CN103435780A - Preparation method of phosphor-bromine composite flame-retardant epoxy resin - Google Patents
Preparation method of phosphor-bromine composite flame-retardant epoxy resin Download PDFInfo
- Publication number
- CN103435780A CN103435780A CN2013103916937A CN201310391693A CN103435780A CN 103435780 A CN103435780 A CN 103435780A CN 2013103916937 A CN2013103916937 A CN 2013103916937A CN 201310391693 A CN201310391693 A CN 201310391693A CN 103435780 A CN103435780 A CN 103435780A
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- feed liquid
- product feed
- composite flame
- bisphenol
- 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.)
- Pending
Links
Landscapes
- Fireproofing Substances (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses a preparation method of phosphor-bromine composite flame-retardant epoxy resin. The preparation method comprises the following steps: (1), adding bisphenol A epoxy resin, tetrabromobisphenol A and a catalyst into a solvent, heating up a system to a reflux state under stirring, keeping the reflux temperature for reacting for 2-3 hours to obtain intermediate product feed liquid; (2), adding ODOPB (10-(2,5-Dihydroxyphenyl)-9,10-Dihydro-9-Xa-10-Phosphaphenanthrene-10-Oxide)) to the intermediate product feed liquid, heating up the intermediate product feed liquid to the reflux state, preserving the heat for reacting for 1-2 hours under stirring to obtain product feed liquid; (3), carrying out reduced pressure distillation to remove a solvent in the product feed liquid to obtain a crude product; and (4), enabling the crude product to continuously react for 3-4 hours at 120 DEG C-140 DEG C, and obtaining the phosphor-bromine composite flame-retardant epoxy resin after the reaction is completed. The phosphor-bromine composite flame-retardant epoxy resin prepared by the preparation method disclosed by the invention is good in flame retardant efficiency, low in production cost and small in harms to the environment.
Description
Technical field
The present invention relates to a kind of preparation method of phosphorus bromine composite flame-proof epoxy resin.
Background technology
Epoxy resin has good electric insulating quality and very high bounding force, is widely used in the fields such as coating, sizing agent, electronics are built, embedding.But the epoxy resin thermotolerance is not high, belongs to combustible material, this has hindered it in the application in field widely.
In recent years, along with industrial development, people have higher requirement for the over-all properties that comprises flame retardant resistance of epoxy resin, and this is conducted in-depth research.Present stage, the research emphasis of fire-retardant epoxy resin mainly concentrates on brominated fire retarding epoxide resin and the phosphorous large class of fire retarding epoxide resin two.
Brominated fire retarding epoxide resin bromine content high flame retardant is effective, but its disadvantage is exactly in use and removal process, owing to decomposing, can produce bromide gas, can be to environment.Phosphorous fire retarding epoxide resin is because the harm to environment is little, more and more come into one's own, but the flame retardant effect of the fire retarding epoxide resin that present stage is phosphorous does not reach expection, main restricting factor is that its phosphorus content is generally lower, according to existing production technique, improve phosphorus content and certainly will greatly increase production cost, the increase of phosphorus content simultaneously can reduce the physical and mechanical properties of epoxy resin, causes its use limited.
Invent a kind of phosphorus, bromine content not high, be beneficial to reduce the phosphorus bromine composite epoxy resin of environmental hazard and production cost reduction and good flame retardation effect, just seem very necessary.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of phosphorus bromine composite flame-proof epoxy resin, to reach environmental contamination reduction, reduce production costs and not reduce the purpose of the physical and mechanical properties of epoxy resin.
