CN113929871B - Preparation method of poly sulfate type epoxy resin - Google Patents
Preparation method of poly sulfate type epoxy resin Download PDFInfo
- Publication number
- CN113929871B CN113929871B CN202111307982.5A CN202111307982A CN113929871B CN 113929871 B CN113929871 B CN 113929871B CN 202111307982 A CN202111307982 A CN 202111307982A CN 113929871 B CN113929871 B CN 113929871B
- Authority
- CN
- China
- Prior art keywords
- polysulfate
- epoxy resin
- type epoxy
- bisphenol
- preparation
- 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
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 invention relates to a preparation method of a poly sulfate type epoxy resin, which comprises the following steps: (1) preparing polysulfate with the number average molecular weight of 1000-10000g/mol and the terminal group of hydroxyl; (2) heating and dissolving the polysulfate in epihalohydrin; (3) continuously adding a ring-opening catalyst to react the epihalohydrin with the polysulfate; (4) continuously adding a ring-closing catalyst to change the end group of the polysulfate into an epoxy structure; (5) the product was precipitated and purified. The preparation method provided by the invention can realize large-scale industrial production and has the advantages of simple post-treatment process and little pollution.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a preparation method of a polysulfate type epoxy resin.
Background
The fluorine sulfur exchange (SuFEx) click reaction is a new generation of click chemistry reported by professor Sharpless in 2014. The system adopts cheap industrial pesticide sulfuryl fluoride (SO) 2 F 2 ) Reacting with phenolic compounds to prepare substrates for SuFEx click reactions. The synthesized polysulfate material has acid resistance, alkali resistance, higher glass transition temperature and excellent mechanical property.
The high-valence main group fluoride has high chemical stability, but the activation of the high-valence main group fluoride under specific conditions can realize extremely efficient chemical bond transformation and linkage, and the combination of the special stability and the reactivity determines that the compound has unique potential application in organic synthetic chemistry, material chemistry, chemical biology and medicinal chemistry. The success of the hexavalent sulfur fluorine exchange reaction (SuFEx) is based on the specific reactivity of the hexavalent sulfur fluorine bond. Since 2014, the teaching of sharp (angel. chem. int.ed.2014,9430) firstly proposed and successfully realized the exchange reaction of hexavalent sulfur and fluorine, the reaction has attracted extensive attention in the aspects of organic synthesis chemistry, material chemistry, pharmaceutical chemistry, chemical biology, particularly protein molecule selective marking and modification, etc., and has shown good application prospect, which is called as the new generation click chemistry, and becomes a new hot point of the current fluorine chemistry research.
Although the polysulfate is generally superior in acid-base resistance, solvent resistance and the like, the polysulfate belongs to thermoplastic resin, the molecular weight is not high generally, and the defect of poor mechanical property after the polysulfate is prepared into a coating is existed, so that the application of the polysulfate is limited.
Disclosure of Invention
Based on the above, the invention aims to provide a preparation method of a polysulfate type epoxy resin, so as to solve the defects of the existing polysulfate in terms of mechanical properties, and the polysulfate type epoxy resin obtained by the preparation method can also be used in the field with higher anticorrosive requirements.
In order to achieve the above object, the present invention provides a method for preparing a polysulfate type epoxy resin, comprising the steps of:
(1) preparing polysulfate with the number average molecular weight of 1000-10000g/mol and the terminal group of hydroxyl;
(2) heating and dissolving the polysulfate in epihalohydrin;
(3) continuously adding a ring-opening catalyst to react the epihalohydrin with the polysulfate;
(4) continuously adding a ring-closing catalyst to change the end group of the polysulfate into an epoxy structure;
(5) the product was isolated and purified.
The preparation method of the polysulfate type epoxy resin provided by the invention is preferably that the number average molecular weight of the polysulfate is 2000-4000g/mol, and the preparation method comprises the following steps: controlling the reaction monomer bisphenol A: the molar ratio of bisphenol A bis sulfonyl fluoride is 1:0.9-0.5, catalyst sodium carbonate or potassium carbonate is added, reaction is carried out at 140 ℃ and 180 ℃ for 4-8h, and the polysulfate with lower molecular weight can be obtained after purification.
