CN102532520A - Method for preparing phosphorous polyphenylene oxide resin with low molecular weight - Google Patents
Method for preparing phosphorous polyphenylene oxide resin with low molecular weight Download PDFInfo
- Publication number
- CN102532520A CN102532520A CN201110456224XA CN201110456224A CN102532520A CN 102532520 A CN102532520 A CN 102532520A CN 201110456224X A CN201110456224X A CN 201110456224XA CN 201110456224 A CN201110456224 A CN 201110456224A CN 102532520 A CN102532520 A CN 102532520A
- Authority
- CN
- China
- Prior art keywords
- phosphorous
- molecular weight
- oxide resin
- low molecular
- polyphenylene oxide
- 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
Abstract
The invention relates to a method for preparing phosphorous polyphenylene oxide resin with low molecular weight. The method comprises the steps as follows: in step one, phosphorous phenolic compounds and raw material polyphenylene oxide resin are provided, wherein the number average molecular weight of the raw material polyphenylene oxide resin is more than 10000; in step two, the raw material polyphenylene oxide resin is dissolved in solvent so as to prepare a raw material polyphenylene oxide resin solution; in step three, the phosphorous phenolic compounds are added in the raw material polyphenylene oxide resin solution; in step four, initiator is added, and redistribution reaction is performed under the reaction temperature that is more than 60 DEG C under the action of the initiator; and in step five, products that are phosphorous polyphenylene oxide resin with low molecular weight are obtained after the reaction is finished, and the number average molecular weight of the phosphorous polyphenylene oxide resin ranges from 1000 to 6000. In the method, the phosphorous phenolic compounds are dispersed in the polyphenylene oxide resin solution, and the redistribution reaction is performed under the action of the initiator so as to prepare the phosphorous polyphenylene oxide resin with low molecular weight; the prepared phosphorous polyphenylene oxide resin with low molecular weight achieves good manufacturability, and is suitable for matrix resin of composite material of a high-frequency circuit board and the like or addition ingredients of other polymer material.
Description
Technical field
The present invention relates to a kind of polyphenylene oxide resin preparation method, relate in particular to a kind of preparation method of phosphorous low molecular weight polyphenylene ether resins.
Background technology
Current, electric industrial development is swift and violent, and the developing direction of electronic product is lightening, high performance, high reliability and environmental protection etc.The specific requirement of electronic circuit board also shows as high heat-resisting, low thermal coefficient of expansion, high moisture-proof heat, environmental protection flame retardant, low-k and dielectric loss and high elastic coefficient etc.Therefore, traditional epoxy resin can't satisfy the growth requirement of electronic circuit board fully, and it is also more and more outstanding to have the application of polyphenylene oxide resin in electronic circuit board of high heat resistance, low-k and dielectric loss, good-toughness.But traditional polyphenylene oxide resin is too high because of its molecular weight, aspect processing, still has deficiency.
Because halogen flame retardant to the problems such as pollution of environment, generally adopts P contained compound to wait in the industry at present and realizes flame retardant effect, luxuriant and rich with fragrance type Compound D OPO and verivate thereof etc. are arranged as phosphorous.The Halogen polyphenyl ether resin composition that is used for electronic circuit board at present adopts the phosphonium flame retardant of addition type to realize fire-retardant requirement usually, but there is deficiency in it at aspects such as humidity resistance and chemical resistant propertiess.And because the phosphorated phenolic cpd is insoluble in non-polar solvents such as toluene, so adopt the method for reporting in japanese kokai publication hei 9-235349 communique, No. 3248424 document such as communique of Japanese Patent of in solution, reallocating also can't make the phosphorated low-molecular polyphenylene ether.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of phosphorous low molecular weight polyphenylene ether resins, the phosphorous low molecular weight polyphenylene ether resins manufacturability of gained is good, is applicable to that high-frequency circuit board uses matrix resin.
