CN102127205A - Phosphorus-containing epoxy resin semi-cured material and preparation method thereof - Google Patents
Phosphorus-containing epoxy resin semi-cured material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a phosphorus-containing epoxy resin semi-cured material and a preparation method thereof. The preparation method comprises the step of performing chain extension reaction on phosphorus-containing bisphenol in a formula (i), epoxy resin in a formula (ii) and a catalyst to generate the phosphorus containing epoxy resin semi-cured material in a formula (I), wherein n is an integer of 1-9, and R is methyl or phenyl.
Description
Technical field
The invention relates to a kind of phosphorus series compound and manufacture method thereof, and particularly relevant for a kind of Resins, epoxy and manufacture method thereof with phosphorus series bisphenols compound.
Background technology
Traditional printed circuit board (PCB) manufacturing mainly is to add the flame retardant with halogen and antimonous oxide in Resins, epoxy, will make the flame resistant printed circuit board (PCB) behind the epoxy resin cure again.Yet, when the epoxy resin cured product of halogen-containing flame retardant burns, not only can produce corrosive gases, also can produce harmful carcinogenic gas such as dioxin (dioxin) and cumarone (benzofuran).
In recent years, organo phosphorous compounds is found for high molecular polymer, has preferable anti-combustion characteristic.And compared to halogen-containing flame retardant, organo phosphorous compounds can not produce smog and toxic gas.In addition, research is also found the organophosphorus reactive group is imported in the high molecular structure, can make polymkeric substance have more anti-combustion effect.
A kind of phosphorous biphenol monomer (structural formula is as follows) is used to import Resins, epoxy at present, forms Resins, epoxy semicure thing.Resins, epoxy semicure thing has excellent flame retardancy via the cured article after hardening.
Owing in a plurality of manufacturing steps of follow-up printed circuit board (PCB), all need use alkali lye to handle.For example, need to use alkali lye (sodium hydroxide, potassium hydroxide or tetramethyl ammonium hydroxide) to develop behind the photoresistance exposure, also can use the alkali lye stripping during stripping, also or after having gone up green lacquer, during if need rework, also can use 10% sodium hydroxide under 70-80 ℃, to boil 1-2 hour to peel green lacquer off.Therefore the epoxy resin cured product after the sclerosis also must have alkali resistance.Yet the hydrogen of C-H belongs to active hydrogen in the above-mentioned phosphorous biphenol monomer structure, thereby makes the alkali resistance variation of formed Resins, epoxy semicure thing, and is not enough for the stability of alkali lye.
Summary of the invention
Therefore, the object of the present invention is to provide the preferable phosphorus of a kind of alkali resistance is Resins, epoxy semicure thing, and preparation method thereof.
It is Resins, epoxy semicure thing (phosphrous-containing advanced epoxy resin) that an aspect of the present invention provides a kind of phosphorus, has suc as formula the structure shown in (I):
Wherein, n is the integer of 1-9, and R comprises methyl or phenyl, and Y is selected from the group that is made up of following radicals:
X and Z are selected from the group that is made up of hydrogen, C1-C6 alkyl, C1-C6 alkoxyl group, CF3, phenyl, halogen, phenoxy group and C3-C7 cycloalkyl respectively.
Another aspect of the present invention provides the preparation method that a kind of phosphorus is Resins, epoxy semicure thing.This phosphorus is that Resins, epoxy semicure thing is by phosphorus series bisphenols monomer and Resins, epoxy, forms through chain extension.Employed phosphorus series bisphenols monomer makes the active hydrogen of traditional phosphorus series bisphenols into methyl or phenyl, to increase the alkali resistance of synthetic Resins, epoxy semicure thing.And this phosphorus is after Resins, epoxy semicure thing can further solidify, to have good thermal properties, flame retardant resistance and alkali resistance.
According to one embodiment of the invention, a kind of phosphorus is the preparation method of Resins, epoxy semicure thing, comprise the phosphorus series bisphenols of formula (i), formula Resins, epoxy and catalyzer (ii) carried out the chain extension reaction, and be Resins, epoxy semicure thing with the phosphorus of production (I).
Wherein R is a methyl or phenyl, and Y is selected from the group that is made up of following radicals:
X and Z are selected from the group that is made up of hydrogen, C1-C6 alkyl, C1-C6 alkoxyl group, CF3, phenyl, halogen, phenoxy group and C3-C7 cycloalkyl respectively.
