CN108373531A - A kind of preparation method of solvent epoxy varnish - Google Patents
A kind of preparation method of solvent epoxy varnish Download PDFInfo
- Publication number
- CN108373531A CN108373531A CN201810308031.1A CN201810308031A CN108373531A CN 108373531 A CN108373531 A CN 108373531A CN 201810308031 A CN201810308031 A CN 201810308031A CN 108373531 A CN108373531 A CN 108373531A
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- preparation
- bisphenol
- solvent
- dimethylbenzene
- 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.)
- Granted
Links
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
Abstract
The present invention provides a kind of preparation methods of solvent epoxy varnish, using epoxychloropropane and bisphenol-A as raw material, etherification reaction and polymerisation are carried out under same reaction condition, pass through the direct synthetic type epoxy resin of one-step method, method relative to traditional two-step method synthetic type epoxy resin, present invention eliminates the loaded down with trivial details synthesis technologies of bisphenol-A liquid epoxy resin, synthetic method is simple and convenient, on the basis of not increasing " three wastes " amount, reduce reaction time and solvent usage amount, effectively reduce production cost, production efficiency is substantially increased while ensureing product quality.
Description
Technical field
The present invention relates to chemical products technology field more particularly to a kind of preparation methods of solvent epoxy varnish.
Background technology
Epoxy resin is a kind of important high molecular material, widely used, it has excellent chemical stability, electrical isolation
Property, corrosion resistance and excellent mechanical performance and physical property, while epoxy resin also has good technological operation performance, energy
It is widely used in coating industry, machinery industry, electronics industry, transportation, auto manufacturing, construction industry, aerospace etc.
Field.In recent years, the demand of Chinese epoxy resin was used with the industries such as annual 15% speed increase, especially electronics, coating
High-quality epoxy resin more with annual 20%~25% speed increase, there are prodigious market prospects.
Coating industry largely uses solvent epoxy varnish, because it has many advantages, such as that viscosity is low, simple operation, therefore by compared with
Multiple enterprises are welcome.Currently, solvent epoxy varnish is mainly synthesized using two step additive process, two step additive process synthetic types
Epoxy resin method is as follows：Bisphenol-A liquid epoxy resin is first produced as raw material using epoxychloropropane and bisphenol-A, then with bisphenol-A
Type liquid epoxies and bisphenol-A are raw material, it is certain with when catalyst action under hard resin is obtained by the reaction, add
The dimethylbenzene of required ratio is dissolved, then obtains corresponding solvent type resin.However, the conjunction of bisphenol-A liquid epoxy resin
It is more loaded down with trivial details at process, low production efficiency.
Invention content
The purpose of the present invention is to provide a kind of preparation methods of solvent epoxy varnish, simplify production technology, are ensureing
Production efficiency is greatly improved while product quality.
In order to achieve the above-mentioned object of the invention, the present invention provides following technical scheme：
The present invention provides a kind of preparation methods of solvent epoxy varnish, include the following steps：
(1) sodium hydroxide solution, bisphenol-A are mixed with epoxychloropropane and carries out etherification reaction, obtain etherificate material；It is described
The molar ratio of sodium hydroxide is 1: 1.0-2.0: 2.0-3.0 in bisphenol-A, epoxychloropropane and sodium hydroxide solution；The etherificate
The temperature of reaction is 80-100 DEG C, and the time of etherification reaction is 20-30min；
(2) etherificate material in the step (1) is mixed with dimethylbenzene and carries out polymerisation, obtained containing epoxy resin
Polymer material；
(3) polymer material containing epoxy resin in the step (2) is dissolved using dimethylbenzene, obtains dissolved matter
Material；
(4) dissolved material in the step (3) is post-processed, obtains solvent epoxy varnish.
Preferably, the mass concentration of sodium hydroxide solution is 8-25% in the step (1).
Preferably, in the step (2) dimethylbenzene dosage be epoxychloropropane and bisphenol-A quality summation 30-45%.