For realizing above-mentioned purpose, the present invention provides a kind of preparation method of phosphorous low molecular weight polyphenylene ether resins, and it comprises that step is following:
Step 1, phosphorous phenolic cpd and the number-average molecular weight raw material polyphenylene oxide resin more than 10000 is provided;
Step 2, the raw material polyphenylene oxide resin is dissolved in processes raw material polyphenylene oxide resin solution in the solvent;
Step 3, phosphorous phenolic cpd is added in the raw material polyphenylene oxide resin solution;
Step 4, input initiator carry out redistribution reaction in temperature of reaction more than 60 ℃ under action of evocating;
After step 5, reaction are accomplished, obtain the phosphorous low molecular weight polyphenylene ether resins of product, its number-average molecular weight is 1000～6000.
The mass ratio of said raw material polyphenylene oxide resin and phosphorous phenolic cpd is 100: 80～100: 4.
Said phosphorous phenolic cpd is the P contained compound that contains one or two and above phenolic hydroxyl group thereof; This phosphorous phenolic cpd is 9; The 10-dihydro-9-oxy is assorted-10-phospho hetero phenanthrene-10-oxide compound respectively with benzoquinones, 1; The affixture of 4-naphthoquinones, para hydroxybenzene maleimide or rosolic acid, and one or more the combination in other phosphorated phenolic cpds.
In the step 2, the proportioning of raw material polyphenylene oxide resin and solvent is 4: 100～200: 100, and solvent is one or more the combination in benzene,toluene,xylene, butanone, acetone, propyl carbinol, isopropylcarbinol or the Virahol etc.
In the step 3, phosphorous phenolic cpd is dispersed in the raw material polyphenylene oxide resin solution.
Said initiator is dicumyl peroxide, tert-butyl hydroperoxide cumyl, di-t-butyl peroxide, tert-butylperoxy isopropyl carbonate, 2; 5-dimethyl--2; 5-di-t-butyl cumyl peroxy hexin-3,2,5-dimethyl-2,5-di-t-butyl hexane peroxide, peroxo-are to alkane in the Meng; 1, two (tert-pentyl peroxide) hexanaphthenes of 1-, hydrogen peroxide diisopropyl benzene, Lucidol, and the Lucidol verivate in one or more combination.
In the step 4, the investing method of initiator is disposable or muptiple-use adding; Dropping into initiator afterreaction material needs under temperature of reaction, to be incubated more than 30 minutes.
In the step 4, also add catalyzer, catalyzer is before initiator drops into or drop into the back adding, and said catalyzer is selected from the metal-salt, vanadium pentoxide, aniline, amine compound, quaternary ammonium salt, imidazoles Yi of naphthenic acid Ji one or more in the phosphonium salt.
In the step 5, reaction makes water or the phosphorous low molecular weight polyphenylene ether resins of alkaline solution washed product after accomplishing, and this washing procedure at room temperature or more than 60 ℃ carries out.
Beneficial effect of the present invention: the present invention is through being scattered in phosphorous phenolic cpd in the raw material polyphenylene oxide resin solution; In the presence of initiator, carry out redistribution reaction and make phosphorous low molecular weight polyphenylene ether resins; Prepared phosphorous low molecular weight polyphenylene ether resins manufacturability is good, is applicable to the matrix resin of matrix materials such as high-frequency circuit board or the interpolation component of other macromolecular materials.
Embodiment
Phosphorous phenolic cpd is insoluble to non-polar solvents such as toluene, phosphorous phenolic cpd and high-molecular-weight poly phenylate can't coexist as same mutually in, therefore can't utilize the reaction of traditional solution system to obtain low-molecular-weight phosphorous low molecular weight polyphenylene ether resins.The inventor furthers investigate; Discovery is dispersed in phosphorous phenolic cpd in the raw material ppe solution; Through the initiation of superoxide etc., can carry out the redistribution reaction of ppe at a certain temperature, and through after the reaction; Originally the biphase reaction mass also can become a phase, and the phosphorous polyphenylene oxide resin that promptly obtains has good solvability in non-polar solvent.The manufacturability of the phosphorous low molecular weight polyphenylene ether resins of gained is good, through cooperating with thermosetting resins such as epoxy resin, cyanates, is applicable to that high-frequency circuit board uses matrix resin.
