CN103570918A - Synthesis method of dimer acid glycidyl ester - Google Patents
Synthesis method of dimer acid glycidyl ester Download PDFInfo
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- CN103570918A CN103570918A CN201310470251.1A CN201310470251A CN103570918A CN 103570918 A CN103570918 A CN 103570918A CN 201310470251 A CN201310470251 A CN 201310470251A CN 103570918 A CN103570918 A CN 103570918A
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- glycidyl ester
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Abstract
The invention relates to a synthesis method of dimer acid glycidyl ester, which comprises the following steps: 1) under the action of a catalyst 1, carrying out addition reaction on dimer acid and epoxy chloropropane to obtain an intermediate containing chlorinol ester structure; and 2) under the action of a catalyst 2, esterifying the intermediate containing chlorinol ester structure in alkali liquor to obtain the dimer acid glycidyl ester. The synthesized dimer acid modified epoxy resin has the advantages of high epoxide number, low hydrolytic chlorine, low viscosity and the like; and the cured resin has the advantages of favorable flexibility, favorable bonding strength and stable product indexes, and can be used for industrial production.
Description
Technical field
The present invention relates to a kind of synthetic method of dimeracid glycidyl ester, belong to resin preparation field.
Background technology
In recent years, China has developed a series of snappiness epoxy resin, can be divided into Racemic glycidol ether type epoxy and glycidyl ester type epoxy resin, and dimeracid glycidyl ester is exactly a classification in its glycidyl ester type epoxy resin.With dimeracid, synthesize the epoxy resin of preparing dimeracid glycidyl ester and modification thereof, its cured product has good elasticity, toughness, so the pliability epoxy resin that is otherwise known as.
Dimeracid glycidyl ester type snappiness epoxy resin is a kind of epoxy resin of complete novel molecular structure, perfect formulating of recipe system and curing process condition.Make its cured article there is higher bonding strength, shearing resistance, electrical insulation capability and chemical resistance.The more important thing is, dimeracid glycidyl ester type flexible-epoxy cured article system has fabulous snappiness, elasticity and high unit elongation.
Snappiness epoxy resin is applied to traditional epoxy resin Application Areas, can improve splitting resistance and the heatproof degree impact of assimilate, and the performance of pouring into a mould product is improved greatly.Aspect the dry insulation system at electric product, snappiness epoxy resin, for electric insulation mould material, contributes to solve the long-term stress cracking that is perplexing the epoxy resins insulation layer in the manufacturing processedes such as poured with epoxy resin power transformer, mutual inductor, reactor, switch and puts problem with office.In addition, the epoxy resin encapsulated of electronic devices and components and assembly, seal with technique for sticking technology in, low-stress due to snappiness epoxy resin-hardener formula system curing reaction, the aspects such as the parametric stability after the encapsulation of counter stress sensitive components and the caused cracking of STRESS VARIATION producing because of machinery, temperature in elimination, decreasing insulating, more can bring into play the effect of its uniqueness.
< < C
36the synthetic > > (Nie little An etc. of dimeracid 2-glycidyl ester type epoxy resin, thermosetting resin, the 3rd phase, P11) disclose the preparation method of two kinds of dimeracid ethylene oxidic ester epoxy resins, wherein, the temperature of reaction of single stage method is 110 ℃, reaction times is 3h, the oxirane value of products obtained therefrom is 0.229 equivalent/100g, and content of organic chloride is 0.038 equivalent/100g, and viscosity is 0.95Pas; Two step method temperature of reaction is 30 ℃, and the reaction times is 12h, and the oxirane value of products obtained therefrom is 0.145 equivalent/100g, and content of organic chloride is 0.084 equivalent/100g, and viscosity is 1.4Pas; But from the result of two kinds of methods, content of organic chloride and the viscosity of products obtained therefrom are higher, and performance need further raising.
Summary of the invention
The synthetic method that the object of this invention is to provide a kind of dimeracid glycidyl ester.
In order to realize object of the present invention, the present invention adopts following technical scheme.
A synthetic method for dimeracid glycidyl ester, comprises the steps:
1), under the effect of catalyzer 1, dimeracid and epoxy chloropropane addition reaction obtain the intermediate of chloride alcohol ester structure;
2), under the effect of catalyzer 2, there is esterification and obtain dimeracid glycidyl ester in the intermediate of chloride alcohol ester structure in alkali lye.
Wherein, in step 1), described catalyzer 1 is KOH and/or NaOH; Described catalyzer 1 add-on is the 1%-5% of dimeracid quality;
In step 1), described dimeracid and epoxy chloropropane mol ratio are 1:16-20; Described addition reaction temperature is 80 ℃-100 ℃, and the reaction times is 2-4h;
In step 2) in, described esterification condition is that vacuum tightness is 120-150Torr, temperature of reaction is 60 ℃-70 ℃;
In step 2) in, it is NaOH solution or the KOH solution of 30%-50% that described alkali lye is selected mass percent concentration, and add-on is the 25%-40% of dimeracid quality; The rate of addition of described alkali lye is 1.6-2.3g/min;
In step 2) in, ammonium chloride or brometo de amonio that described catalyzer 2 replaces for alkyl, its consumption is the 0.8%-3% of dimeracid quality.
