CN1139104A - Granular polybenzoxazine intermediate and its preparation - Google Patents
Granular polybenzoxazine intermediate and its preparation Download PDFInfo
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- CN1139104A CN1139104A CN 95111413 CN95111413A CN1139104A CN 1139104 A CN1139104 A CN 1139104A CN 95111413 CN95111413 CN 95111413 CN 95111413 A CN95111413 A CN 95111413A CN 1139104 A CN1139104 A CN 1139104A
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- polybenzoxazine
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Abstract
Polyphenol, monoamine and formalin react to syntheseze polybenzooxazine intermediate and through pelletizing with high-speed stirring by using water as dispersing medium and suspending agent, cooling, washing, filtration and drying, granular polybenzooxazine intermediate is obtained. The said intermediate has a free phenol and amine content lower than 2% and a melting temp lower than 100 deg.C and it may be used directly in producing various structural, insulating and braking material used at 150-180 deg.C.
Description
The present invention relates to a kind of polybenzoxazine (1-Evil-3-azoles tetraline) intermediate and preparation method thereof, this method, is disperseed under high-speed stirring and suspension agent effect as dispersion medium with water, granulation, makes the polybenzoxazine intermediate.Contain two above benzoxazine ring texturees in each molecule of intermediate, its melt temperature is lower than 100 ℃, makes the high-performance pnenolic aldehyde plastics through ring-opening polymerization.
The forties, abroad to phenolic compound, aminated compounds and formaldehyde reaction have carried out systematic research, have synthesized to contain benzoxazine (Benzoxazine) ring compound.
R=hydrogen, halogen atom, alkyl, alkoxyl group etc.
R ＇=aliphatics or aromatic group
Compare with the condensation reaction of other relevant phenolic aldehyde, an outstanding feature of this reaction is that phenolic hydroxyl group has been participated in ring-closure reaction.
Since the seventies, the ring-opening polymerization research with regard to benzoxazine abroad obtains preliminary progress, applies for a patent several pieces.The present inventor has applied for " ring-opening polymerization resol and fibre reinforced composites " number of patent application 94111852.5 in Patent Office of the People's Republic of China, synthetic and the ring-opening polymerization of having summarized benzoxazine compound prepares the domestic and international research situation of novel phenoplast, this matrix material has good forming process, physical and mechanical properties is good, be suitable for high-temperature-resistant structure material and the electrically insulating material of making 150～180 ℃ of life-time service, but this benzoxazine compound is through the solution method synthetic in organic solvent, what obtain is resin solution or heavy-gravity arborescens product, the cost height, the complete processing complexity has hindered the suitability for industrialized production and the application of benzoxazine compound.
The objective of the invention is provides a kind of granular polybenzoxazine intermediate and preparation method thereof at the deficiencies in the prior art, this method is by the synthetic polybenzoxazine intermediate of polyphenol, monoamine and formaldehyde reaction, and with water dispersion medium, granulation under high-speed stirring and the suspension agent effect, through cooling, washing, filtration, drying, obtain granular benzoxazine intermediate.This method reacting balance, cyclisation rate height, yield height, environmental pollution is little, and production cost is low, is easy to realize the industrialization continuous production, gained partical free phenol or unhindered amina content≤2%, melt temperature are lower than 100 ℃, can be directly used in to make various high performance phenoplast goods.
Granular polybenzoxazine intermediate of the present invention and preparation method thereof, the recipe ingredient of starting raw material (by weight) is:
Polyphenol compound (available dihydroxyphenyl propane, Bisphenol F, bisphenol S, '-biphenyl diphenol, dihydroxy diphenyl ether, Resorcinol, Resorcinol, adjacent diallyl bisphenol, three (p-hydroxybenzene) methane or the high contraposition lacquer resins of lower molecular weight) 40-70 part monoamine compound (available aniline, benzylamine, methylamine or ethamine)
30-60 part formalin (30-40%) 45-100 part
Suspension agent (available gelatin, polyvinyl alcohol, polyacrylic acid sodium salt, methylcellulose gum, Natvosol or styrene maleic anhydride copolymer sodium salt)
0.1-1 part
The building-up reactions of benzoxazine intermediate:
2H
2N－R＇＋4CH
2O
0-50℃↓H
2O
By above-mentioned prescription weighing, in reactor, add formalin and monoamine, behind the stirring reaction, add dihydric phenolic compounds, in 80-95 ℃ of backflow 1-5 hour, generate the bi-benzoxazine intermediate.
