CN111548477A - Preparation method of high-purity bisphenol X (X = A, F, S) type epoxy resin - Google Patents
Preparation method of high-purity bisphenol X (X = A, F, S) type epoxy resin Download PDFInfo
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- CN111548477A CN111548477A CN202010497543.4A CN202010497543A CN111548477A CN 111548477 A CN111548477 A CN 111548477A CN 202010497543 A CN202010497543 A CN 202010497543A CN 111548477 A CN111548477 A CN 111548477A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
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Abstract
The invention provides a method for preparing high-purity bisphenol X (X = A, F, S) type epoxy resin from bisphenol X (X = A, F, S), which adopts a cheap phase transfer catalyst, takes epichlorohydrin as an epoxidation reagent, and adds alkali and an organic solvent into a reaction system. The method has the advantages that: the catalyst is cheap and easy to obtain; the reaction condition is mild, safe and reliable; the selectivity of the obtained target product is more than 98%, and the conversion rate of bisphenol X (X = A, F, S) is as high as 99.9%. The method overcomes the defects of poor reaction selectivity, complicated reaction steps, low yield, the need of using reagents harmful to the environment and the like in the traditional synthesis of the bisphenol A epoxy resin, and has good industrial application prospect.
Description
Technical Field
The invention relates to the field of application catalytic synthesis of bisphenol X (X = A, F, S) type epoxy resin, in particular to a method for preparing high-purity bisphenol X (X = A, F, S) type epoxy resin by using bisphenol X (X = A, F, S).
Background
The epoxy resin has excellent physical and mechanical properties, electrical insulation performance, corrosion resistance and bonding performance, and can be used as an organic coating, a casting material, a molding material, an adhesive and a laminated material to be directly or indirectly used in various aspects from daily necessities to national economy in high-tech fields. For example: epoxy resins are used for high-speed rails, high-molecular composite materials in airplanes and spacecrafts, packaging materials for large-scale integrated circuits, insulating materials for power generators, coatings of steel and wood, adhesives for machinery, civil engineering and construction, inner wall coatings of food cans, metal anti-corrosion electrophoretic coatings and the like. Its yield and application level may also reflect the degree of industrial technology development in a country from one side.
In europe, commercial cycloaliphatic epoxy resins were made available in the early 60's of the 20 th century. In the mid 70's, the united states, canada, uk, swiss, west, belgium, argentina, mexico, poland, czech slovak, and soviet all began to make bisphenol a epoxy resins and some new epoxy resins. At present, the epoxy resin in the world is mainly universal bisphenol A, and accounts for about 70-80% (about 95% in China); the proportion of the special epoxy resin in the United states, Western Europe and Japan is higher and is about 10-15%, and the proportion of the special epoxy resin in other countries is lower and is usually about 5%. The special epoxy resin comprises 12-16% of flame-retardant brominated epoxy resin, 1-4% of phenolic epoxy resin, about 1% of alicyclic epoxy resin and about 2% of other various epoxy resins. Due to the increase of epoxy resin varieties and the development of application technologies, the application of epoxy resin in the fields of electrical insulation, anticorrosive coatings, metal structure bonding and the like has a breakthrough.
Epoxy resin enterprises in China mainly concentrate on east China and south China, and the capacity of the epoxy resin enterprises accounts for more than 66% of the total production capacity. The productivity in east China is most concentrated and accounts for about 50% of the total productivity; wherein the capacity of the special epoxy resin is 8.4 ten thousand tons/year, which accounts for about 67.2 percent of the total production capacity; the capacity of the south China is almost all in Guangdong province, about 15.3 million tons/year, wherein the capacity of the special epoxy is 2 million tons/year. The newly built and planned extension device in 2015 year in the whole country has the capacity of about 54.7 ten thousand tons per year. The production capacity of the special epoxy is 11.7 ten thousand tons/year, the total production capacity of the special epoxy can reach 24 ten thousand tons/year, and the annual growth rate of 2010-2015 is 14.1%. With more strict national environmental protection requirements and rising raw material cost, some small enterprises producing common epoxy resin will be gradually eliminated. The capacity is eliminated by 40 ten thousand tons/year in 2015, the total capacity is maintained at more than 190 ten thousand tons/year, and the annual growth rate is 3.2% in 2010-2015.
