CN1803887A - Benzoxazine resin containing aralkyl structure, its preparation method and use - Google Patents
Benzoxazine resin containing aralkyl structure, its preparation method and use Download PDFInfo
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- CN1803887A CN1803887A CN 200510022499 CN200510022499A CN1803887A CN 1803887 A CN1803887 A CN 1803887A CN 200510022499 CN200510022499 CN 200510022499 CN 200510022499 A CN200510022499 A CN 200510022499A CN 1803887 A CN1803887 A CN 1803887A
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Abstract
The preparation method for benzoazine with aralkyl group comprises: adding phenols compound as 80-100 weight shares and 80-120 aralkyl compound into the reaction kettle; with 1-4 acidic catalyst, stirring to react for 1-3h at 80-140Deg; cooling to below 50Deg; adding 30-40% formaldehyde liquid as 160-360 weight shares and 4-8 basic catalyst to adjust pH value within 6-9; adding solvent and 40-120 diamine to reflux reaction for 2-8h at 85-95Deg; finally, vacuum dewatering at 80-40Deg. This product is used mainly to manufacture high-performance constructional material fit more than 180Deg, the electrically insulating material, or glass fabric and extruding material with vitrifying temperature more than 175Deg.
Description
Technical field
The invention belongs to the synthetic field of thermosetting resin, relate to a kind of benzoxazine resin that contains aralkyl structure 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 the synthetic general of benzoxazine resin adopts common phenols (as phenol at present, cresols, dihydroxyphenyl propane etc.), aminated compounds (aniline, aliphatic diamine, aromatic diamine etc.) make (as CN1451679A with formaldehyde reaction, CN111572A, CN1379779A, CN149637A8 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.
Aralkyl phenols (as methoxyl group parylene monomer and oligopolymer, xylene formaldehyde resin etc.) and aralkyl ethers (methoxyl group phenyl ether monomer and oligopolymer thereof, diphenyl ether) resin are the important high temperature resistant thermosetting resins of a class.This two resinoid all can under the certain temperature under Fu Shi catalyzer (AlCl3, SnCl4, dodecyl phenyl ether sulfonic acid etc.) effect progressively polycondensation become insoluble infusible polymer, constantly deviate from the polycondensation process by the first alcohol and water, but temperature and time that this process need is higher are longer, the first alcohol and water of emitting is difficult for getting rid of, therefore when using as high temperature resistant composite matrix resin, its moulding process extreme difference, the cured article cross-linking density is low, is difficult to be formed with the product of actual value.Therefore it to be carried out modification,, make it have the operability of suitability for industrialized production to improve cross-linking density, to obtain better moulding process.At present aralkyl phenols and the resinoid method of modifying of aralkyl ethers mostly are to make itself and phenol, formaldehyde reaction, synthesize the resol that contains aralkyl structure, polycondensation under the hexamethylenetetramine effect again, crosslinked generation build macromole.This method of modifying has characteristics such as cost is low, solidification value is low and is widely used in recent years, because this technological line adopts hexamethylenetetramine as curing catalysts, it is long that goods exist the aftertreatment time, still have a large amount of small molecules to emit during curing, defective such as bigger, the hot physical strength conservation rate of goods voidage is lower.
Summary of the invention
Purpose of the present invention is intended to overcome above-mentioned deficiency of the prior art, a kind of benzoxazine resin that contains aralkyl structure and its production and use is provided, the present invention combines aralkyl phenols and aralkyl ethers resinoid inherent thermostability, 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.Adopt this resin can make fire-resistant high-performance matrix material, electrically insulating material or the second-order transition temperature (Tg) of use more than 180 ℃ at the glass fabric layer more than 175 ℃, moulding material.
