CN103059266B - A kind of preparation method of phosphorous cresol novolac epoxy resins - Google Patents
A kind of preparation method of phosphorous cresol novolac epoxy resins Download PDFInfo
- Publication number
- CN103059266B CN103059266B CN201310016979.7A CN201310016979A CN103059266B CN 103059266 B CN103059266 B CN 103059266B CN 201310016979 A CN201310016979 A CN 201310016979A CN 103059266 B CN103059266 B CN 103059266B
- Authority
- CN
- China
- Prior art keywords
- epoxy resins
- cresol novolac
- novolac epoxy
- phosphorous
- equivalent
- 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.)
- Expired - Fee Related
Links
- 229930003836 cresol Natural products 0.000 title claims abstract description 90
- 239000004843 novolac epoxy resin Substances 0.000 title claims abstract description 89
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 title claims abstract description 81
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 18
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000008569 process Effects 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- JDVIRCVIXCMTPU-UHFFFAOYSA-N ethanamine;trifluoroborane Chemical compound CCN.FB(F)F JDVIRCVIXCMTPU-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000002844 melting Methods 0.000 claims abstract description 6
- 230000008018 melting Effects 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000004090 dissolution Methods 0.000 claims abstract description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 16
- 150000001896 cresols Chemical class 0.000 claims description 9
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 7
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 5
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims 3
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 125000005842 heteroatom Chemical group 0.000 abstract description 6
- 239000000463 material Substances 0.000 description 13
- 230000009477 glass transition Effects 0.000 description 11
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 description 8
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000003351 stiffener Substances 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical class CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000011152 fibreglass Substances 0.000 description 2
- 229940015043 glyoxal Drugs 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- USEUJPGSYMRJHM-UHFFFAOYSA-N formaldehyde;4-methylphenol Chemical compound O=C.CC1=CC=C(O)C=C1 USEUJPGSYMRJHM-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000003017 phosphorus Chemical class 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
Abstract
The present invention is a kind of preparation method of phosphorous cresol novolac epoxy resins, and it comprises following steps: A), a cresol novolac epoxy resins is provided; By the cresol novolac epoxy resins and 9 of part, the heating and melting mixing at 170 DEG C to 200 DEG C temperature of the assorted-10-phospho hetero phenanthrene-10-oxide compound of 10-dihydro-9-oxy, and opening is carried out under the existence of the boron trifluoride ethylamine of 60ppm to 80ppm, reaction to oxirane value is 2.8 equivalent/1,000 gram to 3 equivalent/1,000 gram; B), by above-mentioned intermediate be down to temperature 90 DEG C to 60 DEG C, and add solvent in the process of cooling, forming one, to comprise oxirane value be 2.65 equivalent/1,000 gram to 2.95 equivalent/1, the intermediate of 000 gram and the mixture of solvent; C), by another part and with the cresol novolac epoxy resins of dissolution with solvents join in said mixture, a phosphorous cresol novolac epoxy resins can be obtained.The inventive method is novel, technical process is reasonable, easy, easy handling, good product quality.
Description
Technical field:
The present invention is a kind of synthetic method of organic compound, particularly a kind of preparation method of phosphorous cresol novolac epoxy resins, belongs to the manufacture method technical field of chemical substance.
Background technology:
Cresol novolac epoxy resins is an epoxy resin with better thermostability and insulativity, is used in widely on the field such as semi-conductor or printed circuit board (PCB).But the flame retardancy of this cresol novolac epoxy resins is not good, along with the development and application of superpower electric equipment products, long-time use likely makes parts have amount of heat to produce, and therefore, the improvement of p-cresol formaldehyde epoxy resin flame retardancy becomes the focus of scientific research.
The method of the flame retardancy of current lifting cresol novolac epoxy resins imports 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide in its chemical structure, is called for short DOPO, makes it to synthesize phosphorous cresol novolac epoxy resins.But though this synthetic method can promote the flame retardancy of cresol novolac epoxy resins, for the hardening thing that cresol novolac epoxy resins material is formed, the glass transition temperature of the hardening thing that this phosphorous cresol novolac epoxy resins is formed is poor.Main because DOPO can with the epoxy reaction in cresol novolac epoxy resins, when causing forming hardening thing, cross-linking density diminishes, and then makes hardening thing glass transition temperature reduce.In sum, providing a kind of preparation method of phosphorous cresol novolac epoxy resins of novelty and promote the glass transition temperature of the hardening thing generated by it, is the problem that the present invention need solve.Glass transition temperature refers to the temperature of glass state material between vitreous state and elastomeric state during mutual conversion.
