CN104693421A - Self-inflaming-retarding epoxy resin curing agent containing phosphorus-nitrogen and preparation method thereof - Google Patents
Self-inflaming-retarding epoxy resin curing agent containing phosphorus-nitrogen and preparation method thereof Download PDFInfo
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- CN104693421A CN104693421A CN201510138212.0A CN201510138212A CN104693421A CN 104693421 A CN104693421 A CN 104693421A CN 201510138212 A CN201510138212 A CN 201510138212A CN 104693421 A CN104693421 A CN 104693421A
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Abstract
The invention discloses a self-inflaming-retarding epoxy resin curing agent containing phosphorus-nitrogen and a preparation method thereof and relates to epoxy resin curing agents. The method comprises the steps that N-phenyl-1, 4-phenylenediamine and 4-hydroxy benzaldehyde are added into a container provided with a condensation pipe and a stirrer for reacting with first solvent, the reaction system is filtered, and solids obtained after the filtering are washed and dried, so that an intermediate body is obtained; the intermediate body, DOPO and second solvent are added into a container provided with a condensation pipe and a stirrer for reacting, the reaction system is filtered, and solids obtained after the filtering are washed and dried, so that the self-inflaming-retarding epoxy resin curing agent containing the phosphorus-nitrogen is obtained; or alternatively, the N-phenyl-1, the 4-phenylenediamine, the 4-hydroxy benzaldehyde and the DOPO are added into a container provided with a condensation pipe and a stirrer sequentially for reacting with solvent, the reaction system is filtered, and articles obtained after the filtering are washed and dried, so that the self-inflaming-retarding epoxy resin curing agent containing the phosphorus-nitrogen is obtained. The curing agent contains two active imino groups, one active hydroxyl group and P and N synergistic flame retardant elements simultaneously and can be used for epoxy resin curing and inflaming retardation.
Description
Technical field
The present invention relates to epoxy curing agent, specifically relate to simultaneously containing two active imino group and an activity hydroxy, and the self-antiflaming epoxy resin curing agent of curable a kind of phosphorus-nitrogen containing of P, N cooperative flame retardant and preparation method thereof.
Background technology
Epoxy resin is widely used in the fields such as machinery, aerospace, electronics, lamination material, caking agent, coating.But because of himself poor-performing, after must being cured with solidifying agent, just good physical and chemical performance can be shown.In addition, along with industry increases day by day to epoxy resin reliability, security requirement, for the performance of epoxy resin, especially fire-retardant and resistance toheat requires to improve gradually.
At present, the solidifying agent for epoxy resin cure mainly contains polynary amine, imidazole and its derivants, polyphenol, polyvalent alcohol, anhydrides.As Chinese patent CN102942682A discloses a kind of two imidazolidine hydrocarbon compound as epoxy curing agent, have active high, fusing point is low, with the feature such as resin compatible is good; Chinese patent CN103435781A discloses a kind of epoxy curing agent and is made up of polyamine, mercaptan acid compounds and amino-polyether, and this solidifying agent has low-temperature curing, toughening effect is good, prepares the advantages such as simple.But these solidifying agent only play crosslinking curing effect, then also need to add the fire retardant of anti-flaming function as the heat-resisting of epoxy resin and flame retardant properties need be improved.
Fire retardant can be divided into halogen containing flame-retardant and halogen-free flame retardants again, wherein halogen containing flame-retardant is widely used because it has excellent flame retardant effect Zeng Zuowei fire retardant material, but because Halogen fire retardant material can produce a large amount of smog and poisonous corrosive gases in fire-retardant process, cause into secondary harm, thus disabled gradually.And traditional condensed phase halogen-free flame-retardant system is relevant to P, Si, N element, they effectively can promote the generation of stable intumescent char layer, suppress base material to continue thermal oxidative reaction occurs, improve the thermal degradation temperature of curing system, mass loss temperature and coke growing amount.Halogen-free flame retardants can be divided into addition type and response type according to use mechanism difference.As Chinese patent CN101838538A reports the fire retardant of polyphosphate of a kind of DOPO side based structures, can be used as additive flame retardant; As Chinese patent CN103073746A reports a kind of response type phosphonium flame retardant containing DOPO and activity double key.But the use of these fire retardants generally needs mixing or the pre-reaction of carrying out the long period before adding solidifying agent, makes complicated operation, and additive flame retardant easily decomposes loss, the shortcomings such as poor in processability in addition in addition.
