CN106750183A - A kind of DOPO modified anhydrides ethoxyline resin antiflaming curing agent and preparation method thereof - Google Patents
A kind of DOPO modified anhydrides ethoxyline resin antiflaming curing agent and preparation method thereof Download PDFInfo
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- CN106750183A CN106750183A CN201611108466.9A CN201611108466A CN106750183A CN 106750183 A CN106750183 A CN 106750183A CN 201611108466 A CN201611108466 A CN 201611108466A CN 106750183 A CN106750183 A CN 106750183A
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- Prior art keywords
- curing agent
- dopo
- anhydrides
- preparation
- epoxy resin
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- 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 title claims abstract description 32
- 150000008064 anhydrides Chemical class 0.000 title claims abstract description 24
- 229920005989 resin Polymers 0.000 title claims abstract description 21
- 239000011347 resin Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 34
- 239000003822 epoxy resin Substances 0.000 claims abstract description 16
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 16
- 239000003063 flame retardant Substances 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 6
- 239000011574 phosphorus Substances 0.000 claims abstract description 6
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- 239000012298 atmosphere Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims abstract description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical class C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- CSHJJWDAZSZQBT-UHFFFAOYSA-N 7a-methyl-4,5-dihydro-3ah-2-benzofuran-1,3-dione Chemical class C1=CCCC2C(=O)OC(=O)C21C CSHJJWDAZSZQBT-UHFFFAOYSA-N 0.000 abstract 2
- 238000010992 reflux Methods 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 231100000053 low toxicity Toxicity 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- -1 Phthalate anhydride Chemical group 0.000 description 2
- 235000019504 cigarettes Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
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
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4238—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof heterocyclic
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657172—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Epoxy Resins (AREA)
Abstract
A kind of DOPO modified anhydrides ethoxyline resin antiflaming curing agent and preparation method thereof, is related to a kind of chemical synthesis agent and preparation method thereof, and preparing raw material includes：DOPO, 2 methyl tetrahydrophthalic anhydrides, the preparation process of the fire retardant is simple, only needs single step reaction can be prepared by, i.e., mix DOPO, 2 methyl tetrahydrophthalic anhydrides and solvent under atmosphere of inert gases, react at a certain temperature a few hours, revolving is except obtaining product after molten；Or react a few hours in the absence of solvent, it is cooled to room temperature and obtains required product, the product obtained under different conditions of mixture ratios is colourless liquid to weak yellow liquid.Can well mix with epoxy resin in process, can solidify with epoxy resin and be integrated, both can effectively improve the fire resistance of epoxy resin again as the curing agent of epoxy resin.Preparation method is simple, can according to demand prepare the modified anhydride curing agent of different phosphorus contents.
Description
Technical field
The present invention relates to a kind of curing agent and preparation method thereof, more particularly to a kind of DOPO modified anhydrides epoxy resin resistance
Combustion curing agent and preparation method thereof.
Background technology
Epoxy resin is that a class has the thermosetting of the performances such as excellent bonding, anti-corrosion, insulation, processing and forming, high intensity high
Molecular material, has superior performance in terms of mechanics, heat and chemical-resistant resistance.It is widely used in coating, adhesive, insulation material
In material, electric, optical-mechanical, Aero-Space and other many industrial circles.Epoxy resin pole is found during
Easy firing.Inflammability causes that the range of application of epoxy resin is extremely restricted.Therefore, research ethoxyline resin antiflaming performance for
Expand it to be had great significance in electric, aerospace field application.
The research of ethoxyline resin antiflaming performance increasingly tends to non-halogen.Develop efficient, low cigarette or the smokeless, Halogen of low toxicity
Environment friendly flame retardant and novel flame-retardant epoxide resin material become the important research direction of domestic and foreign scholars.
Ethoxyline resin antiflaming curing agent can be chemically reacted with epoxy resin, and link can be deposited in the form of chemical bond
To in epoxy resin, the fire resistance of epoxy resin can be significantly improved.
The content of the invention
It is an object of the invention to provide a kind of DOPO modified anhydrides ethoxyline resin antiflaming curing agent and preparation method thereof, this
Invention curing agent contains ignition-proof element phosphorus, while the solidification of epoxy resin can be participated in.With flame retarding efficiency is high and Halogen, low
The features such as cigarette, low toxicity, meet the requirement that current people preserve the ecological environment.
The purpose of the present invention is achieved through the following technical solutions：
A kind of DOPO modified anhydrides ethoxyline resin antiflaming curing agent, the DOPO modified anhydrides ethoxyline resin antiflaming curing agent raw material
Including：DOPO and 2- methyl tetrahydrophthalic anhydrides, flame retardant curing agent have following structure：
。
A kind of DOPO modified anhydrides ethoxyline resin antiflaming curing agent preparation method, the step of preparation one of the flame retardant curing agent is anti-
Should, i.e., DOPO, 2- methyl tetrahydrophthalic anhydride and solvent are mixed under atmosphere of inert gases, react at a certain temperature
A few hours, product obtains colourless liquid to weak yellow liquid through revolving, standing；Said process is expressed as with chemical equation：
。
A kind of described DOPO modified anhydrides ethoxyline resin antiflaming curing agent preparation method, in the flame retardant curing agent,
The change of DOPO and 2- methyl tetrahydrophthalic anhydride molar ratios prepares phosphorus content, and in 0%-8.1%, (2- methyl tetrahydrochysene is adjacent
Phthalate anhydride excess) DOPO modified anhydrides；Solvent for use be toluene, dimethylbenzene, chlorobenzene, dioxane in one kind or its
The mixture of arbitrary proportion reacts under condition of no solvent.