Content of the present invention is: a kind of benzoxazine resin that contains aralkyl structure is characterized in that: have following constitutional features:
R
1=-O-,-OC
2H
5,-OCH
3,-CH
3Deng
n＝1～3 m＝1～3
R=-O-,-OC
2H
4,-OCH
2,-CH
2Deng
And/or:
R
3=-O-,-OC
2H
3,-OCH
3,-CH
3Deng
The benzoxazine resin that contains aralkyl structure 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.The benzoxazine resin free phenol content of aralkyl structure of the present invention is low, and the melt temperature of resin or softening temperature are 100 ℃～140 ℃.Adopt resin of the present invention to have stable electrical insulation properties and higher mechanical properties and halogen-free flame-retardance as the glass fibre laminated and pressing of matrix resin (tackiness agent) preparation.The raising of mechanical property is mainly reflected in the benzoxazine resin glass layer of cloth that contains aralkyl structure, hot (180 ℃) flexural strength of pressing can reach more than the 400Mpa, and (200 ℃) flexural strength can reach more than the 300Mpa.The heat-proof aging index can reach 180 grades or 200 grades.
Another content of the present invention is: a kind of preparation method who contains the benzoxazine resin of aralkyl structure is characterized in that comprising the following steps:
(1) batching: adopt the starting raw material component and the formulation by weight of aralkyl compound modified benzoxazine resin to be:
80～100 parts of phenolic compounds
80～120 parts of aralkyl compounds
Binary amine compound 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, with phenolic compound, aralkyl compound and an acidic catalyst add and have agitator, in the reactor of reflux exchanger and thermometer, under an acidic catalyst effect, in 80～140 ℃ of stirring reactions of temperature 1～3 hour, cool to below 50 ℃, add formalin again, the molar ratio of phenolic compound and formaldehyde is 1: 0.9～2.2 preferably, regulate PH=6～9 with basic catalyst, add solvent, the binary amine compound after 2～8 hours, promptly makes the benzoxazine resin that contains aralkyl structure in 85～95 ℃ of back flow reaction of temperature in 80～140 ℃ of vacuum hydro-extractions; Add solvent and can obtain containing the solution of the benzoxazine resin of aralkyl structure.
Another content of the present invention can also be: a kind of preparation method who contains the benzoxazine resin of aralkyl structure is characterized in that comprising the following steps:
(1) batching: adopt the starting raw material component and the formulation by weight of aralkyl compound modified benzoxazine resin to be:
80～100 parts of phenolic compounds
80～140 parts of diamine compounds that contain aralkyl phenol structure
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, phenolic 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 formaldehyde and phenolic compound is 1: 1.2～2.7 preferably, the diamine compound that add solvent, contains aralkyl phenol structure after 1～6 hour, promptly makes the benzoxazine resin that contains aralkyl structure in 75～105 ℃ of back flow reaction of temperature in 80～140 ℃ of vacuum hydro-extractions; Add solvent and can obtain containing the solution of the benzoxazine resin of aralkyl structure.
In another content 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, the Resorcinol.
In another content of the present invention: described aralkyl compound is at least a in the aralkyl phenols (as methoxyl group parylene monomer and oligopolymer, xylene formaldehyde resin etc.), aralkyl ethers (as methoxyl group phenyl ether monomer and oligopolymer thereof, diphenyl ether).
In another content of the present invention: described binary amine compound is quadrol, butanediamine, hexanediamine, decamethylene diamine in the aliphatic diamine etc., in the aromatic diamine 4,4 ' diaminodiphenylmethane (MDA), 4,4 ' diaminodiphenylsulfone(DDS), 4,4 ' diaminodiphenyl oxide etc., and the diamine compound that contains aralkyl structure of structure such as figure below is at least a:
n＝1～3 m＝1～3
R=-O-,-OC
2H
3,-OCH
3,-CH
3Deng
In another content of the present invention: described basic catalyst is sodium hydroxide, ammoniacal liquor, urotropine, potassium hydroxide and other metal oxides, oxyhydroxide.
In another content 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 another content of the present invention: described solvent is that toluene, alcohol, acetone, butanone are or/and methane amide.