Therefore, the present invention provides a kind of preparation method of phosphorous low molecular weight polyphenylene ether resins, and it comprises that step is following:
Step 1, supply raw materials: phosphorous phenolic cpd and the number-average molecular weight raw material polyphenylene oxide resin more than 10000; Under sufficient initiator and reaction conditions; The ingredient proportion of phosphorous phenolic cpd is high more; The number-average molecular weight of products therefrom polyphenylene oxide resin is low more; Number-average molecular weight (Mn) that it is generally acknowledged polyphenylene oxide resin used in the electronic circuit board should be controlled at 1000～6000, and therefore, the mass ratio of preferred feedstock polyphenylene oxide resin and phosphorous phenolic cpd is 100: 80～100: 4.Said phosphorous phenolic cpd is the P contained compound that contains one or two and above phenolic hydroxyl group thereof; This phosphorous phenolic cpd is 9; The 10-dihydro-9-oxy is assorted-10-phospho hetero phenanthrene-10-oxide compound (DOPO) respectively with benzoquinones, 1; The affixture (being respectively DOPO-HQ, DOPO-NQ, DOPO-HPM and DOPO-triol etc.) of 4-naphthoquinones, para hydroxybenzene maleimide or rosolic acid etc., and one or more the combination in other phosphorated phenolic cpds.The chemical structural formula of DOPO-HQ, DOPO-NQ, DOPO-HPM and DOPO-triol is as follows respectively:
Formula one: DOPO-HQ formula two: DOPO-NQ
Formula three: DOPO-HPM formula four: DOPO-triol
Step 2, the raw material polyphenylene oxide resin is dissolved in processes polyphenylene oxide resin solution in the solvent; The proportioning of polyphenylene oxide resin and solvent is 4: 100～200: 100; This raw material polyphenylene oxide resin adopts the commercially available polyphenylene oxide resin of number-average molecular weight more than 10000 to get final product, and solvent is one or more the combination in benzene,toluene,xylene, butanone, acetone, propyl carbinol, isopropylcarbinol or the Virahol etc.
Step 3, phosphorous phenolic cpd is added in the raw material polyphenylene oxide resin solution.In the present invention, need phosphorous phenolic cpd is dispersed in the raw material polyphenylene oxide resin solution.
Step 4, input initiator carry out redistribution reaction in temperature of reaction more than 60 ℃ under action of evocating.The investing method of initiator can be disposable or muptiple-use adding, preferred muptiple-use adding, more preferably with 0.1 mass parts/minute below speed add.
Said initiator is dicumyl peroxide, tert-butyl hydroperoxide cumyl, di-t-butyl peroxide, tert-butylperoxy isopropyl carbonate, 2; 5-dimethyl--2; 5-di-t-butyl cumyl peroxy hexin-3,2,5-dimethyl-2,5-di-t-butyl hexane peroxide, peroxo-are to alkane in the Meng; 1, the combination of one or more in the superoxide such as two (tert-pentyl peroxide) hexanaphthenes of 1-, hydrogen peroxide diisopropyl benzene, Lucidol, Lucidol verivate.
Said temperature of reaction is preferred more than 80 ℃, and the reaction mass reaction was carried out soon more when temperature of reaction was high, but should temperature be controlled at below the boiling point of solvent.Adding initiator afterreaction material needs under temperature of reaction, to be incubated more than 30 minutes.
In this step, also can add catalyzer, promoting the efficient of initiator, said catalyzer is selected from the metal-salt, vanadium pentoxide, aniline, amine compound, quaternary ammonium salt, imidazoles Yi of naphthenic acid Ji one or more in the phosphonium salt etc.Catalyzer can or drop into the back before initiator drops into and add in the reaction mass, does not advise adding together after catalyzer and the initiator mixing.
After step 5, reaction are accomplished, obtain the phosphorous low molecular weight polyphenylene ether resins of product, its number-average molecular weight is 1000～6000.In this step, reaction preferably makes water or alkaline solution washed product after accomplishing, and this washing procedure can at room temperature be implemented, and also can carry out more than 60 ℃, is preferably carrying out more than 60 ℃.
Now the embodiment of the invention is specified as follows, but the present invention is confined to scope of embodiments.
