CN106554480B - A kind of preparation method of bisphenol A type epoxy resin - Google Patents
A kind of preparation method of bisphenol A type epoxy resin Download PDFInfo
- Publication number
- CN106554480B CN106554480B CN201510632890.2A CN201510632890A CN106554480B CN 106554480 B CN106554480 B CN 106554480B CN 201510632890 A CN201510632890 A CN 201510632890A CN 106554480 B CN106554480 B CN 106554480B
- Authority
- CN
- China
- Prior art keywords
- bisphenol
- preparation
- auxiliary agent
- epoxychloropropane
- molar ratio
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention discloses a kind of preparation methods of bisphenol A type epoxy resin for this; by bisphenol-A, epoxychloropropane, auxiliary agent according to the molar ratio of bisphenol-A and epoxychloropropane be 1:2-10; auxiliary agent is the 0.05-5% of bisphenol-A quality, and under nitrogen protection, stirring makes it completely dissolved；Solid base is added thereto again, the alkali of addition and the molar ratio of bisphenol-A are 2-3:1, reaction；Filtering；By filtrate stratification, it is evaporated under reduced pressure after removing water layer, obtains product.The waste water that the penetrating odor that the preparation method simply, in whole preparation process generates is few, generates greatly reduces compared with the prior art, is good for the environment.
Description
Technical field
The present invention relates to a kind of preparation methods of bisphenol A type epoxy resin.
Background technique
For bisphenol A type epoxy resin as Representative Cultivars most general in epoxy resin, solidfied material has many excellent spies
Property, such as adhesion strength is high, shrinking percentage is low, chemical-resistant and electrical insulating property are good, in coating, adhesive, composite material, weaving
It has a wide range of applications with national economy every field such as construction materials.Its chemical structural formula of bisphenol A type epoxy resin are as follows:
N=0~1.8 are liquid epoxies in formula.
In existing technology, bisphenol-A liquid epoxy resin is generated using bisphenol-A (BPA) and epoxychloropropane (ECH)
Generally comprise the processes such as pre-reaction, reaction, purification, desolventizing.Specifically comprises the processes of: step 1: BPA, excessive ECH and a small amount of
NaOH solution carries out pre-reaction 1-3h under the conditions of 45-65 DEG C of temperature and generates bisphenol-A chloro alcohol；Step 2: in temperature 55-
70 DEG C, under condition of negative pressure, are added NaOH solution with certain flow rate, are reacted, react the ECH gas in the water and system of generation
Body is constantly discharged outside kettle, and ECH gas is condensed back to reaction kettle through condenser and continues to participate in reaction, until reaction terminates,
General time-consuming 2-6h.Step 3: steaming water under condition of negative pressure and excess ECH obtaining thick epoxy resin；Step 4: in 70-
Under the conditions of 100 DEG C of temperature, NaOH solution is added in third time, carries out refining reaction to thick epoxy resin, removing remains in crude resin
On hydrolyzable chlorine, reaction time 1-3h.Step 5: being extracted with organic solvent, and carried out being washed to neutrality with water.The
Six steps: the organic solvent removed in resin under condition of negative pressure obtains product.
The prior art has the disadvantage in that
1. prior art process carries out altogether three times plus alkali reacts, reaction step is more, and the time is long, complex process.
2. prior art is reacted using liquid alkaline, for the concentration of alkali between 10-50%, water content is high；The water especially post-processed
It washes journey and expends a large amount of water, to generate a large amount of waste water, usual 1 ton of epoxy resin of every production can produce 1.84 tons of waste water,
Easily cause water pollution.
In addition, disclosing one step of one kind in patent document 200410024371.X adds alkali reaction synthesis low molecule bisphenol A-type
The synthesis technology of epoxy resin.It is characterized in that bisphenol-A, epoxychloropropane and polar solvent are mixed, heating reaction, reaction terminates
After be evaporated under reduced pressure out polar solvent, water and excessive epoxychloropropane, add toluene equal solvent and filter desalination after mixing evenly,
Desolventizing again.The reaction is although fairly simple, but excessive epoxychloropropane is distilled off simultaneously with water and polar solvent,
Separation may be relatively difficult.Moreover, bringing harm because the organic solvents such as toluene are added in post-processing to production process, also making to produce
Product are because the minimal residue of solvent brings smell.