Preferably, the temperature of polymerisation is 80-100 DEG C in the step (2), and the time of polymerisation is 40-
80min。
Preferably, the weight average molecular weight of the polymer material epoxy resin containing epoxy resin is in the step (2)
800-1000。
Preferably, in the step (3) dimethylbenzene dosage be epoxychloropropane and bisphenol-A quality summation 70-80%.
Preferably, the temperature dissolved in the step (3) is 60-90 DEG C, and the time of dissolving is 20-40min.
Preferably, the post-processing includes the following steps：
By dissolved material stratification, gained organic layer is subjected to neutralization washing, the water in removing gained organic phase and portion
Divide solvent, then filters, obtain solvent epoxy varnish.
Preferably, the solid content of the solvent epoxy varnish is 74-76%.
The present invention provides a kind of preparation methods of solvent epoxy varnish, using epoxychloropropane and bisphenol-A as raw material,
Etherification reaction and polymerisation are carried out under same reaction condition, i.e., by the direct synthetic type epoxy resin of one-step method, relatively
In traditional two-step method synthetic type epoxy resin method (first with epoxychloropropane and bisphenol-A be raw material produce bisphenol A-type
Liquid epoxies, then produce solvent type resin by raw material of bisphenol-A liquid epoxy resin), present invention eliminates bisphenol A-types
The loaded down with trivial details synthesis technology of liquid epoxies, synthetic method is simple and convenient, on the basis of not increasing " three wastes " amount, reduces anti-
(the one-step synthesis method time of the present invention is 14~16h, and conventional two-step generated time is 20~22h) and solvent use between seasonable
Amount, effectively reduces production cost, production efficiency is substantially increased while ensureing product quality.
Specific implementation mode
The present invention provides a kind of preparation methods of solvent epoxy varnish, include the following steps：
(1) sodium hydroxide solution, bisphenol-A are mixed with epoxychloropropane and carries out etherification reaction, obtain etherificate material；It is described
The molar ratio of sodium hydroxide is 1: 1.0-2.0: 2.0-3.0 in bisphenol-A, epoxychloropropane and sodium hydroxide solution；The etherificate
The temperature of reaction is 80-100 DEG C, reaction time 20-30min；
(2) etherificate material in the step (1) is mixed with dimethylbenzene and carries out polymerisation, obtained containing epoxy resin
Polymer material；
(3) polymer material containing epoxy resin in the step (2) is dissolved using dimethylbenzene, obtains dissolved matter
Material；
(4) dissolved material in the step (3) is post-processed, obtains solvent epoxy varnish.
The present invention, which mixes sodium hydroxide solution, bisphenol-A with epoxychloropropane, carries out etherification reaction, obtains etherificate material；
The molar ratio of sodium hydroxide is 1: 1.0-2.0: 2.0-3.0 in the bisphenol-A, epoxychloropropane and sodium hydroxide solution；It is described
The temperature of etherification reaction is 80-100 DEG C, reaction time 20-30min.In the present invention, the etherification reaction is preferably in nitrogen
Protection is lower to be carried out.In the present invention, the mass concentration of the sodium hydroxide solution is preferably 8-25%, more preferably 15~
20%.In the present invention, the molar ratio of sodium hydroxide is preferably 1 in the bisphenol-A, epoxychloropropane and sodium hydroxide solution:
1.5∶2.5；The temperature of the etherification reaction is preferably 90 DEG C, and the reaction time is preferably 25min.In the present invention, the hydrogen-oxygen
Change sodium and is used as catalyst in etherification reaction.In the present invention, the etherification reaction process is as follows：
After completing the etherification reaction, gained is etherified in material comprising unreacted bisphenol-A and epoxychloropropane and ether
Change reaction product bisphenol-A chloro alcohol.In the present invention, the etherification reaction material need not be post-processed, and directly be carried out
Subsequent polymerisation reaction.
After obtaining etherificate material, the present invention, which mixes the etherificate material with dimethylbenzene, carries out polymerisation, is contained
The polymer material of epoxy resin.In the present invention, the temperature of the polymerisation is preferably 80-100 DEG C, more preferably 85-95
DEG C, the reaction time is preferably 40-80min, more preferably 50-70min.In the present invention, the dosage of the dimethylbenzene is preferably
The 30-45% of epoxychloropropane and bisphenol-A quality summation, more preferably 35-40%.