The advantages such as the dimer acid modified epoxy resin oxirane value that the present invention synthesizes is high, and hydrolysis chlorine is low, and viscosity is little, and after this resin solidification, there is good snappiness and bonding strength, product index is stable, and can be used for suitability for industrialized production.
Embodiment
Following examples are used for illustrating the present invention, but are not used for limiting the scope of the invention.
Embodiment 1
In 1L reaction flask, add 178g dimeracid, 569g epoxy chloropropane and 2.5g NaOH, stir, be warmed up to 90 ℃, maintain 90 ℃ of temperature of reaction, 2h, obtain the intermediate of chloropharin ester structure, continue to add 2.67g benzyl trimethyl ammonium chloride in system, then system vacuum tightness is risen to 140torr, temperature is controlled at 65 ℃, in 3 hours, at the uniform velocity drip 50% NaOH solution 53.36g, after being added dropwise to complete, in this temperature, continue stirring reaction 1 hour.Vacuum breaker, adds 200g80 ℃ of deionized water after completion of the reaction, stirs 5min standing, and separatory is sloughed salt, sloughs excessive unreacted epoxy chloropropane, filters to obtain product dimeracid glycidyl ester 202g.Epoxy equivalent (weight) 412g/eq, hydrolysis chlorine 3850ppm.
Embodiment 2
In 1L reaction flask, add 178g dimeracid, 569g epoxy chloropropane and 5g NaOH, stir, be warmed up to 85 ℃, maintain 85 ℃ of 4h of temperature of reaction, obtain the intermediate of chloropharin ester structure, continuation adds 5.34g benzyltriethylammoinium chloride in system, then system vacuum tightness is risen to 140torr, temperature is controlled at 65 ℃, at the uniform velocity drips 50% NaOH solution 49.48g in 2 hours, after being added dropwise to complete, in this temperature, continue stirring reaction 1 hour.Vacuum breaker, adds 200g80 ℃ of deionized water after completion of the reaction, stirs 5min standing, and separatory is sloughed salt, sloughs excessive unreacted epoxy chloropropane, filters to obtain product dimeracid glycidyl ester 196g.Epoxy equivalent (weight) 425g/eq, hydrolysis chlorine 4542ppm.
Embodiment 3
In 1L reaction flask, add 178g dimeracid, 569g epoxy chloropropane and 5g KOH, stir, be warmed up to 90 ℃, maintain 90 ℃ of 2h of temperature of reaction, obtain the intermediate of chloropharin ester structure, continuation adds 2.67g 4 bromide in system, then system vacuum tightness is risen to 130torr, temperature is controlled at 60 ℃, at the uniform velocity drips 50% NaOH solution 48.13g in 2 hours, after being added dropwise to complete, in this temperature, continue stirring reaction 1 hour.Vacuum breaker, adds 200g80 ℃ of deionized water after completion of the reaction, stirs 5min standing, and separatory is sloughed salt, sloughs excessive unreacted epoxy chloropropane, filters to obtain product dimeracid glycidyl ester 198g.Epoxy equivalent (weight) 436g/eq, hydrolysis chlorine 5210ppm.
Embodiment 4
In 1L reaction flask, add 178g dimeracid, 569g epoxy chloropropane and 2.5g KOH, stir, be warmed up to 85 ℃, maintain 85 ℃ of 4h of temperature of reaction, obtain the intermediate of chloropharin ester structure, continuation adds 5.34g tetramethyl ammonium chloride in system, then system vacuum tightness is risen to 130torr, temperature is controlled at 60 ℃, at the uniform velocity drips 50% NaOH solution 51.48g in 2 hours, after being added dropwise to complete, in this temperature, continue stirring reaction 1 hour.Vacuum breaker, adds 200g80 ℃ of deionized water after completion of the reaction, stirs 5min standing, and separatory is sloughed salt, sloughs excessive unreacted epoxy chloropropane, filters to obtain product dimeracid glycidyl ester 201g.Epoxy equivalent (weight) 443g/eq, hydrolysis chlorine 4530ppm.
Piglet s colibacillosis
Embodiment 1-4 epoxy resin is carried out to performance test, and by < < C
36in the synthetic > > of dimeracid 2-glycidyl ester type epoxy resin, single stage method gained epoxy resin, as comparative example, the results are shown in Table 1.