In order to realize the foregoing invention purpose, the preparation method of phosphorus bromine composite flame-proof epoxy resin provided by the present invention comprises the following steps:
(1) bisphenol A epoxide resin, tetrabromo-bisphenol and catalyzer are joined in solvent, stir lower reacting by heating system to reflux state, keep reflux temperature to make it to react 2～3 hours, make the intermediate product feed liquid;
(2) add ODOPB in the intermediate product feed liquid, heating intermediate product feed liquid, to reflux state, stirs lower insulation reaction 1～2 hour, makes the product feed liquid;
(3) solvent in the product feed liquid is removed in underpressure distillation, obtains crude product;
(4) make crude product continue reaction 3～4h at 120～140 ℃ of temperature, after having reacted, obtain phosphorus bromine composite flame-proof epoxy resin;
The consumption of described solvent, tetrabromo-bisphenol, ODOPB and catalyzer is respectively 1.5～4,0.112～0.253,0.821～0.966 and 0.0005～0.0015 times of bisphenol A epoxide resin quality.ODOPB is the abbreviation of 10-(2,5-dihydroxy phenyl)-10-hydrogen-9-oxa--10-phospho hetero phenanthrene-10-oxide compound.
Described bisphenol A epoxide resin is E51 type bisphenol A epoxide resin.
Described solvent is selected from a kind of in acetone, tetrahydrofuran (THF), ethyl acetate and ethanol.
Described catalyzer is selected from a kind of in tetramethyl ammonium chloride, tetraethylammonium bromide and triphenyl phosphorus.
The present invention uses two-step approach to prepare phosphorus bromine composite flame-proof epoxy resin: first take bisphenol A epoxide resin and tetrabromo-bisphenol as the synthetic brominated epoxy resin of raw material process back flow reaction, then add ODOPB to synthesize phosphorus bromine composite flame-proof epoxy resin.Reaction in above-mentioned steps (1) and (2) is back flow reaction, and the back flow reaction temperature changes to some extent according to used solvent difference.
The preparation method of phosphorus bromine composite flame-proof epoxy resin provided by the invention compared with prior art has the following advantages: (1), than brominated fire retarding epoxide resin or phosphorous fire retarding epoxide resin, the phosphorus bromine composite flame-proof ethoxyline resin antiflaming that this preparation method makes is effective; (2), with respect to brominated fire retarding epoxide resin, phosphorus bromine composite flame-proof epoxy resin is little to environmental influence; (3), with respect to phosphorous fire retarding epoxide resin, phosphorus bromine composite flame-proof epoxy resin production cost is low; (4) synthesis technique is simple, and synthesis under normal pressure is lower to equipment requirements; (5) material loss is few, and productive rate is high.
Embodiment
Further set forth the present invention below in conjunction with specific embodiment, these embodiment only do not limit the scope of the invention for the present invention is described.
Embodiment 1
(1) take E51 type bisphenol A epoxide resin 100.3g, tetrabromo-bisphenol 11.3g, acetone 155.4g, catalyzer tetraethylammonium bromide 0.06g, add in the 500ml four-hole boiling flask that stirring, condensing reflux pipe, thermometer are housed, four-hole boiling flask is placed in to oil bath pan, opens overhead type stirrer, agitator speed is 70r/min, heat up, when temperature reaches reflux temperature, insulation reaction 2 hours, make the intermediate product feed liquid.(2) take ODOPB 82.4g and add in the intermediate product feed liquid, keep agitator speed 70r/min, heating intermediate product feed liquid, to reflux state insulation reaction 1 hour, makes the product feed liquid.(3) underpressure distillation product feed liquid is removed acetone, obtains crude product.(4) allow crude product react 3 hours under 120 ℃ of conditions of temperature, obtain phosphorus bromine composite flame-proof epoxy resin after having reacted.
Embodiment 2
(1) take E51 type bisphenol A epoxide resin 100.3g, tetrabromo-bisphenol 15.5g, acetone 202.6g, catalyzer tetraethylammonium bromide 0.07g, add in the 500ml four-hole boiling flask that stirring, condensing reflux pipe, thermometer are housed, four-hole boiling flask is placed in to oil bath pan, opens overhead type stirrer, agitator speed is 100r/min, heat up, when temperature reaches reflux temperature, insulation reaction 2.5 hours, make the intermediate product feed liquid.(2) take ODOPB 86.3g and add in the intermediate product feed liquid, keep agitator speed 100r/min, heating intermediate product feed liquid, to reflux state insulation reaction 1.5 hours, makes the product feed liquid.(3) underpressure distillation product feed liquid is removed acetone, obtains crude product.(4) allow crude product react 3.5 hours under 130 ℃ of conditions of temperature, obtain phosphorus bromine composite flame-proof epoxy resin after having reacted.
