CN102432837A - Phosphor and nitrogen containing flame retardant curing agent, preparation method and application thereof - Google Patents
Phosphor and nitrogen containing flame retardant curing agent, preparation method and application thereof Download PDFInfo
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- CN102432837A CN102432837A CN2011103080146A CN201110308014A CN102432837A CN 102432837 A CN102432837 A CN 102432837A CN 2011103080146 A CN2011103080146 A CN 2011103080146A CN 201110308014 A CN201110308014 A CN 201110308014A CN 102432837 A CN102432837 A CN 102432837A
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Abstract
The invention discloses a phosphor and nitrogen containing flame retardant curing agent, a preparation method and application thereof. The curing agent has a phosphorylurea structure, contains active ammonia and hydrogen atoms, has dual functions of both a flame retarding agent and a curing agent, and can be directly used for curing epoxy resin. In a curing progress, flame retardant elements are embedded into an epoxy structure, thus avoiding phase separation phenomenon due to introduction of additive type flame retarding agent. Phosphor elements mainly function in flame retarding of a condensed phase while a urea structure mainly functions in flame retarding of a gas phase. The curing agent can react with common epoxy resin to obtain uniform and transparent cured object; in addition, the curing agent has low phosphorus content, passes 1.6 mm UL 94 V0 level, reaches oxygen index as high as 29-34%, and has excellent flame retardance; in thermo-gravimetric analysis, the maximum thermal decomposition temperature is as high as 400 DEG C; the char yield of the curing agent at 700 DEG C is 35%; and glass transition temperature of the curing agent is as high as 150 DEG C. The curing agent can also realize co-curing together with common curing agents, such as, diaminodiphenyl sulfone and anhydride-type epoxy curing agents. The curing agent is low in cost, simple in production process, and available for industrial production.
Description
Technical field
The present invention relates to flame retardant resistance solidifying agent field, particularly, relate to a kind of fire-retardant solidifying agent of phosphorous nitrogen.
Background technology
Epoxy resin cured product is because performances such as its excellent mechanical intensity, electric insulation, resistance to chemical attack, has been widely used in bonding, the encapsulation of electronic devices and components and the manufacturing of printed circuit board (PCB), become the mainstay that supports electric industry.Yet the same with most of macromolecular materials, the curable epoxide thing very easily fires, and modal in the industry is halogen-containing flame retardant epoxy cured article.
" the electric and electronics offal treatment method (WEEE) " of European Union and " some objectionable impurities instruction (RoHS) is used in restriction in the electronic electric equipment " draft for amendments; To Halogen, unleaded environmental protection electronic material standard in addition, clearly regulation lead, mercury, cadmium, chromium (6 valency), PBBs (PBB) and six kinds of chemical substances of polybromodiphenyl ether (PBDE) forbade in electronic and electrical equipment, using from July 1st, 2006.How to realize in industry that the halogen-free flameproof and the resistance toheat of curable epoxide thing have very big challenge.
The fire retardant of epoxy resin can be divided into response type and addition type.Additive flame retardant epoxy resin is to add fire retardant in the sensing epoxy resin cured product to reach flame retardant effect.Additive flame retardant mainly contains SULPHOSUCCINIC ACID ESTER, nitrogenous compound (trimeric cyanamide etc.) and mineral filler (Marinco H, talcum powder and polynite etc.) etc.The additive flame retardant addition is big, and is poor with the epoxy matrix consistency, is prone to problems such as frost, limited the industrial production requirement of epoxy resin.
The reactive group that reactive flame retardant can be through containing ignition-proof element and the epoxy group(ing) of resin or the active epoxy thing ring-opening reaction flame retardant resistance group that induces one; The also available solidifying agent that contains ignition-proof element comes cured epoxy resin.For example, Chinese patent CN1916049A discloses a kind of preparation method of phosphorous epoxy resin solidifying agent, and after the curing, the fire-retardant oxygen index of epoxy can reach 29, but its second-order transition temperature that solidifies the back epoxy less than 100 ℃, and it is bigger to give birth to the cigarette amount during burning.People such as Jeng (European Polymer Journal 2002; 38; 683-693) synthesized multiple phosphorus curing agent PPDCD230 and DCPD230 etc., the flame retardant properties of solidifying the cured article that obtains behind the BE188 is greatly improved, but second-order transition temperature has only 72 ℃ and 45 ℃.
The purpose of this invention is to provide a kind of novel flame-retardant solidifying agent preparation method, this kind fire retardant can be participated in the solidification process of epoxy resin directly, has solved the compatibility problem between epoxy resin and the fire retardant; In the fire retardant structure, introduce the phosphorus urea structure simultaneously; Phosphorus oxygen benzene ring structure can promote into charcoal, stablizes the charcoal layer, and urea groups can discharge rare gas element under heating condition; Dilution inflammable gas and concentration of oxygen, thereby the flame retardant properties of raising epoxy resin.The cured article that this solidifying agent and ordinary epoxy resin effect obtain can pass through 1.6mm UL 94 V0 levels, and second-order transition temperature can reach 150 ℃ simultaneously.This kind solidifying agent with low cost, production process is simple, can carry out industrial production.
