CN103834169A - Flame-retardant benzoxazine resin and preparation method thereof - Google Patents
Flame-retardant benzoxazine resin and preparation method thereof Download PDFInfo
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- CN103834169A CN103834169A CN201410107930.7A CN201410107930A CN103834169A CN 103834169 A CN103834169 A CN 103834169A CN 201410107930 A CN201410107930 A CN 201410107930A CN 103834169 A CN103834169 A CN 103834169A
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- benzoxazine
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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Abstract
The invention relates to thermosetting resin and provides flame-retardant benzoxazine resin which is good in flame retardancy, high in heat resistance and high in compatibility of a flame-retardant modifier and a resin matrix, and a preparation method thereof. The flame-retardant benzoxazine resin consists of the following components by mass: 100 parts of benzoxazine matrix resin, 1-40 parts of ammonium polyphosphate and 0-150 parts of a solvent. The dry preparation method comprises the steps of adding the ammonium polyphosphate into the benzoxazine matrix resin, uniformly stirring, performing pre-polymerization, and cooling to room temperature to obtain the flame-retardant benzoxazine resin. The flame-retardant benzoxazine resin prepared by the dry method can be used for an adhesive, composite material matrix resin and the like. The wet preparation method comprises the steps of adding the solvent into the benzoxazine matrix resin, uniformly stirring, adding the ammonium polyphosphate, and uniformly stirring again to obtain the flame-retardant benzoxazine resin. The flame-retardant benzoxazine resin prepared by the wet method can be used for wet-preparation of fiber prepregs and the like.
Description
Technical field
The present invention relates to thermosetting resin, especially relate to a kind of flame retardant type benzoxazine colophony and preparation method thereof.
Background technology
Thermosetting resin and matrix material thereof are widely used in the industrial circles such as aerospace, automobile, electronic apparatus, building with its excellent dimensional stability, rigidity and thermotolerance, but resin matrix is easy firing mostly, the loss that fire causes brings great effect to national economy, therefore the flame-retardant modified of resin is studied in recent years widely.
Epoxy resin, bimaleimide resin are conventional high-performance thermosetting resin matrixes, epoxy resin has good thermostability and dielectric properties, bimaleimide resin has high thermal resistance, chemical proofing, radiation resistance and excellent mechanical property, but epoxy resin easy firing, oxygen index is no more than 25(Levchik, S.V. conventionally, Weil, E.D., Thermal decomposition, combustion and flame ?retardancy of epoxy resins-a review of the recent literature[J] .Polymer International.2004, 53 (12), 1901-1929), although bimaleimide resin has certain self-extinguishing, but need toughening modifying to cause its oxygen index to be generally less than 24(Chih-hsiung Huang when application, Mei Qilin, Qin Yan, Deng. the research .[J of reaction-type flame-retarding modified bismaleimide resin] the journal .2002 of Wuhan University of Technology, 24 (2): 5-8).The research and development of the flame retardant properties modification of original thermosetting resin and novel flame-retardant type thermosetting resin have important value.
Benzoxazine colophony is a kind of novel ring-opening polymerization resol, not only has the heat-resisting and flame retardant resistance that traditional resol is good, and emits without small molecules in forming and hardening, and volume approaches zero contraction, has low water absorption and stable insulativity.In addition, this synthetic technology of resins is simple, cost is low, strengthen and prepare matrix material with glass fibre or carbon fiber, processibility is fine, almost identical with epoxy resin, and physical strength under high temperature (180 ℃) and double-dimaleic type polyimide approach, and make benzoxazine colophony obtain applying more and more widely.It is higher that the oxygen index of benzoxazine is compared epoxy resin, generally at 30 left and right (M.Sponton, J.C.Ronda, M.Galia`, V.Ca ' diz, Studies on thermal and flame retardant behaviour of mixtures of bis (m-aminophenyl) methyl-phosphine oxide based benzoxazine and glycidylether of bisphenol A[J], Polym.Degrad.Stab.2008,93,2158 – 2165), fire-retardantly require high occasion still to need it to carry out flame-retardant modified but be applied to.
