CN101555368A - Rosin ester anhydride epoxy curing agent for powder coating and preparation method thereof - Google Patents
Rosin ester anhydride epoxy curing agent for powder coating and preparation method thereof Download PDFInfo
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- CN101555368A CN101555368A CNA200910066958XA CN200910066958A CN101555368A CN 101555368 A CN101555368 A CN 101555368A CN A200910066958X A CNA200910066958X A CN A200910066958XA CN 200910066958 A CN200910066958 A CN 200910066958A CN 101555368 A CN101555368 A CN 101555368A
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Abstract
The invention relates to a rosin ester anhydride epoxy curing agent for a powder coating and a preparation method thereof. The esterification is carried out on rosin by polyol, and the Diels-Alder addition reaction is further carried out with maleic anhydride, so as to prepare the rosin ester anhydride epoxy curing agent which can initiate solid powder epoxy resin to carry out ring-opening cross-linking for generating a mesh structure; and the epoxy resin for curing comprises bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin and cycloaliphatic epoxy resin. The heat resistance and the electrical insulation performance are excellent after curing the coating. The acid value of the rosin ester anhydride epoxy curing agent for the power coating is 90-200mg KOH/g; and the melting temperature range is 60-125 DEG C. The anhydride curing agent prepared by the rosin which is a abundant renewable resource has low cost and can avoid the poison of the curing agent to human body when in use.
Description
Technical field
The present invention relates to a kind of rosin ester anhydride epoxy curing agent that is used for powder coating and preparation method thereof.
Background technology
Powder coating is one of coating variety of tool development prospect in world today's scope.Compare with conventional solvent type coating, it saves the energy and resource, minimizing environmental pollution because of having, technology is easy, coating is sturdy and durable, the recyclable utilization of powder, Application Areas are extensive etc., and characteristics obtain develop rapidly.Epoxy powder coating is a kind of common powder coating, and its using method is under the solidifying agent effect, and epoxy addition is cross-linked into the product of tridimensional network.Used solidifying agent comprises amine, anhydrides, resol etc. in the epoxy powder coating.Wherein acid anhydrides is a class epoxy powder coating solidifying agent commonly used, and it can make Resins, epoxy form the cured product that cross-linking density height, thermotolerance and electrical insulating property are good, the drug-resistant performance is good.Therefore, the epoxy powder coating of using as electronics, electrical apparatus insulation generally all adopts acid anhydrides to make solidifying agent.[with reference to books: powder coating, Chemical Industry Press, in July, 2004]
Rosin mainly refines from the secretory product of pine tree, is the extremely abundant a kind of natural resin of nature.Premium propertiess such as rosin is anticorrosion, moistureproof owing to structural characteristics have, insulation, bonding, emulsification are widely used.Also can utilize the rosiny functional group to comprise the two keys of a carboxyl and two simultaneously, in addition modification of other materials, to introduce the advantage on the rosin structure properties.Hydrogen phenanthrene ring structure in the rosin molecular skeleton has certain rigidity, and the acid anhydride type curing agent with hydrogen phenanthrene ring structure can more effectively improve resistance toheat and the electrical insulation capability that epoxy powder coating solidifies the back coating.[with reference to books: rosin chemistry and use Chemical Industry Press, in September, 2005] will be grafted to through the rosin of polyvalent alcohol esterification on the maleic anhydride, can also reduce the melt temperature of solidifying agent, help the enforcement of curing reaction.With this abundant renewable resources of rosin is the anhydride curing agent of feedstock production, not only can reduce production costs, and can also avoid solidifying agent in use to the toxicity and the pungency of human body.
Summary of the invention
The invention provides a kind of rosin ester anhydride epoxy curing agent that is used for powder coating and preparation method thereof.