Compared with prior art, phosphorus of the present invention is that Resins, epoxy semicure thing has preferable alkali resistance.
Description of drawings
For above and other objects of the present invention, feature, advantage and embodiment can be become apparent, appended the description of the drawings is as follows:
Figure 1A and Figure 1B are dissolved in the 1HNMR spectrogram of alkali lye front and back for the two nitro-derivatives that illustrate embodiment 1 respectively.
Fig. 2 A and Fig. 2 B are dissolved in the 1HNMR spectrogram of alkali lye front and back for the two nitro-derivatives that illustrate comparative example 1 respectively.
Fig. 3 A and Fig. 3 B are dissolved in the 1H NMR spectrogram of alkali lye front and back for the epoxy derivative that illustrates embodiment 1 respectively.
Fig. 4 A and Fig. 4 B are dissolved in the 1H NMR spectrogram of alkali lye front and back for the epoxy derivative that illustrates comparative example 1 respectively.
Embodiment
(1) preparation method of phosphorus series bisphenols
In the embodiments of the present invention, propose a kind of preparation method of phosphorus series bisphenols, comprise the compound shown in the organic ring-type phosphorus compound shown in the formula (a), the formula (b), phenol and the acid catalyst shown in the formula (c) are reacted, to generate phosphorus series bisphenols.
R is a methyl or phenyl in the compound shown in the above-mentioned formula (b).
The compound of organic ring-type phosphorus compound, formula (b) and the mole ratio of phenol are 1: 5: 1.According to one embodiment of the invention, organic ring-type phosphorus compound is 9, and the 10-dihydro-9-oxy is mixed-10-phosphorus phenanthrene-10-oxide compound, is called for short DOPO.In addition, when R was methyl in the compound of formula (b), the compound of formula (b) was 4 '-hydroxy acetophenone (4 '-Hydroxyacetophenone).And when R was phenyl in the compound of formula (b), the compound of formula (b) was 4-dihydroxy benaophenonel (4-Hydroxybenzophenone).
Above-mentioned acid catalyst then is the 0.1wt%～5.0wt% of organic ring-type phosphorus compound.Acid catalyst can be protonic acid or Lewis acid.Above-mentioned protonic acid can be right-toluene sulfonic acide, methylsulphonic acid, sulfuric acid, oxalic acid, hydrogenchloride, hydrogen bromide or hydrogen iodide.
Particularly, the preparation method of phosphorus series bisphenols is for to insert 250 milliliter of three neck reactor with compound, phenol and the acid catalyst of organic ring-type phosphorus compound, formula (b).Then, the rising temperature of reaction reaches 130 ℃, keeps reaction and stops after 24 hours stirring.With reactor cooling to room temperature, after separating out part naturally and cleaning with ethanol, filtering drying, the gained white powder is phosphorus series bisphenols.
Utilize the phosphorus series bisphenols of method for preparing, have as shown in the formula the structure shown in (i).Wherein R is a methyl or phenyl.
Get 10.81 gram (0.05 mole) organic ring-type phosphorus compound DOPO (9, the 10-dihydro-9-oxy is assorted-10-phosphorus phenanthrene-10-oxide compound), 23.5 gram (0.25 mole) phenol, 6.81 gram (0.05 mole) 4 '-hydroxy acetophenones, 0.432 gram (4wt% of DOPO usage quantity) are right-acid of methylbenzene semi-annular jade pendant, insert 250 milliliter of three neck reactor.Then, the rising temperature of reaction reaches 130 ℃, keeps reaction and stops after 24 hours stirring.With reactor cooling to room temperature.At this moment, after the part of separating out is naturally cleaned with ethanol, filtering drying, the gained white powder is phosphorus series bisphenols, and its structural formula is as shown below.
Productive rate 85%, fusing point are 306 ℃.Resolve the m/z value that mass spectrum (FAB+) is analyzed this phosphorus series bisphenols with height, analytical value is 429.1266, and chemical formula is C
26H
22O
4(theoretical value is 428.1177 to P, and chemical formula is C
26H
21O
4P).The analytical value of ultimate analysis is C:72.48%; H:4.65%; (theoretical value is C:72.89% to O:14.90%; H:4.94%; O:14.94%).
