CN101220151A - Production method for oxazine resin - Google Patents
Production method for oxazine resin Download PDFInfo
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- CN101220151A CN101220151A CNA200710032522XA CN200710032522A CN101220151A CN 101220151 A CN101220151 A CN 101220151A CN A200710032522X A CNA200710032522X A CN A200710032522XA CN 200710032522 A CN200710032522 A CN 200710032522A CN 101220151 A CN101220151 A CN 101220151A
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Abstract
The invention provides a method used for preparing oxaxine resin, which comprises steps that: primary amine, hydroxybenzene and paraform are mixed at a temperature lower than 40 DEG C with the mol ratio of 1:1:2; the mixture are added into a reactor for reacting at 50-130 DEG C batch by batch, with 5-10 minutes reaction for each batch; or the mixture is continuously added into the 50-130 DEG C reactor for reacting, the adding of which is finished within 60-120 minutes; then the temperature is raised to 110-140 DEG C to vaporize moisture produced by the reaction; the oxaxine resin is obtained after the discharging of material. The preparation method of the invention is simple and stable, the reaction is stably carried out in standard atmosphere without a catalyzer and the byproduct of is water without pollution. The preparation method has low requirement on devices, with low manufacturing cost, thereby being easy to realize industrialized production.
Description
Technical field
The invention belongs to high molecular synthetic material field, be specifically related to the preparation method of Yi Zhong oxazine resin.
Background technology
Benzoxazine colophony has high heat resistance, and uninflammability can be used as composite resin matrix, insullac, potting compound etc., has wide practical use in fields such as space flight, aviation, navigations.Patent CN 1884376A, " thermotolerance benzo uh the resin complexes and its production and use of tremnbling " is with benzoxazine colophony intermediate 50-95 weight part, contain aldehyde radical phenolic compound liquid resin or solid powder 0-50 weight part and/or contain aldehyde radical benzoxazine colophony intermediate 50-0 weight part, ℃ be dissolved in the solvent in room temperature-50, obtain thermostable benzoxazine resin compound solution, adopt coating or impregnation technology to prepare the resin compounded prepreg of fiber or fabric this solution then, perhaps make the liquid or solid resin complexes through melting mixing or mechanically mixing, preparation is 150 ℃ of moulding and heat-treat the acquisition thermostable benzoxazine resin compound at 180 ℃.
Benzoxazine colophony can with other resin and usefulness, improve the resistance toheat of material etc.Patent CN1115772 " ring-opening polymerization resol and fibre reinforced composites " has introduced benzoxazine colophony and epoxy blend, prepares fabric reinforced composite through overregulating solvent, catalyzer or solidifying agent kind.This product has higher thermostability, and is electric, physical and mechanical property is good, and especially high-temperature machinery intensity is outstanding, is suitable for resistant to elevated temperatures structured material and the electrically insulating material of making 150-180 ℃ of life-time service.Patent CN1451679, " can be used for modified benzoxazine resin of RTM and preparation method thereof ", with 50～100 parts in low viscosity benzoxazine intermediate, 50～0 parts of Resins, epoxy or aryl ethane resins, add and to have in the reactor of thermometer, agitator and reflux exchanger,, add 0.1～2 part of catalyzer 50～100 ℃ of hybrid reactions of temperature 5～10 minutes, blending reaction 5～10 minutes, acquisition can be used for the benzoxazine colophony of RTM moulding; Perhaps with 50～100 parts in low viscosity benzoxazine intermediate, 50～0 parts of bimaleimide resins 120～130 ℃ of prepolymerization reactions of temperature 20～30 minutes, add 0.1～2 part of catalyzer, blending reaction 5～10 minutes, acquisition can be used for the benzoxazine colophony of RTM moulding.The pour mass of this RTM resins and fibre composite can solidify moulding in 6～10 hours in 170～200 ℃ of scopes of temperature.It is benzoxazine colophony intermediate, benzoxazine colophony and the resin cured matter that feedstock production gets that patent CN 1900068A " benzoxazine colophony intermediate, resin, cured article and its production and use " provides with cyano group side group diamine.Patent (application number 200610021851.X) provide double end group ortho-benzene dimethyl nitrile-benzo oxazine resin, cured article and its production and use.This invention belongs to high molecular synthetic material field, is specifically related to a kind of double end group ortho-benzene dimethyl nitrile-benzo oxazine resin, cured article and preparation method thereof.This invention provides a kind of 4-amino-benzene oxygen-phthalonitrile monomer, and is the double end group ortho-benzene dimethyl nitrile-benzo oxazine resin that feedstock production obtains with it.This invention double end group ortho-benzene dimethyl nitrile-benzo oxazine resin has activity of curing reaction preferably, the performance that had both had the low-temperature curing of benzoxazine colophony, the resistance and high temperature resistance property that has o-phthalonitrile resin again, both reduced the curing processing temperature significantly, and can under harsher hot environment, use again.