Embodiment 3
(1) take E51 type bisphenol A epoxide resin 100.3g, tetrabromo-bisphenol 20.0g, ethanol 261.2g, catalyzer tetraethylammonium bromide 0.10g, add in the 500ml four-hole boiling flask that stirring, condensing reflux pipe, thermometer are housed, four-hole boiling flask is placed in to oil bath pan, opens overhead type stirrer, agitator speed is 150r/min, heat up, when temperature reaches reflux temperature, insulation reaction 3 hours, make the intermediate product feed liquid.(2) take ODOPB 90.5g and add in the intermediate product feed liquid, keep agitator speed 150r/min, heating intermediate product feed liquid, to reflux state insulation reaction 2 hours, makes the product feed liquid.(3) underpressure distillation product feed liquid is removed ethanol, obtains crude product.(4) allow crude product react 4 hours under 140 ℃ of conditions of temperature, obtain phosphorus bromine composite flame-proof epoxy resin after having reacted.
Embodiment 4
(1) take E51 type bisphenol A epoxide resin 100.3g, tetrabromo-bisphenol 18.7g, tetrahydrofuran (THF) 250.5g, catalyzer tetramethyl ammonium chloride 0.08g, add in the 500ml four-hole boiling flask that stirring, condensing reflux pipe, thermometer are housed, four-hole boiling flask is placed in to oil bath pan, opens overhead type stirrer, agitator speed is 200r/min, heat up, when temperature reaches reflux temperature, insulation reaction 2.5 hours, make the intermediate product feed liquid.(2) take ODOPB 88.4g and add in the intermediate product feed liquid, keep agitator speed 200r/min, heating intermediate product feed liquid, to reflux state insulation reaction 1.5 hours, makes the product feed liquid.(3) underpressure distillation product feed liquid is removed tetrahydrofuran (THF), obtains crude product.(4) allow crude product react 3.5 hours under 130 ℃ of conditions of temperature, obtain phosphorus bromine composite flame-proof epoxy resin after having reacted.
Embodiment 5
(1) take E51 type bisphenol A epoxide resin 100.3g, tetrabromo-bisphenol 25.1g, tetrahydrofuran (THF) 400.0g, catalyzer tetramethyl ammonium chloride 0.13g, add in the 1000ml four-hole boiling flask that stirring, condensing reflux pipe, thermometer are housed, four-hole boiling flask is placed in to oil bath pan, opens overhead type stirrer, agitator speed is 250r/min, heat up, when temperature reaches reflux temperature, insulation reaction 3 hours, make the intermediate product feed liquid.(2) take ODOPB 96.5g and add in the intermediate product feed liquid, keep agitator speed 250r/min, heating intermediate product feed liquid, to reflux state insulation reaction 2 hours, makes the product feed liquid.(3) underpressure distillation product feed liquid is removed tetrahydrofuran (THF), obtains crude product.(4) allow crude product react 4 hours under 140 ℃ of conditions of temperature, obtain phosphorus bromine composite flame-proof epoxy resin after having reacted.
Embodiment 6
(1) take E51 type bisphenol A epoxide resin 100.3g, tetrabromo-bisphenol 18.5g, ethyl acetate 250.6g, catalyzer triphenyl phosphorus 0.09g, add in the 500ml four-hole boiling flask that stirring, condensing reflux pipe, thermometer are housed, four-hole boiling flask is placed in to oil bath pan, opens overhead type stirrer, agitator speed is 150r/min, heat up, when temperature reaches reflux temperature, insulation reaction 2.5 hours, make the intermediate product feed liquid.(2) take ODOPB 86.7g and add in the intermediate product feed liquid, keep agitator speed 150r/min, heating intermediate product feed liquid, to reflux state insulation reaction 1.5 hours, makes the product feed liquid.(3) underpressure distillation product feed liquid is removed ethyl acetate, obtains crude product.(4) allow crude product react 3.5 hours under 130 ℃ of conditions of temperature, obtain phosphorus bromine composite flame-proof epoxy resin after having reacted.