Described a kind of DOPO modified anhydrides ethoxyline resin antiflaming curing agent preparation method, in synthesis DOPO acid modified anhydro rings
In oxygen tree fat flame retardant curing agent, reaction temperature is controlled at 100-140 DEG C；Reaction time is 6-12h.
A kind of described DOPO modified anhydrides ethoxyline resin antiflaming curing agent preparation method, it is during the course of the reaction, used lazy
Property gas be nitrogen, argon gas or helium in one kind.
The present invention need not carry out numerous and diverse post processing, and the modifier that different phosphorus contents are prepared according to the actual requirements can be used for
The fire-retardant solidification of epoxy resin.
Advantages of the present invention is with effect：
1st, a kind of DOPO modified anhydrides ethoxyline resin antiflaming curing agent that the present invention is provided, can consolidating as a kind of epoxy resin
Agent, has a flame retardant effect again.
2nd, a kind of DOPO modified anhydrides ethoxyline resin antiflaming curing agent that the present invention is provided, with low toxicity, high-efficiency environment friendly
Advantage, is conducive to sustainable development.
3rd, the preparation method that the present invention is provided is simple, and mild condition, it is easy to control can according to demand prepare different phosphorus contents
DOPO modified anhydrides, without carry out complexity post processing.
Specific embodiment
With reference to embodiment, the present invention is described in detail.
Embodiment 1：
To equipped with reflux condensing tube, thermometer, N2160ml dioxane is added to make in the 250ml there-necked flasks of ingress pipe and magneton
It is solvent, adds 86.4gDOPO, is passed through N2Protection.Heating stirring adds 66.47g2- methyl tetrahydrochysene adjacent after it is completely dissolved
12h is reacted under phthalate anhydride, reflux temperature, room temperature is down to, rotated, standing cools down to obtain weak yellow liquid.
Embodiment 2：
To equipped with reflux condensing tube, thermometer, N286.4gDOPO is added in the 250ml there-necked flasks of ingress pipe and magneton, N is passed through2
Protection.Heat temperature raising, adds 66.47g2- methyl tetrahydrophthalic anhydrides after it is melted completely, stirring is opened, in 140 DEG C
Lower reaction 6h, is down to room temperature, stands overnight, and obtains weak yellow liquid.
Embodiment 3：
To equipped with reflux condensing tube, thermometer, N2160ml toluene is added in the 250ml there-necked flasks of ingress pipe and magneton as molten
Agent, adds 36gDOPO, is passed through N2Protection.Heating stirring adds 66.47g2- methyl tetrahydrochysene O-phthalics after it is completely dissolved
8h is reacted under acid anhydrides, reflux temperature, room temperature is down to, rotated, stand to obtain colourless transparent liquid.
Claims (5)
1. a kind of DOPO modified anhydrides ethoxyline resin antiflaming curing agent, it is characterised in that the DOPO modified anhydrides epoxy resin
Flame retardant curing agent raw material includes：DOPO and 2- methyl tetrahydrophthalic anhydrides, flame retardant curing agent have following structure：
。
2. a kind of DOPO modified anhydrides ethoxyline resin antiflaming curing agent preparation method, it is characterised in that the system of the flame retardant curing agent
Standby single step reaction, i.e., mix DOPO, 2- methyl tetrahydrophthalic anhydride and solvent under atmosphere of inert gases, in a constant temperature
Degree lower reaction a few hours, product obtains colourless liquid to weak yellow liquid through revolving, standing；Said process chemical equation table
It is shown as：
。
3. a kind of DOPO modified anhydrides ethoxyline resin antiflaming curing agent preparation method according to claim 2, its feature exists
In in the flame retardant curing agent, the change of DOPO and 2- methyl tetrahydrophthalic anhydride molar ratios prepares phosphorus content and exists
The DOPO modified anhydrides of 0%-8.1% (2- methyl tetrahydrophthalic anhydrides excess)；Solvent for use be toluene, dimethylbenzene, chlorobenzene,
The mixture of one kind or its arbitrary proportion in dioxane reacts under condition of no solvent.