Get 10.81 gram (0.05 mole) organic ring-type phosphorus compound DOPO (9, the 10-dihydro-9-oxy is assorted-10-phosphorus phenanthrene-10-oxide compound), 23.5 gram (0.25 mole) phenol, 9.91 gram (0.05 mole) 4-dihydroxy benaophenonels, 0.216 gram (2wt% of DOPO usage quantity) are right-acid of methylbenzene semi-annular jade pendant, insert 250 milliliter of three neck reactor.Then, the rising temperature of reaction reaches 130 ℃, keeps reaction and stops after 24 hours stirring.Reactor cooling to room temperature, after dissolving away with ethanol, is poured in the hot water and separated out.With the precipitate filtering drying, promptly get phosphorus series bisphenols as shown below, productive rate 87%, fusing point are 288 ℃.
(2) phosphorus is the preparation method of Resins, epoxy semicure thing
Then, a kind of phosphorus is the preparation method of Resins, epoxy semicure thing, with the phosphorus series bisphenols shown in the formula (i), formula epoxide and the catalyzer shown in (ii), carries out the chain extension reaction, is Resins, epoxy semicure thing with the phosphorus shown in the production (I).
N in the formula (I) is the integer of 1-9.Formula (i) is a methyl or phenyl with R shown in the formula (I).Formula (ii) is selected from the group that is made up of following radicals with Y shown in the formula (I):
X and Z are respectively hydrogen, C1-C6 alkyl, C1-C6 alkoxyl group, CF3, phenyl, halogen, phenoxy group or C3-C7 cycloalkyl.
Aforementioned chain extension reacts on 100 ℃-200 ℃ to carry out.The phenolic group equivalents ratio of the phosphorus series bisphenols of the epoxide equivalent number of formula Resins, epoxy (ii) and formula (i) is 1: 1-10: 1.Catalyst levels is the 0.1wt%-5wt% of formula content of epoxy resin (ii).
Aforementioned employed catalyzer is imidazolium compounds, three grades of phosphines, tertiary amine, quaternary alkylphosphonium salt, boron trifluoride complexing salt, lithiumation thing or quaternary ammonium salts.Imidazolium compounds can be 2-phenylimidazole (2-phenylimidazole) or glyoxal ethyline (2-methylimidazole).Three grades of phosphines can be triphenylphosphine (triphenylphosphine).Quaternary ammonium salt can be benzyltriethylammonium chloride (benzyltrimethyl ammonium chloride), Benzyl Chloride ester three second ammoniums (benzyltriethyl ammonium chloride) or tetrabutylammonium chloride (tetrabutylammonium chloride).Quaternary alkylphosphonium salt can be ethyl triphenyl acetic acid phosphine (ethyltriphenylphosphonium acetate) or triphenyl ethyl halogenation phosphine (ethyltriphenyl phosphoniumhalides).
Particularly, formula Resins, epoxy is (ii) inserted in 100 milliliters of reactors, and after being warming up to 150 ℃, stirred 1 hour.Then behind the phosphorus series bisphenols and catalyzer of adding formula (i), temperature maintenance is continued reaction after 2 hours in 150 ℃, product is poured out to be phosphorus be Resins, epoxy semicure thing.
Because used composition ratio is various, has enumerated the representational embodiment of part in the table 1.With phosphorus series bisphenols, the formula Resins, epoxy and the catalyzer (ii) of different sorts and weight, synthesize the different phosphorus of phosphorus content is Resins, epoxy semicure thing to each embodiment respectively.
Employed phosphorus series bisphenols is previous embodiment 1 or embodiment 2.Formula Resins, epoxy (ii) then can be bisphenol A epoxide resin (Diglycidyl ether of bisphenol A, DGEBA, epoxy equivalent (weight) 188 gram/equivalents, formula Y (ii) is Y1), bisphenol F epoxy resin (Diglycidyl ether of bisphenolF, DGEBF, epoxy equivalent (weight) 175 gram/equivalents, formula Y (ii) is Y2) or cyclopentadiene Resins, epoxy (Dicyclopentadiene epoxy, DCPDE, epoxy equivalent (weight) 250 gram/equivalents, formula Y (ii) is Y3).
Catalyzer then is triphenylphosphine or glyoxal ethyline.Table 1 is listed every kind of gram number that composition adds among each embodiment, and the formed phosphorus of each embodiment is the theoretical phosphorus content and the epoxy equivalent (weight) of Resins, epoxy semicure thing.