The preparation method of the polysulfate type epoxy resin of the present invention, wherein the preparation method preferably further comprises: purifying the polysulfate prepared in the step (1) and then performing the step (2); further preferably, the purification process comprises: distilling with ethanol at 90-100 deg.C for 1-3 times, and distilling with purified water at 100-140 deg.C for 1-3 times.
In the method for producing a polysulfate-type epoxy resin according to the present invention, it is preferable that the polysulfate is a bisphenol a-type polysulfate, a bisphenol S-type polysulfate or a bisphenol F-type polysulfate.
In the method for producing a polysulfate-type epoxy resin according to the present invention, the epihalohydrin is preferably epifluoropropane, epichlorohydrin or epibromohydrin.
In the method for preparing the polysulfate type epoxy resin, the ring-opening catalyst is preferably tetrabutylammonium bromide, the ring-closing catalyst is preferably a sodium hydroxide solution, and the concentration of the sodium hydroxide solution is 10-100wt%, and more preferably 20-30 wt%.
In the method for preparing the polysulfate type epoxy resin of the present invention, the conditions of the step (2) are preferably as follows: stirring for 4-6h at 160-190 ℃; the conditions of the step (3) are as follows: stirring for 6-8h at 60-90 ℃.
In the method for preparing the polysulfate type epoxy resin, the precipitation process is preferably as follows: settling the solution prepared in the step (4) into a cosolvent which is freely miscible with the epoxy chloropropane; further preferably, the cosolvent is methanol or ethanol.
In the method for preparing the polysulfate type epoxy resin, the purification process is preferably as follows: distilled for 1 to 3 times by purified water at 100 to 140 ℃ and then distilled for 1 to 3 times by cosolvent at 80 to 100 ℃.
In the method for preparing the polysulfate type epoxy resin, the structural general formula of the polysulfate prepared in the step (1) is preferably as follows:
in the formula, R 1 is-Me, -Et, -Ph, -iPr or-H; r is 2 is-Me, -Et, -Ph, -iPr or-H; x is-C, -Si; n is 10 to 1000.
The preparation method of the poly sulfate type epoxy resin provided by the invention specifically comprises the following steps:
(1) controlling the reaction monomer bisphenol A: the molar ratio of bisphenol A bis sulfonyl fluoride is between 1:0.9 and 0.5, the polysulfate with the number average molecular weight of 1000-10000g/mol and the terminal group of hydroxyl is prepared, and then ethanol and purified water are used for distillation purification at high temperature and high pressure in sequence.
(2) Epichlorohydrin is used as a solvent, and polysulfate is added into the solvent, and then the mixture is heated and stirred for 2 hours at the temperature of 80 ℃.
(3) And continuously adding a ring-opening catalyst tetrabutylammonium bromide, heating and stirring at 90 ℃ for 3 hours to enable the solvent to react with the polysulfate.
(4) The sodium hydroxide solution was continuously added to change the terminal groups to epoxy structures.
(5) And continuously adding ethanol, steaming at high temperature and high pressure, steaming with purified water at high temperature and high pressure, removing residual solvent, catalyst and monomer, and purifying the product.
Due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. the invention prepares the poly sulfate type epoxy resin by using the polysulfate as a main raw material.
2. The epoxy resin provided by the invention utilizes the acid and alkali resistance of the polysulfate, so that the acid and alkali resistance of the epoxy resin is better.
3. The polysulfate type epoxy resin prepared by the invention utilizes the advantage that the epoxy resin is thermosetting plastic after being cured, and overcomes the defect of low thermal property of polysulfate.
4. The synthesis method has the advantages of mild reaction conditions, easy control, simple reaction flow, easy operation, economy, less by-products and easy industrial production.