A kind of rosin ester anhydride epoxy curing agent that is used for powder coating has following structural formula:
N=1～4, on behalf of polyvalent alcohol, alphabetical P be in the formula:
HOCH
2CH
2OH、HOCH
2CH
2CH
2OH、HOCH
2CHOHCH
2OH、C(CH
2OH)
4、
HOCH
2CH
2OCH
2CH
2OH, HOCH
2CH
2OCH
2CH
2OCH
2CH
2OH or
HOCH
2CH
2OCH
2CH
2OCH
2CH
2OCH
2CH
2OH。
A kind of preparation method who is used for the rosin ester anhydride epoxy curing agent of powder coating is that raw material sets out by carrying out esterification with polyvalent alcohol with rosin, carries out the Diels-Alder addition reaction with maleic anhydride then and obtains rosin ester anhydride epoxy curing agent.Reaction equation is as follows:
N=1～4, on behalf of polyvalent alcohol, alphabetical P be in the formula:
HOCH
2CH
2OH、HOCH
2CH
2CH
2OH、HOCH
2CHOHCH
2OH、C(CH
2OH)
4、
HOCH
2CH
2OCH
2CH
2OH, HOCH
2CH
2OCH
2CH
2OCH
2CH
2OH or
HOCH
2CH
2OCH
2CH
2OCH
2CH
2OCH
2CH
2OH；
In being arranged, heating unit, rectifier unit and churned mechanically three mouthfuls of reactors add rosin, at N
2Be heated to fusion under the protection, drop into the catalyzer that accounts for rosin quality 0.1～0.5%, account for the polyvalent alcohol of rosin quality 8.8～27.0%, be heated under 220～260 ℃ of stirrings and carry out esterification, react to acid number and finish during less than 20mg KOH/g, be evacuated to 3mmHg, remove excessive polyvalent alcohol; Described esterification catalyzer is nano-ZnO or p-methyl benzenesulfonic acid;
Add catalyzer that accounts for rosin quality 0.1～0.5% and the maleic anhydride that accounts for rosin quality 25.0～30.0% again, under 180 ℃～220 ℃, carry out the Diels-Alder addition reaction, reaction is evacuated to 3mmHg after finishing, remove excessive maleic anhydride and lower-boiling impurity, product is cooled to room temperature, grind powdered, obtain a kind of rosin ester anhydride epoxy curing agent that is used for powder coating;
Described polyvalent alcohol purity is more than or equal to 98%, and it is one or more the mixture in ethylene glycol, propylene glycol, glycerol, tetramethylolmethane, glycol ether, Triethylene glycol and the tetraethylene-glycol;
Described rosin, its sylvic acid mass content is more than or equal to 85%;
Described maleic anhydride, its purity is more than or equal to 95%;
The used catalyzer of described Diels-Alder addition reaction is phosphoric acid, Resorcinol or p-methyl benzenesulfonic acid.
Beneficial effect: be used for powder coating rosin ester anhydride epoxy curing agent can cause the crosslinked generation reticulated structure of solid state powder shape Resins, epoxy open loop; Can cause the crosslinked generation reticulated structure of liquid epoxies open loop.Reduce the solidifying agent cost, avoid poisoning.The solidifying agent melt temperature is low, is beneficial to the enforcement curing reaction.Behind the paint solidification, thermotolerance and electrical insulation capability are good.The acid number that is used for the rosin ester anhydride epoxy curing agent of powder coating is 90～200mg KOH/g; The melt temperature scope is 60～125 ℃.Solidified Resins, epoxy comprises bisphenol A epoxide resin, hydrogenated bisphenol A epoxy resin, cycloaliphatic epoxy resin.
Description of drawings
Figure 1A, Figure 1B, Fig. 1 C are the XPS photoelectron spectruies of product.
Figure 1A is that XPS composes entirely, proves a carbon containing and two kinds of elements of oxygen in the product.
Figure 1B provides two kinds of chemical shifts of oxygen, and a kind of is singlet oxygen in the ester bond, bound energy 532.2ev; Another kind is the two key oxygen in the ester bond, and bound energy is 533.5ev.
Fig. 1 C provides three kinds of carbon geochemistry displacements of carbon spectrum, and bound energy is the corresponding aliphatic carbon chain (CH of peak difference of 285.0ev, 286.9ev, 289.0ev
2-) in carbon, the mesomethylene carbon (CH that links to each other with oxygen
2-O-) and ester bond
In carbon.