In the present invention, the temperature of the polymerisation is preferably identical as the temperature of the etherification reaction, described in completion
After etherification reaction, it is etherified addition dimethylbenzene in material in gained and directly carries out subsequent polymerisation reaction as solvent, it is anti-without changing
Condition is answered, i.e., solvent epoxy varnish is prepared by one-step method.
In the present invention, the polymerisation preferably includes following procedure：
1) the bisphenol-A chloro alcohol generated in etherification reaction material is reacted with NaOH generates bis-phenol A glycidyl ether：
2) bis-phenol A glycidyl ether is further reacted with bisphenol-A, epoxychloropropane, generates epoxy resin：
In the present invention, the weight average molecular weight of the polymer material epoxy resin containing epoxy resin is preferably 800-
1000。
After obtaining the polymer material containing epoxy resin, the present invention is using dimethylbenzene to the polymerization containing epoxy resin
Material is dissolved, and dissolved material is obtained.In the present invention, the dosage of the dimethylbenzene is preferably epoxychloropropane and bisphenol-A
The 70-80% of quality summation, more preferably 72-78%.In the present invention, the temperature of the dissolving is preferably 60-90 DEG C, more excellent
It is selected as 70-80 DEG C；The time of dissolving is preferably 20-40min, more preferably 25-35min.
After obtaining dissolved material, the present invention post-processes the dissolved material, obtains solvent epoxy varnish.At this
In invention, the solid content of the solvent epoxy varnish is preferably 74-76%.In the present invention, the post-processing preferably includes
Following steps：
By dissolved material stratification, gained organic layer is subjected to neutralization washing, the water in removing gained organic phase and portion
Divide solvent, then filters, obtain solvent epoxy varnish.
The present invention does not have the stratification special restriction, using stratification well known to those skilled in the art
Technical solution.The present invention removes brackish water in dissolved material by stratification.In the present invention, the neutralization washing
Used washing reagent is preferably acid acceptor；It is special that the present invention does not have the type of the acid acceptor and source
It limits, selects the acid acceptor of those skilled in the art's known type and source.The present invention is by neutralizing washing removal
Remaining salt and NaOH in the organic layer.The present invention does not have the method for removing water and partial solvent in the organic phase
Special restriction using removing water well known to those skilled in the art and organic solvent, can make resulting material reach solvent type
The technical solution of solid content needed for resin；In an embodiment of the present invention, specifically at 135~145 DEG C, to neutralizing water
Gained organic phase carries out circulation dehydration and removing partial solvent after washing.The present invention does not have the mode of the filtering special limit
It is fixed, select mode well known to those skilled in the art.The present invention is removed by filtration the solid impurity and water that reaction generates
Wash the solid salt particles not exclusively remained in resin.
The preparation method of solvent epoxy varnish provided by the invention is described in detail with reference to embodiment, but
It is that they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
In N2It is under protection, 228g bisphenol-As and 1000g NaOH solutions (mass concentration 8%), 185g epoxychloropropane is mixed
It closes, is warming up to 80 DEG C, carry out etherification reaction 30min, obtain etherificate material；
The dimethylbenzene of 244g is added into the etherificate material, continues to carry out polymerisation 80min at 80 DEG C, be contained
There is the polymer material of epoxy resin；Wherein, the weight average molecular weight of the epoxy resin is 941.6；
The dimethylbenzene that 376g is added dissolves resulting polymers material, and 60 DEG C of solution temperature, dissolution time 40min is obtained
To dissolved material；
Stratification is carried out to the dissolved material, 200g water and 1g acid acceptors are added into gained organic layer, into
Row neutralizes washing, ensures that remaining salt and NaOH are completely removed in organic layer；
Under the conditions of 140 DEG C, circulation dehydration and removing partial solvent are carried out to gained organic phase after neutralizing washing, until gained
The solid content of material reaches 74.4%；
Above-mentioned system is filtered, solvent epoxy varnish is obtained.