The preparation of benzoxazine colophony is to be generated by phenols, amine and aldehyde reaction.Different phenol and amine, the performance difference of prepared resin.Patent (application number 200410052834.3) " end capped poly(silicon aether) benzoxazine colophony of aryne and preparation method thereof ", be that aryne and the halogenated silanes that replaces with bis-phenol, formaldehyde or polyoxymethylene, amino is raw material, at first utilize the condensation reaction of bis-phenol and halogenated silanes to make the end capped poly(silicon aether) of phenolic hydroxyl group, and then with formaldehyde or polyoxymethylene and the amino aryne polycondensation that replaces, form the end capped poly(silicon aether) benzoxazine colophony of sweet-smelling alkynyl.This resin has processibility preferably, becomes the good cross-linked resin of thermostability at heat, light or radiation parameter curable, has good mechanical property and electrical insulation properties.
Because exothermic heat of reaction, and resin that negative reaction, Gao Chenghuan lead is arranged normally under catalyst action, prepared in reaction in solvent.The manufacture method that patent CN1496378A " manufacture method of benzoxazine colophony " has described a kind of benzoxazine colophony is that phenolic compound, aldehyde cpd and primary amine are reacted in the presence of organic solvent.Condensation water that is generated after reaction is finished and organic solvent vacuumize outside the above decompression of the 260 mmhg discharge system by heating.It is by many nothings phenol that patent 95111413.1 " granular polybenzoxazine intermediate and preparation method " has been described a kind of granular polybenzoxazine intermediate and preparation method thereof, monoamine and the synthetic benzoxazine intermediate of formalin reaction, and with water decomposition media, high-speed stirring granulation under the effect of suspension agent, after cooling, washing, filter, dry, obtain the granular polybenzoxazine intermediate, free phenol and unhindered amina content≤2%, melt temperature is lower than 100 ℃, can be directly used in, make the high performance structures material and the electrically insulating material of various 150-180 ℃ use, and brake material.United States Patent (USP) 5,543, the 516 a kind of solvent-free methods of describing that prepare benzoxazine colophony are to carry out in withstand voltage reactor, become ring rate 50%～70%.One-tenth ring rate than catalyzed reaction gained resin in the solvent is low.
Summary of the invention
The objective of the invention is deficiency, provide the preparation method of Yi Zhong oxazine resin, this method simple and stable at existing benzoxazine colophony technology of preparing.
The preparation method of benzoxazine colophony of the present invention comprises the steps:
(1) primary amine, phenol and Paraformaldehyde 96 are mixed, mixing temperature is lower than 40 ℃, and wherein, primary amine: the phenolic hydroxyl group in the phenol: the mol ratio of Paraformaldehyde 96 is 1: 1: 2;
(2) mixture that step (1) is obtained adds 50～130 ℃ reaction kettle for reaction in batches, every batch reaction 5～10 minutes; Or, in 60-120 minute, add the continuous reaction kettle for reaction that adds 50～130 ℃ of mixture that step (1) obtains;
(3) product that step (2) is obtained is warming up to 110～140 ℃, steams the moisture that reaction generates, discharging, and De is Dao the oxazine resin.
Described phenol is dihydroxyphenyl propane or phenol.
Preparation method's simple and stable of the present invention reacts under normal pressure, and reacting balance need not catalyzer, and by product is a water, and is pollution-free, and equipment requirements is low, and production cost is low, is easy to realize suitability for industrialized production.
Embodiment
Embodiment 1: with aniline 270 grams (3mol), and dihydroxyphenyl propane 342 grams (3.0mol phenolic hydroxyl group), Paraformaldehyde 96 180 grams (6mol) are in mixing in beaker under the room temperature.Pour 1/10 mixture in 1000 ml flasks.When the heating flask was warming up to 70 ℃, reaction was violent, and question response is steady, after about 5 minutes, adds the 2nd batch of 1/10 mixture.Successively remaining mixture is added.After raw material finishes, keep temperature of reaction at 110 ℃, reaction is 10-15 minute under the small amount of moisture reflux state.Then, remove reflux, change into and steam moisture.Steam moisture at 130 ℃.After half an hour, discharging while hot gets Yi Zhong oxazine resin in Stainless Steel Disc.Resin yield 95%, 73 ℃ of resin softening points become ring rate about 61%.