Fig. 2 is the infrared spectrogram of product, 1735cm
-1The place is (C=O) the eigen vibration peak of carbonyl after the esterification.
Embodiment
Get 10.03g rosin and place the 100ml there-necked flask, feed N
2Protection, heat fused is started agitator; add the 0.05g nano-ZnO simultaneously and make catalyzer; when being warming up to 220 ℃, open the reflux exchanger water coolant, add ethylene glycol 1.10g, be warming up to 240 ℃; reaction was kept 4.5 hours; put water of condensation, vacuumized 1 hour, stop heating; naturally cool to room temperature, get rosin ethylene glycol ester.Sampling detecting acid number is 20mg KOH/g.
Continue heat fused, add the 0.03g Resorcinol and make catalyzer, add maleic anhydride 3.22g when being warming up to 180 ℃, be warming up to 200 ℃, holding temperature reaction 2.5 hours vacuumized 1 hour, stop heating, naturally cool to room temperature, get the rosin ethylene glycol ester maleic anhydride.It is 126mg KOH/g that sampling measures acid number.
Get 11.50g rosin and place the 100ml there-necked flask, feed N
2When protection, heat fused extremely can promote, start agitator; add the 0.05g p-methyl benzenesulfonic acid simultaneously and make catalyzer; when being warming up to 220 ℃, open the reflux exchanger water coolant, add tetramethylolmethane 1.20g, be warming up to 240 ℃; reaction was kept 4.5 hours; put water of condensation, vacuumized 1 hour, stop heating; naturally cool to room temperature, get pentalyn.Sampling detecting acid number is 19mgKOH/g.
When the continuation heat fused extremely can be stirred, add 0.05g H
3PO
4Make catalyzer, add maleic anhydride 3.00g when being warming up to 180 ℃, be warming up to 200 ℃, holding temperature reaction 2.5 hours vacuumized 1 hour, stopped heating, naturally cooled to room temperature, got the pentalyn maleic anhydride.Sampling detecting acid number is 97mg KOH/g.
Embodiment 3
Get 11.50g rosin and place the 100ml there-necked flask, feed N
2Protection, heat fused is started agitator; add the 0.05g nano-ZnO simultaneously and make catalyzer; when being warming up to 220 ℃, open the reflux exchanger water coolant, add Triethylene glycol 2.50g, be warming up to 240 ℃; reaction was kept 4.5 hours; put water of condensation, vacuumized 1 hour, stop heating; naturally cool to room temperature, get the rosin Triethylene Glycol.Sampling detecting acid number is 21mg KOH/g.
Continue heat fused, add 0.03g p-methyl benzenesulfonic acid H
3PO
4Make catalyzer, add maleic anhydride 3.20g when being warming up to 180 ℃, be warming up to 200 ℃, kept this thermotonus 2.5 hours, vacuumized 1 hour, stop heating, naturally cool to room temperature, get rosin Triethylene Glycol maleic anhydride.It is 110mg KOH/g that sampling measures acid number.
Get 11.50g rosin and place the 100ml there-necked flask, feed N
2Protection, heat fused is started agitator; add the 0.05g p-methyl benzenesulfonic acid simultaneously and make catalyzer, when being warming up to 220 ℃, open the reflux exchanger water coolant, add ethylene glycol 0.45g simultaneously; tetraethylene-glycol 1.40g; be warming up to 240 ℃, reaction was kept 4.5 hours, put water of condensation; vacuumized 1 hour; stop heating, naturally cool to room temperature, get rosin ethylene glycol/tetraethylene-glycol ester.Sampling detecting acid number is 18mg KOH/g.
Continue heat fused, add the 0.03g Resorcinol and make catalyzer, add maleic anhydride 3.50g when being warming up to 180 ℃, be warming up to 200 ℃, holding temperature reaction 2.5 hours vacuumized 1 hour, stop heating, naturally cool to room temperature, get rosin ethylene glycol/tetraethylene-glycol ester maleic anhydride.Sampling detecting acid number is 130mg KOH/g.