Summary of the invention:
The object of this invention is to provide a kind of preparation method of phosphorous cresol novolac epoxy resins, it be with cresol novolac epoxy resins and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide at a certain temperature polymerization reaction take place generate phosphorous cresol novolac epoxy resins.The phosphorous cresol novolac epoxy resins material hardening thing that the phosphorous cresol novolac epoxy resins obtained by this preparation method and stiffening agent are formed has high glass transition temperature, and this hardening thing is in the process of processing pressing, has good mobility.
The preparation method of the cresol novolac epoxy resins that the present invention is phosphorous, comprises the following steps:
A), cresol novolac epoxy resins is provided, by a part of cresol novolac epoxy resins and 9, the heating and melting mixing at 170 DEG C to 200 DEG C temperature of the assorted-10-phospho hetero phenanthrene-10-oxide compound of 10-dihydro-9-oxy, and opening is carried out under the existence of 60ppm to 80ppm boron trifluoride ethylamine catalyzer, reacting to oxirane value is that 2.8 equivalent/1000 are gram to 3 equivalent/1000 gram;
B), above-mentioned intermediate is down to temperature 90 DEG C to 60 DEG C, and in the process of cooling, add corresponding solvent, react and still slowly do not carry out being down under temperature of reaction, forming one, to comprise oxirane value be the intermediate of 2.65 equivalent/1000 gram to 2.95 equivalent/1000 gram and the mixture of solvent;
C), finally, join by another part and with the cresol novolac epoxy resins of dissolution with solvents in said mixture, phosphorous cresol novolac epoxy resins can be obtained.
Second feature of the present invention is in the total amount of this cresol novolac epoxy resins for weight 100%, and the usage quantity scope of the cresol novolac epoxy resins that should react with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 77% to 79%.
3rd feature of the present invention is that total usage quantity of this cresol novolac epoxy resins is 81.5% to 83.5% in the total amount of this 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and cresol novolac epoxy resins with weight 100%.
One or more mixture of the 4th feature of the present invention to be solvent used be butanone, propylene glycol monomethyl ether or 1-Methoxy-2-propyl acetate.
5th feature of the present invention is in the total amount of this mixture with weight 100%, and the usage quantity scope of this solvent is 31.0% to 33.0%.
In sum: advantage of the present invention under: (one) polymerization technology simple flow of the present invention, easy handling, method are novel; (2) the present invention adopts batch-type to add cresol novolac epoxy resins, in contrast to once and enoughly add cresol novolac epoxy resins and DOPO reacts the phosphorous cresol novolac epoxy resins formed, under identical phosphorus content and close oxirane value, react with dicyandiamide hardener, the hardening thing that the phosphorous cresol novolac epoxy resins of the present invention is formed has higher glass transition temperature 182 DEG C to 190 DEG C.Meanwhile, the cresol novolac epoxy resins do not reacted with DOPO that the phosphorous cresol novolac epoxy resins of the present invention has second time to add, makes formed hardening thing in the process of following process pressing, has good mobility; (3) cresol novolac epoxy resins that, the present invention is phosphorous can be applicable in the manufacture field of semi-conductor or printed circuit board (PCB), as encapsulation material, purposes such as insulation material or insulated substrate etc.
The title molecular structural formula of reactant or additive and source:
1, cresol novolac epoxy resins:
Molecular structural formula:
2,9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide:
Be called for short: DOPO
Molecular structural formula:
3, solvent: butanone, propylene glycol monomethyl ether and 1-Methoxy-2-propyl acetate
(1) butanone
Molecular structural formula:
(2) propylene glycol monomethyl ether
Molecular structural formula:
(3) 1-Methoxy-2-propyl acetate
Molecular structural formula:
4, catalyzer, boron trifluoride ethylamine
Molecular structural formula: BF
3cH
3cH
2nH
2
Accompanying drawing illustrates:
The present invention is temporarily without accompanying drawing.