Traditional flame-proof modifier contains halogen more, although this based flame retardant flame retarding efficiency is high, when burning, produces a large amount of toxic substance serious environment pollutions, is replaced gradually in recent years by halogen-free flame retardants.Inorganic combustion inhibitor is as a large class of fire retardant except having good flame retardant effect, and often toxicity is low, corrosion-free, cheap, but large usage quantity and larger on material property impact often.The people such as Gu Yi (Ling Hong, Gu Yi. magnesium hydroxide flame retardant gathers Polybenzoxazine [J]. polymer material science and engineering, 2013,29 (7): 76-79; Ling Hong, leaf bateau, Gu Yi. the research [J] of Modified by Aluminum Hydroxide benzoxazine and flame retardant resistance. material engineering, 2011, (6): 5-10) be added into aluminium hydroxide, magnesium hydroxide as fire retardant and in benzoxazine colophony, carry out modification, after addition is more than or equal to 20%, can reach UL-94V0 level, be combined and then affect other performances with organic resin matrix but addition has influence on inorganic modified dose compared with conference.The people such as Lu Jun (Lu Jun, door is slight, Zhang Hongchun, etc. the preparation method of diamin type high fire-retardancy benzoxazine resin containing phosphor: China, CN101220152B[P] .2010.06.09; Lu Jun, door slightly, Zhang Hongchun, Deng. the preparation method of dihydric phenol type high fire-retardancy benzoxazine resin containing phosphor: China, CN101220153B[P] .2010.04.07) invention fire-retardant benzoxazine colophony be that P contained compound is introduced by chemical reaction in the building-up process of benzoxazine colophony intermediate, the fire-retardant rank of fire-retardant benzoxazine colophony of preparation reaches V-0 level, has good thermal characteristics simultaneously.This type of reaction-type flame-retarding method makes to contain ignition-proof element or group in its molecular chain, can avoid separating out of fire retardant, and can reduce the impact on matrix physicals, but reaction-type flame-retarding will relate to the change of whole polymerization technique process, more complicated.Ammonium polyphosphate is additive flame retardant as a class inorganic phosphorus, inexpensive, toxicity is low, Heat stability is good, usually uses with the composite formation expanding fire retardant of other fire retardants, and what be used as separately resin fire-retardantly also has a good result.
Summary of the invention
The object of the present invention is to provide flame retardant effect and thermotolerance better, a kind of flame retardant type benzoxazine colophony that flame-proof modifier and resin matrix consistency are good and preparation method thereof.
In mass ratio composed as follows of described flame retardant type benzoxazine colophony:
Ammonium polyphosphate 1～40;
Solvent 0～150.
Described ammonium polyphosphate is ammonium polyphosphate crystallization II-type, and the polymerization degree is greater than 1000.
Described benzoxazine matrix resin is selected from least one in diamines type benzoxazine, bisphenol type benzoxazine, monocycle benzoxazine etc.;
The structural formula of described diamines type benzoxazine is:
The structural formula of described bisphenol type benzoxazine is:
The structural formula of described monocycle benzoxazine is:
Described solvent can be selected from least one in tetrahydrofuran (THF), methylene dichloride, chloroform, dimethyl sulfoxide (DMSO), dimethyl formamide, acetone, ethyl acetate, benzene,toluene,xylene etc.
One of preparation method's of described flame retardant type benzoxazine colophony (dry method) concrete steps are as follows:
In benzoxazine matrix resin, add ammonium polyphosphate, stir, after pre-polymerization, be cooled to room temperature, obtain flame retardant type benzoxazine colophony.Adopt the flame retardant type benzoxazine colophony of dry process to can be used for sizing agent, composite matrix resin etc.
The temperature of described stirring can be 110～135 ℃; The time of described pre-polymerization can be 3～120min.