Get molecular weight and be 1075 bisphenol A epoxide resin 2.00g, rosin ethylene glycol ester acid anhydrides 1.00g, 2-ethyl-4-methyl-imidazoles 0.05g fully grinds, the powder that mixes is tiled on the sheet glass, solidified 1 hour down at 150 ℃, be warming up to 180 ℃ again and solidified 20 minutes, obtain rosin ethylene glycol ester anhydride epoxy cured product.
Embodiment 6
Get molecular weight and be 1075 bisphenol A epoxide resin 2.00g, pentalyn acid anhydrides 1.00g, 2-ethyl-4-methyl-imidazoles 0.05g fully grinds, the powder that mixes is tiled on the sheet glass, solidified 1 hour down at 150 ℃, be warming up to 180 ℃ again and solidified 20 minutes, obtain pentalyn anhydride epoxy cured product.
Get molecular weight and be 4000 bisphenol A epoxide resin 3.50g, rosin Triethylene Glycol acid anhydrides 0.50g, 2-ethyl-4-methyl-imidazoles 0.05g fully grinds, the powder that mixes is tiled on the sheet glass, solidified 1 hour down at 150 ℃, be warming up to 180 ℃ again and solidified 20 minutes, obtain rosin Triethylene Glycol anhydride epoxy cured product.
Embodiment 8
Get molecular weight and be 4000 bisphenol A epoxide resin 3.50g, rosin ethylene glycol/tetraethylene-glycol ester acid anhydrides 0.50g, 2-ethyl-4-methyl-imidazoles 0.05g fully grinds, the powder that mixes is tiled on the sheet glass, solidified 1 hour down at 150 ℃, be warming up to 180 ℃ again and solidified 20 minutes, obtain rosin ethylene glycol/tetraethylene-glycol ester anhydride epoxy cured product.
Claims (2)
1. rosin ester anhydride epoxy curing agent that is used for powder coating is characterized in that: have following structural formula:
N=1～4, on behalf of polyvalent alcohol, alphabetical P be in the formula:
HOCH
2CH
2OH、HOCH
2CH
2CH
2OH、HOCH
2CHOHCH
2OH、C(CH
2OH)
4、
HOCH
2CH
2OCH
2CH
2OH, HOCH
2CH
2OCH
2CH
2OCH
2CH
2OH or
HOCH
2CH
2OCH
2CH
2OCH
2CH
2OCH
2CH
2OH。
2. method for preparing rosin ester anhydride epoxy curing agent as claimed in claim 1, it is characterized in that step and condition are as follows: in heating unit, rectifier unit and churned mechanically three mouthfuls of reactors are arranged, add rosin, under the N2 protection, be heated to fusion, input accounts for the catalyzer of rosin quality 0.1～0.5%, account for the polyvalent alcohol of rosin quality 8.8～27.0%, be heated under 220～260 ℃ of stirrings and carry out esterification, react to acid number and finish during less than 20mg KOH/g, be evacuated to 3mmHg, remove excessive polyvalent alcohol; Described esterification catalyzer is nano-ZnO or p-methyl benzenesulfonic acid;
Add catalyzer that accounts for rosin quality 0.1～0.5% and the maleic anhydride that accounts for rosin quality 25.0～30.0% again, under 180 ℃～220 ℃, carry out the Diels-Alder addition reaction, reaction is evacuated to 3mmHg after finishing, remove excessive maleic anhydride and lower-boiling impurity, product is cooled to room temperature, grind powdered, get rosin ester anhydride epoxy curing agent;
Described polyvalent alcohol purity is more than or equal to 98%, and it is one or more the mixture in ethylene glycol, propylene glycol, glycerol, tetramethylolmethane, glycol ether, Triethylene glycol, the tetraethylene-glycol;
Described rosin, its sylvic acid content is more than or equal to 85%;
Described maleic anhydride, its purity is more than or equal to 95%;