Embodiment 2: with aniline 270 grams (3mol), and dihydroxyphenyl propane 342 grams (3.0mol phenolic hydroxyl group), Paraformaldehyde 96 180 grams (6mol) are kept and are stirred down in mixing in the funnel at a night under the room temperature, put into 1/10 mixture in 1000 ml flasks.When the heating flask was warming up to 60 ℃, reaction was violent, and after 10 minutes, reaction tends to be steady.Begin to drip mixture.The control rate of addition added in one hour.Because mixture is solid and liquid mixture, must keeps in the dropping process fully stirring and keep dripping the unimpeded nothing of valve and gather materials.After raw material finishes, keep temperature of reaction at 100-110 ℃, reaction is 60 minutes under the small amount of moisture reflux state.Then, remove reflux, change into and steam moisture.Steam moisture at 110 ℃.Discharging while hot gets Yi Zhong oxazine resin in Stainless Steel Disc.Resin yield 94%, 76 ℃ of resin softening points become ring rate about 71%.
Embodiment 3: with aniline 270 grams (3mol), and phenol 282.3 grams (3mol), Paraformaldehyde 96 180 grams (6mol) are kept and are stirred down in mixing in the funnel at a night under the room temperature, put into 1/10 mixture in 1000 ml flasks.When the heating flask was warming up to 130 ℃, reaction was violent, and question response is steady, after 8 minutes, adds the 2nd batch of 1/10 mixture.Successively remaining mixture is added.After raw material finishes, keep temperature of reaction at 100-110 ℃, reaction is 10 minutes under the small amount of moisture reflux state.Then, remove reflux, change into and steam moisture.Steam moisture at 130～135 ℃.Discharging while hot gets Yi Zhong oxazine resin in Stainless Steel Disc.Resin yield 94%, 76 ℃ of resin softening points.
Embodiment 4: with benzylamine 321 grams (3mol), and dihydroxyphenyl propane 342 grams (3mol phenolic hydroxyl group), Paraformaldehyde 96 180 grams (6mol) are kept stirring in mixing in the funnel at a night under the room temperature.When the heating flask is warming up to 70 ℃, in 80 minutes, add whole mixtures continuously.After raw material finishes, keep temperature of reaction at 100-110 ℃, reaction is 15 minutes under the small amount of moisture reflux state.Then, remove reflux, change into and steam moisture.Steam moisture at 135 ℃.After half an hour, discharging while hot gets Yi Zhong oxazine resin in Stainless Steel Disc.Resin yield 94%, 56 ℃ of resin softening points.
Embodiment 5: with aniline 270 grams (3mol), and dihydroxyphenyl propane 342 grams (3mol phenolic hydroxyl group), Paraformaldehyde 96 180 grams (6mol) are kept stirring in mixing in the funnel at a night under the room temperature.When the heating flask is warming up to 50 ℃, in 60 minutes, add whole mixtures continuously.After raw material finishes, keep temperature of reaction at 140 ℃, reaction is 30 minutes under the small amount of moisture reflux state.Then, remove reflux, change into and steam moisture.Steam moisture at 140 ℃.After 1 hour, discharging while hot gets Yi Zhong oxazine resin in Stainless Steel Disc.Resin becomes ring rate about 50%.Resin yield 93%, 81 ℃ of resin softening points.
Embodiment 6: with aniline 270 grams (3mol), and dihydroxyphenyl propane 342 grams (3mol phenolic hydroxyl group), Paraformaldehyde 96 180 grams (6mol) are kept stirring in mixing in the funnel at a night under the room temperature.When the heating flask is warming up to 130 ℃, in 120 minutes, add whole mixtures continuously.After raw material finishes, keep temperature of reaction at 100-110 ℃, reaction is 30 minutes under the small amount of moisture reflux state.Then, remove reflux, change into and steam moisture.Steam moisture at 140 ℃.After 1 hour, discharging while hot gets Yi Zhong oxazine resin in Stainless Steel Disc.Resin becomes ring rate about 50%.Resin yield 93%, 81 ℃ of resin softening points.