Therefore, molecule containing halogen-free flameproof element can be designed as solidifying agent for solving above-mentioned use fire retardant Problems existing, being incorporated in epoxy resin, playing crosslinking curing effect on the one hand, playing halogen-free flameproof effect on the other hand.
Summary of the invention
The object of the invention is for existing fire retardant and epoxy resin Problems existing, there is provided simultaneously containing two active imino group and an activity hydroxy, and P, N cooperative flame retardant element, can be used for self-antiflaming epoxy resin curing agent of epoxy resin cure and fire-retardant a kind of phosphorus-nitrogen containing and preparation method thereof.
The chemical structural formula of the self-antiflaming epoxy resin curing agent DOPO-RT of described phosphorus-nitrogen containing is as follows:
Wherein, the chemical structural formula of reaction intermediate is as follows:
One of preparation method of the self-antiflaming epoxy resin curing agent of described phosphorus-nitrogen containing, comprises the following steps:
1) in the container being furnished with prolong and agitator, add N-phenyl-Isosorbide-5-Nitrae-phenylenediamine, 4-hydroxy benzaldehyde and the first solvent reaction, reaction system filtered, will leach solids wash, dry, obtain intermediate, gained intermediate is greenish solid product;
2) by step 1) intermediate, DOPO and the second solvent that obtain join in the container being furnished with prolong and agitator and react, reaction system is filtered, solids wash will be leached, dry, obtain the self-antiflaming epoxy resin curing agent of phosphorus-nitrogen containing, the self-antiflaming epoxy resin curing agent of gained phosphorus-nitrogen containing is white solid product.
In step 1) in, the mol ratio of described N-phenyl-Isosorbide-5-Nitrae-phenylenediamine and 4-hydroxy benzaldehyde can be (1 ~ 1.4): 1; Described first solvent can adopt ethanol etc.; The temperature of described reaction can be room temperature, and the time of reaction can be 4 ~ 6h; Described filtration can adopt filter paper filtering; Described washing can adopt the first solvent wash; The condition of described drying can heat up drying in vacuum drying oven, and temperature can be 35 ~ 60 DEG C.
In step 2) in, the mol ratio of described intermediate and DOPO can be 1: (1 ~ 1.2); Described second solvent can be selected from the one in dimethyl formamide (DMF), tetrahydrofuran (THF) (THF) etc.; The temperature of described reaction can be room temperature, and the time of reaction can be 4 ~ 8h; Described filtration can adopt filter paper filtering; Described washing can adopt the one in methyl alcohol, ethanol etc. to wash; The condition of described drying can heat up drying in vacuum drying oven, and temperature can be 35 ~ 60 DEG C.
The preparation method two of the self-antiflaming epoxy resin curing agent of described phosphorus-nitrogen containing, concrete steps are as follows:
N-phenyl-1 is added successively in the container being furnished with prolong and agitator, 4-phenylenediamine, 4-hydroxy benzaldehyde, DOPO and solvent reaction, reaction system is filtered, much filtrate is washed, dry, obtain the self-antiflaming epoxy resin curing agent of phosphorus-nitrogen containing, the self-antiflaming epoxy resin curing agent of gained phosphorus-nitrogen containing is white solid product.