Another content of the present invention is: the benzoxazine resin that contains aralkyl structure of the present invention is that tackiness agent is used to prepare high performance structures material, electrically insulating material or the second-order transition temperature (Tg) of the use more than 180 ℃ with stable electrical insulation properties and higher mechanical properties and halogen-free flame-retardance at the glass fabric layer more than 175 ℃, moulding material as matrix resin.
The solidifying agent that contains the benzoxazine resin system of aralkyl structure of the present invention can be one or more of Witco 1298 Soft Acid, mahogany acid, oxalic acid, glyoxaline compound.
Compared with prior art, the present invention has following characteristics:
(1) the benzoxazine structure is introduced aralkyl phenols (as methoxyl group parylene monomer and oligopolymer, xylene formaldehyde resin etc.) and aralkyl ethers (methoxyl group phenyl ether monomer and oligopolymer thereof, diphenyl ether) resin, the synthetic benzoxazine resin that contains aralkyl structure that combines.This resin has kept aralkyl phenols and aralkyl ethers resinoid inherent thermostability, and has the characteristics of the ring-opening polymerization that benzoxazine colophony has concurrently;
(2) to contain the preparation process of benzoxazine resin of aralkyl structure simple in the present invention, and raw material is inexpensive, and wide material sources have actual use value and Application Prospect;
(3) to contain the building-up reactions of benzoxazine resin of aralkyl structure steady, easy to operate in the present invention, is easy to realize the industrialization continuous production, practical.Resin free phenol content is low, in hot-forming mid-term, later stage curing; thus benzoxazine structure generation ring-opening polymerization forms the build macromolecular structure, and no small molecules is emitted in solidification process, the goods voidage is low has excellent mechanical property, electric property so goods are had;
(4) the present invention's benzoxazine resin of containing aralkyl structure 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) to contain the melt temperature or the softening temperature of the benzoxazine resin of aralkyl structure be 100 ℃～140 ℃ in the present invention, and the ring-opening polymerization temperature is 140 ℃～200 ℃, is easy to forming process;
(6) to contain the product properties of benzoxazine resin of aralkyl structure good in the present invention, can be used for preparing the high-temperature-resistant structure material and the electrically insulating material of 180 grades or 200 grades life-time service, and high Tg copper coated foil plate and multilayer line plate substrate;
(7) the present invention contains the practical function of the benzoxazine resin of aralkyl structure and is:
The one, improved the complete processing of follow-up goods.The benzoxazine resin that contains aralkyl structure 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.Adopt resin of the present invention to have stable electrical insulation properties and higher mechanical properties and halogen-free flame-retardance as the glass fibre laminated and pressing of matrix resin preparation.The raising of mechanical property is mainly reflected in the benzoxazine resin glass layer of cloth that contains aralkyl structure, hot (180 ℃) flexural strength of pressing can reach more than the 400Mpa, and (200 ℃) flexural strength can reach more than the 300Mpa.And hot (180 ℃) flexural strength of existing phenol-modified aralkyl phenols and aralkyl ethers resinoid glass fabric layer, pressing goods only is about 150Mpa.
The 2nd, the heat aging property of the follow-up goods of raising.Existing benzoxazine resin and phenol-modified aralkyl phenols and the resinoid heat-proof aging index of aralkyl ethers only can reach 155 or 180 grades, and the benzoxazine resin heat-proof aging index that contains aralkyl structure of the present invention can reach 180 grades or 200 grades.
The 3rd, realized halogen-free flameproof.Owing to contain nitrogen-atoms in the system, be the characteristic that goods have halogen-free flameproof with flame retardant resistance; Contain the benzoxazine resin glass layer of cloth of aralkyl structure, the flame retardant resistance of pressing can reach FV
0Level, the flame retardant resistance of phenol-modified aralkyl phenols and aralkyl ethers resinoid glass fabric layer, pressing only reaches FV
1Level.