Embodiment 7
(1) take E51 type bisphenol A epoxide resin 100.3g, tetrabromo-bisphenol 24.9g, ethyl acetate 360.4g, catalyzer triphenyl phosphorus 0.12g, add in the 1000ml four-hole boiling flask that stirring, condensing reflux pipe, thermometer are housed, four-hole boiling flask is placed in to oil bath pan, opens overhead type stirrer, agitator speed is 200r/min, heat up, when temperature reaches reflux temperature, insulation reaction 3 hours, make the intermediate product feed liquid.(2) take ODOPB 94.6g and add in the intermediate product feed liquid, keep agitator speed 200r/min, heating intermediate product feed liquid, to reflux state insulation reaction 2 hours, makes the product feed liquid.(3) underpressure distillation product feed liquid is removed ethyl acetate.(4) crude product reacts 4 hours under 140 ℃ of conditions of temperature, obtains phosphorus bromine composite flame-proof epoxy resin after having reacted.
The domestic model of the bisphenol A epoxide resin used in embodiment 1-7 is the E51 type, only take the bisphenol A epoxide resin of this model as example illustrates design philosophy of the present invention, do not illustrate that the bisphenol A epoxide resin of other model is unsuitable for the present invention.Certainly, the bisphenol A epoxide resin of other model such as E55 type, E44 type, E35 type, E42 type, E20 type, E12 type, E06 type, E03 type etc. still are suitable for the present invention, for saving length, at this, no longer with embodiment, describe one by one.
Phosphorus bromine composite flame-proof epoxy resin prepared by the embodiment 1-7 that weighs also calculates productive rate, and result is as shown in table 1 below.
Table 1 quality product is table as a result
| Title | Phosphorus bromine composite flame-proof epoxy resin quality (g) | Productive rate (%) |
| Embodiment 1 | 192.0 | 99.0 |
| Embodiment 2 | 200.0 | 99.0 |
| Embodiment 3 | 207.2 | 98.3 |
| Embodiment 4 | 204.2 | 98.5 |
| Embodiment 5 | 217.4 | 98.0 |
| Embodiment 6 | 203.0 | 98.8 |
| Embodiment 7 | 218.3 | 99.3 |
From table 1, can obviously find out, product yield is higher, all more than 98.0%, illustrates that the synthesis technique material loss of present method is few, and productive rate is high.
Phosphorus bromine composite flame-proof epoxy resin prepared by sampling Detection embodiment 1-7, detected result is in Table 2.
Table 2 product detected result table
| Title | Bromine content (%) | Phosphorus content (%) | Oxygen index (%) | Outward appearance |
| Embodiment 1 | 3.4 | 4.0 | 36.2 | The water white transparency solid |
| Embodiment 2 | 4.5 | 4.0 | 36.6 | The water white transparency solid |
| Embodiment 3 | 5.6 | 4.0 | 37.1 | The water white transparency solid |
| Embodiment 4 | 5.3 | 4.0 | 36.8 | Transparent light yellow solid |
| Embodiment 5 | 6.6 | 4.2 | 38.2 | Transparent light yellow solid |
| Embodiment 6 | 5.3 | 4.0 | 36.7 | The water white transparency solid |
| Embodiment 7 | 6.6 | 4.1 | 38.0 | The water white transparency solid |
Annotate: 1. the product bromine content adopts oxygen flask combustion method to measure.
2. the product phosphorus content adopts combustion method and ion chromatography.
3. the product oxygen index adopts oxygen index measurer (JF-3 type oxygen index measurer, Jiangning analytical instrument factory manufactures) and stopwatch to measure.