Summary of the invention
The present invention is for above-mentioned deficiency in the prior art, and it is an object of the present invention to provide a kind of simple process, environmental protection, safety
High, easily separated, waste water yield greatly reduces compared with the prior art, whole preparation process moderate stimulation smell is few, obtained production
Quality meets the preparation method of the bisphenol A type epoxy resin of actual requirement.
Technical program of the present invention lies in providing a kind of preparation method of bisphenol A type epoxy resin, by bisphenol-A, epoxy chlorine
Propane, auxiliary agent are 1:2-10 according to the molar ratio of bisphenol-A and epoxychloropropane, and auxiliary agent is the 0.05-5% of bisphenol-A quality, in nitrogen
Under gas shielded, stirring is made it completely dissolved；Solid base is added thereto again, the alkali of addition and the molar ratio of bisphenol-A are 2-3:1,
In room temperature to 60 DEG C of reactions；Filtering；By filtrate stratification, it is evaporated under reduced pressure after removing water layer, obtains product；
Wherein, the auxiliary agent is tetrabutylammonium bromide, 4-butyl ammonium hydrogen sulfate, tetrabutylammonium chloride, tetraethyl bromination
Ammonium, dioctadecyl dimethyl ammonium chloride, benzyl group trimethyl ammonium chloride, benzyl group triethyl ammonium chloride, methyl tricapryl ammonium chloride,
One or more of cetyl trimethylammonium bromide, trialkyl methyl ammonium chloride.
The alkali is preferably potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, one in saleratus
Kind is several.
The reaction time is preferably 1-6h.
It preferably further filters, packs after vacuum distillation.
Temperature range in vacuum distillation process is preferably 80-95 DEG C.
More preferred scheme are as follows:
By bisphenol-A, epoxychloropropane, auxiliary agent according to the molar ratio of bisphenol-A and epoxychloropropane be 1:5, auxiliary agent benzyl three
Ethyl ammonium chloride is the 1% of bisphenol-A quality, and under nitrogen protection, stirring makes it completely dissolved；Solid base is added thereto again to add
Enter, the alkali of addition and the molar ratio of bisphenol-A are 2.5:1, are reacted at 40 DEG C；Filtering；By filtrate stratification, subtract after removing water layer
Pressure distillation, obtains product.
By above-mentioned preferred scheme, can integrate to obtain the higher product of quality, and generation wastewater flow rate is few, reaction temperature
Low, highly-safe, control is steady.
Beneficial effects of the present invention:
Although the research of the preparation of bisphenol A type epoxy resin in the prior art is more, belong to a more mature work
Skill, but the requirement with country to the raising and worker of wastewater discharge standard to working environment is higher and higher, existing technique
The requirement for being no longer satisfied production, there are whole preparation process moderate stimulation smell is big, technique is tediously long, and the waste water of generation is a large amount of
The problems such as discharge.
And to solve the above-mentioned problems, a large amount of exploration has also been made in the prior art, but the effect not obtained, the present invention
Inventor pass through a large amount of experimental study, by step in comprehensively control preparation process and parameters, auxiliary agent etc., mention
A kind of simple process, environmental protection, highly-safe, easily separated, waste water yield has been supplied to greatly reduce compared with the prior art, entirely prepare
Penetrating odor is few in the process, and obtained product quality meets the preparation method of the bisphenol A type epoxy resin of actual requirement.
Preparation method of the invention is simple, only includes once adding alkali reaction, and react in entire reaction process of the invention
Temperature is low, highly-safe, control is steady, and in whole preparation process, generated penetrating odor is few, uses in addition to required
Other than reaction raw materials, other organic solvents are not used, the yet residual of organic solvent-free in product.Moreover, the present invention is produced
Raw waste water is few, without the addition of secondary water in entire technical process, only reacts in itself the generation for having a small amount of water, is counted according to theory
It calculates, produces one ton of bisphenol a liquid epoxy resin and generate 0.1059 ton of waste water, be good for the environment.
Specific embodiment
Following embodiment is intended to further illustrate the present invention, rather than limits the scope of protection of the invention.