Embodiment:
The preparation method of the cresol novolac epoxy resins that the present invention is phosphorous, comprises following steps:
A), one cresol novolac epoxy resins is provided;
By the cresol novolac epoxy resins of some and 9, the heating and melting mixing at 170 DEG C to 200 DEG C temperature of the assorted-10-phospho hetero phenanthrene-10-oxide compound of 10-dihydro-9-oxy, and opening is carried out under the existence of the boron trifluoride ethylamine of 60ppm to 80ppm, be 2.8 equivalent/1 to oxirane value, 000 gram to 3 equivalent/1,000 gram;
B), said mixture is cooled the temperature to 90 DEG C to 60 DEG C, and solvent is added in the process of cooling, because reaction is still slowly carried out not being down under temperature of reaction, forming one, to comprise oxirane value be 2.65 equivalent/1,000 gram to 2.95 equivalent/1, the intermediate of 000 gram and the mixture of solvent; Then,
C), add residue and with another part cresol novolac epoxy resins of dissolution with solvents, a phosphorous cresol novolac epoxy resins can be obtained.
Preferably, the weight average molecular weight scope of this cresol novolac epoxy resins is 2,400 to 2,800.Preferably, the epoxy equivalent (weight) scope of this cresol novolac epoxy resins be 190 grams/equivalent to 210 gram/equivalent.Preferably, in the total amount of this 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and cresol novolac epoxy resins for weight 100%, total usage quantity scope of this cresol novolac epoxy resins is 81.5% to 83.5%.
For avoiding the viscosity in reaction process too high, preferably, should with 9, the mix usage quantity of cresol novolac resin of-10-phospho hetero phenanthrene-10-oxide compound reaction of 10-dihydro-9-oxy is greater than the usage quantity of the cresol novolac epoxy resins that this residue adds, more preferably, in the total amount of this cresol novolac epoxy resins for weight 100%, the usage quantity scope of the cresol novolac epoxy resins that should react with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 77% to 79%.
In order to this mixture can be made to be a uniform liquid condition, and the viscosity of this mixture can be reduced, and make follow-up flow process easy to operate.Solvent selects butanone, propylene glycol monomethyl ether or 1-Methoxy-2-propyl acetate, and this three Seed solvent can be used alone or as a mixture, and preferably, in the total amount of this mixture for weight 100%, the usage quantity scope of this solvent is 31.0% to 33.0%.
Add residue and need carry out at 60 DEG C to 90 DEG C with the opportunity of the cresol novolac epoxy resins of dissolution with solvents, carrying out opening to avoid the remaining cresol novolac epoxy resins added.Fashionable for making remaining cresol novolac epoxy resins add, can mix with this mixture, first by this remaining cresol novolac epoxy resins and solvent, a uniform liquid condition can be formed.
Obtained by the preparation method of the cresol novolac epoxy resins system phosphorous cresol novolac epoxy resins from the above mentioned that the present invention is phosphorous.The weight average molecular weight scope of this phosphorous cresol novolac epoxy resins is 3,400 to 3,700.Preferably, in the total amount of the solids component in the cresol novolac epoxy resins that this is phosphorous for weight 100%, this phosphorus content scope is 2.3% to 2.7%.
The present invention will be described further with regard to following examples, but it is to be understood that these embodiments are only the use illustrated, and should not be interpreted as the restriction of the invention process.
< embodiment >
< embodiment 1>
By the cresol novolac epoxy resins of 447 grams (weight average molecular weight: 2,668; Epoxy equivalent (weight): 200 grams/equivalent) and 122 grams 9, assorted-10-phospho hetero phenanthrene-10-oxide compound the heating and melting of 10-dihydro-9-oxy is mixed to 185 DEG C, and opening is carried out under the existence of the boron trifluoride ethylamine of 70ppm, reaction to oxirane value is 2.877 equivalent/1,000 gram, afterwards, cool the temperature to 75 DEG C, and the propylene glycol monomethyl ether of 41.7 grams and the butanone of 225 grams is sequentially added in the process of cooling, it is 2.695 equivalent/1 that formation one comprises oxirane value, the intermediate of 000 gram and the mixture of solvent.Then, at 75 DEG C, add the homogeneous phase mixed solution of the butanone of the cresol novolac epoxy resins comprising 126 grams and 38 grams, be uniformly mixed, the phosphorous cresol novolac epoxy resins material of about 1 kilogram can be obtained, its weight average molecular weight: 3,569; Oxirane value: 3.086 equivalent/1,000 gram; Phosphorus content: 2.52%, solid content is 69.22%.