4. outward appearance adopts appearance method.
Below, carry out the simultaneous test that phosphorus bromine composite flame-proof epoxy resin, brominated fire retarding epoxide resin, phosphorous fire retarding epoxide resin three flame retardant properties are measured, the superiority of the phosphorus bromine composite epoxy resin prepared with explanation the present invention.
The phosphorous fire retarding epoxide resin that the brominated fire retarding epoxide resin that to get the prepared phosphorus bromine of the invention process example 1 composite flame-proof epoxy resin product, bromine content be 7.5% and phosphorus content are 7.5%, make respectively and be of a size of long 100mm, the sample of wide 5.5 ± 0.5mm, high 2mm ± 0.25mm, in same environment, survey respectively under the same conditions the oxygen index of three samples with oxygen index measurer and stopwatch.Detected result is as shown in table 3 below.
The above-mentioned three kinds of sample oxygen index detected results of table 3
| Sample | Bromine content (%) | Phosphorus content (%) | Oxygen index (%) |
| Phosphorus bromine composite flame-proof epoxy resin | 3.4 | 4.0 | 36.2 |
| The brominated epoxy resin that bromine content is 7.5% | 7.5 | 0 | 26.1 |
| The phosphorous epoxy resin that phosphorus content is 7.5% | 0 | 7.5 | 29.7 |
Annotate: 1. above-mentioned simultaneous test brominated fire retarding epoxide resin used is that to take bisphenol A epoxide resin and tetrabromo-bisphenol be the raw material preparation, and phosphorous fire retarding epoxide resin used is to be prepared by raw material with bisphenol A epoxide resin and ODOPB.
2. the product bromine content adopts oxygen flask combustion method to measure.
3. the product phosphorus content adopts combustion method and ion chromatography.
4. the product oxygen index adopts oxygen index measurer (JF-3 type oxygen index measurer, Jiangning analytical instrument factory manufactures) and stopwatch to measure.
From table 3, can obviously find out, the oxygen index of phosphorus bromine composite flame-proof epoxy resin is apparently higher than brominated fire retarding epoxide resin and phosphorous fire retarding epoxide resin, illustrates this law to invent described method to prepare phosphorus bromine composite flame-proof ethoxyline resin antiflaming effective.Bromine content in phosphorus bromine composite flame-proof epoxy resin is lower, thereby the harm to environment reduces greatly with respect to brominated fire retarding epoxide resin; And phosphorus content wherein is also lower, not only can not reduces the mechanical property of epoxy resin, and also greatly reduce with respect to the production cost of phosphorous fire retarding epoxide resin.
Claims (4)
1. the preparation method of a phosphorus bromine composite flame-proof epoxy resin is characterized in that comprising the following steps:
(1) bisphenol A epoxide resin, tetrabromo-bisphenol and catalyzer are joined in solvent, stir lower reacting by heating system to reflux state, keep reflux temperature to make it to react 2～3 hours, make the intermediate product feed liquid;
(2) add ODOPB in the intermediate product feed liquid, heating intermediate product feed liquid, to reflux state, stirs lower insulation reaction 1～2 hour, makes the product feed liquid;
(3) solvent in the product feed liquid is removed in underpressure distillation, obtains crude product;
(4) make crude product continue reaction 3～4h at 120～140 ℃ of temperature, after having reacted, obtain phosphorus bromine composite flame-proof epoxy resin;
The consumption of described solvent, tetrabromo-bisphenol, ODOPB and catalyzer is respectively 1.5～4,0.112～0.253,0.821～0.966 and 0.0005～0.0015 times of bisphenol A epoxide resin quality.
2. the preparation method of phosphorus bromine composite flame-proof epoxy resin according to claim 1, is characterized in that described bisphenol A epoxide resin is E51 type bisphenol A epoxide resin.
3. the preparation method of phosphorus bromine composite flame-proof epoxy resin as claimed in claim 1, is characterized in that described solvent is selected from a kind of in acetone, tetrahydrofuran (THF), ethyl acetate and ethanol.