The mol ratio of described N-phenyl-Isosorbide-5-Nitrae-phenylenediamine, 4-hydroxy benzaldehyde, DOPO can be 1 ~ 1.4: 1: 1 ~ 1.2; Described solvent can be selected from the one in dimethyl formamide (DMF), tetrahydrofuran (THF) (THF) etc.; The temperature of described reaction can be room temperature, and the time of reaction can be 5 ~ 12h; Described filtration can adopt filter paper filtering; Described washing can adopt the one in methyl alcohol, ethanol etc. to wash; The condition of described drying can heat up drying in vacuum drying oven, and temperature can be 35 ~ 60 DEG C.
The present invention is with N-phenyl-1,4-phenylenediamine and 4-hydroxy benzaldehyde react, obtain intermediate, again intermediate and DOPO are reacted in a solvent, obtain simultaneously containing an active phenolic hydroxyl group and two imino-s, and also have the curable reaction-type flame-retarding monomer molecule DOPO-RT of phosphorus, nitrogen two kinds of halogen-free flameproof elements, can be used in the solidification of epoxy resin and fire-retardant.In addition, preparation method of the present invention is simple, mild condition, productive rate are high, containing multiple reaction active groups, good with resin compatible, and because itself is containing phosphorus, nitrogen cooperative flame retardant element, has good halogen-free flameproof performance.
Compared with prior art the present invention has following characteristics:
1) halogen-free flameproof element phosphor, nitrogen are incorporated in molecule, play the effect of cooperative flame retardant, obtain a kind of novel flame retardant curing agent having no report, both can play crosslinking curing effect, and halogen-free flameproof effect can be played again.
2) this flame retardant curing agent (DOPO-RT) is simultaneously containing two active imino group and a hydroxyl, reactive behavior is high, good with the consistency of matrix resin, solidification process is simple to operate, will have good application prospect in the solidification of epoxy resin and flame retardant area.
3) preparation of this flame retardant curing agent (DOPO-RT) is simple, and condition is easily controlled, and raw material is cheaply easy to get, and productive rate is high, is convenient to commercially produce.
Accompanying drawing explanation
Fig. 1 is intermediate
1h NMR nuclear magnetic spectrogram.
Fig. 2 is solidifying agent DOPO-RT's
1h NMR nuclear magnetic spectrogram.
Fig. 3 is the magnified partial view of Fig. 2.
Fig. 4 is solidifying agent DOPO-RT's
31p NMR nuclear magnetic spectrogram.
Embodiment
Below in conjunction with drawings and Examples, the invention will be further described, but be not limited to following examples:
Embodiment 1:
1) synthesis of intermediate
N-phenyl-1 is added in the 250ml there-necked flask being furnished with prolong and agitator stirring, 4-phenylenediamine (18.424g, 0.1mol), 4-hydroxy benzaldehyde (12.212g, 0.1mol) and 100ml alcohol solvent, at room temperature, reaction 4h, by reaction system filter paper filtering, will leach solid alcohol solvent and wash 4 times, put into vacuum drying oven intensification (50 DEG C) dry, obtain greenish solid product 27.96g, be intermediate, productive rate reaches 91.27%.
2) synthesis of solidifying agent DOPO-RT
By the intermediate (14.418g of above-mentioned reaction gained, 0.05mol), DOPO (10.8g, 0.05mol) join with 100ml dimethyl formamide (DMF) solvent and be furnished with in 250ml container that prolong and agitator stir, at room temperature, reaction 6h, by reaction system filter paper filtering, by much filtrate with washing with alcohol several times, put into vacuum drying oven (50 DEG C) dry, obtain white solid product 23.58g, be flame retardant curing agent DOPO-RT, productive rate reaches 93.5%.
Embodiment 2:
1) synthesis of intermediate
N-phenyl-1 is added in the 250ml there-necked flask being furnished with prolong and agitator stirring, 4-phenylenediamine (22.1088g, 0.12mol), 4-hydroxy benzaldehyde (12.212g, 0.1mol) and 100ml alcohol solvent, at room temperature, reaction 3h, by reaction system filter paper filtering, will leach solid alcohol solvent and wash 4 times, put into vacuum drying oven intensification (35 DEG C) dry, obtain greenish solid product 31.21g, be intermediate, productive rate reaches 90.94%.