< comparative example 1>
By the cresol novolac epoxy resins of 577 grams (weight average molecular weight: 2,688; Epoxy equivalent (weight): 200 grams/equivalent) and 123 grams 9, assorted-10-phospho hetero phenanthrene-10-oxide compound the heating and melting of 10-dihydro-9-oxy is mixed to 185 DEG C, and opening is carried out under the existence of the boron trifluoride ethylamine of 70ppm, question response is 3.134 equivalent/1 to forming an oxirane value, after 000 gram, cool the temperature to 80 DEG C, and the propylene glycol monomethyl ether of 50 grams and the butanone of 250 grams is sequentially added in the process of cooling, be uniformly mixed, the phosphorous cresol novolac epoxy resins of about 1 kilogram can be obtained, its weight average molecular weight: 3,762; Oxirane value: 3.024 equivalent/1,000 gram; Phosphorus content: 2.52%, solid content is 69.98%.
[test item]
1, glass transition temperature (Tg, DEG C) measures:
By the phosphorous cresol novolac epoxy resins material of 100 grams of embodiments 1 and 28.0947 grams of dicyandiamide solution (2.5076 grams of Dyhard RU 100s and 0.0464 gram of glyoxal ethyline and 25.5407 grams of dimethyl formamides) mixing, form a mixed solution, one base material (as woven fiber glass) to be immersed in this mixed solution about 30 minutes, then, to take out and after toasting 90 minutes in a normal atmosphere and at 190 DEG C, be cooled to room temperature, form sample to be tested.
By the phosphorous cresol novolac epoxy resins material of 100 grams of comparative examples 1 and 27.8326 grams of dicyandiamide solution (2.4842 grams of Dyhard RU 100s and 0.0460 gram of glyoxal ethyline and 25.3023 grams of dimethyl formamides) mixing, form a mixed solution, one base material (as woven fiber glass) to be immersed in this mixed solution about 30 minutes, then, take out and after a normal atmosphere toasts 90 minutes at 190 DEG C, be cooled to room temperature, form sample to be tested.Finally get instrument and carry out detection two base materials acquisition data.
The correlation data table of table 1 embodiment 1 and comparative example
From the last experimental data of upper table, the present invention adopts batch-type to add cresol novolac epoxy resins, the cresol novolac epoxy resins making the present invention phosphorous reacts with once enough cresol novolac epoxy resins and DOPO the phosphorous cresol novolac epoxy resins formed, with under close oxirane value under identical phosphorus content, react with stiffening agent, the hardening thing that the phosphorous cresol novolac epoxy resins material of the present invention is formed has higher glass transition temperature.And the preparation method of the present invention can obtain the phosphorous cresol novolac epoxy resins material promoting hardening thing glass transition temperature really, and the glass transition temperature of hardening thing is improve 6.3 DEG C.
In sum, the present invention adopts batch-type to add cresol novolac epoxy resins, the cresol novolac epoxy resins making the present invention phosphorous reacts with once enough cresol novolac epoxy resins and DOPO the phosphorous cresol novolac epoxy resins formed, under identical phosphorus content and close oxirane value, react with stiffening agent, the phosphorous cresol novolac epoxy resins material of the present invention can make formed hardening thing have higher glass transition temperature.Meanwhile, the phosphorous cresol novolac epoxy resins of the present invention, because of containing the cresol novolac epoxy resins do not reacted with DOPO, makes the hardening thing formed by it in the processing procedure of follow-up pressing, has good mobility, therefore really can reach the object of the present invention.
In sum; be only the preferred embodiment of the present invention; when can not limit the scope of the invention process with this, namely every simple equivalence done according to the present patent application the scope of the claims and description of the invention content changes and modifies, and all still belongs in the scope of patent protection of the present invention.