Table 1
After aforementioned epoxy resins semicure thing and the stiffening agent reaction, can form the phosphorous epoxy resin cured article.This phosphorous epoxy resin cured article has good thermal properties, follows property and flame retardant resistance, can be applicable to printed circuit board (PCB) and semiconductor packages material.Aforementioned stiffening agent can be 4, and 4 '-diaminodiphenylsulfone(DDS) (4,4 '-diaminodiphenylsulfone, DDS).
Particularly, curing reaction be with phosphorous epoxy resin semicure thing and stiffening agent with the equivalent uniform mixing after, again mixture is hardened via high-temperature cross-linking, the phosphorous epoxy resin cured article.Crosslinked sclerous reaction can after 2 hours, be reacted 2 hours down in 220 ℃ in reaction under 180 ℃ again.
(3) property detection
The phosphorous biphenol monomer and the comparative example 1 of previous embodiment 1 are carried out the alkali resistance test.The structure of comparative example 1 is that R shown in the aforementioned formula (i) is hydrogen (structure is as follows).
The alkali resistance testing method is as described below.At first, utilize embodiment 1 and comparative example 1 synthetic two nitro-derivatives respectively, and with
1H NMR analytical structure.Two nitro-derivative structures of embodiment 1 are suc as formula shown in (iii), and two nitro-derivative structures of comparative example 1 are suc as formula shown in (iv).
Two nitro-derivatives of getting 1 gram again are dissolved in 19 milliliters dimethyl formamide (DMF) and 1 milliliter the water, add 0.3 sodium hydroxide that restrains, stir after 12 hours, with
1The structure of compound in the H NMR analytical solution.
Figure 1A and Figure 1B are that two nitro-derivatives of embodiment 1 are dissolved in the alkali lye front and back
1H NMR spectrogram, Fig. 2 A and Fig. 2 B then are dissolved in the alkali lye front and back for two nitro-derivatives of comparative example 1
1H NMR spectrogram.By Figure 1A and Figure 1B as can be known, the two nitro-derivative structures that are dissolved in the embodiment 1 before and after the alkali lye there is no considerable change.And clearly can be observed by Fig. 2 A and Fig. 2 B, two nitro-derivatives of comparative example 1 are dissolved in alkali lye and through after stirring, the CH that is produced because of producing behind biphenyl phosphinate (biphenyl phosphinate) scission of link appears in the position of about 4.1ppm in Fig. 2 B
2(circle frame choosing place among Fig. 2 B).
Another kind of alkali resistance testing method is under sodium hydroxide catalysis, makes embodiment 1 and comparative example 1 carry out epoxidation reaction respectively, produces epoxy derivative, and with
1H NMR analyzes the structure before and after the epoxy reaction.The epoxy derivative structure of embodiment 1 is suc as formula (v), the epoxy derivative structure of comparative example 1 is suc as formula (vi).
Fig. 3 A and Fig. 3 B illustrate embodiment 1 and epoxy derivative thereof respectively
1H NMR spectrogram.Fig. 4 A and Fig. 4 B illustrate comparative example 1 and epoxy derivative thereof respectively
1H NMR spectrogram.By Fig. 3 A and Fig. 3 B as can be known, in embodiment 1 and the epoxy derivative structure thereof, the benzene ring hydrogen there is no change, and biphenyl phosphinate (biphenylene phosphinate) group in expression embodiment 1 structure is stable at the alkali environment.And can be observed by Fig. 4 A and Fig. 4 B, the epoxy derivative of comparative example 1, the signal of hydrogen has obvious variation on the phenyl ring.For example, comparison diagram 4A and Fig. 4 B, the hydrogen signal of about 8.0ppm position obviously reduces (circle a frame choosing place among Fig. 4 B) in Fig. 4 B, and has new signal to generate in the 6.9ppm position.Same, originally obviously reduce (circle b frame choosing place among Fig. 4 B) at the CH of 4.5ppm position signal, and new Ph-CH is arranged in the 4.0ppm position
2-Ph signal generates.Biphenyl phosphinate (biphenylene phosphinate) group in expression comparative example 1 structure has the situation of fracture under alkaline environment.In other words, biphenyl phosphinate (biphenylene phosphinate) group in comparative example 1 structure is unsettled at the alkali environment.
The above results shows that compared to comparative example 1, the phosphorus series bisphenols monomer of embodiment 1 has preferable alkali resistance.Therefore, with 1 synthetic phosphorous epoxy resin of embodiment semicure thing, also can have preferable alkali resistance.