In conclusion, the preparation method of the poly sulfate type epoxy resin provided by the invention solves the problems that the molecular weight of the poly sulfate is lower, the glass transition temperature is lower and the solvent resistance is difficult to further improve, has the advantages of simple and stable reaction process, economy and saving, recoverable raw materials, small environmental pollution, higher corrosion resistance and solvent resistance and better mechanical property, and has wide application prospect in the fields of ships, petrochemical industry and other industries with higher corrosion resistance requirements.
Detailed Description
The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions.
Example 1
The preparation method of the polysulfate type epoxy resin provided by the embodiment comprises the following steps:
1. preparation of low molecular weight polysulfate
(1-1) 400g of bisphenol A, 300g of bisphenol A disulfonyl fluoride, 1.2kg of sulfolane and 250g of potassium carbonate were charged into a 50L autoclave and reacted at 170 ℃ for 4 hours to prepare a polythioester.
(1-2) after the polysulfate is settled out, the polysulfate is boiled twice with ethanol at 100 ℃, boiled three times with high-purity water at 140 ℃, filtered and dried at 80 ℃, and the number average molecular weight Mn is measured to be 3562 g/mol.
2. Preparation of epoxy resins
(2-1) taking 500g of the treated bisphenol A type polysulfate, adding 2.5kg of epoxy chloropropane as a solvent, and heating and stirring at 80 ℃ for 2 hours to fully dissolve the polysulfate.
(2-2) adding 15g of tetrabutylammonium bromide serving as a ring-opening catalyst into the solution obtained in the step (2-1), and stirring at 90 ℃ for 3 hours to react epichlorohydrin serving as a solvent with the polysulfate.
(2-3) adding a closed-loop catalyst sodium hydroxide solution into the solution obtained in the step (2-2) with stirring, wherein the concentration of the sodium hydroxide solution is 30wt%, and then heating with stirring at 70 ℃ for 3 hours to change the terminal group of the polysulfate into an epoxy structure.
And (2-4) pouring the solution obtained in the step (2-3) into 5L of methanol for sedimentation, and taking out the precipitate.
(2-5) adding the precipitate, namely the epoxy resin obtained in the step (2-4), into a 10L high-pressure kettle, adding 4L of purified water, boiling for 5 hours at 120 ℃, repeating for 1 time, drying, then repeatedly boiling once at 100 ℃ with 4L of methanol solution, and drying to obtain the poly sulfate type epoxy resin.
Example 2
The preparation method of the polysulfate type epoxy resin provided by the embodiment comprises the following steps:
1. preparation of Low molecular weight Polysulfates, as in example 1
2. Preparation of epoxy resins
(2-1) taking 500g of the treated bisphenol A type polysulfate, adding 3.0kg of epoxy chloropropane serving as a solvent, and heating and stirring at the temperature of 80 ℃ for 2 hours to fully dissolve the polysulfate.
(2-2) to the solution obtained in the step (2-1), 15g of tetrabutylammonium bromide as a ring-opening catalyst was added and the mixture was stirred at 90 ℃ for 3 hours.
(2-3) adding a ring-closure catalyst sodium hydroxide solution into the solution obtained in the step (2-2) by stirring, wherein the concentration of the sodium hydroxide solution is 30wt%, and then heating for 3 hours at 70 ℃ by stirring.
(2-4) pouring the solution obtained in the step (2-3) into 5L of methanol for sedimentation, and taking out the precipitate.
(2-5) adding the precipitate, namely the epoxy resin obtained in the step (2-4), into a 10L high-pressure kettle, adding 4L of purified water, boiling for 5 hours at 120 ℃, repeating for 1 time, drying, then repeatedly boiling once at 100 ℃ with 4L of methanol solution, and drying to obtain the poly sulfate type epoxy resin.
Example 3
The preparation method of the polysulfate type epoxy resin provided by the embodiment comprises the following steps:
1. preparation of Low molecular weight Polysulfate ester as in example 1
2. Preparation of epoxy resins
(2-1) taking 500g of the treated bisphenol A type polysulfate, adding 3.0kg of epoxy chloropropane serving as a solvent, and heating and stirring at the temperature of 80 ℃ for 2 hours to fully dissolve the polysulfate.