Claims (2)
1. a preparation method for phosphorous cresol novolac epoxy resins, comprises above step successively:
A), cresol novolac epoxy resins is provided, by a part of cresol novolac epoxy resins and 9, the assorted-10-phosphine phenanthrene-10-of 10-dihydro-9-oxy containing phosphorous oxides heating and melting mixing at 170 ° ~ 200 DEG C temperature, and under the existence of 60ppm ~ 80ppm boron trifluoride ethylamine catalyzer, carry out opening, react to oxirane value be 2.8 equivalent/1000 gram ~ 3 equivalent/1000 gram;
B), said mixture is down to temperature 60 ° ~ 90 DEG C, and in the process of cooling, add corresponding solvent, react and still slowly do not carry out being down under temperature of reaction, forming one, to comprise oxirane value be the intermediate of 2.65 equivalent/1000 gram ~ 2.95 equivalent/1000 gram and the mixture of solvent;
C), finally, join by another part and with the cresol novolac epoxy resins of dissolution with solvents in said mixture, phosphorous cresol novolac epoxy resins can be obtained;
Wherein in this 9,10-dihydro-9-oxy mixes the total amount of-10-phosphine phenanthrene-10-containing phosphorous oxides and cresol novolac epoxy resins with weight 100%, total usage quantity of this cresol novolac epoxy resins is 81.5% ~ 83.5%;
Wherein in the total amount of this cresol novolac epoxy resins for weight 100%, should with 9, the mix usage quantity scope of cresol novolac epoxy resins that-10-phosphine phenanthrene-10-reacts containing phosphorous oxides of 10-dihydro-9-oxy is 77% ~ 79%;
Wherein in the total amount of this mixture with weight 100%, the usage quantity scope of this solvent is 31.0% ~ 33.0%.
2. the preparation method of a kind of phosphorous cresol novolac epoxy resins according to claim 1, is characterized in that solvent used is one or more mixture of butanone, propylene glycol monomethyl ether or 1-Methoxy-2-propyl acetate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310016979.7A CN103059266B (en) | 2013-01-17 | 2013-01-17 | A kind of preparation method of phosphorous cresol novolac epoxy resins |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310016979.7A CN103059266B (en) | 2013-01-17 | 2013-01-17 | A kind of preparation method of phosphorous cresol novolac epoxy resins |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103059266A CN103059266A (en) | 2013-04-24 |
| CN103059266B true CN103059266B (en) | 2015-10-14 |
Family
ID=48102186
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310016979.7A Expired - Fee Related CN103059266B (en) | 2013-01-17 | 2013-01-17 | A kind of preparation method of phosphorous cresol novolac epoxy resins |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103059266B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106279586B (en) * | 2016-08-31 | 2018-07-06 | 四川国能高科生物树脂有限公司 | A kind of phosphorous linear phenol-aldehyde resin as epoxy curing agent and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000239525A (en) * | 1999-02-16 | 2000-09-05 | Sumitomo Bakelite Co Ltd | Flame-retardant resin composition and layer insulation adhesive |
| JP2002161151A (en) * | 2000-11-27 | 2002-06-04 | Matsushita Electric Works Ltd | Prepreg and laminated board |
| EP1930326B1 (en) * | 2006-12-04 | 2009-05-13 | Nan Ya Plastics Corporation | Synthesis of new dihydrobenzoxazine |
| CN101445520A (en) * | 2007-11-26 | 2009-06-03 | 中国科学院化学研究所 | Phosphoric organic silicon compound, preparation method and application thereof |
| CN102002210A (en) * | 2009-09-01 | 2011-04-06 | 联茂电子股份有限公司 | Halogen-free resin composition and film and substrate made of the halogen-free resin composition |
| CN102051025A (en) * | 2010-12-11 | 2011-05-11 | 宏昌电子材料股份有限公司 | Halogen-free flame-retardant epoxy resin composition and application thereof |
| CN102051024A (en) * | 2010-12-11 | 2011-05-11 | 宏昌电子材料股份有限公司 | Halogen-free flame-retardant epoxy resin composition and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI397533B (en) * | 2008-04-11 | 2013-06-01 | Chang Chun Plastics Co Ltd | Novel phosphorus-containing compounds and their preparing process and use |
-
2013
- 2013-01-17 CN CN201310016979.7A patent/CN103059266B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000239525A (en) * | 1999-02-16 | 2000-09-05 | Sumitomo Bakelite Co Ltd | Flame-retardant resin composition and layer insulation adhesive |