Perhaps
By above-mentioned prescription weighing, in reactor, add phenol, formalin, regulate PH=1～2 with acid (hydrochloric acid, oxalic acid, sulfuric acid or phosphoric acid), in 80-95 ℃ of back flow reaction 1～3 hour, obtain the high contraposition lacquer resins of lower molecular weight, be cooled to below 50 ℃ standby.The molar ratio of phenol and formaldehyde is 1: 0.6～0.92, can obtain number-average molecular weight at 400～2400 prepolymer.Use alkali (sodium hydroxide, ammoniacal liquor, potassium hydroxide or hydrated barta) to regulate PH=7～8 then, add unary primary amine and formalin by the prescription weighing, in 80-95 ℃ of back flow reaction 1-5 hour, obtain the polybenzoxazine intermediate, the molar ratio of monoamine and formaldehyde is 1: 2, the mol ratio of phenol nuclear can be 0.7～1.0 in monoamine and the high contraposition lacquer resins: change between 1.0, thereby guarantee that closed loop is complete, and the content of benzoxazine ring texture in the control product.
The suspension agent of above-mentioned two kinds of reactions all can add in initial reaction stage or reaction later stage, and dispersion, granulation through cooling, washing, filtration, drying, obtain granular Ben Bing oxazine intermediate under high-speed stirring.The particle diameter of intermediate is by the control of suspension agent consumption, and general suspension agent consumption is the 0.1-1% of the water yield in the system.This granular benzoxazine intermediate is dissolved in organic solvents such as trichloromethane, tetrahydrofuran (THF), toluene, acetone, ethylene glycol monomethyl ether, butanone, N-Methyl pyrrolidone, dimethyl formamide, dioxane, melt temperature or softening temperature are between 50-100 ℃, and be different and different with the structure of polyphenol and monoamine.The free phenol of this granular benzoxazine intermediate and unhindered amina content≤2%, can use separately, also can or contain compound bearing active hydrogen (as phenolic compound, aminated compounds etc.) and mix use, also can add six methynes, four ammonia, mineral acid (as sulfuric acid, hydrochloric acid, phosphoric acid etc.), organic acid (as oxalic acid, tosic acid etc.) and Lewis acid (as FeCl with lower molecular weight solid resins such as lacquer resinss
3, AlCl
3, SnCl
2, ZnCl
2, CuCl
2, FeCl
2, BF
3) wait solidifying agent or catalyzer ring-opening polymerization in 140-200 ℃ of temperature range, the phenoplast of preparation low porosity, the second-order transition temperature of cured resin is about 200 ℃, and elongation at break is about 2%.In addition, this granular intermediate also can directly mix with mineral fillers such as asbestos, short glass fiber, mica powder, wood powder, silicon-dioxide, aluminium sesquioxides, makes various high performance structures materials, electrically insulating material or various types of brake material.
The present invention has following advantage:
1, adopt suspension method can directly make the granular polybenzoxazine intermediate, reacting balance, cyclisation rate height, the yield height, free phenol or unhindered amina content≤2%, easy to operate, be easy to realize the industrialization continuous production.
2, the synthetic granular polybenzoxazine intermediate of suspension method is as dispersion medium, solvent-free with water, has reduced production cost, has avoided the environmental pollution that brings because of solvent.
3, granular benzoxazine intermediate can use separately, also can mix with other low-molecular-weight resin powder or directly mix with mineral filler and make various phenoplast goods.
4, the melt temperature of granular benzoxazine intermediate or softening temperature are 50-100 ℃, and the ring-opening polymerization temperature is 140-200 ℃, is easy to forming process.
5, the plastics porosity that is made by granular benzoxazine intermediate is low, and excellent property is suitable for resistant to elevated temperatures structured material and the electrically insulating material of making 150-180 ℃ of life-time service, and the high-performance brake material.
Embodiment
1, in the 250ml three-necked bottle, add the 25mlNaOH aqueous solution (pH11), add 4.65g (0.05mole) aniline under the room temperature, 7.6ml (0.1mole) formalin (37%), reaction is after 1 hour under stirring, the room temperature, add 5.79g (0.025mole) dihydroxyphenyl propane, be heated to 90 ℃ and refluxed 5 hours.Then the 0.7g polyvinyl alcohol is dissolved in the 50ml water, pours in the reaction system of high-speed stirring and disperse granulation, naturally cooling, washing, filtration, dry below 50 ℃, faint yellow particulate 11.5g, yield 94%, 69 ℃ of softening temperatures,
1It is 85% that H-NMR detects the cyclisation rate.