The 4th, improved the second-order transition temperature (Tg) of glass colth laminate.Its second-order transition temperature of copper coated foil plate that employing contains the benzoxazine resins of aralkyl structure can reach 175 ℃～180 ℃, and 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: 100 parts of methoxyl group parylene monomers, 120 parts of phenol and 2 parts of tosic acid are added in the reactor, heat temperature raising (being no more than 140 ℃) dewaters, cooling cooling when the water of deviating from reaches a certain amount of, add 360 parts in formaldehyde then, be 6～10, add toluene with the pH value of 8 parts of regulation system of basic catalyst, 4,4 ' diaminodiphenylmethane (MDA) is carried out the temperature rising reflux reaction after 6 hours for 120 parts, promptly makes the benzoxazine resin that contains aralkyl structure in 80～140 ℃ of vacuum hydro-extractions; Add solvent, obtain the henna benzoxazine stable resin solution that contains aralkyl structure of even clear.It is 1～8min/160 ℃ that this resin solution can add promotor adjusting molding time according to the difference of use.
Embodiment 2: with 80 parts of methoxyl group phenyl ether monomers, 80 parts of phenol and 1 part add reactor to hydrochloric acid, heat temperature raising (being no more than 140 ℃) dewaters, cooling cooling when the water of deviating from reaches a certain amount of, add 160 parts in formaldehyde then, pH value with 6 parts of regulation system of basic catalyst is 6～10, add toluene, quadrol carries out the temperature rising reflux reaction after 6 hours for 40 parts, promptly make the benzoxazine resin that contains aralkyl structure in 80～140 ℃ of vacuum hydro-extractions, add solvent, obtain the henna benzoxazine stable resin solution that contains aralkyl structure of even clear.It is 1～8min/160 ℃ that this resin solution can add promotor adjusting molding time according to the difference of use.
Embodiment 3: with 100 parts of methoxyl group phenyl ether monomers, 80 parts of phenol and 3 parts of tosic acid add reactor, heat temperature raising (being no more than 140 ℃) dewaters, cooling cooling when the water of deviating from reaches a certain amount of, add 160 parts in formaldehyde then, pH value with 4 parts of regulation system of basic catalyst is 6～10, add toluene, quadrol carries out the temperature rising reflux reaction after 4 hours for 40 parts, promptly make the benzoxazine resin that contains aralkyl structure in 80～140 ℃ of vacuum hydro-extractions, add solvent, obtain the henna benzoxazine stable resin solution that contains aralkyl structure of even clear.It is 1～8min/160 ℃ that this resin solution can add promotor adjusting molding time according to the difference of use.
Embodiment 4: with 100 parts of xylene formaldehyde resins, 120 parts of phenol and 2 parts of sulfuric acid add in the reactor, heat temperature raising (being no more than 140 ℃) dewaters, cooling cooling when the water of deviating from reaches a certain amount of, add 360 parts in formaldehyde then, pH value with 8 parts of regulation system of basic catalyst is 6～10, add toluene, 4,4 ' diaminodiphenylsulfone(DDS) carries out the temperature rising reflux reaction after 6 hours for 70 parts, promptly make the benzoxazine resin that contains aralkyl structure in 80～140 ℃ of vacuum hydro-extractions, add solvent, obtain the henna benzoxazine stable resin solution that contains aralkyl structure of even clear.It is 1～8min/160 ℃ that this resin solution can add promotor adjusting molding time according to the difference of use.
Embodiment 5: with 100 parts of polydiphenyl ether resins, 120 parts of xylenols and 3 parts of hydrochloric acid add in the reactor, heat temperature raising (being no more than 140 ℃) dewaters, cooling cooling when the water of deviating from reaches a certain amount of, add 200 parts in formaldehyde then, pH value with 8 parts of regulation system of basic catalyst is 6～10, add toluene, hexanediamine carries out the temperature rising reflux reaction after 3 hours for 90 parts, promptly make the benzoxazine resin that contains aralkyl structure in 80～140 ℃ of vacuum hydro-extractions, add solvent, obtain the henna benzoxazine stable resin solution that contains aralkyl structure of even clear.It is 1～8min/160 ℃ that this resin solution can add promotor adjusting molding time according to the difference of use.