2) synthesis of solidifying agent DOPO-RT
By the intermediate (14.418g of above-mentioned reaction gained, 0.05mol), DOPO (12.96g, 0.05mol) join with 100ml dimethyl formamide (DMF) solvent and be furnished with in 250ml container that prolong and agitator stir, at room temperature, reaction 5h, by reaction system filter paper filtering, by much filtrate with washing with alcohol several times, put into vacuum drying oven (35 DEG C) dry, obtain white solid product 27.378g, be flame retardant curing agent DOPO-RT, productive rate reaches 91.7%.
Embodiment 3:
N-phenyl-1 is added successively in the 250ml there-necked flask being furnished with prolong and agitator stirring, 4-phenylenediamine (20.2664g, 0.11mol), 4-hydroxy benzaldehyde (12.212g, 0.1mol), DOPO (21.6g, 0.1mol) with 150ml dimethyl formamide (DMF) solvent, at room temperature react 8h, by reaction system filter paper filtering, by much filtrate methanol wash 3 times, put into vacuum drying oven intensification (40 DEG C) dry, obtain white solid product 54.0784g, productive rate reaches 91.29%, is flame retardant curing agent DOPO-RT.
Embodiment 4:
N-phenyl-1 is added successively in the 250ml there-necked flask being furnished with prolong and agitator stirring, 4-phenylenediamine (22.1088g, 0.12mol), 4-hydroxy benzaldehyde (12.212g, 0.1mol), DOPO (25.92g, 0.1mol) with 150ml dimethyl formamide (DMF) solvent, at room temperature react 8h, by reaction system filter paper filtering, by much filtrate methanol wash 4 times, put into vacuum drying oven intensification (60 DEG C) dry, obtain white solid product 54.80g, productive rate reaches 91.07%, is flame retardant curing agent DOPO-RT.
The reaction process of above embodiment is as follows:
Intermediate
1h NMR nuclear magnetic spectrogram is see Fig. 1, and its structural formula is as follows:
Solidifying agent DOPO-RT's
1h NMR nuclear magnetic spectrogram is see Fig. 2 and 3, and its structural formula is as follows:
Solidifying agent DOPO-RT's
31p NMR nuclear magnetic spectrogram is see Fig. 4.
Claims (10)
1. a self-antiflaming epoxy resin curing agent for phosphorus-nitrogen containing, is characterized in that its chemical structural formula is as follows:
Wherein, the chemical structural formula of reaction intermediate is as follows:
2. the preparation method of a kind of self-antiflaming epoxy resin curing agent of phosphorus-nitrogen containing as claimed in claim 1, is characterized in that comprising the following steps:
1) in the container being furnished with prolong and agitator, add N-phenyl-Isosorbide-5-Nitrae-phenylenediamine, 4-hydroxy benzaldehyde and the first solvent reaction, reaction system filtered, will leach solids wash, dry, obtain intermediate, gained intermediate is greenish solid product;
2) by step 1) intermediate, DOPO and the second solvent that obtain join in the container being furnished with prolong and agitator and react, reaction system is filtered, solids wash will be leached, dry, obtain the self-antiflaming epoxy resin curing agent of phosphorus-nitrogen containing, the self-antiflaming epoxy resin curing agent of gained phosphorus-nitrogen containing is white solid product.
3. the preparation method of a kind of self-antiflaming epoxy resin curing agent of phosphorus-nitrogen containing as claimed in claim 2, is characterized in that in step 1) in, the mol ratio of described N-phenyl-Isosorbide-5-Nitrae-phenylenediamine and 4-hydroxy benzaldehyde is (1 ~ 1.4): 1.
4. the preparation method of a kind of self-antiflaming epoxy resin curing agent of phosphorus-nitrogen containing as claimed in claim 2, is characterized in that in step 1) in, described first solvent adopts ethanol; The temperature of described reaction can be room temperature, and the time of reaction can be 4 ~ 6h; Described filtration can adopt filter paper filtering; Described washing can adopt the first solvent wash; The condition of described drying can heat up drying in vacuum drying oven, and temperature can be 35 ~ 60 DEG C.