4. the preparation method of phosphorus bromine composite flame-proof epoxy resin according to claim 1, is characterized in that described catalyzer is selected from a kind of in tetramethyl ammonium chloride, tetraethylammonium bromide and triphenyl phosphorus.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013103916937A CN103435780A (en) | 2013-09-02 | 2013-09-02 | Preparation method of phosphor-bromine composite flame-retardant epoxy resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013103916937A CN103435780A (en) | 2013-09-02 | 2013-09-02 | Preparation method of phosphor-bromine composite flame-retardant epoxy resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103435780A true CN103435780A (en) | 2013-12-11 |
Family
ID=49689507
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2013103916937A Pending CN103435780A (en) | 2013-09-02 | 2013-09-02 | Preparation method of phosphor-bromine composite flame-retardant epoxy resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103435780A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103756254A (en) * | 2013-12-14 | 2014-04-30 | 大连理工大学 | Epoxy resin used for liquid oxygen environment, preparation method and application thereof |
| WO2017020462A1 (en) * | 2015-08-03 | 2017-02-09 | 广东生益科技股份有限公司 | Epoxy resin composition for copper clad laminate, and application of epoxy resin composition |
| CN106751460A (en) * | 2016-11-17 | 2017-05-31 | 无锡市长安曙光手套厂 | One kind preimpregnation wet method pressure stochastic distribution |
| CN108192076A (en) * | 2017-12-29 | 2018-06-22 | 纽宝力精化(广州)有限公司 | A kind of preparation method of insulation board brominated epoxy resin and preparation method thereof and insulation board |
| CN113956750A (en) * | 2021-11-12 | 2022-01-21 | 中国林业科学研究院林产化学工业研究所 | Benzoxazine/epoxy resin composite flame-retardant anticorrosive coating and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01123892A (en) * | 1987-11-09 | 1989-05-16 | Dai Ichi Kogyo Seiyaku Co Ltd | Novel reactive flame retardant |
| CN1148605A (en) * | 1995-08-25 | 1997-04-30 | 东都化成株式会社 | Fire-retardant compound, process for producing said fire-retardant compound and fire-retarding thermoplastic resin composition including said fire-retardant compound |
| EP1059329A1 (en) * | 1999-06-09 | 2000-12-13 | Matsushita Electric Works, Ltd. | Flame retardant resin composition |
| CN1415642A (en) * | 2001-10-29 | 2003-05-07 | 株式会社国都化学 | P or si modified flame vesistant ether resin |
| CN101165076A (en) * | 2006-10-17 | 2008-04-23 | 比亚迪股份有限公司 | Anti-flaming phosphorus-containing epoxy resin, preparation method thereof and composition containing the same |
-
2013
- 2013-09-02 CN CN2013103916937A patent/CN103435780A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01123892A (en) * | 1987-11-09 | 1989-05-16 | Dai Ichi Kogyo Seiyaku Co Ltd | Novel reactive flame retardant |
| CN1148605A (en) * | 1995-08-25 | 1997-04-30 | 东都化成株式会社 | Fire-retardant compound, process for producing said fire-retardant compound and fire-retarding thermoplastic resin composition including said fire-retardant compound |
| EP1059329A1 (en) * | 1999-06-09 | 2000-12-13 | Matsushita Electric Works, Ltd. | Flame retardant resin composition |
| CN1415642A (en) * | 2001-10-29 | 2003-05-07 | 株式会社国都化学 | P or si modified flame vesistant ether resin |
| CN101165076A (en) * | 2006-10-17 | 2008-04-23 | 比亚迪股份有限公司 | Anti-flaming phosphorus-containing epoxy resin, preparation method thereof and composition containing the same |
Non-Patent Citations (2)
| Title |
|---|
| 梁静: ""含磷菲环环氧树脂制备、表征及性能研究"", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
| 许长清: "《合成树脂及塑料手册》", 30 November 1991, 化学工业出版社 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103756254A (en) * | 2013-12-14 | 2014-04-30 | 大连理工大学 | Epoxy resin used for liquid oxygen environment, preparation method and application thereof |