Summary of the invention
The object of the invention provides a kind of preparation method of difunctional flame retardant epoxy solidifying agent of novel phosphorus-containing nitrogen, and the characteristic of this solidifying agent is to have the phosphinylidyne urea structure, owing to contain active ammonia Wasserstoffatoms in the structure, can directly be used for cured epoxy resin.In solidification process, ignition-proof element is embedded in the epoxy construction, has avoided because the phenomenon of phase separation that the interpolation of additive flame retardant causes makes epoxy resin when improving its flame retardant properties, keep original character preferably.Simultaneously, this kind solidifying agent can also carry out synergistic curing with solidifying agent commonly used.
A kind of difunctional flame retardant epoxy solidifying agent of phosphorous nitrogen has following structural formula:
The R substituting group is alkoxyl group, phenoxy or derivatives thereof, alkyl, phenyl, piperazidine base, pyrazine base, 1-skatole base, 1,1-dimethylsilyl, triazolyl, carbazyl or 9,9-dimethyl-fluorenyl.
The preparation method of the difunctional flame retardant epoxy solidifying agent of described phosphorous nitrogen may further comprise the steps:
POCl3 and dihydric phenol with 1:1～10:1 mol ratio mix, and feed rare gas element at 80～100 ℃ of following stirring reaction 1～8h; Remove behind the excessive POCl3 and the active reaction thing is made solvent with anhydrous acetonitrile, add catalyzer, filter at 75～90 ℃ of reaction 1～10h down, washing, filtrating is revolved to steam and is obtained midbody; With the midbody and the diamine of 1:1～10:1 mol ratio ,-20～-5 ℃ are reacted 1～3h down, and 20～28 ℃ are reacted 2～5h down, and 60～80 ℃ of refluxed 2～15h filter, and washing obtains the difunctional flame retardant epoxy solidifying agent white product of phosphorous nitrogen;
Said dihydric phenols material is compounds such as Resorcinol, pyrocatechol, Resorcinol, dihydroxyphenyl propane, bisphenol S, Bisphenol F and naphthalenediol.
Said active reaction thing is the active reaction thing that contains amino, urea groups, alkylamino radical, anilino, NCO, benzyl amino, piperazinyl, imidazolyl or indyl.
Said catalyzer is a phase-transfer catalyst.Its phase-transfer catalyst is PEG-400, PEG-600 or crown ether etc.
The application of the solidifying agent of above-mentioned phosphorous nitrogen obtains the flame retardant epoxy cured product of phosphorous nitrogen behind the solidifying agent of said phosphorous nitrogen and the polymerization of epoxy resins, concrete polymerization procedure is following:
The fire-retardant solidifying agent of 100 weight part epoxy resin and the said phosphorous nitrogen of 5～50 weight parts is stirred under 60～100 ℃; After 20～60 ℃ of vacuum conditions outgas down; At 80～100 ℃ of following curing reaction 1～2h, 100～120 ℃ solidify 2～3h down, and 120～150 ℃ solidify 4～6h down; 150 ℃ solidify 2～12h down, obtain the flame retardant epoxy cured product of said phosphorous nitrogen.
Said vacuum condition is 0.02～0.06Mpa.
The flame retardant rating of the curable epoxide product of said phosphorous nitrogen is 1.6mm UL 94 V-0 levels, and oxygen index is 29～34, and second-order transition temperature is 100～150 ℃.
The present invention has following advantage: this solidifying agent has good flame property, and the maximum heat decomposition temperature is 400 ℃, and the charring rate in the time of 700 ℃ is 35%.This solidifying agent can be used for the cured article that ordinary epoxy resin obtains homogeneous transparent.Curable epoxide thing phosphorus content is lower, has only 1.6～2.0 wt%, and this solidifying agent has good flame retardant property simultaneously, and oxygen index can reach 29～34%, through UL-94 V0 (1.6mm) level.The second-order transition temperature of cured article is at 100～150 ℃, and is with low cost, produces simply, can be suitable for industrial applications.
Description of drawings
Fig. 1 is the proton nmr spectra of midbody of the difunctional flame retardant epoxy solidifying agent of a kind of phosphorous nitrogen of obtaining of embodiment 1;
Fig. 2 be a kind of phosphorous nitrogen of obtaining of embodiment 1 difunctional flame retardant epoxy solidifying agent midbody nucleus magnetic resonance phosphorus spectrum;
Fig. 3 obtains a kind of difunctional flame retardant epoxy solidifying agent infrared spectrum of phosphorous nitrogen for exemplifying embodiment 1.