(1) it reacts: bisphenol-A and epoxychloropropane is added in reaction kettle according to the ratio of molar ratio 1:2-10, be added
The auxiliary agent of the 0.05-5% of bisphenol-A quality, under nitrogen protection, stirring makes it completely dissolved；Solid base is added to reaction kettle
In, the molar ratio of alkali and bisphenol-A is 2-3:1, under conditions of room temperature is to 60 DEG C, reacts 1-6h；
(2) it filters: the solid matter formed in reaction system is filtered out；
(3) liquid separation: water layer will be removed after filtered mother liquor stratification；
(4) it takes off epoxychloropropane: under conditions of vacuum distillation, removing unreacted epoxychloropropane, obtain crude product
Epoxy resin.
(5) it filters, packaging obtains product.
Embodiment
Table 1
By above-described embodiment 1-5 it is found that the quality for the bisphenol A type epoxy resin that the present invention is prepared meets Vehicles Collected from Market
It is required that purity is higher, content of organic chloride is low, is able to satisfy current requirement.Moreover, the present invention is with respect to traditional handicraft
Wastewater flow rate greatly reduce, the wastewater flow rate that traditional handicraft generates almost is 1.84 ton/ton products, and preparation method of the invention
The wastewater flow rate of generation is up to 0.1059 ton/ton product.
And generated penetrating odor is seldom in the whole preparation process of embodiment 1-5, the working environment of worker is preferable.
Claims (6)
1. a kind of preparation method of bisphenol A type epoxy resin, which is characterized in that by bisphenol-A, epoxychloropropane, auxiliary agent according to double
The molar ratio of phenol A and epoxychloropropane is 1:2-10, and auxiliary agent is the 0.05-5% of bisphenol-A quality, and under nitrogen protection, stirring makes
It is completely dissolved；Be added solid base thereto again, the alkali of addition and the molar ratio of bisphenol-A are 2-3:1, room temperature to 60 DEG C it is anti-
It answers；Filtering；By filtrate stratification, it is evaporated under reduced pressure after removing water layer, obtains product；
Wherein, the auxiliary agent be tetrabutylammonium bromide, it is 4-butyl ammonium hydrogen sulfate, tetrabutylammonium chloride, tetraethylammonium bromide, double
Octadecyldimethyl ammonium chloride, benzyltrimethylammonium chloride, benzyltriethylammoinium chloride, methyl tricapryl ammonium chloride, 16
The one or more of alkyl trimethyl ammonium bromide.
2. preparation method according to claim 1, which is characterized in that the alkali be potassium hydroxide, sodium hydroxide, in
It is one or more of.
3. preparation method according to claim 1 or 2, which is characterized in that the reaction time is 1-6h.
4. preparation method according to claim 1 or 2, which is characterized in that further filter, pack after vacuum distillation.
5. preparation method according to claim 1, which is characterized in that the temperature range in vacuum distillation process is 80-95
℃。
6. preparation method described according to claim 1 or 2 or 5, which is characterized in that press bisphenol-A, epoxychloropropane, auxiliary agent
It is 1:5 according to the molar ratio of bisphenol-A and epoxychloropropane, auxiliary agent benzyltriethylammoinium chloride is the 1% of bisphenol-A quality, in nitrogen
Under protection, stirring is made it completely dissolved；Solid base is added thereto again, the alkali of addition and the molar ratio of bisphenol-A are 2.5:1,
40 DEG C of reactions；Filtering；By filtrate stratification, it is evaporated under reduced pressure after removing water layer, obtains product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510632890.2A CN106554480B (en) | 2015-09-29 | 2015-09-29 | A kind of preparation method of bisphenol A type epoxy resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510632890.2A CN106554480B (en) | 2015-09-29 | 2015-09-29 | A kind of preparation method of bisphenol A type epoxy resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106554480A CN106554480A (en) | 2017-04-05 |
| CN106554480B true CN106554480B (en) | 2019-01-22 |
Family
ID=58414631