2, in the 250ml three-necked bottle, add 9.39g (0.01mole) aniline, 17g (0.2mole) formalin (37%) and 20ml water after stirring at room 3-5 minute, add 5.5g (0.05mole) Resorcinol, and 90 ℃ were refluxed 5 hours.Under high-speed stirring, add the aqueous solution 100ml that is dissolved with gelatin 1g, disperse granulation, cooling, washing, filtration drying, get light yellow particulate 14g, yield 74%, 87 ℃ of softening temperatures.
3, in the 250ml three-necked bottle, add benzylamine 10.7g (0.1mole), 37% formalin 17g (0.2mol), water 50ml, stirring at room 5 minutes adds dihydroxyphenyl propane 11.4g (0.05mole), is warming up to 90 ℃ and refluxes 5 hours, add the aqueous solution 70ml that is dissolved with gelatin 1g under the high-speed stirring, disperse granulation, get faint yellow particulate 24g, yield 86%, 79 ℃ of softening temperatures, cyclisation rate 67%.
4, in the 500ml three-necked bottle, add 18.6g (0.2mole) aniline, 35g (0.4mole) formalin (37%), 100ml water stirred 3 minutes, added the adjacent diallyl bisphenol of 30.8g (0.1mole), and 90 ℃ were refluxed 5 hours.Add the 100ml water that is dissolved with the 3g gelatin then, disperse granulation, get light brown partical 47g, yield 87%, cyclisation rate 90%.
5, in the 500ml three-necked bottle, add phenol 47g (0.5mole), 37% formalin 34g (0.4mole), transfer PH＜2 with HCl, temperature rising reflux, the system for the treatment of is cooled to below 50 ℃ after muddy 0.5 hour, be neutralized to neutrality with NaOH, add aniline 46.5g (0.5mole), 37% formalin 83g (1.0mole) then, 90 ℃ of backflows added the aqueous solution 100ml that is dissolved with gelatin 3g after 5 hours under the high-speed stirring, disperse granulation, get yellow fine product 102g, yield 91%, 51 ℃ of softening temperatures.
6, in the 500ml three-necked bottle, add phenol 47g (0.5mole), 37% formaldehyde and solution 38.3g (0.46mole), all the other operation stepss are with example 4, and all the other charging capacitys are aniline 37.2g (0.4mole), 37% formalin 67g (0.8mole).At last yellow partical 91g, yield 92%, 84 ℃ of softening temperatures.
7, by the granular intermediate of embodiment 1 gained, solidified 3 hours at 120 ℃ behind the heating and melting, 140 ℃ solidified 2 hours, 160 ℃ solidified 3 hours, and 180 ℃ solidified 3 hours, and 200 ℃ solidified 2 hours, obtain the reddish-brown transparent sample, tensile strength is 34MPa under the room temperature, elongation at break 1.95%, 190 ℃ of second-order transition temperatures.
8, by 70 parts in the granular intermediate of embodiment 1 gained, 30 parts of lacquer resinss, 3 parts of hexamethylenetetramines, 1.5 parts of Zinic stearass, 400 parts in asbestos, after the mixing, in 160 ℃ of mold pressings moulding in 1 hour, then in 140 ℃-2h, 160 ℃-1h, 180 ℃-2h thermal treatment.The pressing shock strength is 3.85dJ/cm
2, Brinell hardness is 56.2.By same recipe, the shock strength of the pressing that is made by lacquer resins is 3.34dJ/cm
2, Brinell hardness is 55.3.
9,, made automobile brake sheet in 10 minutes then in 150-160 ℃ of thermal treatment 24 hours 160 ℃ of mold pressings by 30 parts of fillers such as 12 parts in the granular intermediate of embodiment 6 gained, 6 parts of linear phenolic resins, 1 part of hexamethylenetetramine, 2 parts in styrene-butadiene rubber(SBR), 2 parts on copper wire, frictional property regulators, after roller refines, pulverizes, sieves, mix for 45 parts with asbestos.The frictional coefficient of 100 ℃, 150 ℃, 200 ℃, 250 ℃ of this automobile brake sheet temperature-rise periods and 300 ℃ is 0.42,0.45,0.46,0.46,0.42; The frictional coefficient of 250 ℃, 200 ℃, 250 ℃ of temperature-fall periods and 100 ℃ is 0.41,0.42,0.42,0.42.Notched Izod impact strength 3.47dJ/cm
2, Rockwell hardness (HRL) 73.
Claims (7)
1, a kind of granular polybenzoxazine intermediate is characterized in that the starting raw material recipe ingredient (by weight) of this granular polybenzoxazine intermediate is:
Polyhydric phenols 40-70 part
Monoamine compound 30-60 part
Formalin 30-40% 45-100 part
Suspension agent is the 0.1-1% of the water yield in the system
2, according to the described granular polybenzoxazine intermediate of claim 1, the polyhydric phenols that it is characterized in that this granular polybenzoxazine intermediate is dihydroxyphenyl propane, Bisphenol F, bisphenol S, '-biphenyl diphenol, dihydroxy diphenyl ether, Resorcinol, Resorcinol, adjacent diallyl bisphenol, three (p-hydroxybenzene) methane or the high contraposition lacquer resins of lower molecular weight.