Claims (2)
1. the preparation method of Yi Zhong oxazine resin is characterized in that, comprises the steps:
(1) primary amine, phenol and Paraformaldehyde 96 are mixed, mixing temperature is lower than 40 ℃, and wherein, primary amine: the phenolic hydroxyl group in the phenol: the mol ratio of Paraformaldehyde 96 is 1: 1: 2;
(2) mixture that step (1) is obtained adds 50～130 ℃ reaction kettle for reaction in batches, every batch reaction 5～10 minutes; Or
The continuous reaction kettle for reaction that adds 50～130 ℃ of mixture with step (1) obtains added in 60-120 minute;
(3) product that step (2) is obtained is warming up to 110～140 ℃, steams the moisture that reaction generates, discharging, and De is Dao the oxazine resin.
2. preparation method according to claim 1 is characterized in that, described phenol is dihydroxyphenyl propane or phenol.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710032522XA CN101220151B (en) | 2007-12-14 | 2007-12-14 | Production method for oxazine resin |
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| CN200710032522XA CN101220151B (en) | 2007-12-14 | 2007-12-14 | Production method for oxazine resin |
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| CN101220151A true CN101220151A (en) | 2008-07-16 |
| CN101220151B CN101220151B (en) | 2010-09-01 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101824146A (en) * | 2010-04-15 | 2010-09-08 | 华烁科技股份有限公司 | Preparation method of bisphenol A benzoxazine resin with high stability |
| CN101831073A (en) * | 2010-04-15 | 2010-09-15 | 华烁科技股份有限公司 | Method for preparing bisphenol-A phenolic benzoxazine resin |
| CN101750896B (en) * | 2008-12-16 | 2014-04-09 | 华东理工大学 | Method for preparing fluorine-containing silicon low-surface-energy material for nano-imprinting |
| CN104356084A (en) * | 2014-10-22 | 2015-02-18 | 苏州太湖电工新材料股份有限公司 | Preparation method of benzoxazine compound |
| CN109337501A (en) * | 2018-07-26 | 2019-02-15 | 福建师范大学 | The preparation method of anticorrosive paint based on benzoxazine resin |
| CN113388106A (en) * | 2021-06-17 | 2021-09-14 | 电子科技大学 | Phthalonitrile resin suitable for hot-melt presoaking and preparation method thereof |
| CN115073785A (en) * | 2022-08-11 | 2022-09-20 | 四川金象赛瑞化工股份有限公司 | Phthalonitrile resin film and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5543516A (en) * | 1994-05-18 | 1996-08-06 | Edison Polymer Innovation Corporation | Process for preparation of benzoxazine compounds in solventless systems |
| CN100580009C (en) * | 2005-12-31 | 2010-01-13 | 四川东材科技集团股份有限公司 | Preparation process of boron-containing bene oxazine resin |
-
2007
- 2007-12-14 CN CN200710032522XA patent/CN101220151B/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101750896B (en) * | 2008-12-16 | 2014-04-09 | 华东理工大学 | Method for preparing fluorine-containing silicon low-surface-energy material for nano-imprinting |
| CN101824146A (en) * | 2010-04-15 | 2010-09-08 | 华烁科技股份有限公司 | Preparation method of bisphenol A benzoxazine resin with high stability |
| CN101831073A (en) * | 2010-04-15 | 2010-09-15 | 华烁科技股份有限公司 | Method for preparing bisphenol-A phenolic benzoxazine resin |
| CN101824146B (en) * | 2010-04-15 | 2011-09-21 | 华烁科技股份有限公司 | Preparation method of bisphenol A benzoxazine resin with high stability |
| CN104356084A (en) * | 2014-10-22 | 2015-02-18 | 苏州太湖电工新材料股份有限公司 | Preparation method of benzoxazine compound |
| CN109337501A (en) * | 2018-07-26 | 2019-02-15 | 福建师范大学 | The preparation method of anticorrosive paint based on benzoxazine resin |
| CN113388106A (en) * | 2021-06-17 | 2021-09-14 | 电子科技大学 | Phthalonitrile resin suitable for hot-melt presoaking and preparation method thereof |
| CN115073785A (en) * | 2022-08-11 | 2022-09-20 | 四川金象赛瑞化工股份有限公司 | Phthalonitrile resin film and preparation method thereof |
| CN115073785B (en) * | 2022-08-11 | 2023-10-03 | 四川金象赛瑞化工股份有限公司 | Phthalonitrile resin film and preparation method thereof |
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| CN101220151B (en) | 2010-09-01 |
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