The concrete steps of the preparation method of described flame retardant type benzoxazine colophony two (wet methods) are as follows:
In benzoxazine matrix resin, add solvent, after stirring, add again ammonium polyphosphate, then after stirring, obtain flame retardant type benzoxazine colophony.The flame retardant type benzoxazine colophony that adopts wet method to prepare can be used for wet method and prepares fiber prepreg material etc.
Ammonium polyphosphate is as the inorganic additive flame retardant of one, and nontoxicity is not halogen-containing, Heat stability is good, and environmental pollution is little, and the method cost is lower, simple to operate, can meet the requirement of suitability for industrialized production.
The flame-retardant modified benzoxazine colophony of the present invention's application ammonium polyphosphate, adopt wet method and dry process to prepare flame retardant type benzoxazine colophony, resin flame retardant effect significantly improves, and original excellent heat resistance of resin is kept substantially, and flame-proof modifier and resin matrix have good consistency.Flame retardant type benzoxazine colophony product of the present invention can be applied to separately fire-retardant occasion, also can with the strongthener such as glass fibre, carbon fiber Application of composite.The method convenient operation, has certain prospects for commercial application.Fire-retardant preparation method in the present invention, except ammonium polyphosphate, is equally applicable to magnesium hydroxide, aluminium hydroxide, antimonous oxide, micro encapsulation red phosphorus, the zinc borate situation as fire retardant.
Accompanying drawing explanation
Fig. 1 is the microscopic appearance of ammonium polyphosphate in benzoxazine colophony.
Fig. 2 is local fluffy charcoal layer SEM figure after fire-retardant benzoxazine colophony burning.
Fig. 3 is partial bores bubble structure SEM figure after fire-retardant benzoxazine colophony burning.
Fig. 4 is the DMTA figure of flame-retardant modified front benzoxazine colophony.
Fig. 5 is the DMTA figure after the flame-retardant modified benzoxazine colophony of 10% ammonium polyphosphate.
Fig. 6 is the DMTA figure after the flame-retardant modified benzoxazine colophony of 20% ammonium polyphosphate.
Embodiment
Embodiment 1
Get 100 parts of benzoxazine matrix resins, add 1 part of ammonium polyphosphate to stir, then be warmed up to 110 ℃ of stirring 120min, molten resin and ammonium polyphosphate are fully mixed, be cooled to room temperature, obtain dry method flame retardant type benzoxazine colophony.
Above-mentioned dry method flame retardant type benzoxazine colophony, in 125 ℃ of vacuum defoamations, is prepared to casting matrix by 150 ± 5 ℃/1h+160 ± 5 ℃/1h+170 ± 5 ℃/1h+180 ± 5 ℃/2h+200 ± 5 ℃/2h curing process, and measuring its oxygen index is 32.5.
Embodiment 2
Get 100 parts of benzoxazine matrix resins, add 10 parts of ammonium polyphosphates to stir, then be warmed up to 135 ℃ of stirring 3min, molten resin and ammonium polyphosphate are fully mixed, be cooled to room temperature, obtain dry method flame retardant type benzoxazine colophony.Above-mentioned dry method flame retardant type benzoxazine colophony, in 125 ℃ of vacuum defoamations, is prepared to casting matrix by 150 ± 5 ℃/1h+160 ± 5 ℃/1h+170 ± 5 ℃/1h+180 ± 5 ℃/2h+200 ± 5 ℃/2h curing process, and measuring its oxygen index is 36.5.
Embodiment 3
Get 100 parts of benzoxazine matrix resins, add 20 parts of ammonium polyphosphates to stir, then be warmed up to 120 ℃ of stirring 40min, molten resin and ammonium polyphosphate are fully mixed, be cooled to room temperature, obtain dry method flame retardant type benzoxazine colophony.Above-mentioned dry method flame retardant type benzoxazine colophony, in 125 ℃ of vacuum defoamations, is prepared to casting matrix by 150 ± 5 ℃/1h+160 ± 5 ℃/1h+170 ± 5 ℃/1h+180 ± 5 ℃/2h+200 ± 5 ℃/2h curing process, and measuring its oxygen index is 40.3.