| JP2002161151A (en) * | 2000-11-27 | 2002-06-04 | Matsushita Electric Works Ltd | Prepreg and laminated board |
| EP1930326B1 (en) * | 2006-12-04 | 2009-05-13 | Nan Ya Plastics Corporation | Synthesis of new dihydrobenzoxazine |
| CN101445520A (en) * | 2007-11-26 | 2009-06-03 | 中国科学院化学研究所 | Phosphoric organic silicon compound, preparation method and application thereof |
| CN102002210A (en) * | 2009-09-01 | 2011-04-06 | 联茂电子股份有限公司 | Halogen-free resin composition and film and substrate made of the halogen-free resin composition |
| CN102051025A (en) * | 2010-12-11 | 2011-05-11 | 宏昌电子材料股份有限公司 | Halogen-free flame-retardant epoxy resin composition and application thereof |
| CN102051024A (en) * | 2010-12-11 | 2011-05-11 | 宏昌电子材料股份有限公司 | Halogen-free flame-retardant epoxy resin composition and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| DOPO与邻甲酚醛环氧树脂反应特性的研究;梁静;《热固性树脂》;20070930;第22卷(第5期);8-13页 * |
| 新型含磷环氧树脂的合成及其反应动力学研究;叶坤;《中国胶粘剂》;20080331;第17卷(第3期);1-3页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103059266A (en) | 2013-04-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| RU2480465C2 (en) | Non-halogen benzoxazine-based curable compositions with high glass transition temperature | |
| CN103865101B (en) | A kind of efficiently phosphorus-nitrogen containing flame retardant and preparation method | |
| EP3279261B1 (en) | Resin composition, electroconductive resin composition, adhesive, electroconductive adhesive, paste for forming electrodes, and semiconductor device | |
| CN105315454B (en) | The application of the organic-silicon-modified method for preparing siliceous double hydroxyl polyphenylene oxide and product | |
| CN102558233B (en) | From the derivative phosphorus series bisphenols of benzoxazine, its epoxy resin semicure thing, its epoxy resin cured product and manufacture method thereof | |
| KR102268343B1 (en) | Curable composition and cured product thereof | |
| TWI739976B (en) | Alkenyl-containing resin, curable resin composition and hardened product | |
| CN103059266B (en) | A kind of preparation method of phosphorous cresol novolac epoxy resins | |
| CN112079978A (en) | DCPD-bisphenol type benzoxazine resin and copper-clad plate composition and preparation method thereof | |
| TW201319228A (en) | Low dielectric flame-retardant bi-functional benzoxazine resin and its manufacturing method | |
| CN110922720A (en) | Ternary thermosetting resin composition for semiconductor device packaging | |
| CN110903604B (en) | A ternary resin composition for power device encapsulation | |
| CN110872281B (en) | Preparation methods of tertiary phenol-furfuryl amine type benzoxazine monomer, cured resin and copolymer resin thereof | |
| CN115850155B (en) | Active ester compound, active ester mixture, resin composition and application of resin composition | |
| CN115073711B (en) | MDI modified epoxy resin solution for copper-clad plate glue solution fluidity improver and preparation method and application thereof | |
| CN114752037B (en) | Preparation method of low-dielectric flame-retardant epoxy resin | |
| TW201134875A (en) | Sulfone group-containing polyhydroxy polyether resin, resin composition containing such resin, curable resin composition containing such regin, and film obtained from these resins or resin composition | |
| CN101024680B (en) | Binaphthyl-radicle-contained di-phenol A-type resin and its preparing method | |
| CN103951943A (en) | Insulating resin composition and preparation method thereof | |
| CN105542161B (en) | A kind of fire-retardant cyanate ester resin and preparation method thereof | |
| CN115124684A (en) | Epoxy resin-imidazole-isocyanate resin material and preparation method and application thereof | |
| CN107325627A (en) | Electrically conductive ink low-temperature setting composition and preparation method thereof | |
| CN110156572B (en) | Preparation method of epoxy resin curing agent | |
| CN102558475A (en) | Phenolic resin containing maleinimide | |
| TWI733824B (en) | Method for producing polycyclic aromatic amine phenol compound and resin composition, the above-mentioned polycyclic aromatic amine phenol compound, resin composition, and cured product |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20151014 Termination date: 20190117 |