The contrast of table 1 Properties of Epoxy Resin
As shown in Table 1, it is high that epoxy resin prepared by the present invention has oxirane value, and hydrolysis chlorine is low, the advantage that viscosity is little, and synthesis technique of the present invention is simple, and productive rate is high.
Although above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements, all belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (8)
1. a synthetic method for dimeracid glycidyl ester, is characterized in that, comprises the steps:
1), under the effect of catalyzer 1, dimeracid and epoxy chloropropane addition reaction obtain the intermediate of chloride alcohol ester structure;
2), under the effect of catalyzer 2, there is esterification and obtain dimeracid glycidyl ester in the intermediate of chloride alcohol ester structure in alkali lye.
2. method according to claim 1, is characterized in that, in step 1), described catalyzer 1 is KOH and/or NaOH; Described catalyzer 1 add-on is the 1%-5% of dimeracid quality.
3. method according to claim 1, is characterized in that, in step 1), described dimeracid and epoxy chloropropane mol ratio are 1:16-20.
4. method according to claim 1, is characterized in that, in step 1), described addition reaction temperature is 80 ℃-100 ℃, and the reaction times is 2-4h.
5. method according to claim 1, is characterized in that, in step 2) in, described esterification condition is vacuum tightness 120-150Torr, temperature of reaction is 60 ℃-70 ℃.
6. method according to claim 1, is characterized in that, in step 2) in, it is NaOH solution or the KOH solution of 30%-50% that described alkali lye is selected mass percent concentration, and add-on is the 25%-40% of dimeracid quality.
7. method according to claim 1, is characterized in that, in step 2) in, the rate of addition of described alkali lye is 1.6-2.3g/min.
8. method according to claim 1, is characterized in that, in step 2) in, ammonium chloride or brometo de amonio that described catalyzer 2 replaces for alkyl, its consumption is the 0.8%-3% of dimeracid quality.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107513024A (en) * | 2017-07-20 | 2017-12-26 | 上海应用技术大学 | A kind of tridecandioic acid ethylene oxidic ester modified amine curing agent and preparation method and application |
| CN108299638A (en) * | 2017-12-29 | 2018-07-20 | 浙江皇马科技股份有限公司 | A kind of synthetic method of allyl alcohol polyethenoxy ether carboxylic acid ethylene oxidic ester |
| CN110105540A (en) * | 2019-05-08 | 2019-08-09 | 浙江大学 | A kind of preparation method of glycidyl ester type self curable epoxy resin |
| CN111793410A (en) * | 2020-07-28 | 2020-10-20 | 上海麦加涂料有限公司 | Low-viscosity high-performance solvent-free epoxy coating for container and preparation method thereof |
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| CN101544744A (en) * | 2009-04-17 | 2009-09-30 | 中国科学院广州化学研究所 | Acrylic acid rosin and epoxy resin prepolymer and preparation method thereof |
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2013
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101544744A (en) * | 2009-04-17 | 2009-09-30 | 中国科学院广州化学研究所 | Acrylic acid rosin and epoxy resin prepolymer and preparation method thereof |
Non-Patent Citations (2)
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| 聂小安等: "C36二聚酸二缩水甘油酯型环氧树脂的合成", 《热固性树脂》, no. 3, 31 December 1997 (1997-12-31), pages 11 - 16 * |
| 郁文汉: "一种柔性环氧树脂的制备", 《粘接》, 31 December 2012 (2012-12-31), pages 68 - 69 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107513024A (en) * | 2017-07-20 | 2017-12-26 | 上海应用技术大学 | A kind of tridecandioic acid ethylene oxidic ester modified amine curing agent and preparation method and application |
| CN107513024B (en) * | 2017-07-20 | 2019-08-30 | 上海应用技术大学 | A kind of tridecandioic acid ethylene oxidic ester modified amine curing agent and preparation method and application |
| CN108299638A (en) * | 2017-12-29 | 2018-07-20 | 浙江皇马科技股份有限公司 | A kind of synthetic method of allyl alcohol polyethenoxy ether carboxylic acid ethylene oxidic ester |
| CN108299638B (en) * | 2017-12-29 | 2020-04-28 | 浙江皇马科技股份有限公司 | Synthesis method of allyl alcohol polyoxyethylene ether carboxylic glycidyl ester |
| CN110105540A (en) * | 2019-05-08 | 2019-08-09 | 浙江大学 | A kind of preparation method of glycidyl ester type self curable epoxy resin |
| CN111793410A (en) * | 2020-07-28 | 2020-10-20 | 上海麦加涂料有限公司 | Low-viscosity high-performance solvent-free epoxy coating for container and preparation method thereof |
| WO2022021905A1 (en) * | 2020-07-28 | 2022-02-03 | 麦加芯彩新材料科技(上海)股份有限公司 | Low-viscosity, high-performance, and solvent-free epoxy coating for containers and preparation method therefor |
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| CN103570918B (en) | 2015-11-18 |
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