Embodiment 1
In the reaction vessel that has stirring, thermometric and condensing works, add 100 parts of toluene as solvent; Add 50 umber average molecular weights and be 20000 raw material ppe (Asahi Chemical Corp; Trade(brand)name: S201A), be heated to 90 ℃ and stir raw material ppe is dissolved fully.(Huizhou flourishing age reaches Science and Technology Ltd., trade(brand)name: ODOPB) be dispersed in the reaction mass with 10 parts of DOPO-HQ.Then to wherein with added in 40 minutes 8 parts of Lucidols (Dongguan health novel agent, trade(brand)name: Lucidol), 90 ℃ of reactions 120 minutes.The sodium bicarbonate aqueous solution thorough washing is used in cooling, removes the aqueous solution then.Product is the tawny clear solution, no suspended substance, and recording product number-average molecular weight (Mn) with the GPC method is 2670, MWD is 2.3 for (Mw/Mn), promptly gets phosphorous low molecular weight polyphenylene ether resins.
Embodiment 2
In the reaction vessel that has stirring, thermometric and condensing works, add 100 parts of toluene as solvent; Add 50 umber average molecular weights and be 20000 raw material ppe (Asahi Chemical Corp; Trade(brand)name: S201A), be heated to 90 ℃ and stir raw material ppe is dissolved fully.(Huizhou flourishing age reaches Science and Technology Ltd., trade(brand)name: ODOPB) be dispersed in the reaction mass with 8 parts of DOPO-HQ.Then to wherein with added in 40 minutes 6 parts of Lucidols (Dongguan health novel agent, trade(brand)name: Lucidol), 90 ℃ of reactions 120 minutes.The sodium bicarbonate aqueous solution thorough washing is used in cooling, removes the aqueous solution then.Product is the tawny clear solution, no suspended substance, and recording product number-average molecular weight (Mn) with the GPC method is 3015, MWD is 2.2 for (Mw/Mn), promptly gets phosphorous low molecular weight polyphenylene ether resins.
In sum; The present invention is through being scattered in phosphorous phenolic cpd in the polyphenylene oxide resin solution; In the presence of initiator, carry out redistribution reaction and make phosphorous low molecular weight polyphenylene ether resins; Prepared phosphorous low molecular weight polyphenylene ether resins manufacturability is good, is applicable to the matrix resin of matrix materials such as high-frequency circuit board or the interpolation component of other macromolecular materials.
The above for the person of ordinary skill of the art, can make other various corresponding changes and distortion according to technical scheme of the present invention and technical conceive, and all these changes and distortion all should belong to the scope that the present invention protects.
Claims (9)
1. the preparation method of a phosphorous low molecular weight polyphenylene ether resins is characterized in that, it comprises that step is following:
Step 1, phosphorous phenolic cpd and the number-average molecular weight raw material polyphenylene oxide resin more than 10000 is provided;
Step 2, the raw material polyphenylene oxide resin is dissolved in processes raw material polyphenylene oxide resin solution in the solvent;
Step 3, phosphorous phenolic cpd is added in the raw material polyphenylene oxide resin solution;
Step 4, input initiator carry out redistribution reaction in temperature of reaction more than 60 ℃ under action of evocating;
After step 5, reaction are accomplished, obtain the phosphorous low molecular weight polyphenylene ether resins of product, its number-average molecular weight is 1000～6000.
2. the preparation method of phosphorous low molecular weight polyphenylene ether resins as claimed in claim 1 is characterized in that, the mass ratio of said raw material polyphenylene oxide resin and phosphorous phenolic cpd is 100: 80～100: 4.
3. the preparation method of phosphorous low molecular weight polyphenylene ether resins as claimed in claim 1; It is characterized in that; Said phosphorous phenolic cpd is the P contained compound that contains one or two and above phenolic hydroxyl group thereof, and this phosphorous phenolic cpd is 9, the 10-dihydro-9-oxy is assorted-10-phospho hetero phenanthrene-10-oxide compound respectively with benzoquinones, 1; The affixture of 4-naphthoquinones, para hydroxybenzene maleimide or rosolic acid, and one or more the combination in other phosphorated phenolic cpds.
