CN103539924A - Low-electrical impedance epoxy resin and preparation method thereof - Google Patents
Low-electrical impedance epoxy resin and preparation method thereof Download PDFInfo
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- CN103539924A CN103539924A CN201310446758.3A CN201310446758A CN103539924A CN 103539924 A CN103539924 A CN 103539924A CN 201310446758 A CN201310446758 A CN 201310446758A CN 103539924 A CN103539924 A CN 103539924A
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- epoxy resin
- low electric
- electric impedance
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Abstract
The invention discloses a low-electrical impedance epoxy resin and a preparation method thereof. The low-electrical impedance epoxy resin is formed by an anti-static compound intermediate, a calcium metal complex ion intermediate and an epoxy resin through a polymerization. The conductive type epoxy resin disclosed by the invention has excellent heat resistance and mechanical performance. A product prepared from the low-electrical impedance epoxy resin has the advantages of low toxicity and no odor, and furthermore, both the impact strength and the bending strength can meet requirements in an actual use.
Description
Technical field
The present invention relates to a kind of epoxy resin, particularly relate to a kind of low electric impedance epoxy resin containing antistatic compound structure and preparation method thereof.
Background technology
Epoxy resin is a kind of important thermosetting resin, is range of application one of material the most widely in common polymer composite.Epoxy resin not only has good adhesive property, coating property, mechanical property, wear resisting property and electrical insulation capability, and its stable chemical performance, and erosion resistance is good, good thermal stability, and shrinking percentage low, be easy to machine-shaping, cheap.Epoxy resin itself as one of three large interchangeable heat thermosetting resins is the isolator of excellent performance, and its intrinsic volume specific resistance is 10
14～10
16between Ω cm.
The volume specific resistance of low electric impedance epoxy resin (approaches semi-conductor) between conductor and semi-conductor, by volume the difference of resistivity can be used for general antistatic floor, anti-riot level conduction terrace, hazardous chemical hold-up vessel inwall and oil and gas pipeline interior finishing, electromagnetic wave shielding coating etc.
Low electric impedance epoxy resin can be divided into two kinds of addition type and eigenmodes.Addition type refers to and in epoxy resin, adds metal-powder, conductive filler materials such as carbon black and form low electric impedance epoxy resin blend, the advantage of addition type low electric impedance epoxy resin is low cost of manufacture, technical maturity is constructed with being easy to, its major defect is filler itself and has neither part nor lot in the crosslinking reaction of epoxy resin, but utilize between the particle of conductive filler material own, contact with each other and conduction current, while being used for conducting electricity terrace, can cause terrace to be full of defect and obstruction, make mechanical property variation, conductivity is unstable and make conductivity disappearance etc. owing to wearing away in using.As Chinese patent " for epoxy resin compound and the preparation thereof of anti-electrostatic " (publication number CN1220284) discloses a kind of preparation method of antistatic epoxy resin compound, by materials such as epoxy resin diluent, doping agent, mixed solvent and solidifying agent, formed, this epoxy resin by adding doping agent, rely on ion in doping agent along with the motion of the segment in cross-linked network realizes anti-static function, because doping agent and epoxy resin are that physical property is combined, thereby anti-static function is unstable, in use procedure, be difficult to control volume specific resistance 7 * 10
8below Ω cm.
And eigenmode refers to that introducing antistatic compound structure on epoxy resin main chain forms low electric impedance epoxy resin, because needs are controlled at 7 * 10 by volume specific resistance
8Ω cm is following to reach anti-electrostatic, anti-riot object, thereby manufacturing cost is high, complicated process of preparation.
Chinese patent " manufacture method of the epoxide resin polymer of low electric impedance and products thereof and application " (publication number CN1275593) discloses a kind of preparation technology of low electric impedance epoxide resin polymer, comprise by the bridging agent copolymerization crosslinking reaction of intermediate polymer, epoxy resin host and the cross-linking reaction of low electric impedance and hardening, then combo is closed the copolymerization epoxide resin polymer of the low electric impedance that colorant weighting material and auxiliary agent make.The shortcoming of this low electric impedance epoxide resin polymer is that simple dependence is introduced " π " electron conjugated structure and possessed antistatic performance, thereby antistatic performance is not good and preparation technology is comparatively complicated.