Comparative example 2-4 replaces embodiment 1 with comparative example 1, and utilizing aforementioned phosphorus is that the phosphorus of the different phosphorus contents of preparation method institute synthetic of Resins, epoxy semicure thing is Resins, epoxy semicure thing.The phosphorus content of comparative example 2-4 is respectively 1.5wt%, 2.0wt%, 2.5wt%.Then, embodiment 3-7 and comparative example 2-4 are reacted with stiffening agent respectively, form the phosphorous epoxy resin cured article and test to carry out thermal properties, heat stability testing and flame retardant resistance, and the actual phosphorus content in the calculating cured article.
Thermal properties for utilize dynamic thermomechanometry (Dynamic Mechanical Analysis, DMA) glass of the cured article of test implementation example transfer temperature (glass transition temperature, Tg).Heat stability testing is for utilizing thermogravimetric analyzer (Thermogravimetric Analyzer, TGA) the thermo-cracking temperature of the cured article of test implementation example and remaining rate test.The thermo-cracking temperature is the temperature when getting each embodiment and comparative example weight loss 5%.Residual volume then is meant when being heated to 800 ℃, not burned weight percent totally.
The flame retardant resistance test then is the UL94 combustion testing.The UL94 combustion testing is a kind of internationally recognized standard burn test step.Difficulty combustion characteristic degree methods with UL94 combustion testing judgement sample is according to after the horizontal or vertical burning of standard test piece, whether can be fast after flame is removed from putting out (combustion time with combustion time) for the first time for the second time, and in the certain hour gap, have or not incendiary to melt body drippage (hang down and drip) to be judged.Table 2 is the result of thermal properties, thermostability and the flame retardant test of embodiment 3-7 after solidifying in the table 1.
Table 2
According to the result of table 2, the glass of the cured article of the foregoing description transfer temperature is at 177-202 ℃, and the increase of phosphorus content can cause glass transfer temperature to descend.In addition, along with the increase of phosphorus content, though also can make the thermo-cracking temperature of embodiment reduce, remaining rate increases (rising to 31wt% from 19wt%) thereupon.Equally, when the phosphorus content of comparative example increases, also can cause the glass tansition temperature to decline to a great extent.Therefore, compared to each comparative example, phosphorous epoxy resin semicure thing of the present invention still has good thermal properties and thermostability after solidifying.
Aspect flame retardant resistance, phosphorous epoxy resin semicure thing of the present invention is after solidifying, and its UL94 test grade all more than the V-1 grade, has flame retardant effect.And, can reach UL94 test V0 grade when actual phosphorus content during greater than 1.73wt%.The V0 grade refers to after each flame is removed, do not have fiery tear down to from the surgery of test piece 305 centimeters with continuous flower and make its burning-point catch fire, and test piece extinguished in 10 seconds, afterflaming is no more than 30 seconds.The V1 grade does not then have under the fiery tear after flame is removed equally, but then to increase be in 30 seconds the test piece extinction time, and afterflaming is no more than 60 seconds.
Table 3 is the glass transfer temperature and the UL94 test grade of the listed embodiment 8-12 of table 1 formed cured article after solidifying.The theoretical value of embodiment 8-12 phosphorus content is all 1.75wt%, and difference is that each embodiment is formed by reacting with different phosphorus series bisphenols, Resins, epoxy and catalyzer.
Table 3
| |
|
|
|
|
|
| Tg | 194℃ | 213℃ | 205℃ | 197℃ | 216℃ |
| The UL94 grade | V0 | V0 | V0 | V0 | V0 |
Except aforementioned phosphorus content can influence the glass transfer temperature of cured article of embodiment, according to the result of table 3 as can be known, the kind of Resins, epoxy also can influence the glass transfer temperature of the cured article of embodiment.Aspect flame retardant resistance, the foregoing description is after solidifying, and UL94 test grade all can reach UL94 test V0 grade.
Claims (10)
1. a phosphorus is Resins, epoxy semicure thing, has suc as formula the structure shown in (I):
Wherein, n is 1～9 integer, and this R is a methyl or phenyl, and Y is selected from the group that is made up of following radicals:
X and Z are selected from the group that is made up of hydrogen, C1-C6 alkyl, C1-C6 alkoxyl group, CF3, phenyl, halogen, phenoxy group and C3-C7 cycloalkyl respectively.