Embodiment 4
Get 100 parts of benzoxazine matrix resins, after adding 150 parts of tetrahydrofuran solvents to mix, then add 40 parts of ammonium polyphosphates to stir, obtain wet method flame retardant type benzoxazine colophony.Above-mentioned wet method flame retardant type benzoxazine colophony is heated to 95 ℃ and removes vacuum defoamation again after most of solvent, prepare casting matrix by 150 ± 5 ℃/1h+160 ± 5 ℃/1h+170 ± 5 ℃/1h+180 ± 5 ℃/2h+200 ± 5 ℃/2h curing process, measuring its oxygen index is 47.
Embodiment 5
Get 100 parts of benzoxazine matrix resins, after adding 80 parts of tetrahydrofuran solvents to mix, then add 20 parts of ammonium polyphosphates to stir, obtain wet method flame retardant type benzoxazine colophony.Above-mentioned wet method flame retardant type benzoxazine colophony is heated to 95 ℃ and removes vacuum defoamation again after most of solvent, prepare casting matrix by 150 ± 5 ℃/1h+160 ± 5 ℃/1h+170 ± 5 ℃/1h+180 ± 5 ℃/2h+200 ± 5 ℃/2h curing process, measuring its oxygen index is 40.3.
Embodiment 6
Get 100 parts of benzoxazine matrix resins, after adding 60 parts of tetrahydrofuran solvents to mix, then add 10 parts of ammonium polyphosphates to stir, obtain wet method flame retardant type benzoxazine colophony.Above-mentioned wet method flame retardant type benzoxazine colophony is heated to 95 ℃ and removes vacuum defoamation again after most of solvent, prepare casting matrix by 150 ± 5 ℃/1h+160 ± 5 ℃/1h+170 ± 5 ℃/1h+180 ± 5 ℃/2h+200 ± 5 ℃/2h curing process, measuring its oxygen index is 36.5.
The flame retardant type benzoxazine colophony flame retardant effect that application diphenylmethane diamine type benzoxazine matrix resin and ammonium polyphosphate prepare improves significantly, the modified system oxygen index that adds 3% ammonium polyphosphate just increases to 34.5 from 31.5 of benzoxazine matrix resin, shows good flame-retardant modified effect.Flame-retardant modified system is more less than the raw cigarette amount of matrix resin burning, microscopic appearance shows that ammonium polyphosphate and matrix resin have good consistency and interface performance (see figure 1), the rare gas element discharging after burning makes surface have Cell structure, and the isolated polymkeric substance of charcoal layer of formation contacts with oxygen and play fire retardation (seeing Fig. 2 and 3).Flame retardant type benzoxazine colophony of the present invention has good resistance toheat concurrently simultaneously, when ammonium polyphosphate addition is 10%, 207 ℃ of second-order transition temperatures, less than 211 ℃ of declines of matrix resin, when even addition reaches 20%, second-order transition temperature still remains on 203 ℃ (seeing Fig. 4～6).
Claims (8)
1. a flame retardant type benzoxazine colophony, is characterized in that in mass ratio composed as follows:
Benzoxazine matrix resin 100;
Ammonium polyphosphate 1～40;
Solvent 0～150.
2. a kind of flame retardant type benzoxazine colophony as claimed in claim 1, is characterized in that described benzoxazine matrix resin is selected from least one in diamines type benzoxazine, bisphenol type benzoxazine, monocycle benzoxazine;
The structural formula of described diamines type benzoxazine is:
The structural formula of described bisphenol type benzoxazine is:
The structural formula of described monocycle benzoxazine is:
3. a kind of flame retardant type benzoxazine colophony as claimed in claim 1, is characterized in that described ammonium polyphosphate is ammonium polyphosphate crystallization II-type, and the polymerization degree is greater than 1000.