Embodiment 6: with 80 parts of methoxyl group parylene monomers, 120 parts of phenol and 2 parts of hydrochloric acid add 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 280 parts in formaldehyde then, pH value with 8 parts of regulation system of basic catalyst is 6～10, add toluene, 4,4 ' diaminodiphenyl oxide carries out the temperature rising reflux reaction after 8 hours for 80 parts, promptly make the benzoxazine resin that contains aralkyl structure in 80～140 ℃ of vacuum hydro-extractions, add solvent, obtain the henna benzoxazine stable resin solution that contains aralkyl structure of even clear.It is 1～8min/160 ℃ that this resin solution can add promotor adjusting molding time according to the difference of use.
Embodiment 7: 80 parts of phenol and 160 parts of formaldehyde addings are had in the reactor of agitator, reflux exchanger and thermometer, regulate PH=7～11 with basic catalyst, add solvent, add 80 parts of diamine compounds that contain aralkyl phenol structure in 95～100 ℃ of back flow reaction of temperature after 6 hours, promptly make the benzoxazine resin that contains aralkyl structure in 80～140 ℃ of vacuum hydro-extractions, add solvent, obtain the henna stabilizing solution that contains the benzoxazine resin of aralkyl structure of even clear.It is 1～8min/160 ℃ that this resin solution can add promotor adjusting molding time according to the difference of use.
Embodiment 8: 100 parts of cresols and 360 parts of formaldehyde addings are had agitator, in the reactor of reflux exchanger and thermometer, regulate PH=7～11 with alkali, add solvent, add 140 parts of diamine compounds that contain the aralkyl ethers structure in 95～100 ℃ of back flow reaction of temperature after 5 hours, promptly make the benzoxazine resin that contains aralkyl structure in 80～140 ℃ of vacuum hydro-extractions, add solvent, obtain the henna stabilizing solution that contains the benzoxazine resin of aralkyl structure of even clear.It is 1～8min/160 ℃ that this resin solution can add promotor adjusting molding time according to the difference of use.
Embodiment 9: 80 parts of cresols and 180 parts of formaldehyde addings are had agitator, in the reactor of reflux exchanger and thermometer, regulate PH=7～11 with alkali, add solvent, add 40 parts of diamine compounds that contain the aralkyl ethers structure in 95～100 ℃ of back flow reaction of temperature after 6 hours, promptly make the benzoxazine resin that contains aralkyl structure in 80～140 ℃ of vacuum hydro-extractions, add solvent, obtain the henna stabilizing solution that contains the benzoxazine resin of aralkyl structure of even clear.It is 1～8min/160 ℃ that this resin solution can add promotor adjusting molding time according to the difference of use.
Embodiment 10: 80 dihydroxyphenyl propanes, 300 parts of formaldehyde are added in the reactor, regulate PH=7～11 with alkali, add solvent, add 100 parts of diamine compounds that contain aralkyl phenol structure in 95～100 ℃ of back flow reaction of temperature after 8 hours, promptly make the benzoxazine resin that contains aralkyl structure in 80～140 ℃ of vacuum hydro-extractions, add solvent, obtain the henna stabilizing solution that contains the benzoxazine resin of aralkyl structure of even clear.It is 1～8min/160 ℃ that this resin solution can add promotor adjusting molding time according to the difference of use.
Embodiment 11: 100 parts of bisphenol Ss, 260 parts of formaldehyde are added in the reactor, regulate PH=7～11 with alkali, add solvent, add 140 parts of diamine compounds that contain the aralkyl ethers structure in 85～100 ℃ of back flow reaction of temperature after 8 hours, promptly make the benzoxazine resin that contains aralkyl structure in 80～140 ℃ of vacuum hydro-extractions, add solvent, obtain the henna stabilizing solution that contains the benzoxazine resin of aralkyl structure of even clear.It is 1～8min/160 ℃ that this resin solution can add promotor adjusting molding time according to the difference of use.
Embodiment 12: 80 parts of phenol and 180 parts of formaldehyde addings are had agitator, in the reactor of reflux exchanger and thermometer, regulate PH=7～11 with alkali, add solvent, add 40 parts of diamine compounds that contain the aralkyl ethers structure in 95～100 ℃ of back flow reaction of temperature after 6 hours, promptly make the benzoxazine resin that contains aralkyl structure in 80～140 ℃ of vacuum hydro-extractions, add solvent, obtain the henna stabilizing solution that contains the benzoxazine resin of aralkyl structure of even clear.It is 1～8min/160 ℃ that this resin solution can add promotor adjusting molding time according to the difference of use.
Embodiment 13: 100 parts of p-tert-butylphenols and 360 parts of formalins addings are had agitator, in the reactor of reflux exchanger and thermometer, regulate PH=7～11 with alkali, add solvent, add 100 parts of diamine compounds that contain the aralkyl ethers structure in 95～100 ℃ of back flow reaction of temperature after 6 hours, promptly make the benzoxazine resin that contains aralkyl structure in 80～140 ℃ of vacuum hydro-extractions, add solvent, obtain the henna stabilizing solution that contains the benzoxazine resin of aralkyl structure of even clear.It is 1～8min/160 ℃ that this resin solution can add promotor adjusting molding time according to the difference of use.
Embodiment 14: with 100 parts of methoxyl group parylene monomers, 100 parts of phenol and 2 parts of tosic acid add in the reactor, heat temperature raising (being no more than 140 ℃) dewaters, cooling cooling when the water of deviating from reaches a certain amount of, add 360 parts in formaldehyde then, pH value with the basic catalyst regulation system is 6～10, add toluene, 4,4 ' diaminodiphenyl oxide carries out the temperature rising reflux reaction after 6 hours for 100 parts, promptly make the benzoxazine resin that contains aralkyl structure in 80～140 ℃ of reflux dewaterings, add solvent, obtain the henna benzoxazine stable resin solution that contains aralkyl structure of even clear.It is 1～8min/160 ℃ that this resin solution can add promotor adjusting molding time according to the difference of use.
Embodiment 15: with 100 parts of methoxyl group phenyl ether monomers, 120 parts of phenol and 4 parts of hydrochloric acid add reactor, heat temperature raising (being no more than 140 ℃) dewaters, cooling cooling when the water of deviating from reaches a certain amount of, add 180 parts in formaldehyde then, pH value with the basic catalyst regulation system is 6～10, add toluene, hexanediamine carries out the temperature rising reflux reaction after 6 hours for 80 parts, promptly make the benzoxazine resin that contains aralkyl structure in 80～140 ℃ of reflux dewaterings, add solvent, obtain the henna benzoxazine stable resin solution that contains aralkyl structure of even clear.It is 1～8min/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 composite of part Example formulations preparation and with the performance comparison of benzoxazine glass cloth laminated board plate and phenol-modified phenyl ether 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.
Table 1: performance comparison.