So far, the synthesis of bisphenol a epoxy resin has several problems in terms of raw material quality, production safety, product stability, epoxy value, purity and the like, and the synthesis technology has great difficulty, the key technology of the high-purity bisphenol X (X = a, F, S) type epoxy resin is mainly mastered in several companies in the countries of america, japan and the like, and China mainly depends on import in terms of high-purity high-epoxy value type epoxy resin, special epoxy resin and the like.
In view of the shortcomings of the conventional epoxy resin synthesis process, the industry is focusing on developing a method for efficiently and selectively synthesizing a corresponding epoxy resin with a high epoxy value from stable, cheap and easily available bisphenol X (X = a, F, S) and epichlorohydrin.
Disclosure of Invention
The invention aims to provide a preparation method for synthesizing high-purity bisphenol X (X = A, F, S) epoxy resin with high efficiency and high selectivity by using cheap and easily-obtained bisphenol X (X = A, F, S) as a raw material and epoxy chloropropane as an epoxidation reagent, so as to overcome the defects in the prior art.
The invention comprises the following steps:
(1) taking reaction amount of alkali, catalyst, epichlorohydrin and organic solvent in N2Or placing the mixture in a reaction container with a constant-pressure dropping funnel and a return pipe under the air atmosphere for mixing;
(2) dissolving a reaction amount of bisphenol X (X = A, F, S) compound in an organic solvent, and dissolving the bisphenol X (X = A, F, S) compound in N2Or adding the mixture into a constant-pressure dropping funnel on a reactor in an air atmosphere, controlling the dropping speed, dropwise adding the mixture into the reactor, and reacting for 0.5-10 hours at 25-120 ℃ under stirring to obtain the corresponding high-purity bisphenol X (X = A, F, S) type epoxy resin;
the specific reaction formula is as follows:
wherein R is a methyl group (bisphenol A), a hydrogen atom (bisphenol F).
In the above method for synthesizing high purity bisphenol X (X = a, F, S) type epoxy resin, the organic solvent in the reaction steps (1) and (2) is epichlorohydrin, tetrahydrofuran, diethyl ether, toluene, methyl tert-butyl ether, epichlorohydrin, ethanol, ethyl acetate, butyl acetate, or the like,N,N-dimethylformamide,N-one or more of methyl pyrrolidone, cyclohexane or acetonitrile.
In the above method for synthesizing a high-purity bisphenol X (X = a, F, S) type epoxy resin, the epoxidizing agent is epichlorohydrin during the reaction.
In the above method for synthesizing a high purity bisphenol X (X = a, F, S) type epoxy resin, the base in the reaction step (1) is one or more selected from triethylamine, sodium bicarbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, cesium carbonate, or potassium phosphate.
In the above method for synthesizing a high purity bisphenol X (X = a, F, S) type epoxy resin, in the reaction step (1), the catalyst is one or more selected from the group consisting of polyethylene glycol-500, polyethylene glycol-2000, tetrabutylammonium iodide, tetrabutylammonium bromide, 18-crown-6-ester, benzyltriethylammonium chloride, tributylammonium chloride, and dodecyltrimethylammonium chloride.
In the above method for synthesizing a high purity bisphenol X (X = a, F, S) type epoxy resin, the molar ratio of the bisphenol X compound to the base in the reaction step (1) is 1: [1 to 1.05 ].
In the above method for synthesizing a high-purity bisphenol X (X = a, F, S) type epoxy resin, the molar ratio of the bisphenol X compound to epichlorohydrin in the reaction step (1) is 1: [2.0 to 60 ].
In the above method for synthesizing a high purity bisphenol X (X = a, F, S) type epoxy resin, the molar ratio of the bisphenol X-based compound to the catalyst in the reaction step (1) is 1: [0.01 to 0.5 ].
The method for synthesizing the high-purity bisphenol X type epoxy resin from the bisphenol X, the alkali and the epichlorohydrin has the advantages of mild and easily controlled reaction process and high efficiency and selectivity. The method is simple and easy to implement while obtaining high yield and 98 percent selectivity, and the used catalyst is cheap and easy to obtain, is simple to prepare and has good industrial application prospect.