(2-2) to the solution obtained in the step (2-1), 15g of tetrabutylammonium bromide as a ring-opening catalyst was added and the mixture was stirred at 90 ℃ for 3 hours.
(2-3) adding a ring-closure catalyst sodium hydroxide solution into the solution obtained in the step (2-2) by stirring, wherein the concentration of the sodium hydroxide solution is 20 wt%, and then heating the solution for 3 hours at 70 ℃ by stirring.
(2-4) pouring the solution obtained in the step (2-3) into 5L of methanol for sedimentation, and taking out the precipitate.
(2-5) adding the precipitate, namely the epoxy resin obtained in the step (2-4), into a 10L high-pressure kettle, adding 4L of purified water, boiling for 5 hours at 120 ℃, repeating for 1 time, drying, then repeatedly boiling once at 100 ℃ with 4L of methanol solution, and drying to obtain the poly sulfate type epoxy resin.
Example 4
The preparation method of the polysulfate type epoxy resin provided by the embodiment comprises the following steps:
1. preparation of Low molecular weight Polysulfate ester as in example 1
2. Preparation of epoxy resins
(2-1) taking 500g of the treated bisphenol A type polysulfate, adding 3.0kg of epoxy chloropropane serving as a solvent, and heating and stirring at the temperature of 80 ℃ for 2 hours to fully dissolve the polysulfate.
(2-2) to the solution obtained in the step (2-1), 10g of tetrabutylammonium bromide as a ring-opening catalyst was added and the mixture was stirred at 90 ℃ for 3 hours.
(2-3) adding a ring-closure catalyst sodium hydroxide solution into the solution obtained in the step (2-2) with stirring, wherein the concentration of the sodium hydroxide solution is 30wt%, and then heating with stirring at 70 ℃ for 3 hours.
And (2-4) pouring the solution obtained in the step (2-3) into 5L of methanol for sedimentation, and taking out the precipitate.
(2-5) adding the precipitate, namely the epoxy resin obtained in the step (2-4), into a 10L high-pressure kettle, adding 4L of purified water, boiling for 5 hours at 120 ℃, repeating for 1 time, drying, then repeatedly boiling once at 100 ℃ with 4L of methanol solution, and drying to obtain the poly sulfate type epoxy resin.
Example 5
1. Preparation of low molecular weight polysulfates
(1) 400g of bisphenol A, 250g of bisphenol A disulfonyl fluoride, 1.1kg of sulfolane and 250g of potassium carbonate were put into a 50L autoclave and reacted at 170 ℃ for 4 hours.
(2) After the polysulfate is settled out, the polysulfate is boiled twice with ethanol at 100 ℃, and is boiled three times with high-purity water at 140 ℃, and after filtration and drying at 80 ℃, the molecular weight Mn is 2639 g/mol.
2. Preparation of epoxy resins
(2-1) taking 500g of the treated bisphenol A type polysulfate, adding 2.5kg of epoxy chloropropane as a solvent, and heating and stirring at 80 ℃ for 2 hours to fully dissolve the polysulfate.
(2-2) to the solution obtained in the step (2-1), 15g of tetrabutylammonium bromide as a ring-opening catalyst was added and the mixture was stirred at 90 ℃ for 3 hours.
And (2-3) adding the closed-loop catalyst sodium hydroxide into the solution obtained in the step (2-2) by stirring, and adding the catalyst after the catalyst is diluted to 30% by water. Heated at 70 ℃ for 3 hours with stirring.
(2-4) pouring the solution obtained in the step (2-3) into 5L of methanol for sedimentation, and taking out the precipitate.
(2-5) adding the precipitate, namely the epoxy resin obtained in the step (2-4), into a 10L high-pressure kettle, adding 4L of purified water, boiling for 5 hours at 120 ℃, repeating for 1 time, drying, then repeatedly boiling once at 100 ℃ with 4L of methanol solution, and drying to obtain the poly sulfate type epoxy resin.
Example 6
(1) 500g of the low-molecular-weight bisphenol A-type polysulfate obtained in example 5 was taken, 2.5kg of epichlorohydrin solvent was added thereto, and the mixture was heated and stirred at 80 ℃ for 2 hours to sufficiently dissolve the polysulfate.