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510632890.2A Active CN106554480B (en) | 2015-09-29 | 2015-09-29 | A kind of preparation method of bisphenol A type epoxy resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106554480B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107236256B (en) * | 2017-06-28 | 2019-06-14 | 德州联合拓普复合材料科技有限公司 | A kind of preparation method of carbon fiber prepreg epoxy resin |
| CN109836584A (en) * | 2017-11-29 | 2019-06-04 | 中国石油化工股份有限公司 | A kind of modified bisphenol A type solid epoxy and its synthetic method and the application in low damp luminosity powdery paints |
| CN109705311A (en) * | 2018-12-27 | 2019-05-03 | 昆山市淀山湖宝波树脂涂料厂 | A kind of epoxy resin |
| CN109806821A (en) * | 2018-12-27 | 2019-05-28 | 昆山市淀山湖宝波树脂涂料厂 | A kind of production equipment of epoxy resin |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101265320A (en) * | 2007-03-16 | 2008-09-17 | 西北工业大学 | Method for preparing low content of organic chlorine epoxy resin |
| CN101429273A (en) * | 2008-12-17 | 2009-05-13 | 湘潭大学 | Process for producing wind electricity grade of bisphenol F epoxy resin |
| CN101613458A (en) * | 2008-06-25 | 2009-12-30 | 中国石油化工集团公司 | A kind of preparation method of bisphenol-A liquid epoxy resin |
| CN102292372A (en) * | 2008-12-18 | 2011-12-21 | 陶氏环球技术有限责任公司 | Method of separating solid salt from epoxy resin solutions |
-
2015
- 2015-09-29 CN CN201510632890.2A patent/CN106554480B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101265320A (en) * | 2007-03-16 | 2008-09-17 | 西北工业大学 | Method for preparing low content of organic chlorine epoxy resin |
| CN101613458A (en) * | 2008-06-25 | 2009-12-30 | 中国石油化工集团公司 | A kind of preparation method of bisphenol-A liquid epoxy resin |
| CN101429273A (en) * | 2008-12-17 | 2009-05-13 | 湘潭大学 | Process for producing wind electricity grade of bisphenol F epoxy resin |
| CN102292372A (en) * | 2008-12-18 | 2011-12-21 | 陶氏环球技术有限责任公司 | Method of separating solid salt from epoxy resin solutions |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106554480A (en) | 2017-04-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106554480B (en) | A kind of preparation method of bisphenol A type epoxy resin | |
| JP5822465B2 (en) | Production of dichloropropanol | |
| CN111689508B (en) | Method for treating tetrachloro sodium aluminate solid slag | |
| CN104387291A (en) | Preparation method of 1,3,6-hexanetricarbonitrile | |
| CN102391072B (en) | Method for separating oil-phase dichloropropanol from mixed aqueous solution of dichloropropanol and chlorine hydride | |
| CN106008482A (en) | Method for preparing electronic grade triglycidyl isocyanurate | |
| CN104477962A (en) | Co-production method of calcium carbonate and hydrogen chloride gas by distilled ammonia waste liquid of sodium carbonate industry | |
| CN107513065B (en) | Preparation method of entecavir intermediate IV | |
| CN115028606A (en) | Preparation method of benzyl glycidyl ether | |
| CN108358749A (en) | A kind of production method of propargyl alcohol | |
| CN102827202B (en) | Technology for preparing diethyl phosphite by by-product of triethyl phosphite | |
| CN104447367A (en) | Preparation method of 1-amino-anthraquinone | |
| CN104086439A (en) | Method for recovering pregabalin intermediate resolving agent (R)-(+)-alpha-phenylethylamine | |
| CN113955753A (en) | Method for recovering waste lithium iron phosphate battery powder | |
| CN105669384B (en) | The method that one kind catalyzes and synthesizes high 44 ' content of isomer Bisphenol F | |
| CN107082740B (en) | Method for improving yield of prenol prepared by chlorination process | |
| CN103497214A (en) | Clean preparation method of ethyl chloride with high purity | |
| CN109134197B (en) | Method for separating dichloropropanol from dichloropropanol hydrochloric acid solution by using alkane entrainer | |
| CN111253201A (en) | Preparation method of 1,2,3, 4-tetramethyl-1, 3-cyclopentadiene | |
| CN102675243A (en) | Process for synthesizing intermediate of (S)-2,6-diamino-4,5,6,7-tetralinbenzothiazole of anti-parkinson drug | |
| CN105779123A (en) | Clean technology for enriching unsaturated fatty acid methyl ester | |
| CN102992288B (en) | Method for preparing high pure phosphoric acid from calcium hydrogen phosphate | |
| CN106316956A (en) | Industrial production method for pyrazole | |
| CN108373435A (en) | A kind of 1,1- is bis-（T-butylperoxy）The recoverying and utilizing method of -3,3,5- trimethyl-cyclohexane soda-wash waters | |
| CN103979503A (en) | Method for preparing telluric acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |