CN100580009C - Preparation process of boron-containing bene oxazine resin - Google Patents
Preparation process of boron-containing bene oxazine resin Download PDFInfo
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- CN100580009C CN100580009C CN200510138202A CN200510138202A CN100580009C CN 100580009 C CN100580009 C CN 100580009C CN 200510138202 A CN200510138202 A CN 200510138202A CN 200510138202 A CN200510138202 A CN 200510138202A CN 100580009 C CN100580009 C CN 100580009C
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Abstract
The process of preparing boron-containing benzoxazine resin includes the following steps: 1. preparing materials including boric acid 20-70 weight portions, phenolic compound 80-240 weight portions, amine compound 40-120 weight portions, water solution of formaldehyde 160-360 weight portions, acid catalyst 1-4 weight portions and alkaline catalyst 4-8 weight portions; and 2. reaction of boric acid, phenolic compound and acid catalyst in a reactor, and heated reflux dewatering to obtain borate; heating to 50 deg.c, adding partial formaldehyde to synthesize boron-containing linear phenolic resin; adding alkaline catalyst to regulate pH to 6-9, adding amine compound and the rest formaldehyde to reflux react at 85-95 deg.c for 2-8 hr, and vacuum dewatering or reflux dewatering at 80-140 deg.c to obtain the boron-containing benzoxazine resin. The resin is used in producing electrically insulating material and product in high flame retarding level.
Description
Technical field
The invention belongs to the synthetic field of thermosetting resin, relate to a kind of boron-containing bene oxazine resin and its production and use.
Background technology
The forties in 20th century, abroad to phenolic compound, aminated compounds and formaldehyde reaction have carried out systematic research, have synthesized the compound that contains benzoxazine (Benzoxazine) ring texture.Compare with the condensation reaction of other relevant phenolic aldehyde, the outstanding feature of this reaction is that phenolic hydroxyl group has been participated in ring-closure reaction.
R=hydrogen, halogen atom, alkyl, alkoxyl group etc.
R '=aliphatics or aromatic group
Since the seventies in 20th century, carried out preliminary study with regard to the ring-opening polymerization and the goods exploitation of benzoxazine abroad.After the nineties, both at home and abroad carried out extensive studies, applied for a patent tens of pieces at synthetic, the ring-opening polymerization and the aspects such as structure and property relationship of benzoxazine resin.But synthesizing of benzoxazine resin generally adopted common phenols at present, aminated compounds and formaldehyde reaction make (as CN1451679A, CN1379779A, CN1496378A etc.), or adopt plant oil modified phenol-formaldehyde resin to prepare benzoxazine resin (as CN1259530A) and employing N-allylic cpd or aryne compound benzoxazine resin methods such as (as CN1472205A), the benzoxazine resin and the matrix material of above-mentioned synthetic method preparation have good preparation and forming process, physical and mechanical properties is good, is suitable for high-temperature-resistant structure material and the electrically insulating material of making 150～180 ℃ of life-time service.
Boron bakelite resin is the important development direction of resol high performance, the boron urea formaldehyde is a kind of novel performance resins of boron of having induced one in the resol molecule, it also has high tenacity, wear resistance is good, heat decomposition temperature is high characteristics such as (can reach 438 ℃) except having general resol excellent acid, alkaline resistance properties.But because there is the solidification value height in simple boron modification urea formaldehyde, solvability is relatively poor in ordinary organic solvents, adopt hexamethylenetetramine or other amine substances as curing catalysts, still have a large amount of small molecules to emit during curing, defectives such as the goods voidage is bigger, cause problems such as its moulding process is relatively poor, unstable properties thus, thereby limited its development.
Summary of the invention
Purpose of the present invention is intended to overcome deficiency of the prior art, and a kind of boron-containing bene oxazine resin and preparation method thereof is provided.The present invention introduces the synthetic boron-containing bene oxazine resin of benzoxazine structure with the inorganic rigid element boron, this resin has kept outside the characteristics such as boron modification urea formaldehyde inherent thermostability, high tenacity, and having the characteristics of the ring-opening polymerization that benzoxazine colophony has concurrently, resin free phenol content is low, do not have when solidifying that small molecules is emitted, the goods voidage is low, the hot physical strength height of goods, excellent mechanical property, electric property and halogen-free flameproof performance are arranged.