4. the preparation method of phosphorous low molecular weight polyphenylene ether resins as claimed in claim 1; It is characterized in that; In the step 2; The proportioning of raw material polyphenylene oxide resin and solvent is 4: 100～200: 100, and solvent is one or more the combination in benzene,toluene,xylene, butanone, acetone, propyl carbinol, isopropylcarbinol or the Virahol.
5. the preparation method of phosphorous low molecular weight polyphenylene ether resins as claimed in claim 1 is characterized in that, in the step 3, phosphorous phenolic cpd is dispersed in the raw material polyphenylene oxide resin solution.
6. the preparation method of phosphorous low molecular weight polyphenylene ether resins as claimed in claim 1; It is characterized in that; Said initiator is dicumyl peroxide, tert-butyl hydroperoxide cumyl, di-t-butyl peroxide, tert-butylperoxy isopropyl carbonate, 2,5-dimethyl--2,5-di-t-butyl cumyl peroxy hexin-3,2; 5-dimethyl-2; 5-di-t-butyl hexane peroxide, peroxo-be to alkane in the Meng, 1, two (tert-pentyl peroxide) hexanaphthenes of 1-, hydrogen peroxide diisopropyl benzene, Lucidol, and the Lucidol verivate in one or more combination.
7. the preparation method of phosphorous low molecular weight polyphenylene ether resins as claimed in claim 1 is characterized in that, in the step 4, the investing method of initiator is disposable or muptiple-use adding; Dropping into initiator afterreaction material needs under temperature of reaction, to be incubated more than 30 minutes.
8. the preparation method of phosphorous low molecular weight polyphenylene ether resins as claimed in claim 1; It is characterized in that; In the step 4; Also add catalyzer, catalyzer is before initiator drops into or drop into the back adding, and said catalyzer is selected from the metal-salt, vanadium pentoxide, aniline, amine compound, quaternary ammonium salt, imidazoles Yi of naphthenic acid Ji one or more in the phosphonium salt.
9. the preparation method of phosphorous low molecular weight polyphenylene ether resins as claimed in claim 1; It is characterized in that said step 5 is after reaction is accomplished; Make water or the phosphorous low molecular weight polyphenylene ether resins of alkaline solution washed product, this washing procedure at room temperature or more than 60 ℃ carries out.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110456224XA CN102532520A (en) | 2011-12-29 | 2011-12-29 | Method for preparing phosphorous polyphenylene oxide resin with low molecular weight |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110456224XA CN102532520A (en) | 2011-12-29 | 2011-12-29 | Method for preparing phosphorous polyphenylene oxide resin with low molecular weight |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102532520A true CN102532520A (en) | 2012-07-04 |
Family
ID=46340654
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110456224XA Pending CN102532520A (en) | 2011-12-29 | 2011-12-29 | Method for preparing phosphorous polyphenylene oxide resin with low molecular weight |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102532520A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106700475A (en) * | 2016-12-28 | 2017-05-24 | 广东生益科技股份有限公司 | Flame retardant polyphenyl ether resin composition |
| WO2018058760A1 (en) * | 2016-09-28 | 2018-04-05 | 广东生益科技股份有限公司 | Silicone epoxy resin containing phosphine imide, preparation method therefor and application thereof |
| CN111423708A (en) * | 2020-05-06 | 2020-07-17 | 信之高新材料(浙江)有限公司 | Modified PPE resin and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100835785B1 (en) * | 2007-06-26 | 2008-06-09 | 주식회사 두산 | Resine composition for printed circuit board and composite substrate and copper laminates using the same |
| CN101389691A (en) * | 2006-02-21 | 2009-03-18 | 旭化成化学株式会社 | Process for producing low-molecular polyphenylene ether |
| CN101643650A (en) * | 2009-08-24 | 2010-02-10 | 广东生益科技股份有限公司 | Phosphorus-containing flame retardant and preparation method thereof |
| CN102093670A (en) * | 2010-12-23 | 2011-06-15 | 广东生益科技股份有限公司 | Halogen-free flame retardant epoxy resin composition and copper clad plate prepared from same |
-
2011