Embodiment 2
In N2Under protection, by 342g bisphenol-As and 720g NaOH solutions (mass concentration 15%), 138.75g epoxychloropropane
Mixing is warming up to 100 DEG C, carries out etherification reaction 20min, obtains etherificate material；
The dimethylbenzene of 216g is added into the etherificate material, continues to carry out polymerisation 40min at 100 DEG C, obtain
Polymer material containing epoxy resin；Wherein, the weight average molecular weight of the epoxy resin is 1000.0；
The dimethylbenzene that 336g is added dissolves resulting polymers material, and 90 DEG C of solution temperature, dissolution time 30min is obtained
To dissolved material；
Stratification is carried out to the dissolved material, 300g water and 1.5g acid acceptors are added into gained organic layer,
Neutralization washing is carried out, ensures that remaining salt and NaOH are completely removed in organic layer；
Under the conditions of 140 DEG C, circulation dehydration and removing partial solvent are carried out to gained organic phase after neutralizing washing, until gained
The solid content of material reaches 76%；
Above-mentioned system is filtered, solvent epoxy varnish is obtained.
Embodiment 3
In N2Under protection, by 456g bisphenol-As and 800g NaOH solutions (mass concentration 20%), 277.5g epoxychloropropane
Mixing is warming up to 85 DEG C, carries out etherification reaction 30min, obtains etherificate material；
The dimethylbenzene of 220g is added into the etherificate material, continues to carry out polymerisation 80min at 80 DEG C, be contained
There is the polymer material of epoxy resin；Wherein, the weight average molecular weight of the epoxy resin is 800；
The dimethylbenzene that 550g is added dissolves resulting polymers material, and 90 DEG C of solution temperature, dissolution time 30min is obtained
To dissolved material；
Stratification is carried out to the dissolved material, 200g water and 1.25g acid acceptors are added into gained organic layer,
Neutralization washing is carried out, ensures that remaining salt and NaOH are completely removed in organic layer；
Under the conditions of 140 DEG C, circulation dehydration and removing partial solvent are carried out to gained organic phase after neutralizing washing, until gained
The solid content of material reaches 74%；
Above-mentioned system is filtered, solvent epoxy varnish is obtained.
Embodiment 4
In N2It is under protection, 320g bisphenol-As and 877gNaOH solution (mass concentration 16%), 259g epoxychloropropane is mixed
It closes, is warming up to 100 DEG C, carry out etherification reaction 25min, obtain etherificate material；
The dimethylbenzene of 231g is added into the etherificate material, continues to carry out polymerisation 50min at 90 DEG C, be contained
There is the polymer material of epoxy resin；Wherein, the weight average molecular weight of the epoxy resin is 948.8；
The dimethylbenzene that 434g is added dissolves resulting polymers material, and 70 DEG C of reaction temperature, reaction time 20min is obtained
To dissolved material；
Stratification is carried out to the dissolved material, 250g water and 1.3g acid acceptors are added into gained organic layer,
Neutralization washing is carried out, ensures that remaining salt and NaOH are completely removed in organic layer；
Under the conditions of 140 DEG C, circulation dehydration and removing partial solvent are carried out to gained organic phase after neutralizing washing, until gained
The solid content of material reaches 75.1%；
Above-mentioned system is filtered, solvent epoxy varnish is obtained.
Comparative example 1
Two-step method synthetic type epoxy resin.Bisphenol-A and epoxychloropropane Depressor response under the conditions of NaOH first, instead
The product that should be obtained obtains liquid epoxies product after washing, precipitation, filtering, and liquid epoxies and bisphenol-A are in height
Catalysis reaction generates high molecular weight solid epoxy resin under the conditions of temperature, adds the solvent type ring that solvent is configured to certain solid content
Oxygen resin.
Embodiment 5
To the processing quality of solvent epoxy varnish obtained by Examples 1 to 4 and consumption and solvent type epoxy obtained by two-step method
The processing quality of resin and consumption are compared, and concrete outcome is shown in Tables 1 and 2.