Summary of the invention
The object of the invention is to overcome the shortcoming that epoxy resin antistatic performance is unstable, product performance are poor, a kind of antistatic compound structure and π of simultaneously containing be provided " the low electric impedance epoxy resin of electron conjugated structure and preparation method thereof.
The technical solution adopted in the present invention is as follows:
An epoxy resin, the low electric impedance cured article being formed by antistatic compound intermediate, calcium metal complexing ion intermediate, epoxy resin and solidifying agent polyreaction, general formula is as follows:
Wherein, antistatic compound is the compound containing quaternary ammonium salt structure, and solidifying agent is polyamine, and the volume specific resistance of low electric impedance epoxy resin is 7.546 * 10
6Ω cm.
Meanwhile, the present invention also provides a kind of preparation method of low electric impedance epoxy resin, and it comprises the steps:
(1), dihydroxyphenyl propane is reacted under alkaline condition with epoxy chloropropane, then add antistatic compound epoxypropyl trimethyl ammonium, obtain the epoxy resin containing quaternary ammonium salt structure;
(2), at the CaCl of excessive hydrochloric acid
2in solution, add glycerol, then carry out twice dehydration under differing temps, generate calcium metal complexing ion intermediate;
(3), the epoxy resin of the antistatic compound structure described in above-mentioned (1) is added to the calcium metal complexing ion intermediate described in above-mentioned (2), then add polyamine curing reaction to obtain low electric impedance epoxy resin cured product.
Beneficial effect of the present invention is:
On epoxy resin main chain, introduce antistatic compound structure and " π " electron conjugated structure, good machinery and the resistance toheat of prepared conductivity type epoxy resin tool simultaneously.
Embodiment
The preparation of low electric impedance epoxy resin, comprises the steps:
(1) antistatic compound structural epoxy resins is synthetic:
The NaOH aqueous solution that is 12% by dihydroxyphenyl propane and concentration adds stirred-tank reactor, after heating for dissolving, be cooled to 45 ℃, add epoxy chloropropane, after reaction certain hour, add the antistatic compound epoxypropyltrimethylchloride chloride of appropriate quaternary ammonium salt, continue reaction, question response liquid water layer pH value is constant, and reaction finishes, after hot wash is neutrality to pH, remove moisture and excessive epoxy chloropropane under reduced pressure, must be containing the epoxy resin of antistatic compound structure.
(2) calcium metal complexing ion intermediate is synthetic:
With graduated cylinder, measure the concentrated hydrochloric acid 25ml that claims 36.5%, add the dilution of 25ml deionized water, then take 7 grams of anhydrous calcium oxides, both are neutralized, make the CaCl containing excessive hydrochloric acid
2solution.
By gained CaCl
2solution and 85% strong phosphoric acid 25ml, add in the 250mL four-hole boiling flask that thermometer, prolong, dropping funnel and agitator are housed, and is warming up to 80 ℃, then get 18ml glycerol, by dropping funnel, slowly splash in flask, react 4 hours, make glycerol that dehydration for the first time occur.
In a glycerol molecule, containing two primary hydroxyls and a secondary hydroxyl, wherein primary hydroxyl is sloughed than secondary hydroxyl is more difficult, and what when temperature is 80 ℃, slough is secondary hydroxyl, generate 3-hydroxyl-1-vinylcarbinol, and enol is unstable, and having Partial Conversion is 3-HPA.
Temperature is risen to 170 ℃, react 40～50 minutes, until dripless flows down in prolong.Now 3-HPA continues to occur dehydration for the second time, sloughs a primary hydroxyl, generates propenal; Due to carbon-to-carbon double bond in propenal and the two key conjugation of carbon-oxygen, part propylene aldehyde is converted into special ion in the acid system of 170 ℃
+cH
2-CH=CH-O
-; This ion reacts with calcium ion and generates calcium metal complexing ion intermediate;
Be cooled to normal temperature, get proper ammonia and the volume ratio dilution with 1:1 with deionized water, then the ammoniacal liquor after dilution is dropwise splashed in flask to neutral;
Product is poured out, vacuum filtration with deionized water wash repeatedly, the whiter paste solid leaching is put into culture dish, and then put in the lump vacuum drying oven dry 12 hours, temperature is made as 90 ℃.Gained white powder is calcium metal complexing ion intermediate.
(3) low electric impedance epoxy resin and cured article thereof is synthetic
Get the antistatic compound epoxy resin that above-mentioned (1) makes, with appropriate tetrahydrofuran (THF) dissolved dilution, add again the calcium metal complexing ion intermediate in above-mentioned (2), be heated to 60 ℃ of reactions 3 hours, with vacuum pump, vacuumize 10 to 15 minutes again and remove tetrahydrofuran (THF), add a certain amount of polynary amine curing agent to obtain low molecule impedance epoxy resin as quadrol, diethylenetriamine curing reaction, the volumetric usage of polyamine is calculated as follows:
The volumetric usage that in formula, V is polyamine, the quality that m is epoxy resin, the density that ρ is polyamine, quadrol value is 0.8995(g/ml), diethylenetriamine value is 0.9586(g/ml); A is the Theoretical Mass umber that the polyamine consuming occurs to solidify the epoxy resin of a quality, can be calculated as follows:
The relative molecular mass that in formula, M is polyamine, the oxirane value that E is epoxy resin, the reactive hydrogen atom number that n is polyamine, quadrol is 4, diethylenetriamine is 5; B is the purity of polyamine, and general value is 100%.
Preferably, in above-mentioned low electric impedance epoxy resin preparation process, using epoxy resin E-51 as resin matrix.
More preferably, antistatic compound structural epoxy resins in above-mentioned (1) and the mass ratio of the calcium metal complexing ion intermediate in above-mentioned (2) are 10:2, using diethylenetriamine (DETA) as solidifying agent, in self-vulcanizing two days later, adopt digital multimeter to measure the volume resistance R of cured product, with following formula, be converted into volume specific resistance ρ again
In formula, L is the thickness of sample after solidifying, the cross-sectional area that S is sample, the i.e. area (4cm of stainless steel thin slice
2), measuring cured article volume specific resistance in above-mentioned (3) is 7.546 * 10
7Ω cm.
By the mechanical property comparison of pure epoxy resin cured article and low electric impedance epoxy resin cured product of the present invention.From following table, to introduce after calcium metal complexing ion intermediate, the shock strength of low electric impedance epoxy resin cured product of the present invention just slightly declines, and in same level, its erosion-resisting characteristics is good with the shock strength of pure epoxy resin cured article.Both flexural strengths and modulus in flexure are also very approaching, show to introduce after calcium metal complexing ion intermediate, and the toughness of low electric impedance epoxy resin cured product is not subject to significantly sacrificing.And both hardness and coating adhesion be all in same level, these show to introduce the mechanical property that calcium metal complexing ion intermediate does not affect cured article.
The mechanical property comparison of two kinds of cured articles
Applicant's statement, person of ordinary skill in the field is on the basis of above-described embodiment, by the concrete content point value of above-described embodiment component, combined with the technical scheme of summary of the invention part, thereby the new numerical range producing, also be one of record scope of the present invention, the application, for making specification sheets simple and clear, is no longer enumerated these numerical ranges.
Claims (9)
1. a low electric impedance epoxy resin, is characterized in that the low electric impedance cured article that it is formed by antistatic compound intermediate, calcium metal complexing ion intermediate, epoxy resin and solidifying agent polyreaction, and general formula is as follows:
2. according to low electric impedance epoxy resin claimed in claim 1, it is characterized in that: described antistatic compound is the compound containing quaternary ammonium salt structure.
3. according to low electric impedance epoxy resin claimed in claim 1, it is characterized in that: described solidifying agent is polyamine.
4. according to low electric impedance epoxy resin claimed in claim 1, it is characterized in that: the volume specific resistance of this low electric impedance epoxy resin is 7.546 * 10
6Ω/cm.
5. a preparation method for low electric impedance epoxy resin described in claim 1, is characterized in that comprising the steps:
(1) preparation contains the epoxy resin of antistatic compound structure:
Dihydroxyphenyl propane is reacted under alkaline condition with epoxy chloropropane, then add antistatic compound epoxypropyl trimethyl ammonium, obtain the epoxy resin containing quaternary ammonium salt structure;
(2) prepare calcium metal complexing ion intermediate:
CaCl at excessive hydrochloric acid
2in solution, add glycerol, then carry out twice dehydration under differing temps, generate calcium metal complexing ion intermediate;
(3) prepare low electric impedance epoxy resin:
Antistatic compound structural epoxy resins described in above-mentioned (1) is added to the calcium metal complexing ion intermediate described in above-mentioned (2), then add polyamine curing reaction to obtain low electric impedance epoxy resin cured product.
6. according to the preparation method of low electric impedance epoxy resin described in claim 5, it is characterized in that the epoxy resin containing antistatic compound structure in preparation process (1) comprises following process:
The NaOH aqueous solution that is 12% by dihydroxyphenyl propane and concentration adds stirred-tank reactor, after heating for dissolving, be cooled to 45 ℃, add epoxy chloropropane, after reaction certain hour, add appropriate antistatic compound epoxypropyltrimethylchloride chloride, continue reaction, question response liquid water layer pH value is constant, and reaction finishes, after hot wash is neutrality to pH, remove moisture and excessive epoxy chloropropane under reduced pressure, must be containing the epoxy resin of antistatic compound structure.
7. according to the preparation method of low electric impedance epoxy resin described in claim 5, it is characterized in that the calcium metal complexing ion intermediate in preparation process (2) comprises following process:
By the CaCl containing excessive hydrochloric acid
2solution adds tank reactor with appropriate phosphoric acid, be warming up to 80 ℃, drip after appropriate glycerol reaction 4h, again temperature is risen to after 170 ℃ of reaction 40～50min, be cooled to normal temperature, get proper ammonia diluent and splash into reactor to neutral, vacuum filtration is also used deionized water wash, by the white solid leaching in vacuum drying oven in 110 ℃ of dry 12h, obtain calcium metal complexing ion intermediate.
8. according to the preparation method of low electric impedance epoxy resin described in claim 5, it is characterized in that the low electric impedance epoxy resin in preparation process (3) comprises following process:
By appropriate tetrahydrofuran solution dilution for the antistatic compound structural epoxy resins described in above-mentioned (1), add again the calcium metal complexing ion intermediate described in above-mentioned (2), be heated to 60 ℃ of reaction 3h, vacuumize and remove tetrahydrofuran (THF), add a certain amount of quadrol or diethylenetriamine curing reaction to obtain low molecule impedance epoxy resin.
9. according to the preparation method of low electric impedance epoxy resin described in claim 8, it is characterized in that: the weight ratio of the epoxy resin of described antistatic compound structure and described calcium metal complexing ion intermediate is 10:2.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104945849A (en) * | 2015-06-26 | 2015-09-30 | 苏州荣昌复合材料有限公司 | Method for preparing anti-static modified plastics |
| CN106279639A (en) * | 2016-08-25 | 2017-01-04 | 安徽善孚新材料科技股份有限公司 | Low-electrical impedance epoxy resin and preparation method thereof and product |
| CN116376437A (en) * | 2023-04-26 | 2023-07-04 | 广东绿树环保涂料科技有限公司 | Terrace paint for parking lot and preparation method thereof |
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| CN101177477A (en) * | 2007-12-11 | 2008-05-14 | 蓝星化工新材料股份有限公司无锡树脂厂 | Epoxy resin catalytic refining process |
-
2013
- 2013-09-27 CN CN201310446758.3A patent/CN103539924A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101177477A (en) * | 2007-12-11 | 2008-05-14 | 蓝星化工新材料股份有限公司无锡树脂厂 | Epoxy resin catalytic refining process |
Non-Patent Citations (3)
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|---|
| CHANTAL BONNANS-PLAISANCE ET AL: "Synthèse d’une résine antistatique par introduction de sites ioniques dans le système Epikote 1001-Euredur 423", 《DIE ANGEWANDTE MAKROMOLEKULARE CHEMIE》, vol. 253, no. 1, 31 December 1997 (1997-12-31), pages 111 - 130, XP000737012, DOI: 10.1002/apmc.1997.052530109 * |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104945849A (en) * | 2015-06-26 | 2015-09-30 | 苏州荣昌复合材料有限公司 | Method for preparing anti-static modified plastics |
| CN106279639A (en) * | 2016-08-25 | 2017-01-04 | 安徽善孚新材料科技股份有限公司 | Low-electrical impedance epoxy resin and preparation method thereof and product |
| CN116376437A (en) * | 2023-04-26 | 2023-07-04 | 广东绿树环保涂料科技有限公司 | Terrace paint for parking lot and preparation method thereof |
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Application publication date: 20140129 |