The content that realizes the object of the invention is: a kind of boron-containing bene oxazine resin is characterized in that: as the starting raw material of synthesis modification benzoxazine resin, it has following constitutional features to adopt boron-containing compound (boric acid or boric acid phenol fat):
Boron-containing bene oxazine resin of the present invention can satisfy the requirement of different use occasions, use temperature according to different needs by the kind that changes phenols, aldehydes and aralkyl compound.Synthetic boron-containing bene oxazine resin free phenol content of the present invention is low, and the melt temperature of resin or softening temperature are 80 ℃～120 ℃.Adopt resin of the present invention to have stable electrical insulation properties and higher mechanicalness and halogen-free flame-retardance as the glass fibre laminated and pressing of matrix resin (tackiness agent) preparation.Also have high tenacity, low characteristics of being fuming simultaneously.Hot (180 ℃) flexural strength that the raising of mechanical property is mainly reflected in boron-containing bene oxazine resin glass fabric layer, pressing can reach more than the 400Mpa,, (200 ℃) flexural strength can reach more than the 300Mpa.Notched Izod impact strength reaches 100kJ/m
2More than.The heat-proof aging index can reach more than 180 grades.
Another content of the present invention is: a kind of preparation method of boron-containing bene oxazine resin is characterized in that comprising the following steps:
(1) batching: adopt the starting raw material component and the weight proportion of the synthetic benzoxazine resin of boron-containing compound to be:
20～70 parts of boric acid
80～240 parts of phenolic compounds
Aminated compounds 40-120 part
The formaldehyde weight percentage is 160～360 parts of the formalins of 30-40%
1～4 part of an acidic catalyst
4～8 parts of basic catalysts.
(2) technological process: (1) described proportioning set by step, boric acid, phenolic compound and an acidic catalyst added have in the reactor of agitator, reflux exchanger and thermometer, preliminary temperature rising reflux dehydration makes boric acid fat; Cool to below 50 ℃, add the part formalin, synthetic boracic linear phenolic resin under acidic conditions; Add basic catalyst and regulate PH=6～9, adding aminated compounds, remaining formalin after 2～4 hours, promptly make boron-containing bene oxazine resin in 80～140 ℃ of vacuum hydro-extractions or reflux dewatering in 85～95 ℃ of back flow reaction of temperature; The adding solvent obtains the solution of boron-containing bene oxazine resin.
Another content of the present invention can also be: a kind of preparation method of boron-containing bene oxazine resin is characterized in that comprising the following steps:
(1) batching: adopt the starting raw material component and the weight proportion of the synthetic benzoxazine resin of boron-containing compound to be:
80～240 parts of boric acid phenol fat compounds
Aminated compounds 40-120 part
The formaldehyde weight percentage is 160～360 parts of the formalins of 30-40%
4～8 parts of basic catalysts
(2) technological process: (1) described proportioning set by step, boric acid phenol fat compound and formalin adding are had in the reactor of agitator, reflux exchanger and thermometer, regulate PH=7～11 with basic catalyst, the molar ratio of boric acid phenol fat compound and formaldehyde is 1: 1.2～2.7 preferably, adding solvent, adding aminated compounds after 1～6 hour, promptly make boron-containing bene oxazine resin in 80～140 ℃ of vacuum hydro-extractions in 75～105 ℃ of back flow reaction of temperature; The adding solvent obtains the solution of boron-containing bene oxazine resin.
Another content of the present invention can also be: a kind of preparation method of boron-containing bene oxazine resin is characterized in that comprising the following steps:
(1) batching: adopt the starting raw material component and the weight proportion of the synthetic benzoxazine resin of boron-containing compound to be:
20～70 parts of boric acid
80～240 parts of phenolic compounds
Aminated compounds 40-120 part
The formaldehyde weight percentage is 160～360 parts of the formalins of 30-40%
4～8 parts of basic catalysts
(2) technological process: (1) described proportioning set by step, boric acid, phenolic compound are added and have in the reactor of agitator, reflux exchanger and thermometer, the dehydration that heats up makes boric acid fat; Cool to below 50 ℃, add formalin, the molar ratio of phenolic compound and formaldehyde is 1: 0.9～2.2 preferably, regulate PH=6～9 with basic catalyst, add aminated compounds and after 2～8 hours, promptly make boron-containing bene oxazine resin in 80～140 ℃ of vacuum hydro-extractions or reflux dewatering in 85～95 ℃ of back flow reaction of temperature; The adding solvent obtains the solution of boron-containing bene oxazine resin.
In the foregoing of the present invention: described phenolic compound is at least a in phenol, xylenol, p-cresol, p-tert-butylphenol, meta-cresol, para-chlorophenol, p-NP, 4-hydroxybenzonitrile, dihydroxyphenyl propane, bisphenol S, Resorcinol, the boric acid phenol fat compound (as boric acid triphen fat, boric acid hexichol fat, boric acid benzene fat, boric acid cresols fat etc.).
In the foregoing of the present invention: described aminated compounds is 4 in what aromatic diamine such as the quadrol, butanediamine, hexanediamine, decamethylene diamine in methylamine, aniline, ammonia, urea and the aliphatic diamine, 4 ' diaminodiphenylmethane (MDA), 4,4 ' diaminodiphenylsulfone(DDS), 4,4 ' diaminodiphenyl oxide etc., and at least a in the diamine compound that contains aralkyl structure of structure such as figure below.
n＝1～3 m＝1～3
R=-O-,-OC
2H
5,-OCH
3,-CH
3Deng
In the foregoing of the present invention: described basic catalyst is sodium hydroxide, ammoniacal liquor, urotropine, potassium hydroxide and other metal oxides, oxyhydroxide.
In the foregoing of the present invention: described an acidic catalyst is organic or inorganic acid and acid anhydrides such as hydrochloric acid, tosic acid, sulfuric acid, nitric acid, Witco 1298 Soft Acid, sulfovinic acid, mahogany acid, oxalic acid, hydrochloric acid, phosphoric acid, boric acid, acetic acid, sulfonic acid, tosic acid, acetic anhydride, phenylformic acid, toxilic acid, cis-butenedioic anhydride.
In the foregoing of the present invention: described solvent is that toluene, alcohol, acetone, butanone are or/and methane amide.
Boron-containing bene oxazine resin of the present invention as matrix resin (tackiness agent) be used to prepare have stable electrical insulation properties and higher mechanical properties and halogen-free flameproof, lowly be fuming, high performance structures material, electrically insulating material or the second-order transition temperature (Tg) used more than 180 ℃ of high tenacity be at the glass fabric layer more than 175 ℃, moulding material.
The solidifying agent of resin system of the present invention can be one or more in Witco 1298 Soft Acid, mahogany acid, oxalic acid, the glyoxaline compound.
The described aldehydes of content of the present invention is meant formaldehyde.
The described aralkyl compound of content of the present invention is at least a in aralkyl phenols (as methoxyl group parylene monomer and oligopolymer, xylene formaldehyde resin etc.), the aralkyl ethers (methoxyl group phenyl ether monomer and oligopolymer thereof, diphenyl ether).
Compared with prior art, the present invention has following characteristics:
(1) preparation method of employing boron-containing compound synthesizing new boron-containing bene oxazine resin involved in the present invention combines the characteristics that contain boron bakelite resin inherent thermostability, high tenacity, low smokiness, and has the characteristics of the ring-opening polymerization that benzoxazine colophony has concurrently;
(2) preparation process of boron-containing bene oxazine resin of the present invention is simple, raw material is inexpensive, wide material sources, free phenol content is low, do not have when solidifying that small molecules is emitted, the goods voidage is low, simultaneously owing to contain nitrogen, the boron atom with flame retardant resistance in the system, makes goods have the characteristic of halogen-free flameproof, low cigarette.Have very strong actual use value and Application Prospect;
(3) building-up reactions of boron-containing bene oxazine resin of the present invention is steady, and is easy to operate, is easy to realize the industrialization continuous production;
(4) boron-containing bene oxazine resin of the present invention has high reaction activity and high, can also can make halogen-free flame-retardant resin using curing molding under the heating condition separately according to the thermosetting resin blend such as benzoxazine resin of different purposes and Resins, epoxy, resol, bimaleimide resin and other types;
(5) melt temperature of boron-containing bene oxazine resin of the present invention or softening temperature are 90 ℃～120 ℃, the ring-opening polymerization temperature is 140 ℃～200 ℃, virgin resin (about 120 ℃) melt viscosity under mesophilic condition is little, molding time changes slow, helps casting, RTM or other forming process mode machine-shaping;
(6) product properties of boron-containing bene oxazine resin of the present invention is good, can be used for preparing the high-temperature-resistant structure material and the electrically insulating material of 180 grades or above life-time service, and high Tg copper coated foil plate and multilayer line plate substrate;
(7) practical function of boron-containing bene oxazine resin of the present invention is:
The one, improved the complete processing of follow-up goods.Boron-containing bene oxazine resin of the present invention can be according to different needs, satisfy the requirement of different use occasions, use temperature by the kind that changes phenols, aldehydes and aralkyl compound, can make the woven fiber glass of production or glass fibre laminated and pressing have stable electrical insulation properties and higher mechanical properties and halogen-free flame-retardance.Hot (180 ℃) flexural strength that the raising of mechanical property is mainly reflected in boron-containing bene oxazine resin glass fabric layer, pressing can reach more than the 400Mpa, and (200 ℃) flexural strength can reach more than the 300Mpa.Notched Izod impact strength reaches 100kJ/m
2More than.
The 2nd, the heat aging property of the follow-up goods of raising.The heat-proof aging index of existing benzoxazine resin only can reach 155 or 180 grades, and boron-containing bene oxazine resin heat-proof aging index of the present invention can reach more than 180 grades.
The 3rd, realized low being fuming, halogen-free flameproof.The boron-containing bene oxazine resin amount of being fuming is starkly lower than common benzoxazine resin.The virgin resin oxygen index is higher than common benzoxazine resin more than 3%.
The 4th, improved the second-order transition temperature (Tg) of glass colth laminate, adopt its second-order transition temperature of copper coated foil plate of boron-containing bene oxazine resin preparation can reach 175 ℃～180 ℃, this point is even more important for the unleaded of electronic material and multilayer circuit board electronic circuit densification.
Embodiment
Below by embodiment the present invention is specifically described; be necessary to be pointed out that at this following examples only are used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, the person skilled in art can make some nonessential improvement and adjustment according to the present invention.
Embodiment 1: 20 parts of boric acid, 80 parts of phenol are added in the reactor, heat temperature raising (being no more than 160 ℃) dewaters, cooling cooling when the water of deviating from reaches a certain amount of, add 160 parts of formalins then, be 6～10, add toluene with the pH value of basic catalyst regulation system, quadrol carries out the temperature rising reflux reaction after 2 hours for 40 parts, promptly make boron-containing bene oxazine resin in 80～140 ℃ of vacuum hydro-extractions, add solvent, obtain even clear palm fibre xanchromatic boron-containing bene oxazine resin stabilizing solution.It is 5～18min/160 ℃ that this resin solution can add promotor adjusting molding time according to the difference of use.
Embodiment 2: 70 parts of boric acid, 240 parts of phenol are added reactor, heat temperature raising (being no more than 160 ℃) dewaters, cooling cooling when the water of deviating from reaches a certain amount of, add 360 parts of formalins then, be 6～10, add toluene with the pH value of basic catalyst regulation system, 4,4 ' diaminodiphenylmethane (MDA) is carried out the temperature rising reflux reaction after 4 hours for 120 parts, promptly make boron-containing bene oxazine resin in 80～140 ℃ of vacuum hydro-extractions, add solvent, obtain even clear palm fibre xanchromatic boron-containing bene oxazine resin stabilizing solution.It is 5～18min/160 ℃ that this resin solution can add promotor adjusting molding time according to the difference of use.
Embodiment 3: with 70 parts of boric acid, 240 parts of phenol add reactor, heat temperature raising (being no more than 160 ℃) dewaters, cooling cooling when the water of deviating from reaches a certain amount of, add toluene and 160 parts of formalins then, pH value with an acidic catalyst regulation system is 1～3, temperature rising reflux reaction cooling after 2 hours, pH value with the basic catalyst regulation system is 6～10, add 120 parts of aniline, 200 parts of formalins and small amount of toluene, alcohol, heat up in 80～90 ℃ of back flow reaction after 2 hours, promptly make boron-containing bene oxazine resin in 80～120 ℃ of vacuum hydro-extractions, add solvent, obtain the henna boron-containing bene oxazine resin stabilizing solution of even clear.It is 5～18min/160 ℃ that this resin solution can add promotor adjusting molding time according to the difference of use.
Embodiment 4: 80 parts of boric acid phenol fat compounds and 160 parts of formalins addings are had agitator, in the reactor of reflux exchanger and thermometer, regulate PH=7～11 with alkali.Add toluene, quadrol carries out the temperature rising reflux reaction after 3 hours for 40 parts, promptly makes boron-containing bene oxazine resin in 80～140 ℃ of vacuum hydro-extractions, adds solvent, obtains even clear palm fibre xanchromatic boron-containing bene oxazine resin stabilizing solution.It is 5～18min/160 ℃ that this resin solution can add promotor adjusting molding time according to the difference of use.
Embodiment 5: 240 parts of boric acid phenol fat compounds and 140 parts of formalins addings are had agitator, in the reactor of reflux exchanger and thermometer, the pH value of regulation system is 1～3, back flow reaction was lowered the temperature after 1～2 hour, the pH value of regulation system is 6～10, add 160 parts of aniline, 220 parts of formalins and small amount of toluene, alcohol, 80～90 ℃ of back flow reaction that heat up are after 2 hours, promptly make boron-containing bene oxazine resin in 80～120 ℃ of vacuum hydro-extractions, add solvent, obtain the henna boron-containing bene oxazine resin stabilizing solution of even clear.It is 5～18min/160 ℃ that this resin solution can add promotor adjusting molding time according to the difference of use.
Embodiment 6: 20 parts of boric acid, 80 parts of phenol are added in the reactor, the heat temperature raising dehydration, cooling cooling when the water of deviating from reaches a certain amount of, add 160 parts of formalins then, be 6～10, add toluene with the pH value of basic catalyst regulation system, 40 parts of quadrols, 80～90 ℃ of temperature rising reflux reactions promptly made boron-containing bene oxazine resin in 80～140 ℃ of vacuum hydro-extractions after 3 hours, add solvent, obtain even clear palm fibre xanchromatic boron-containing bene oxazine resin stabilizing solution.It is 5～18min/160 ℃ that this resin solution can add promotor adjusting molding time according to the difference of use.
Embodiment 7: 30 parts of boric acid, 120 parts of cresols are added in the reactor, the heat temperature raising dehydration, cooling cooling when the water of deviating from reaches a certain amount of, add 160 parts of formalins then, be 6～10, add toluene with the pH value of basic catalyst regulation system, hexanediamine carries out the temperature rising reflux reaction after 6 hours for 120 parts, promptly make boron-containing bene oxazine resin in 80～140 ℃ of vacuum hydro-extractions, add solvent, obtain even clear palm fibre xanchromatic boron-containing bene oxazine resin stabilizing solution.It is 5～18min/160 ℃ that this resin solution can add promotor adjusting molding time according to the difference of use.
Embodiment 8: 220 parts of boric acid phenol fat compounds and 160 parts of formalins addings are had agitator, in the reactor of reflux exchanger and thermometer, the pH value of regulation system is 1～3, back flow reaction was lowered the temperature after 1～2 hour, the pH value of regulation system is 6～10, add 60 parts of methylamines, 180 parts of formalins and small amount of toluene, alcohol, 80～90 ℃ of temperature rising reflux reactions are after 3 hours, promptly make boron-containing bene oxazine resin in 80～120 ℃ of vacuum hydro-extractions, add solvent, obtain the henna boron-containing bene oxazine resin stabilizing solution of even clear.It is 5～18min/160 ℃ that this resin solution can add promotor adjusting molding time according to the difference of use.
Embodiment 9: 220 parts of boric acid phenol fat compounds and 340 parts of formalins addings are had agitator, in the reactor of reflux exchanger and thermometer, regulate PH=7～11 with alkali, formalin solution, the molar ratio of boric acid phenol fat compound and formalin is 1: 1.2～2.7.Add toluene and carry out the temperature rising reflux reaction after 6 hours with 120 parts of the diamine compounds that contains aralkyl structure, promptly make boron-containing bene oxazine resin in 80～140 ℃ of vacuum hydro-extractions, add solvent, obtain even clear palm fibre xanchromatic boron-containing bene oxazine resin stabilizing solution.It is 5～18min/160 ℃ that this resin solution can add promotor adjusting molding time according to the difference of use.
Embodiment 10: 60 parts of boric acid, 180 parts of phenol are added reactor, heat temperature raising (being no more than 160 ℃) dewaters, cooling cooling when the water of deviating from reaches a certain amount of, add alcohol and 300 parts of formalins then, the pH value of regulation system is 6～10, add 4,80 parts of small amount of toluene of 4 ' diaminodiphenylsulfone(DDS), the temperature rising reflux reaction is after 5～7 hours, promptly make boron-containing bene oxazine resin in 80～120 ℃ of vacuum hydro-extractions, add solvent, obtain the henna boron-containing bene oxazine resin stabilizing solution of even clear.It is 5～18min/160 ℃ that this resin solution can add promotor adjusting molding time according to the difference of use.
Embodiment 11: 60 parts of boric acid, 180 parts of p-tert-butylphenols are added reactor, heat temperature raising (being no more than 160 ℃) dewaters, cooling cooling when the water of deviating from reaches a certain amount of, add alcohol and 300 parts of formalins then, the pH value of regulation system is 6～10, add 4,80 parts of 4 ' diaminodiphenylmethane and small amount of toluene, the temperature rising reflux reaction is after 5～7 hours, promptly make boron-containing bene oxazine resin in 80～120 ℃ of vacuum hydro-extractions, add solvent, obtain the henna boron-containing bene oxazine resin stabilizing solution of even clear.It is 5～18min/160 ℃ that this resin solution can add promotor adjusting molding time according to the difference of use.
Embodiment 8: with 70 parts of boric acid, 240 parts of Resorcinol add reactor, the heat temperature raising dehydration, cooling cooling when the water of deviating from reaches a certain amount of, the pH value that adds alcohol and 160 parts of formalin regulation system is 1～3, back flow reaction was lowered the temperature after 1～2 hour, the pH value of regulation system is 6～10, add 120 parts of aniline, 200 parts of formalins and small amount of toluene, alcohol, the temperature rising reflux reaction is after 2 hours, promptly make boron-containing bene oxazine resin in 80～120 ℃ of vacuum hydro-extractions, add solvent, obtain the henna boron-containing bene oxazine resin stabilizing solution of even clear.It is 5～18min/160 ℃ that this resin solution can add promotor adjusting molding time according to the difference of use.
Table 1 for the performance of the glass cloth laminated board of part Example formulations preparation and with the performance comparison of common benzoxazine glass cloth laminated board.
Above-mentioned specific embodiment only is that the present invention is further described, and can not be interpreted as limiting the scope of the invention, the invention is not restricted to the foregoing description, and content of the present invention is described all can implement and have described good result.
Claims (5)
1. the preparation method of a boron-containing bene oxazine resin is characterized in that comprising the following steps:
(1) batching: adopt the starting raw material component and the weight proportion of the synthetic benzoxazine resin of boron-containing compound to be:
80～240 parts of boric acid phenol fat compounds
Aminated compounds 40-120 part
The formaldehyde weight percentage is 160～360 parts of the formalins of 30-40%
4～8 parts of basic catalysts
(2) technological process: (1) described proportioning set by step, boric acid phenol fat compound and formalin adding are had in the reactor of agitator, reflux exchanger and thermometer, regulate PH=7～11 with basic catalyst, adding solvent, adding aminated compounds after 1～6 hour, promptly make boron-containing bene oxazine resin in 80～140 ℃ of vacuum hydro-extractions in 75～105 ℃ of back flow reaction of temperature.
2. according to the preparation method of the described boron-containing bene oxazine resin of claim 1, it is characterized in that: described boric acid phenol fat compound is at least a in boric acid triphen fat, boric acid hexichol fat, boric acid benzene fat, the boric acid cresols fat.
3. according to the preparation method of the described boron-containing bene oxazine resin of claim 1, it is characterized in that: described aminated compounds is 4 in quadrol, butanediamine, hexanediamine, decamethylene diamine and the aromatic diamine in methylamine, aniline, ammonia, urea and the aliphatic diamine, 4 ' diaminodiphenylmethane, 4, at least a in 4 ' diaminodiphenylsulfone(DDS), 4, the 4 ' diaminodiphenyl oxide.
4. according to the preparation method of the described boron-containing bene oxazine resin of claim 1, it is characterized in that: described basic catalyst is sodium hydroxide, ammoniacal liquor, urotropine or potassium hydroxide.
5. according to the preparation method of the described boron-containing bene oxazine resin of claim 1, it is characterized in that: described solvent is that toluene, alcohol, acetone, butanone are or/and methane amide.
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| CN101220151B (en) * | 2007-12-14 | 2010-09-01 | 华南理工大学 | Production method for oxazine resin |
| EP3110864A4 (en) * | 2014-02-26 | 2017-08-23 | Huntsman Advanced Materials Americas LLC | Reaction hybrid benzoxazine resins and uses thereof |
| CN103965483A (en) * | 2014-05-22 | 2014-08-06 | 陕西太航阻火聚合物有限公司 | Boron hydroquinone ester polymer as well as preparation method and application thereof |
| CN105315221A (en) * | 2014-08-04 | 2016-02-10 | 中国科学院化学研究所 | Aromatic diamine type benzoxazine resin and preparation method thereof |
| CN107651662B (en) * | 2017-07-23 | 2020-04-17 | 北京化工大学 | Method for preparing boron-nitrogen double-doped carbon aerogel |
| CN108559430A (en) * | 2018-05-08 | 2018-09-21 | 温州市赢创新材料技术有限公司 | A kind of phenolic resin glue and preparation method thereof |
| CN109081895B (en) * | 2018-07-27 | 2021-06-08 | 贵州理工学院 | Self-toughening benzoxazine thermosetting resin and preparation method thereof |
| CN109354825B (en) * | 2018-10-12 | 2021-06-22 | 北京玻钢院复合材料有限公司 | High-temperature-resistant hot-melt benzoxazine resin and preparation method thereof |
| CN114957156A (en) * | 2022-05-25 | 2022-08-30 | 成都科宜高分子科技有限公司 | Compound containing benzoxazine structure, resin composition, prepreg and electric copper clad laminate, and preparation method and application thereof |
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| CN1379779A (en) * | 1999-09-08 | 2002-11-13 | 第一制药株式会社 | Process for preparation of benzoxazine derivatives and intermediates therefor |
| CN1496378A (en) * | 2001-03-12 | 2004-05-12 | �������ɹ�ҵ��ʽ���� | Method for producing benzoxazine resin |
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|---|---|---|---|---|
| CN1379779A (en) * | 1999-09-08 | 2002-11-13 | 第一制药株式会社 | Process for preparation of benzoxazine derivatives and intermediates therefor |
| CN1496378A (en) * | 2001-03-12 | 2004-05-12 | �������ɹ�ҵ��ʽ���� | Method for producing benzoxazine resin |
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