(2) 10g of tetrabutylammonium bromide as a ring-opening catalyst was added to the solution obtained in step (1), and the mixture was stirred at 90 ℃ for 3 hours.
(3) Adding a closed-loop catalyst sodium hydroxide solution into the solution obtained in the step (2) by stirring, wherein the concentration of the sodium hydroxide solution is 20 wt%, and then heating for 3 hours at 70 ℃ by stirring.
(4) And (4) pouring the solution obtained in the step (3) into 5L of methanol for sedimentation, and taking out the precipitate.
(5) And (3) adding the precipitate, namely the epoxy resin obtained in the step (4), into a 10L high-pressure kettle, adding 4L of purified water, boiling for 5 hours at 120 ℃, repeating for 1 time, drying, then repeatedly boiling once at 100 ℃ with 4L of methanol solution, and drying to obtain the poly sulfate type epoxy resin.
Comparative example 1
(1) In a 50L autoclave, 800g of bisphenol A, 1000g of bisphenol A disulfonyl fluoride, 2.1kg of sulfolane and 250g of potassium carbonate were charged first, and reacted at 170 ℃ for 6 hours.
(2) After the polysulfate is settled out, the polysulfate is boiled twice with ethanol at 100 ℃, boiled three times with high-purity water at 140 ℃, dried at 80 ℃ after being filtered, and sampled to obtain the molecular weight Mn which is 201781 g/mol.
Comparative example 2
(1) In a 50L autoclave, 800g of bisphenol A, 1100g of bisphenol A disulfonyl fluoride, 2.2kg of sulfolane and 260g of potassium carbonate were charged first, and reacted at 170 ℃ for 6 hours.
(2) After the polysulfate is settled out, the polysulfate is boiled twice with ethanol at 100 ℃, and boiled three times with high-purity water at 140 ℃, dried at 80 ℃ after being filtered, and sampled to obtain the molecular weight Mn which is 62696 g/mol.
Test example 1
Taking 100g of the epoxy resin prepared in each embodiment of the invention, respectively adding 10g of diethylenetriamine, uniformly stirring, pouring into a mold, standing for 24h at 25 ℃, and obtaining the polymer with approximately same molecular weight. The molecular weights of the samples to be tested are 119800g/mol, 102536g/mol, 85980g/mol, 69683g/mol and 92953g/mol respectively. After being cut into granules, the granules and a comparative example are used for detecting the acid and alkali resistance and the solvent resistance.
TABLE 1 acid and alkali resistance test
| Sample source | Comparative example 1 | Comparative example 2 | Example 1 | Example 2 | Example 4 | Example 5 | Example 6 |
| 50％KOH | 14 days | 7 days | 21 days | 19 days | 42 days | 29 days | 17 days |
| HCl | 7 days | 5 days | 20 days | 17 days | 45 days | 25 days | 15 days |
As can be seen from Table 1, the acid and alkali resistance of the polysulfate is greatly improved after the polysulfate is prepared into the epoxy resin and cured.
TABLE 2 solvent resistance test
| Sample source | Comparative example 1 | Comparative example 2 | Example 1 | Example 2 | Example 4 | Example 5 | Example 6 |
| Sulfolane | Soluble in water | Soluble in water | Insoluble matter | Insoluble matter | Insoluble matter | Insoluble matter | Insoluble matter |
| DMSO | Soluble in water | Soluble in water | Insoluble matter | Insoluble matter | Insoluble matter | Insoluble matter | Insoluble matter |
| DMF | Soluble in water | Soluble in water | Insoluble matter | Insoluble matter | Insoluble matter | Insoluble matter | Insoluble matter |
As can be seen from Table 2, the cured polythioester type epoxy resin has good solvent resistance, so that the polythioester type epoxy resin can be well applied to the field with high solvent resistance requirement, and has wide prospect.
The present invention is capable of other embodiments, and various changes and modifications can be made by one skilled in the art without departing from the spirit and scope of the invention.