- 2011-12-29 CN CN201110456224XA patent/CN102532520A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101389691A (en) * | 2006-02-21 | 2009-03-18 | 旭化成化学株式会社 | Process for producing low-molecular polyphenylene ether |
| KR100835785B1 (en) * | 2007-06-26 | 2008-06-09 | 주식회사 두산 | Resine composition for printed circuit board and composite substrate and copper laminates using the same |
| CN101643650A (en) * | 2009-08-24 | 2010-02-10 | 广东生益科技股份有限公司 | Phosphorus-containing flame retardant and preparation method thereof |
| CN102093670A (en) * | 2010-12-23 | 2011-06-15 | 广东生益科技股份有限公司 | Halogen-free flame retardant epoxy resin composition and copper clad plate prepared from same |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018058760A1 (en) * | 2016-09-28 | 2018-04-05 | 广东生益科技股份有限公司 | Silicone epoxy resin containing phosphine imide, preparation method therefor and application thereof |
| CN106700475A (en) * | 2016-12-28 | 2017-05-24 | 广东生益科技股份有限公司 | Flame retardant polyphenyl ether resin composition |
| CN106700475B (en) * | 2016-12-28 | 2019-03-19 | 广东生益科技股份有限公司 | A kind of fire-retardant polyphenyl ether resin composition |
| CN111423708A (en) * | 2020-05-06 | 2020-07-17 | 信之高新材料(浙江)有限公司 | Modified PPE resin and preparation method thereof |
| CN111423708B (en) * | 2020-05-06 | 2023-02-28 | 信之高新材料(浙江)有限公司 | Modified PPE resin and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101033293B (en) | Polyfunctional phenylene ether oligomer, derivative thereof, resin composition containing the same, and use thereof | |
| CN101274226B (en) | Method for preparing polymer anion-exchange membrane | |
| CN106700475B (en) | A kind of fire-retardant polyphenyl ether resin composition | |
| CN105623238A (en) | Phosphorus-containing functionalized poly(arylene ether), and preparation of composition by using phosphorus-containing functionalized poly(arylene ether) as raw material | |
| CN102604075B (en) | Method for preparing dihydroxy-terminated polyphenylene oxide in aqueous medium and product as well as application thereof | |
| WO2013097128A1 (en) | Method for preparing phosphorus-containing polyphenylene oxide resin with low molecular weight | |
| CN102532520A (en) | Method for preparing phosphorous polyphenylene oxide resin with low molecular weight | |
| CN103992472B (en) | The preparation method that a kind of polyether ketone resin and polymerization thereof stop | |
| CN102585480A (en) | Thermosetting resin composition, prepreg prepared from composition, and laminated board prepared from composition and used for printed circuit board | |
| CN102719096A (en) | Resin composition and preparation method thereof | |
| Takamuku et al. | Fully aromatic block copolymers for fuel cell membranes with densely sulfonated nanophase domains | |
| CN104356604B (en) | Composite dielectric material and its production and use | |
| CN104004323B (en) | A kind of resin combination and use its prepreg made and laminate | |
| CN108148196A (en) | A kind of styryl siloxy polyphenylene oxide resin and its preparation method and application | |
| WO2015066008A1 (en) | Curable compositions which form interpenetrating polymer networks | |
| CN103102457A (en) | Styrene modified cashew nut shell oil alkyd resin and preparation method thereof | |
| CN107001547A (en) | Compositions of thermosetting resin | |
| CN103145975B (en) | Method for preparing polyphenyl ether with side chain containing unsaturated carbon-carbon double bond in water medium | |
| CN102702459A (en) | Method for preparing benzene end-capping polyaryletherketone polyme | |
| JP2004339328A (en) | Modified polyphenylene ether compound and method for producing the same | |
| CN101024681A (en) | Method for preparing fluorine-contained multi-function epoxy resin | |
| CN108148162B (en) | A kind of styryl siloxy phenolic resin and its preparation method and application | |
| CN110330635B (en) | Halogen-free flame-retardant heat-resistant water-soluble epoxy resin, composition, preparation method and application thereof | |
| Jutemar et al. | Facile Synthesis and Polymerization of 2, 6‐Difluoro‐2′‐sulfobenzophenone for Aromatic Proton Conducting Ionomers with Pendant Sulfobenzoyl Groups | |
| TWI558740B (en) | Thermal conductive resin and thermal interface material comprising the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20120704 |