The used catalyzer of described Diels-Alder addition reaction is phosphoric acid or Resorcinol or p-methyl benzenesulfonic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA200910066958XA CN101555368A (en) | 2009-05-15 | 2009-05-15 | Rosin ester anhydride epoxy curing agent for powder coating and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA200910066958XA CN101555368A (en) | 2009-05-15 | 2009-05-15 | Rosin ester anhydride epoxy curing agent for powder coating and preparation method thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102250318A (en) * | 2011-05-09 | 2011-11-23 | 中国科学院宁波材料技术与工程研究所 | Full-rosinyl epoxy resin composite and condensate thereof |
| CN102504675A (en) * | 2011-11-08 | 2012-06-20 | 老虎粉末涂料制造（太仓）有限公司 | Weather-resistant hydrogenated bisphenol A-type epoxy powder coating and preparation method and application thereof |
| CN102702813A (en) * | 2012-06-14 | 2012-10-03 | 克拉玛依市贝德化工有限责任公司 | Heat-insulation coating |
| JP2015098466A (en) * | 2013-10-15 | 2015-05-28 | 日本化薬株式会社 | Alicyclic polyfunctional acid anhydride and thermosetting resin composition |
| CN107502197A (en) * | 2017-09-18 | 2017-12-22 | 广西众昌树脂有限公司 | The preparation method of Low-temperature-resiliquid liquid rosin resin |
| CN105733421B (en) * | 2014-12-09 | 2018-12-21 | 比亚迪股份有限公司 | A kind of ultraviolet solidifying protection paint and preparation method thereof |
| CN112011275A (en) * | 2020-09-15 | 2020-12-01 | 中国林业科学研究院林产化学工业研究所 | Edible-grade water-based rosin resin, and preparation method and application thereof |
| CN113480832A (en) * | 2021-08-03 | 2021-10-08 | 安徽众博新材料有限公司 | 180 ℃ vacuum infusion epoxy resin-based composite material with TG of 170- |
-
2009
- 2009-05-15 CN CNA200910066958XA patent/CN101555368A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102250318A (en) * | 2011-05-09 | 2011-11-23 | 中国科学院宁波材料技术与工程研究所 | Full-rosinyl epoxy resin composite and condensate thereof |
| CN102250318B (en) * | 2011-05-09 | 2012-10-03 | 中国科学院宁波材料技术与工程研究所 | Full-rosinyl epoxy resin composite and condensate thereof |
| CN102504675A (en) * | 2011-11-08 | 2012-06-20 | 老虎粉末涂料制造（太仓）有限公司 | Weather-resistant hydrogenated bisphenol A-type epoxy powder coating and preparation method and application thereof |
| CN102504675B (en) * | 2011-11-08 | 2014-04-02 | 老虎粉末涂料制造（太仓）有限公司 | Weather-resistant hydrogenated bisphenol A-type epoxy powder coating and preparation method and application thereof |
| CN102702813A (en) * | 2012-06-14 | 2012-10-03 | 克拉玛依市贝德化工有限责任公司 | Heat-insulation coating |
| CN102702813B (en) * | 2012-06-14 | 2014-07-02 | 克拉玛依市贝德化工有限责任公司 | Heat-insulation coating |
| JP2015098466A (en) * | 2013-10-15 | 2015-05-28 | 日本化薬株式会社 | Alicyclic polyfunctional acid anhydride and thermosetting resin composition |
| CN105733421B (en) * | 2014-12-09 | 2018-12-21 | 比亚迪股份有限公司 | A kind of ultraviolet solidifying protection paint and preparation method thereof |
| CN107502197A (en) * | 2017-09-18 | 2017-12-22 | 广西众昌树脂有限公司 | The preparation method of Low-temperature-resiliquid liquid rosin resin |
| CN112011275A (en) * | 2020-09-15 | 2020-12-01 | 中国林业科学研究院林产化学工业研究所 | Edible-grade water-based rosin resin, and preparation method and application thereof |
| CN113480832A (en) * | 2021-08-03 | 2021-10-08 | 安徽众博新材料有限公司 | 180 ℃ vacuum infusion epoxy resin-based composite material with TG of 170- |
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