1 different process synthetic type resin quality of table compares
2 one-step method of table, the consumption comparison of two-step method synthetic type epoxy resin
As seen from the above embodiment, the present invention provides a kind of preparation method of solvent epoxy varnish, pass through one-step method
Direct synthetic type epoxy resin, relative to the method for traditional two-step method synthetic type epoxy resin, the present invention cancels
The loaded down with trivial details synthesis technology of bisphenol-A liquid epoxy resin, synthetic method is simple and convenient, on the basis for not increasing " three wastes " amount
On, reduce the reaction time, effectively reduce production cost, production efficiency is substantially increased while ensureing product quality.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (9)
1. a kind of preparation method of solvent epoxy varnish, includes the following steps：
(1) sodium hydroxide solution, bisphenol-A are mixed with epoxychloropropane and carries out etherification reaction, obtain etherificate material；The bis-phenol
A, the molar ratio of sodium hydroxide is 1: 1.0-2.0: 2.0-3.0 in epoxychloropropane and sodium hydroxide solution；The etherification reaction
Temperature be 80-100 DEG C, time of etherification reaction is 20-30min；
(2) etherificate material in the step (1) is mixed with dimethylbenzene and carries out polymerisation, obtain the polymerization containing epoxy resin
Material；
(3) polymer material containing epoxy resin in the step (2) is dissolved using dimethylbenzene, obtains dissolved material；
(4) dissolved material in the step (3) is post-processed, obtains solvent epoxy varnish.
2. preparation method according to claim 1, which is characterized in that the quality of sodium hydroxide solution in the step (1)
A concentration of 8-25%.
3. preparation method according to claim 1, which is characterized in that the dosage of dimethylbenzene is epoxy in the step (2)
The 30-45% of chloropropane and bisphenol-A quality summation.
4. preparation method according to claim 1, which is characterized in that the temperature of polymerisation is 80- in the step (2)
100 DEG C, the time of polymerisation is 40-80min.
5. preparation method according to claim 1, which is characterized in that the polymerization containing epoxy resin in the step (2)
The weight average molecular weight of material epoxy resin is 800-1000.
6. preparation method according to claim 1, which is characterized in that the dosage of dimethylbenzene is epoxy in the step (3)
The 70-80% of chloropropane and bisphenol-A quality summation.
7. preparation method according to claim 1, which is characterized in that the temperature dissolved in the step (3) is 60-90
DEG C, the time of dissolving is 20-40min.
8. preparation method according to claim 1, which is characterized in that the post-processing includes the following steps：
By dissolved material stratification, gained organic layer is subjected to neutralization washing, the water and part in removing gained organic phase are molten
Then agent is filtered, solvent epoxy varnish is obtained.
9. preparation method according to claim 1, which is characterized in that the solid content of the solvent epoxy varnish is 74-
76%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810308031.1A CN108373531B (en) | 2018-04-08 | 2018-04-08 | Preparation method of solvent type epoxy resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810308031.1A CN108373531B (en) | 2018-04-08 | 2018-04-08 | Preparation method of solvent type epoxy resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108373531A true CN108373531A (en) | 2018-08-07 |
| CN108373531B CN108373531B (en) | 2020-11-06 |
Family
ID=63032139
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810308031.1A Active CN108373531B (en) | 2018-04-08 | 2018-04-08 | Preparation method of solvent type epoxy resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108373531B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0436274A (en) * | 1990-05-29 | 1992-02-06 | Sanyo Chem Ind Ltd | Production of glycidyl ether |
| US5283124A (en) * | 1990-03-02 | 1994-02-01 | Kansai Paint Co., Ltd. | Coating resin composition |