[ detailed description ] embodiments
The invention is further illustrated below with reference to examples of the invention:
first, testing and analyzing
The structural analysis of the reaction products in the following examples of the present invention employed GC/MS (6890N/5973N) gas-mass spectrometer equipped with HP-5MS capillary chromatography column (30 m.times.0.45 mm.times.0.8 μm) manufactured by Agilent and Bruker Avance-III 500 NMR analyzer manufactured by Bruker. The selectivity and yield of the target product were analyzed by using a high performance liquid chromatograph, Waters-e2695 separation module, equipped with a C18 column (4.6 mm. times.250 mm. times.5 um) manufactured by Waters corporation.
Second, example
Example 1
11.4 g (50 mmol) of bisphenol A are dissolved in 50 mL of epichlorohydrin and transferred to an isobaric dropping funnel; then 5.0 g (125 mmol) of sodium hydroxide, 100 mL of epichlorohydrin and 0.5-5 mmol of catalyst (polyethylene glycol-500, polyethylene glycol-2000, tetrabutylammonium iodide, tetrabutylammonium bromide, 18-crown-6-ester, benzyltriethylammonium chloride, tributylammonium chloride and dodecyltrimethylammonium chloride) are added into a 250 mL three-neck flask under the nitrogen environment, and the mixture is put into a 80 mL three-neck flaskoThe reaction was stirred for 3 hours under C. By HPLC detection analysis, the yield of the coupling reaction can reach 97.2% and the selectivity is 98.2% when tetrabutylammonium bromide is used as a catalyst.
Example 2
11.4 g (50 mmol) of bisphenol A are dissolved in 50 mL of epichlorohydrin and transferred to an isobaric dropping funnel; then 5.0 g (125 mmol) of sodium hydroxide, 50 mL of epichlorohydrin, 5 mmol of tetrabutylammonium bromide and an organic solvent (epichlorohydrin, tetrahydrofuran, diethyl ether, toluene, methyl tert-butyl ether, epichlorohydrin, ethanol, ethyl acetate, butyl acetate, n-butyl acetate,N,N-dimethylformamide,N-methyl pyrrolidone, cyclohexane, acetonitrile) under nitrogen atmosphere into a 250 mL three-necked flask at 80%oThe reaction was stirred for 3 hours under C. According to HPLC detection analysis, when epichlorohydrin is used as an organic solvent, the yield of the coupling reaction can reach 97.2%, and the selectivity is 98.2%.
Example 3
11.4 g (50 mmol) of bisphenol A are dissolved in 50 mL of epichlorohydrin and transferred to an isobaric dropping funnel; then 5.0 g (125 mmol) of sodium hydroxide, 100 mL of epichlorohydrin and 5 mmol of tetrabutylammonium bromide are added into a 250 mL three-neck flask under the nitrogen environment, and the mixture is placed in a flask with the volume of 40-100 percentoThe reaction was stirred for 3 hours under C. Analysis by HPLC detection at 80oC, the yield of the coupling reaction can reach 97.2%, and the selectivity is 98.2% (40)oC yield 81% with selectivity 87.8%; 60oThe yield of C is 92, and the selectivity is 97.7%; 100oThe yield of C is 86 percent, andselectivity 91.1%).
Example 4
10.0 g (50 mmol) of bisphenol F are dissolved in 50 mL of epichlorohydrin and transferred to an isobaric dropping funnel; then 5.0 g (125 mmol) of sodium hydroxide, 100 mL of epichlorohydrin and 5 mmol of tetrabutylammonium bromide are added into a 250 mL three-neck flask under the nitrogen atmosphere, and the mixture is put into a flask with 80 percentoThe reaction was stirred for 3 hours under C. The coupling reaction was able to reach a yield of 91.2% and a selectivity of 96.7% by HPLC detection analysis.
Example 5
12.5 g (50 mmol) of bisphenol S are dissolved in 50 mL of epichlorohydrin and transferred to an isobaric dropping funnel; then 5.0 g (125 mmol) of sodium hydroxide, 100 mL of epichlorohydrin and 5 mmol of tetrabutylammonium bromide are added into a 250 mL three-neck flask under the nitrogen atmosphere, and the mixture is put into a flask with 80 percentoThe reaction was stirred for 3 hours under C. The coupling reaction was able to reach 93.4% yield with 95.1% selectivity as determined by HPLC.