5. the preparation method of a kind of self-antiflaming epoxy resin curing agent of phosphorus-nitrogen containing as claimed in claim 2, is characterized in that in step 2) in, the mol ratio of described intermediate and DOPO is 1: (1 ~ 1.2).
6. the preparation method of a kind of self-antiflaming epoxy resin curing agent of phosphorus-nitrogen containing as claimed in claim 2, is characterized in that in step 2) in, described second solvent is selected from dimethyl formamide or tetrahydrofuran (THF); The temperature of described reaction can be room temperature, and the time of reaction can be 4 ~ 8h; Described filtration can adopt filter paper filtering; Described washing can adopt the one in methyl alcohol, ethanol etc. to wash; The condition of described drying can heat up drying in vacuum drying oven, and temperature can be 35 ~ 60 DEG C.
7. the preparation method of a kind of self-antiflaming epoxy resin curing agent of phosphorus-nitrogen containing as claimed in claim 1, is characterized in that its concrete steps are as follows:
N-phenyl-1 is added successively in the container being furnished with prolong and agitator, 4-phenylenediamine, 4-hydroxy benzaldehyde, DOPO and solvent reaction, reaction system is filtered, much filtrate is washed, dry, obtain the self-antiflaming epoxy resin curing agent of phosphorus-nitrogen containing, the self-antiflaming epoxy resin curing agent of gained phosphorus-nitrogen containing is white solid product.
8. the preparation method of a kind of self-antiflaming epoxy resin curing agent of phosphorus-nitrogen containing as claimed in claim 7, is characterized in that the mol ratio of described N-phenyl-Isosorbide-5-Nitrae-phenylenediamine, 4-hydroxy benzaldehyde, DOPO is 1 ~ 1.4: 1: 1 ~ 1.2.
9. the preparation method of a kind of self-antiflaming epoxy resin curing agent of phosphorus-nitrogen containing as claimed in claim 7, is characterized in that described solvent is selected from dimethyl formamide or tetrahydrofuran (THF); The temperature of described reaction can be room temperature, and the time of reaction can be 5 ~ 12h.
10. the preparation method of a kind of self-antiflaming epoxy resin curing agent of phosphorus-nitrogen containing as claimed in claim 7, is characterized in that described filtration adopts filter paper filtering; Described washing can adopt the one in methyl alcohol, ethanol etc. to wash; The condition of described drying can heat up drying in vacuum drying oven, and temperature can be 35 ~ 60 DEG C.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106554483A (en) * | 2016-11-23 | 2017-04-05 | 厦门大学 | A kind of phospho hetero phenanthrene structural response type fire retardant and its application |
| CN106832413A (en) * | 2017-03-13 | 2017-06-13 | 厦门大学 | A kind of phosphorus-nitrogen containing polymer modification Nano particles of silicon dioxide and its preparation method and application |
| CN107400197A (en) * | 2017-08-04 | 2017-11-28 | 武汉工程大学 | A kind of reaction-type flame-retarding epoxy curing agent and preparation method thereof |
| CN108148095A (en) * | 2017-12-29 | 2018-06-12 | 福建师范大学 | It is a kind of for tertiary amine-type flame retardant curing agent of epoxy resin and preparation method thereof |
| CN109467574A (en) * | 2018-11-13 | 2019-03-15 | 岭南师范学院 | It is a kind of novel based on vanillic aldehyde reactive flame retardant and its preparation, application |
| CN109485916A (en) * | 2018-11-20 | 2019-03-19 | 武汉工程大学 | A kind of synthesis and application of Aminopyrazine based flame retardant |
| CN110511247A (en) * | 2019-08-05 | 2019-11-29 | 厦门大学 | A kind of phosphorous, hydridization activated monomer in transition metal ions synthetic method |