Embodiment
The present invention will do with more detailed explanation technical scheme of the present invention through following specific embodiment, but the present invention is not limited to the embodiment of following proposition.
Embodiment 1
With the 110g Resorcinol A that adds 1mol in the 180mL POCl3 of 2mol.Reaction is 5 hours under 90 ℃ of conditions, and 85 ℃ of vacuum rotary steams are removed excessive POCl3, are dissolved in then in a certain amount of anhydrous acetonitrile; Add PEG-600, stirring and evenly mixing adds the 200g methyl isocyanate of 3.5mol in batches; Normal-temperature reaction 2h is heated to 90～110 ℃, back flow reaction 4h under the logical condition of nitrogen gas.Suction filtration is got filtrating, revolves to steam to obtain yellow thick substances midbody, and productive rate is 70%.
In a certain amount of toluene, add midbody, ice bath drips the mixing solutions of 10mol diamine and toluene down, behind the 2h, is warming up to 70 ℃, back flow reaction 15h.Obtain white solid, i.e. the fire-retardant solidifying agent of the phosphorous nitrogen of product, productive rate is 90%.
The proton nmr spectra of the midbody of the difunctional flame retardant epoxy solidifying agent of a kind of novel phosphorus-containing nitrogen that Fig. 1 obtains for embodiment 1;
1HNMR (ppm): 1.61 (CH
3); 7.14 (Ph-H); 7.18 (Ph-H).
The midbody of the difunctional flame retardant epoxy solidifying agent of a kind of phosphorous nitrogen that Fig. 2 obtains for embodiment 1 nucleus magnetic resonance phosphorus spectrum;
31PNMR (ppm) :-5.28.
Fig. 3 is the infrared spectrum of embodiment 1 resulting product, FTFR (Potassium Bromide, cm
-1): 3305, the N-H stretching vibration; 3057, the stretching vibration of phenyl ring hydrogen; 2969, the methyl stretching vibration on the phenol; 1681, the two key stretching vibrations of C=O; 1540, the N-H flexural vibration; 1453, the phenyl ring skeletal vibration; 1365, the P=O stretching vibration; 1220, C-O stretching vibration (phenol); 1074, the stretching vibration of P-N key; 1109, the P-O-C stretching vibration; 842, the phenyl ring flexural vibration.
With 100 weight part bisphenol A epoxide resins and the above-mentioned product of 25 weight parts is that the fire-retardant solidifying agent of phosphorous nitrogen stirs under 80 ℃, and 40 ℃ of vacuum conditions after the degassing, are poured the tetrafluoroethylene mould into down; Solidify 1h at 100 ℃; 110 solidify 2h, and 120 ℃ solidify 5h, and 140 ℃ solidify 12h.The curable epoxide product that obtains reaches UL 94 V-0 (1.6mm) level, and oxygen index is 30.Second-order transition temperature is 125 ℃.
Embodiment 2
The 110g Resorcinol of 1mol under 50 ℃, is added the 47mL POCl3 of 5mol.Reaction is 5 hours under 90 ℃ of conditions, and 85 ℃ of vacuum rotary steams are removed excessive POCl3, are dissolved in then in a certain amount of anhydrous acetonitrile; Add PEG-400, stirring and evenly mixing adds the 320g methyl isocyanate of 5mol in batches; Normal-temperature reaction 4h is heated to 70～90 ℃, back flow reaction 6h under the logical condition of nitrogen gas.Suction filtration is got filtrating, revolves to steam to obtain yellow thick substances midbody, and productive rate is 75%.
In a certain amount of toluene, add midbody, the mixing solutions of Dropwise 5 mol diamine and toluene under the ice bath behind the 2h, is warming up to 70 ℃, back flow reaction 15h.Obtain white solid, i.e. the fire-retardant solidifying agent of the phosphorous nitrogen of product, productive rate is 90%.
The difunctional fire-retardant solidifying agent of common bisphenol A epoxide resin of 100 weight parts and the phosphorous nitrogen of the above-mentioned product of 27 weight parts is stirred under 80 ℃; After 40 ℃ of vacuum conditions outgas down, pour the tetrafluoroethylene mould into and solidify 1h for 100 ℃, 110 solidify 2h; 120 ℃ solidify 5h, and 150 ℃ solidify 6h.The curable epoxide product that obtains reaches UL 94 V-0 (1.6mm) level, and oxygen index is 33.Second-order transition temperature is 150 ℃.
Claims (10)
1. the fire-retardant solidifying agent of a phosphorous nitrogen is characterized in that, said fire-retardant solidifying agent has following structural formula:
The R substituting group is alkoxyl group, phenoxy or derivatives thereof, alkyl, phenyl, piperazidine base, pyrazine base, 1-skatole base, 1,1-dimethylsilyl, triazolyl, carbazyl or 9,9-dimethyl-fluorenyl.