4. a kind of DOPO modified anhydrides ethoxyline resin antiflaming curing agent preparation method according to claim 2, its feature exists
In in DOPO modified anhydride ethoxyline resin antiflaming curing agent is synthesized, reaction temperature is controlled at 100-140 DEG C；Reaction time is
6-12h。
5. a kind of DOPO modified anhydrides ethoxyline resin antiflaming curing agent preparation method according to claim 2, its feature exists
During the course of the reaction, inert gas used is the one kind in nitrogen, argon gas or helium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611108466.9A CN106750183A (en) | 2016-12-06 | 2016-12-06 | A kind of DOPO modified anhydrides ethoxyline resin antiflaming curing agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611108466.9A CN106750183A (en) | 2016-12-06 | 2016-12-06 | A kind of DOPO modified anhydrides ethoxyline resin antiflaming curing agent and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN106750183A true CN106750183A (en) | 2017-05-31 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611108466.9A Pending CN106750183A (en) | 2016-12-06 | 2016-12-06 | A kind of DOPO modified anhydrides ethoxyline resin antiflaming curing agent and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107383340A (en) * | 2017-07-20 | 2017-11-24 | 沈阳化工大学 | A kind of DOPO modified anhydrides ethoxyline resin antiflaming curing agent and preparation method thereof |
| CN111057217A (en) * | 2019-12-26 | 2020-04-24 | 广东生益科技股份有限公司 | Thermosetting epoxy resin composition and prepreg, laminated board and printed circuit board using same |
| KR20200080311A (en) * | 2017-11-09 | 2020-07-06 | 블루 큐브 아이피 엘엘씨 | Phosphorylated anhydride containing epoxy resin |
| CN112300369A (en) * | 2020-11-06 | 2021-02-02 | 华东理工大学华昌聚合物有限公司 | Reactive flame retardant for epoxy resin and preparation method and application thereof |
| CN112442083A (en) * | 2019-08-28 | 2021-03-05 | 广东广山新材料股份有限公司 | Phosphorus-containing flame retardant with anhydride and preparation method and application thereof |
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| CN102134304A (en) * | 2011-03-03 | 2011-07-27 | 沈阳化工大学 | Reactive type phosphoric epoxy resin flame retardant and preparation method thereof |
| CN103833947A (en) * | 2014-02-21 | 2014-06-04 | 华东理工大学 | Synthesis and application of reaction type halogen-free phosphorus-containing flame retardant for polyurethane |
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- 2016-12-06 CN CN201611108466.9A patent/CN106750183A/en active Pending
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| CN102134304A (en) * | 2011-03-03 | 2011-07-27 | 沈阳化工大学 | Reactive type phosphoric epoxy resin flame retardant and preparation method thereof |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107383340A (en) * | 2017-07-20 | 2017-11-24 | 沈阳化工大学 | A kind of DOPO modified anhydrides ethoxyline resin antiflaming curing agent and preparation method thereof |
| US11479638B2 (en) | 2017-11-09 | 2022-10-25 | Blue Cube Ip Llc | Phosphorated anhydride containing epoxy resin |
| JP7394930B2 (en) | 2017-11-09 | 2023-12-08 | ブルー キューブ アイピー エルエルシー | Epoxy resin containing phosphorylated anhydride |
| CN111542530A (en) * | 2017-11-09 | 2020-08-14 | 蓝立方知识产权有限责任公司 | Epoxy resins containing phosphorus-containing anhydrides |
| JP2021502370A (en) * | 2017-11-09 | 2021-01-28 | ブルー キューブ アイピー エルエルシー | Epoxy resin containing phosphorylated anhydride |
| KR20200080311A (en) * | 2017-11-09 | 2020-07-06 | 블루 큐브 아이피 엘엘씨 | Phosphorylated anhydride containing epoxy resin |
| JP2022166005A (en) * | 2017-11-09 | 2022-11-01 | ブルー キューブ アイピー エルエルシー | Phosphorated anhydride-containing epoxy resin |
| KR102612366B1 (en) * | 2017-11-09 | 2023-12-11 | 블루 큐브 아이피 엘엘씨 | Phosphorized anhydrides containing epoxy resins |
| CN111542530B (en) * | 2017-11-09 | 2023-08-22 | 蓝立方知识产权有限责任公司 | Epoxy resin containing phosphoric anhydride |
| CN112442083A (en) * | 2019-08-28 | 2021-03-05 | 广东广山新材料股份有限公司 | Phosphorus-containing flame retardant with anhydride and preparation method and application thereof |
| WO2021128630A1 (en) * | 2019-12-26 | 2021-07-01 | 广东生益科技股份有限公司 | Thermosetting epoxy resin composition and prepreg, laminated board and printed circuit board using thermosetting epoxy resin composition |
| CN111057217B (en) * | 2019-12-26 | 2021-08-27 | 广东生益科技股份有限公司 | Thermosetting epoxy resin composition and prepreg, laminated board and printed circuit board using same |
| CN111057217A (en) * | 2019-12-26 | 2020-04-24 | 广东生益科技股份有限公司 | Thermosetting epoxy resin composition and prepreg, laminated board and printed circuit board using same |
| CN112300369A (en) * | 2020-11-06 | 2021-02-02 | 华东理工大学华昌聚合物有限公司 | Reactive flame retardant for epoxy resin and preparation method and application thereof |
| CN112300369B (en) * | 2020-11-06 | 2023-02-17 | 华东理工大学华昌聚合物有限公司 | Reactive epoxy resin flame retardant and preparation method thereof |
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