| CN112442168A (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 phenolic hydroxyl groups and preparation method and application thereof |
| CN112679911A (en) * | 2020-12-22 | 2021-04-20 | 常熟生益科技有限公司 | Modified epoxy resin composition and prepreg and laminated board prepared from same |
| CN113754864A (en) * | 2021-08-03 | 2021-12-07 | 中国民用航空飞行学院 | Preparation method of reprocessable circulating dynamic flame-retardant epoxy resin |
| CN116355284A (en) * | 2023-03-28 | 2023-06-30 | 福州大学 | DOPO-based reactive flame retardant for flame-retardant epoxy resin and preparation method thereof |
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| CN106554483B (en) * | 2016-11-23 | 2018-12-28 | 厦门大学 | A kind of phospho hetero phenanthrene structural response type fire retardant and its application |
| CN106554483A (en) * | 2016-11-23 | 2017-04-05 | 厦门大学 | A kind of phospho hetero phenanthrene structural response type fire retardant and its application |
| CN106832413B (en) * | 2017-03-13 | 2019-03-29 | 厦门大学 | A kind of phosphorus-nitrogen containing polymer modification Nano particles of silicon dioxide and its preparation method and application |
| US11046832B2 (en) | 2017-03-13 | 2021-06-29 | Xiamen University | Method of manufacturing modified silicon dioxide nanoparticles |
| WO2018166440A1 (en) * | 2017-03-13 | 2018-09-20 | 厦门大学 | Phosphorus-nitrogen-containing polymer-modified silica nanoparticles, preparation method therefor and use thereof |
| CN106832413A (en) * | 2017-03-13 | 2017-06-13 | 厦门大学 | A kind of phosphorus-nitrogen containing polymer modification Nano particles of silicon dioxide and its preparation method and application |
| CN107400197A (en) * | 2017-08-04 | 2017-11-28 | 武汉工程大学 | A kind of reaction-type flame-retarding epoxy curing agent and preparation method thereof |
| CN108148095B (en) * | 2017-12-29 | 2019-10-18 | 福建师范大学 | A kind of tertiary amine-type flame retardant curing agent and preparation method thereof for epoxy resin |
| CN108148095A (en) * | 2017-12-29 | 2018-06-12 | 福建师范大学 | It is a kind of for tertiary amine-type flame retardant curing agent of epoxy resin and preparation method thereof |
| CN109467574A (en) * | 2018-11-13 | 2019-03-15 | 岭南师范学院 | It is a kind of novel based on vanillic aldehyde reactive flame retardant and its preparation, application |
| CN109467574B (en) * | 2018-11-13 | 2021-03-16 | 岭南师范学院 | Reactive flame retardant based on vanillin as well as preparation and application thereof |
| CN109485916A (en) * | 2018-11-20 | 2019-03-19 | 武汉工程大学 | A kind of synthesis and application of Aminopyrazine based flame retardant |
| CN110511247A (en) * | 2019-08-05 | 2019-11-29 | 厦门大学 | A kind of phosphorous, hydridization activated monomer in transition metal ions synthetic method |
| CN112442168A (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 phenolic hydroxyl groups and preparation method and application thereof |
| CN112679911A (en) * | 2020-12-22 | 2021-04-20 | 常熟生益科技有限公司 | Modified epoxy resin composition and prepreg and laminated board prepared from same |
| CN112679911B (en) * | 2020-12-22 | 2022-12-09 | 常熟生益科技有限公司 | Modified epoxy resin composition and prepreg and laminated board prepared from same |
| CN113754864A (en) * | 2021-08-03 | 2021-12-07 | 中国民用航空飞行学院 | Preparation method of reprocessable circulating dynamic flame-retardant epoxy resin |
| CN113754864B (en) * | 2021-08-03 | 2023-02-21 | 中国民用航空飞行学院 | Preparation method of reprocessable circulating dynamic flame-retardant epoxy resin |
| CN116355284A (en) * | 2023-03-28 | 2023-06-30 | 福州大学 | DOPO-based reactive flame retardant for flame-retardant epoxy resin and preparation method thereof |
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