4. a kind of flame retardant type benzoxazine colophony as claimed in claim 1, is characterized in that described solvent is selected from least one in tetrahydrofuran (THF), methylene dichloride, chloroform, dimethyl sulfoxide (DMSO), dimethyl formamide, acetone, ethyl acetate, benzene,toluene,xylene.
5. a kind of preparation method of flame retardant type benzoxazine colophony as claimed in claim 1, is characterized in that its concrete steps are as follows:
In benzoxazine matrix resin, add ammonium polyphosphate, stir, after pre-polymerization, be cooled to room temperature, obtain flame retardant type benzoxazine colophony.
6. a kind of preparation method of flame retardant type benzoxazine colophony as claimed in claim 5, the temperature that it is characterized in that described stirring is 110～135 ℃.
7. a kind of preparation method of flame retardant type benzoxazine colophony as claimed in claim 5, the time that it is characterized in that described pre-polymerization is 3～120min.
8. a kind of preparation method of flame retardant type benzoxazine colophony as claimed in claim 1, is characterized in that its concrete steps are as follows:
In benzoxazine matrix resin, add solvent, after stirring, add again ammonium polyphosphate, then after stirring, obtain flame retardant type benzoxazine colophony.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104018344A (en) * | 2014-06-06 | 2014-09-03 | 中航复合材料有限责任公司 | Sizing-fire resisting fiber fabric for liquid state forming process, and preparation method of sizing-fire resisting fiber fabric |
| CN104312149A (en) * | 2014-11-03 | 2015-01-28 | 厦门大学 | Wear-resistant benzoxazine resin and preparation method thereof |
| CN105001452A (en) * | 2015-07-13 | 2015-10-28 | 中科院广州化学有限公司南雄材料生产基地 | Phosphorus-nitrogen halogen-free flame retardant and preparation method and application thereof |
| CN105037800A (en) * | 2015-07-13 | 2015-11-11 | 中科院广州化学有限公司南雄材料生产基地 | Silicon-containing polybenzoxazine surface modified ammonium polyphosphate and preparation therefor and application thereof |
| CN105199384A (en) * | 2015-09-21 | 2015-12-30 | 西南石油大学 | Transparent flame-retardant benzoxazine nanocomposite and preparation method thereof |
| CN115584625A (en) * | 2022-11-17 | 2023-01-10 | 成都科宜高分子科技有限公司 | Organic fiber, fiber composite material, preparation method and application thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104018344A (en) * | 2014-06-06 | 2014-09-03 | 中航复合材料有限责任公司 | Sizing-fire resisting fiber fabric for liquid state forming process, and preparation method of sizing-fire resisting fiber fabric |
| CN104018344B (en) * | 2014-06-06 | 2016-03-30 | 中航复合材料有限责任公司 | A kind of liquid condition shaping technique sizing-flame-retardant fibre fabric and preparation method thereof |
| CN104312149A (en) * | 2014-11-03 | 2015-01-28 | 厦门大学 | Wear-resistant benzoxazine resin and preparation method thereof |
| CN105001452A (en) * | 2015-07-13 | 2015-10-28 | 中科院广州化学有限公司南雄材料生产基地 | Phosphorus-nitrogen halogen-free flame retardant and preparation method and application thereof |
| CN105037800A (en) * | 2015-07-13 | 2015-11-11 | 中科院广州化学有限公司南雄材料生产基地 | Silicon-containing polybenzoxazine surface modified ammonium polyphosphate and preparation therefor and application thereof |
| CN105001452B (en) * | 2015-07-13 | 2017-12-26 | 中科院广州化学有限公司南雄材料生产基地 | A kind of phosphorus nitrogen halogen-free flame retardants and preparation method and application |
| CN105199384A (en) * | 2015-09-21 | 2015-12-30 | 西南石油大学 | Transparent flame-retardant benzoxazine nanocomposite and preparation method thereof |
| CN115584625A (en) * | 2022-11-17 | 2023-01-10 | 成都科宜高分子科技有限公司 | Organic fiber, fiber composite material, preparation method and application thereof |
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Application publication date: 20140604 |