2. the preparation method of the fire-retardant solidifying agent of the described phosphorous nitrogen of claim 1 is characterized in that, may further comprise the steps:
With mol ratio is that POCl3 and the dihydric phenol of 1:1～10:1 mixes, and feeds rare gas element at 80～100 ℃ of following stirring reaction 1～8h; Remove behind the excessive POCl3 and the active reaction thing is made solvent with anhydrous acetonitrile, under catalyzer and 75～90 ℃ of conditions of temperature, react 1～10h, filter, washing, filtrating is revolved to steam and is obtained midbody; With mol ratio is said midbody and the diamine mixing of 1:1～10:1, reacts 1～10h down at-20～-5 ℃, and 20～40 ℃ are reacted 2～5h down, 60～80 ℃ of refluxed 2～15h, and filtration, washing obtains the fire-retardant solidifying agent of said phosphorous nitrogen.
3. preparation method according to claim 2 is characterized in that, said dihydric phenol is Resorcinol, pyrocatechol, Resorcinol, dihydroxyphenyl propane, bisphenol S, Bisphenol F or naphthalenediol.
4. preparation method according to claim 2 is characterized in that, said active reaction thing is the active reaction thing that contains amino, urea groups, alkylamino radical, anilino, NCO, benzyl amino, piperazinyl, imidazolyl or indyl.
5. preparation method according to claim 2 is characterized in that, said catalyzer is phase-transfer catalyst PEG-400, PEG-600, PEG-800 or crown ether.
6. a kind of application of fire-retardant solidifying agent of phosphorous nitrogen in the claim 1 is characterized in that, obtains the flame retardant epoxy cured product of phosphorous nitrogen behind the fire-retardant solidifying agent of said phosphorous nitrogen and the polymerization of epoxy resins, and concrete polymerization procedure is following:
The fire-retardant solidifying agent of 100 weight part epoxy resin and the said phosphorous nitrogen of 5～50 weight parts is stirred under 60～100 ℃; After 20～60 ℃ of vacuum conditions outgas down; At 80～100 ℃ of following curing reaction 1～2h, 100～120 ℃ solidify 2～3h down, and 120～150 ℃ solidify 4～6h down; 150 ℃ solidify 2～12h down, obtain the flame retardant epoxy cured product of said phosphorous nitrogen.
7. application according to claim 6 is characterized in that, the phosphorus content of the flame retardant epoxy cured product of said phosphorous nitrogen is 1.6～2.0wt%.
8. application according to claim 6 is characterized in that, the oxygen index of the flame retardant epoxy cured product of said phosphorous nitrogen can reach 29～34%.
9. application according to claim 6 is characterized in that, the flame retardant epoxy cured product second-order transition temperature of said phosphorous nitrogen is 100～150 ℃.
10. application according to claim 6 is characterized in that, said vacuum condition is 0.02～0.06Mpa.
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| CN2011103080146A CN102432837A (en) | 2011-10-12 | 2011-10-12 | Phosphor and nitrogen containing flame retardant curing agent, preparation method and application thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106117515A (en) * | 2016-07-13 | 2016-11-16 | 沈阳化工大学 | A kind of phosphorous, azo-cycle epoxy resins flame retardant curing agent and preparation method thereof |
| CN109897167A (en) * | 2017-12-11 | 2019-06-18 | 广东广山新材料股份有限公司 | A kind of reactive flame retardant and its preparation method and application |
| CN111560112A (en) * | 2020-06-18 | 2020-08-21 | 福建师范大学 | Phosphorus-containing triazole organic amine salt flame-retardant curing agent and application thereof in epoxy resin |
-
2011
- 2011-10-12 CN CN2011103080146A patent/CN102432837A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 赵小敏: "新型磷氮双功能固化剂的合成及环氧纳米复合材料的制备与应用", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106117515A (en) * | 2016-07-13 | 2016-11-16 | 沈阳化工大学 | A kind of phosphorous, azo-cycle epoxy resins flame retardant curing agent and preparation method thereof |
| CN109897167A (en) * | 2017-12-11 | 2019-06-18 | 广东广山新材料股份有限公司 | A kind of reactive flame retardant and its preparation method and application |
| CN111560112A (en) * | 2020-06-18 | 2020-08-21 | 福建师范大学 | Phosphorus-containing triazole organic amine salt flame-retardant curing agent and application thereof in epoxy resin |
| CN111560112B (en) * | 2020-06-18 | 2022-06-21 | 福建师范大学 | Phosphorus-containing triazole organic amine salt flame-retardant curing agent and application thereof in epoxy resin |
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Application publication date: 20120502 |