3, according to claim 1 or 2 described granular polybenzoxazine intermediates, the monoamine compound that it is characterized in that this granular polybenzoxazine intermediate is aniline, benzylamine, methylamine or ethamine.
4, according to the described granular polybenzoxazine intermediate of claim 1, it is characterized in that this granular many benzimidazole dihydrochlorides intermediary suspension agent is a gelatin, the salt of polyvinyl alcohol, polyacrylic acid sodium salt, methylcellulose gum, hydroxy ethyl fiber or styrene maleic anhydride copolymer etc.
5, according to the described granular polybenzoxazine intermediates preparation of claim 1, it is characterized in that:
The building-up reactions of benzoxazine intermediate
2H
2N-R＇＋4CH
2O
0-50 ℃ ↓ H
2O
Perhaps
By above-mentioned prescription weighing, in reactor, add formalin and monoamine, behind the stirring reaction, add dihydric phenolic compounds, in 80-95 ℃ of backflow 1-5 hour, generate the bi-benzoxazine intermediate.Perhaps by above-mentioned prescription weighing, in reactor, add phenol, formalin, the molar ratio of phenol and formaldehyde is 1: 0.6～0.92, regulate PH=1～2 with acid, in 80～95 ℃ of back flow reaction 1-3 hours, obtain number-average molecular weight at 400～2400 high contraposition lacquer resins, be cooled to below 50 ℃ standby.Regulate PH=7～8 with alkali then, add unary primary amine and formalin by the prescription weighing, in 80～95 ℃ of back flow reaction 1-5 hours, obtain the polybenzoxazine intermediate, the molar ratio of monoamine and formaldehyde is 1: 2, the mol ratio of phenol nuclear can be 0.7～1.0 in monoamine and the high contraposition lacquer resins: change between 1.0, suspension agent all can add in initial reaction stage or reaction later stage, under high-speed stirring, disperse, granulation, through cooling, washing, filtration, drying, obtain the granular polybenzoxazine intermediate.
6, according to the purposes of the described granular polybenzoxazine intermediate of claim 1, it is characterized in that the ring-opening polymerization and using separately in the presence of solidifying agent or catalyzer of this intermediate, perhaps, make the high performance structures material, electrically insulating material or the brake material that use more than 155 ℃ with asbestos, short glass fiber, mica powder, wood powder, aluminium sesquioxide, silicon-dioxide, sepiolite and wollastonite mineral filler and blending in of fibers.
7,, it is characterized in that this intermediate ring-opening polymerization is to contain active nitrogen compound, hexamethylenetetramine, mineral acid, organic acid or Lewis acid with solidifying agent or catalyzer according to the described granular how stupid and oxazine intermediate of claim 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95111413A CN1059909C (en) | 1995-06-23 | 1995-06-23 | Granular polybenzoxazine intermediate and its preparation |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95111413A CN1059909C (en) | 1995-06-23 | 1995-06-23 | Granular polybenzoxazine intermediate and its preparation |
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| Publication Number | Publication Date |
|---|---|
| CN1139104A true CN1139104A (en) | 1997-01-01 |
| CN1059909C CN1059909C (en) | 2000-12-27 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95111413A Expired - Fee Related CN1059909C (en) | 1995-06-23 | 1995-06-23 | Granular polybenzoxazine intermediate and its preparation |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1088727C (en) * | 1996-02-09 | 2002-08-07 | 日立化成工业株式会社 | Thermosetting resin composition, solidifying material, preformed material metal armoured laminated plate and circuit board |
| CN101830861A (en) * | 2010-04-15 | 2010-09-15 | 华烁科技股份有限公司 | Preparation method of diphenyl ether supported benzoxazinyl resin |
| CN102532540A (en) * | 2012-01-16 | 2012-07-04 | 四川大学 | Benzoxazine intermediate containing sulfonyl polyphenol and preparation method and use thereof |
| CN103058948A (en) * | 2012-12-17 | 2013-04-24 | 中科院广州化学有限公司 | Benzoxazine resin containing Schiff base structure benzoxazine monomer and preparation thereof |