Claims (10)
1. A preparation method of a poly sulfate type epoxy resin is characterized by comprising the following steps:
(1) preparing polysulfate with the number average molecular weight of 1000-10000g/mol and hydroxyl end group;
(2) heating and dissolving the polysulfate in epihalohydrin;
(3) continuously adding a ring-opening catalyst to react the epihalohydrin with the polysulfate;
(4) continuously adding a ring-closing catalyst to change the end group of the polysulfate into an epoxy structure;
(5) separating out the product and purifying;
the preparation method of the polysulfate comprises the following steps: controlling the reaction monomer bisphenol A: the molar ratio of bisphenol A bis sulfonyl fluoride is 1:0.9-0.5, catalyst sodium carbonate or potassium carbonate is added, reaction is carried out at 140 ℃ and 180 ℃ for 4-8h, and the polysulfate with lower molecular weight can be obtained after purification.
2. The method for preparing a polythioester type epoxy resin as claimed in claim 1, wherein the number average molecular weight of the polythioester is 2000-4000 g/mol.
3. The method of claim 1, further comprising: purifying the polysulfate prepared in the step (1) and then performing the step (2); the purification process comprises the following steps: distilling with ethanol at 90-100 deg.C for 1-3 times, and distilling with purified water at 100-140 deg.C for 1-3 times.
4. The method for producing a polysulfate-type epoxy resin according to claim 1, wherein the polysulfate is a bisphenol A-type polysulfate, a bisphenol S-type polysulfate or a bisphenol F-type polysulfate.
5. The method of producing a polysulfate-type epoxy resin according to claim 1, wherein the epihalohydrin is epifluoropropane, epichlorohydrin or epibromohydrin.
6. The method of claim 1, wherein the ring-opening catalyst is tetrabutylammonium bromide, the ring-closing catalyst is sodium hydroxide solution, and the concentration of the sodium hydroxide solution is 10 to 100 wt%.
7. The method of claim 6, wherein the concentration of the sodium hydroxide solution is 20 to 30 wt%.
8. The method for producing a polysulfate-type epoxy resin according to claim 1, wherein the conditions of step (2) are: stirring for 4-6h at 160-190 ℃; the conditions of the step (3) are as follows: stirring for 6-8h at 60-90 ℃.
9. The method for producing a polysulfate-type epoxy resin according to claim 1, wherein the precipitation process is: settling the solution prepared in the step (4) into a cosolvent which is freely miscible with the epoxy chloropropane; the cosolvent is methanol or ethanol.
10. The method for preparing the polysulfate-type epoxy resin according to claim 1, wherein the purification process comprises: distilled for 1 to 3 times by purified water at 100 to 140 ℃ and then distilled for 1 to 3 times by cosolvent at 80 to 100 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111307982.5A CN113929871B (en) | 2021-11-05 | 2021-11-05 | Preparation method of poly sulfate type epoxy resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111307982.5A CN113929871B (en) | 2021-11-05 | 2021-11-05 | Preparation method of poly sulfate type epoxy resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113929871A CN113929871A (en) | 2022-01-14 |
| CN113929871B true CN113929871B (en) | 2022-09-02 |
Family
ID=79286032
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111307982.5A Active CN113929871B (en) | 2021-11-05 | 2021-11-05 | Preparation method of poly sulfate type epoxy resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113929871B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102648227A (en) * | 2009-12-02 | 2012-08-22 | 陶氏环球技术有限责任公司 | Epoxy resin compositions |
| CN104130379A (en) * | 2014-07-22 | 2014-11-05 | 建滔(番禺南沙)石化有限公司 | Bisphenol A epoxy resin preparation method and product prepared therethrough |
| CN110540647A (en) * | 2018-04-16 | 2019-12-06 | 白银图微新材料科技有限公司 | Polymerization method of sulfuric acid (amine) ester linker polymer |