2. the preparation method of a Resins, epoxy semicure thing comprises at least:
Phosphorus series bisphenols with formula (i):
Formula Resins, epoxy (ii):
Carrying out chain extension reaction with a catalyzer, is Resins, epoxy semicure thing with the phosphorus of production (I), and wherein this R is a methyl or phenyl, and Y is selected from the group that is made up of following radicals:
X and Z are selected from the group that is made up of hydrogen, C1-C6 alkyl, C1-C6 alkoxyl group, CF3, phenyl, halogen, phenoxy group and C3-C7 cycloalkyl respectively.
3. preparation method as claimed in claim 2, wherein chain extension reacts on 100-200 ℃ and carries out.
4. preparation method as claimed in claim 2, the phenolic group equivalents ratio of the phosphorus series bisphenols of the epoxide equivalent number of formula Resins, epoxy (ii) and formula (i) is 1: 1-10: 1.
5. preparation method as claimed in claim 2, this catalyst levels is the 0.1wt%-5wt% of formula content of epoxy resin (ii).
6. preparation method as claimed in claim 2, wherein this catalyzer comprises an imidazolium compounds, one or three grades of phosphines, a tertiary amine, a quaternary alkylphosphonium salt, a boron trifluoride complexing salt, a lithiumation thing or quaternary ammonium salts.
7. preparation method as claimed in claim 6, wherein this imidazolium compounds is 2-phenylimidazole or glyoxal ethyline.
8. preparation method as claimed in claim 6, wherein these three grades of phosphines are triphenylphosphine.
9. preparation method as claimed in claim 6, wherein this quaternary ammonium salt is benzyltriethylammonium chloride, Benzyl Chloride ester three second ammonium or tetrabutylammonium chlorides.
10. preparation method as claimed in claim 6, wherein Gai quaternary alkylphosphonium salt is ethyl triphenyl acetic acid phosphine or triphenyl ethyl halogenation phosphine.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106633052A (en) * | 2015-11-04 | 2017-05-10 | 华中师范大学 | Phosphaphenanthrene-triazine bifunctional oligomer and preparation method and antiflaming application thereof |
| CN107001581A (en) * | 2014-09-30 | 2017-08-01 | 可隆工业株式会社 | The preparation method of fire-retarded epoxy resin, the fire-retarded epoxy resin, and the flame-retardant epoxy resin omposition comprising the fire-retarded epoxy resin |
| CN112851911A (en) * | 2021-01-11 | 2021-05-28 | 中国科学院宁波材料技术与工程研究所 | Bio-based A2+ B3 type hyperbranched epoxy resin precursor, modified composition, preparation method and application thereof |
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| TW498084B (en) * | 2000-07-19 | 2002-08-11 | Chang Chun Plastics Co Ltd | Flame-retardant resin and flame retardant composition containing the same |
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| TW200413467A (en) * | 2003-01-16 | 2004-08-01 | Chang Chun Plastics Co Ltd | Resin composition without containing halogen |
| CN101560226B (en) * | 2008-04-18 | 2013-01-09 | 长春人造树脂厂股份有限公司 | Novel phosphorus series compound as well as preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| TW498084B (en) * | 2000-07-19 | 2002-08-11 | Chang Chun Plastics Co Ltd | Flame-retardant resin and flame retardant composition containing the same |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107001581A (en) * | 2014-09-30 | 2017-08-01 | 可隆工业株式会社 | The preparation method of fire-retarded epoxy resin, the fire-retarded epoxy resin, and the flame-retardant epoxy resin omposition comprising the fire-retarded epoxy resin |
| CN106633052A (en) * | 2015-11-04 | 2017-05-10 | 华中师范大学 | Phosphaphenanthrene-triazine bifunctional oligomer and preparation method and antiflaming application thereof |
| CN106633052B (en) * | 2015-11-04 | 2019-06-25 | 华中师范大学 | Phospho hetero phenanthrene-triazine difunctional oligomer and preparation method thereof and fire-retardant application |
| CN112851911A (en) * | 2021-01-11 | 2021-05-28 | 中国科学院宁波材料技术与工程研究所 | Bio-based A2+ B3 type hyperbranched epoxy resin precursor, modified composition, preparation method and application thereof |
| CN112851911B (en) * | 2021-01-11 | 2023-02-28 | 中国科学院宁波材料技术与工程研究所 | Bio-based A2+ B3 type hyperbranched epoxy resin precursor, modified composition, preparation method and application thereof |
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