| 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 |
| CN104356932A (en) * | 2014-10-22 | 2015-02-18 | 苏州太湖电工新材料股份有限公司 | Solvent-free benzoxazine impregnating varnish and preparation method thereof |
| CN104356083A (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 |
| CN104781308A (en) * | 2012-09-28 | 2015-07-15 | 3M创新有限公司 | Polybenzoxazine composition |
| CN107778427A (en) * | 2017-11-17 | 2018-03-09 | 常州市宏发纵横新材料科技股份有限公司 | A kind of benzoxazine colophony containing cyanate group and preparation method thereof |
| CN108359069A (en) * | 2018-03-27 | 2018-08-03 | 四川理工学院 | A kind of method of chain extension modifying benzoxazine resin in maleimide |
| CN110665540A (en) * | 2019-09-30 | 2020-01-10 | 河北科技大学 | Solid acid and preparation method and application thereof |
| CN111073212A (en) * | 2019-12-20 | 2020-04-28 | 上海电动工具研究所（集团）有限公司 | Preparation method of benzoxazine-based commutator rubber powder material without formaldehyde volatilization |
| CN114478426A (en) * | 2022-01-21 | 2022-05-13 | 中北大学 | Norbornene-type benzoxazine-containing monomer and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4501864A (en) * | 1983-12-22 | 1985-02-26 | Monsanto Company | Polymerizable compositions comprising polyamines and poly(dihydrobenzoxazines) |
| US4557979A (en) * | 1984-02-17 | 1985-12-10 | Monsanto Company | Process for deposition of resin dispersions on metal substrates |
| US4507428A (en) * | 1984-02-17 | 1985-03-26 | Monsanto Company | Aqueous dispersions of polyamines and poly(dihydrobenzoxazines) |
-
1995
- 1995-06-23 CN CN95111413A patent/CN1059909C/en not_active Expired - Fee Related
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1088727C (en) * | 1996-02-09 | 2002-08-07 | 日立化成工业株式会社 | Thermosetting resin composition, solidifying material, preformed material metal armoured laminated plate and circuit board |
| CN101830861A (en) * | 2010-04-15 | 2010-09-15 | 华烁科技股份有限公司 | Preparation method of diphenyl ether supported benzoxazinyl resin |
| CN102532540A (en) * | 2012-01-16 | 2012-07-04 | 四川大学 | Benzoxazine intermediate containing sulfonyl polyphenol and preparation method and use thereof |
| CN102532540B (en) * | 2012-01-16 | 2013-12-04 | 四川大学 | Benzoxazine intermediate containing sulfonyl polyphenol and preparation method and use thereof |
| CN104781308B (en) * | 2012-09-28 | 2016-12-21 | 3M创新有限公司 | Polyphenyl * piperazine compositions |
| CN104781308A (en) * | 2012-09-28 | 2015-07-15 | 3M创新有限公司 | Polybenzoxazine composition |
| CN103058948B (en) * | 2012-12-17 | 2015-04-22 | 中科院广州化学有限公司 | Benzoxazine monomer containing Schiff base structure, benzoxazine resin and preparation thereof |
| CN103058948A (en) * | 2012-12-17 | 2013-04-24 | 中科院广州化学有限公司 | Benzoxazine resin containing Schiff base structure benzoxazine monomer and preparation thereof |
| CN104356083A (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 |
| CN104356932A (en) * | 2014-10-22 | 2015-02-18 | 苏州太湖电工新材料股份有限公司 | Solvent-free benzoxazine impregnating varnish and preparation method thereof |
| 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 |
| CN107778427A (en) * | 2017-11-17 | 2018-03-09 | 常州市宏发纵横新材料科技股份有限公司 | A kind of benzoxazine colophony containing cyanate group and preparation method thereof |
| CN108359069A (en) * | 2018-03-27 | 2018-08-03 | 四川理工学院 | A kind of method of chain extension modifying benzoxazine resin in maleimide |
| CN108359069B (en) * | 2018-03-27 | 2020-05-19 | 四川理工学院 | Method for modifying benzoxazine resin through maleimide internal chain extension |
| CN110665540A (en) * | 2019-09-30 | 2020-01-10 | 河北科技大学 | Solid acid and preparation method and application thereof |
| CN111073212A (en) * | 2019-12-20 | 2020-04-28 | 上海电动工具研究所（集团）有限公司 | Preparation method of benzoxazine-based commutator rubber powder material without formaldehyde volatilization |
| CN111073212B (en) * | 2019-12-20 | 2022-09-16 | 上海电动工具研究所（集团）有限公司 | Preparation method of benzoxazine-based commutator rubber powder material without formaldehyde volatilization |
| CN114478426A (en) * | 2022-01-21 | 2022-05-13 | 中北大学 | Norbornene-type benzoxazine-containing monomer and preparation method thereof |
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