| CN110804183A (en) * | 2019-12-09 | 2020-02-18 | 白银图微新材料科技有限公司 | Copolymerized polysulfate and preparation method thereof |
| CN110922597A (en) * | 2019-12-19 | 2020-03-27 | 白银图微新材料科技有限公司 | Synthesis method of novel bisphenol S derivative type polysulfate |
| CN110917909A (en) * | 2019-12-27 | 2020-03-27 | 白银图微新材料科技有限公司 | Method for preparing separation membrane by using poly (amino) sulfate polymer and modified polymer thereof as membrane preparation material |
-
2021
- 2021-11-05 CN CN202111307982.5A patent/CN113929871B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102648227A (en) * | 2009-12-02 | 2012-08-22 | 陶氏环球技术有限责任公司 | Epoxy resin compositions |
| CN104130379A (en) * | 2014-07-22 | 2014-11-05 | 建滔(番禺南沙)石化有限公司 | Bisphenol A epoxy resin preparation method and product prepared therethrough |
| CN110540647A (en) * | 2018-04-16 | 2019-12-06 | 白银图微新材料科技有限公司 | Polymerization method of sulfuric acid (amine) ester linker polymer |
| CN110804183A (en) * | 2019-12-09 | 2020-02-18 | 白银图微新材料科技有限公司 | Copolymerized polysulfate and preparation method thereof |
| CN110922597A (en) * | 2019-12-19 | 2020-03-27 | 白银图微新材料科技有限公司 | Synthesis method of novel bisphenol S derivative type polysulfate |
| CN110917909A (en) * | 2019-12-27 | 2020-03-27 | 白银图微新材料科技有限公司 | Method for preparing separation membrane by using poly (amino) sulfate polymer and modified polymer thereof as membrane preparation material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113929871A (en) | 2022-01-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110540647B (en) | Polymerization method of sulfuric acid (amine) ester connector polymer | |
| CN113004521B (en) | Polysulfone and preparation method thereof | |
| CN103242509B (en) | Degradable cyclic acetal and cyclic ketal diamine epoxy resin curing agent and application thereof | |
| CN114605640A (en) | High-performance polysulfone resin and preparation method and application thereof | |
| CN110922597B (en) | Synthesis method of bisphenol S derivative type polysulfate | |
| CN101003466A (en) | Method for synthesizing bisphenol fluorine by catalysis of highly acidic cation exchange resin | |
| CN110922598B (en) | Synthetic method of benzenediol derivative type polysulfate | |
| CN114456128B (en) | Application of isovanillin epoxy resin monomer in preparation of silicon-containing polymer | |
| CN114409900B (en) | Preparation method of polysulfone with low cyclic dimer content | |
| CN113929871B (en) | Preparation method of poly sulfate type epoxy resin | |
| CN109721733B (en) | Preparation method of polysulfone resin | |
| CN112608258A (en) | Method for synthesizing 4,4' -dichlorodiphenyl sulfone by sulfoxide oxidation method | |
| CN101255225B (en) | Method for preparing high alpha-order dihydroxy diphenol A type epoxy resins | |
| CN112409596A (en) | Polysulfone and preparation method thereof | |
| CN111040165A (en) | Polysulfonate polymer and polymerization method thereof | |
| CN114752032B (en) | Chain extension method of polysulfate | |
| CN112574229A (en) | Method for preparing isosorbide by dehydrating sorbitol and preparation method of copolymer-based catalyst thereof | |
| CN111646957B (en) | Preparation method of epoxy compound | |
| CN114149586A (en) | Chain-extended polysulfate and preparation method thereof | |
| CN109880098B (en) | Polyarylethersulfone resin with amino as crosslinking group and crosslinked product thereof | |
| CN112707876B (en) | Preparation method of 2,2' -di (4-hydroxycyclohexyl) propane glycidyl ether | |
| CN113881072A (en) | Molecular weight controllable polysulfate crosslinking method | |
| CN114560964A (en) | Synthetic method and application of carboxyl functional polyion liquid | |
| CN85108751A (en) | The synthetic novel polyether ether ketone that has the phthalein side group | |
| CN114797969A (en) | Preparation method of novel multifunctional polyion liquid catalyst and lignin-based aromatic compound prepared by catalysis of novel multifunctional polyion liquid catalyst |
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 |