| CN101370837A (en) * | 2006-01-19 | 2009-02-18 | 日本化药株式会社 | Active energy ray-curable resin composition and use thereof |
| CN103923299A (en) * | 2014-04-15 | 2014-07-16 | 江苏扬农锦湖化工有限公司 | Hard resin production technology |
| CN104072724A (en) * | 2014-04-15 | 2014-10-01 | 江苏扬农锦湖化工有限公司 | Method for synthesizing epoxy resin from dichloropropanol |
| CN105085867A (en) * | 2015-09-25 | 2015-11-25 | 南通星辰合成材料有限公司 | Method for synthesizing phenolic ketone epoxy resin through solvent |
-
2018
- 2018-04-08 CN CN201810308031.1A patent/CN108373531B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5283124A (en) * | 1990-03-02 | 1994-02-01 | Kansai Paint Co., Ltd. | Coating resin composition |
| JPH0436274A (en) * | 1990-05-29 | 1992-02-06 | Sanyo Chem Ind Ltd | Production of glycidyl ether |
| CN101370837A (en) * | 2006-01-19 | 2009-02-18 | 日本化药株式会社 | Active energy ray-curable resin composition and use thereof |
| CN103923299A (en) * | 2014-04-15 | 2014-07-16 | 江苏扬农锦湖化工有限公司 | Hard resin production technology |
| CN104072724A (en) * | 2014-04-15 | 2014-10-01 | 江苏扬农锦湖化工有限公司 | Method for synthesizing epoxy resin from dichloropropanol |
| CN105085867A (en) * | 2015-09-25 | 2015-11-25 | 南通星辰合成材料有限公司 | Method for synthesizing phenolic ketone epoxy resin through solvent |
Non-Patent Citations (3)
| Title |
|---|
| 倪礼忠 等: "《聚合物基复合材料》", 28 February 2007 * |
| 孙书静: "粉末涂料用环氧树脂的合成研究", 《现代涂料与涂装》 * |
| 徐晓虎 等: "粉末涂料用环氧树脂新工艺合成研究", 《科技与创新》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108373531B (en) | 2020-11-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106832249B (en) | The refining methd of low smell polyether polyol with high activity | |
| CN1867609A (en) | Continuous process and system of producing polyether polyols | |
| CN103626999A (en) | Industrial synthesis method of polyarylether sulfone resin | |
| CN106397368A (en) | Fatty alcohol-polyoxyethylene ether glycidyl ether and preparation method thereof | |
| CN103642518A (en) | High-water-cut heavy oil demulsifier used for oil fields and preparation method thereof | |
| CN106831350A (en) | The method of the high-purity '-biphenyl diphenol of 3,3 ', 5,5 ' tetramethyl 4,4 ' of one kind synthesis | |
| CN105754071A (en) | Preparation technology of bisphenol fluorene epoxy resin | |
| CN104492495A (en) | Ionic liquid immobilized magnetic solid acid material catalyst and preparation method thereof | |
| CN110669213A (en) | Preparation method of bisphenol A polyether | |
| CN109320650B (en) | Preparation method of macroporous weakly-alkaline acrylic anion exchange resin | |
| CN108373531A (en) | A kind of preparation method of solvent epoxy varnish | |
| CN104844455B (en) | A kind of technique catalyzing and synthesizing tert-butyl acrylate | |
| CN104592166B (en) | A kind of Supported on Zeolite process for catalytic synthesis of glycidyl allyl ether | |
| CN104603177A (en) | Gas scrubber and related processes | |
| CN111548436B (en) | Preparation method of butyl rubber base rubber solution for halogenation reaction | |
| CN103073521B (en) | Preparation method of rubber vulcanization accelerator N-tert-butyl-2-benzothiazole sulfonamide (NS) | |
| CN108191649A (en) | A kind of preparation method of dibutylester nylon acids | |
| CN105384629B (en) | A kind of energy-conserving and environment-protective production technology of the different monooctyl ester of lactic acid | |
| CN104492485B (en) | Acidic ionic liquid-coated polymeric core solid acid material catalyst and preparation method thereof | |
| CN110918021A (en) | Micro-reaction device and method for preparing xylene formaldehyde resin by using same | |
| CN114409900B (en) | Preparation method of polysulfone with low cyclic dimer content | |
| CN105669384A (en) | Method of catalytically synthesizing biphenol F being high in 4-4' isomer content | |
| CN110105540A (en) | A kind of preparation method of glycidyl ester type self curable epoxy resin | |
| CN112409596A (en) | Polysulfone and preparation method thereof | |
| CN105175342A (en) | Ionic liquid and method for homogeneous phase-modified reed-reinforced PE (polyethylene) composite material thereof |
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 |