It can be seen from the above examples that the method for synthesizing the corresponding high-purity bisphenol X-type epoxy resin by using the bisphenol X compound, the alkali and the epichlorohydrin, adopted by the invention, has the advantages of mild reaction conditions, cheap and easily available catalyst, simple preparation and the like. In addition, the method also has the advantages of wide substrate applicability, high yield, high selectivity (98%) and the like.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (9)
1. A process for preparing high-purity bisphenol X (X = A, F, S) type epoxy resin with the structural formula shown below,
the method is characterized by comprising the following steps:
(1) taking reaction amount of alkali, catalyst, epichlorohydrin and organic solvent in N2Or placing the mixture in a reaction container with a constant-pressure dropping funnel and a return pipe under the air atmosphere for mixing;
(2) dissolving a reaction amount of bisphenol X (X = A, F, S) compound in an organic solvent, and dissolving the bisphenol X (X = A, F, S) compound in N2Or adding the mixture into a constant-pressure dropping funnel on a reactor in an air atmosphere, controlling the dropping speed, dropwise adding the mixture into the reactor, and reacting for 0.5-10 hours at 25-120 ℃ under stirring to obtain the corresponding high-purity bisphenol X (X = A, F, S) type epoxy resin;
wherein R is a methyl group (bisphenol A) or a hydrogen atom (bisphenol F).
2. The method according to claim 1, wherein the bisphenol compound is selected from the group consisting of bisphenol A, bisphenol F, and bisphenol S.
3. The process according to claim 1, steps (1) and (2), characterized in that the organic solvent is epichlorohydrin, tetrahydrofuran, diethyl ether, toluene, methyl tert-butyl ether, epichlorohydrin, ethanol, ethyl acetate, butyl acetate, methyl tert-butyl ether, methyl epichlorohydrin, ethyl alcohol, ethyl acetate, butyl acetate, methyl tert-butyl ether, methyl propyl ether, ethyl methyl ether,N,N-dimethylformamide,N-methylpyrrolidone, cyclohexane or acetonitrile.
4. The process according to claim 1, steps (1) and (2), characterized in that the epoxidizing agent is epichlorohydrin.
5. The preparation process step (1) according to claim 1, wherein the base is selected from triethylamine, sodium bicarbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, cesium carbonate or potassium phosphate.
6. The preparation process step (1) according to claim 1, wherein the catalyst is selected from the group consisting of polyethylene glycol-500, polyethylene glycol-2000, tetrabutylammonium iodide, tetrabutylammonium bromide, 18-crown-6-ester, benzyltriethylammonium chloride, tributylammonium chloride, dodecyltrimethylammonium chloride.
7. The preparation process step (1) according to claim 1, wherein the molar ratio of bisphenol X (X = a, F, S) to base is 1: [2 to 5 ].
8. The preparation process step (1) according to claim 1, characterized in that the molar ratio of bisphenol X (X = a, F, S) to epichlorohydrin is 1: [2.0 to 60 ].
9. The preparation process step (1) according to claim 1, wherein the molar ratio of bisphenol X (X = a, F, S) to catalyst is 1: [0.01 to 0.5 ].
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3035018A (en) * | 1958-12-12 | 1962-05-15 | Devoe & Raynolds Co | Production of high molecular weight dihydric phenols and resins |
| JP2002338657A (en) * | 2001-05-14 | 2002-11-27 | Toto Kasei Co Ltd | Method of manufacturing high-purity epoxy resin |
| CN101265320A (en) * | 2007-03-16 | 2008-09-17 | 西北工业大学 | Method for preparing low content of organic chlorine epoxy resin |
| JP2011017018A (en) * | 2010-09-10 | 2011-01-27 | Mitsubishi Chemicals Corp | Epoxy resin composition and semiconductor device |
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2020
- 2020-06-04 CN CN202010497543.4A patent/CN111548477B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3035018A (en) * | 1958-12-12 | 1962-05-15 | Devoe & Raynolds Co | Production of high molecular weight dihydric phenols and resins |
| JP2002338657A (en) * | 2001-05-14 | 2002-11-27 | Toto Kasei Co Ltd | Method of manufacturing high-purity epoxy resin |
| CN101265320A (en) * | 2007-03-16 | 2008-09-17 | 西北工业大学 | Method for preparing low content of organic chlorine epoxy resin |
| JP2011017018A (en) * | 2010-09-10 | 2011-01-27 | Mitsubishi Chemicals Corp | Epoxy resin composition and semiconductor device |
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