| CN103756254B (en) * | 2013-12-14 | 2016-03-09 | 大连理工大学 | For epoxy resin and preparation method thereof, the application of liquid oxygen environment |
| WO2017020462A1 (en) * | 2015-08-03 | 2017-02-09 | 广东生益科技股份有限公司 | Epoxy resin composition for copper clad laminate, and application of epoxy resin composition |
| CN106751460A (en) * | 2016-11-17 | 2017-05-31 | 无锡市长安曙光手套厂 | One kind preimpregnation wet method pressure stochastic distribution |
| CN108192076A (en) * | 2017-12-29 | 2018-06-22 | 纽宝力精化(广州)有限公司 | A kind of preparation method of insulation board brominated epoxy resin and preparation method thereof and insulation board |
| CN113956750A (en) * | 2021-11-12 | 2022-01-21 | 中国林业科学研究院林产化学工业研究所 | Benzoxazine/epoxy resin composite flame-retardant anticorrosive coating and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103435780A (en) | Preparation method of phosphor-bromine composite flame-retardant epoxy resin | |
| CN106749413B (en) | A kind of preparation method for applying the reactive flame retardant of phosphorus-nitrogen containing sulphur in the epoxy | |
| CN104231309A (en) | Oxaphosphaphenanthrene flame retardant, preparation method and application thereof | |
| CN102134304A (en) | Reactive type phosphoric epoxy resin flame retardant and preparation method thereof | |
| CN102898679A (en) | Method for preparing nitrogen, phosphorus and boron integrated expansion type fire retardant | |
| CN101857674B (en) | Method for synthesizing high-temperature resistant organic silicon resin | |
| CN105131330A (en) | 2,4,6-diethyl triphosphate hydroxymethylphenoxy-1,3,5-triazine flame retardant and preparation method thereof | |
| CN103396434A (en) | Synthesis method of vinyltrimethoxysilane oligomer | |
| CN102675600A (en) | Epoxy resin fire retardant and preparation method thereof | |
| CN105111688A (en) | Phosphorus-nitrogen intumescent epoxy resin flame retardant and preparation method thereof | |
| CN104387388A (en) | Novel method for synthetizing gulf-site n-heterocyclic 3,4:9,10-perylene tetracarboxylic acid diimide | |
| CN110156840A (en) | A kind of Phosphorus-nitrogen flame retardant and preparation method thereof containing DOPO | |
| CN103232333B (en) | A kind of preparation method of ring third acetylene important intermediate Cyclopropyl Methyl Ketone | |
| CN104371108B (en) | A kind of non-halogen non-phosphate Silicone-containing Flame Retardant and preparation method thereof | |
| CN109401707B (en) | Single-component high-temperature-resistant impact-resistant flame-retardant structural adhesive and preparation method thereof | |
| CN106751469A (en) | A kind of fluorine titanium Hybrid fire retardant and preparation method and application | |
| CN106749415B (en) | A kind of rhodamine B is modified three phosphonitrile of ring and its fire retardant and preparation method | |
| CN106134378B (en) | A kind of preparation method of trihydroxy-isoflavone | |
| CN102731547B (en) | Tetra-(tribromophenoxy chloropropyl) silicate fire retardant compound and preparation method thereof | |
| CN105254595A (en) | Preparation method of urushiol biglycidyl ether | |
| CN104710452A (en) | Dimethyl silicic acid-1,3-propylene glycol ester compound as fire retardant and preparation method thereof | |
| Ju et al. | Highly regioselective synthesis of novel 4-O-phosphorylated paeonol analogs | |
| CN204738106U (en) | Alkali -free fibrous zone convenient to tailor | |
| CN104086403A (en) | Acetyl bromide synthesis production process | |
| CN103275322A (en) | Polysiloxane and catalytic synthesis method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20131211 |