacturing ultra-low-temperature, fast-curable epoxy resin, and powder coating composition comprising resin manufactured thereby |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1082578A (en) * | 1992-07-10 | 1994-02-23 | 苏马吕株式会社 | Epoxy resin powder coating composition |
| JPH07168193A (en) * | 1993-09-02 | 1995-07-04 | Loctite Ireland Ltd | Manufacture of liquid crystal display and composition used in method thereof |
| CN1134713A (en) * | 1993-09-24 | 1996-10-30 | 国际壳牌研究有限公司 | Epoxy resin composition |
-
2002
- 2002-11-11 CN CNB021395101A patent/CN1312190C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1082578A (en) * | 1992-07-10 | 1994-02-23 | 苏马吕株式会社 | Epoxy resin powder coating composition |
| JPH07168193A (en) * | 1993-09-02 | 1995-07-04 | Loctite Ireland Ltd | Manufacture of liquid crystal display and composition used in method thereof |
| CN1134713A (en) * | 1993-09-24 | 1996-10-30 | 国际壳牌研究有限公司 | Epoxy resin composition |
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| CN1498910A (en) | 2004-05-26 |
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