| Sequence number | Index name | Unit | The benzoxazine plate | Phenol-modified phenyl ether plate | Example 1 | Example 3 | Example 6 | Example 8 | Example 9 | |
| 1 | Perpendicular layers is to flexural strength | Normality | MPa | 578 | 521 | 613 | 576 | 703 | 637 | 621 |
| 180℃±2℃ | 454 | 273 | 554 | 462 | 613 | 512 | 473 | |||
| 200℃±2℃ | 127 | 102 | 427 | 197 | 471 | 419 | 201 | |||
| 2 | Bond strength | N | 6890 | 6120 | 7249 | 7526 | 7950 | 7565 | 7425 | |
| 3 | Second-order transition temperature | ℃ | 171.2 | 175.7 | 192.4 | 176.4 | 191.2 | 187.6 | 176.8 | |
| 5 | Vertical combustion | Level | FV 0 | FV 1 | FV 0 | FV 0 | FV 0 | FV 0 | FV 0 | |
| 6 | The 1MHz medium consumption factor | ％ | 0.0067 | 0.0078 | 0.0081 | 0.0073 | 0.0063 | 0.0056 | 0.0078 | |
| 7 | The 1MHz specific inductivity | 5.1 | 5.4 | 5.2 | 5.1 | 5.3 | 4.9 | 5.0 | ||
| 8 | Parallel layers is to voltage breakdown | kV | 36.9 | 27.9 | 37.1 | 38.4 | 36.5 | 38.6 | 39.2 | |
| 9 | Volume resistivity | Normality | Ω·m | 2.5×10 13 | 4.7×10 14 | 1.9×10 14 | 6.9×10 14 | 5.6×10 14 | 6.7×10 14 | 4.7×10 14 |
| 180℃±2℃ | 6.6×10 11 | 2.1×10 11 | 7.5×10 12 | 4.3×10 11 | 9.1×10 12 | 8.2×10 12 | 2.7×10 12 | |||
| 200℃±2℃ | 2.0×10 8 | 1.9×10 7 | 6.8×10 10 | 7.8×10 8 | 3.7×10 11 | 7.4×10 11 | 7.9×10 7 | |||
| 10 | Humidity index | ℃ | 155～180 | 180 | 200 | 180 | 200 | 200 | 180 | |
Claims (10)
1. benzoxazine resin that contains aralkyl structure is characterized in that: have following constitutional features:
R
1＝-O-、-OC
2H
5、-OCH
3、-CH
3、
-O-、-OC
2H
4、-OCH
2、-CH
2
n＝1～3 m＝1～3R＝-O-、-OC
2H
4、-OCH
2、-CH
2
And/or:
R
1＝-O-，-OC
2H
5、-OCH
3、-CH
3
The benzoxazine resin free phenol content of aralkyl structure of the present invention is low, and the melt temperature of resin or softening temperature are 100 ℃～140 ℃.
2. a preparation method who contains the benzoxazine resin of aralkyl structure is characterized in that comprising the following steps:
(1) batching: adopt the starting raw material component and the formulation by weight of aralkyl compound modified benzoxazine resin to be:
80～100 parts of phenolic compounds
80～120 parts of aralkyl compounds
Binary amine compound 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, phenolic compound, aralkyl compound and an acidic catalyst adding are had in the reactor of agitator, reflux exchanger and thermometer, under an acidic catalyst effect, in 80～140 ℃ of stirring reactions of temperature 1～3 hour, cool to below 50 ℃, add formalin again, regulate PH=6～9 with basic catalyst, adding solvent, binary amine compound after 2～8 hours, promptly make the benzoxazine resin that contains aralkyl structure in 85～95 ℃ of back flow reaction of temperature in 80～140 ℃ of vacuum hydro-extractions.
3. a preparation method who contains the benzoxazine resin of aralkyl structure is characterized in that comprising the following steps:
(1) batching: adopt the starting raw material component and the formulation by weight of aralkyl compound modified benzoxazine resin to be:
80～100 parts of phenolic compounds
80～140 parts of diamine compounds that contain aralkyl phenol structure
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, phenolic compound and formalin adding are had in the reactor of agitator, reflux exchanger and thermometer, regulate PH=7～11 with basic catalyst, the diamine compound that add solvent, contains aralkyl phenol structure after 1～6 hour, promptly makes the benzoxazine resin that contains aralkyl structure in 75～105 ℃ of back flow reaction of temperature in 80～140 ℃ of vacuum hydro-extractions.
4. according to claim 2 or the 3 described preparation methods that contain the benzoxazine resin of aralkyl structure, it is characterized in that: described phenolic compound is at least a in phenol, p-cresol, p-tert-butylphenol, meta-cresol, para-chlorophenol, p-NP, 4-hydroxybenzonitrile, dihydroxyphenyl propane, bisphenol S, the Resorcinol.
5. according to the described preparation method who contains the benzoxazine resin of aralkyl structure of claim 2, it is characterized in that: described aralkyl compound is aralkyl phenols such as methoxyl group parylene monomer and oligopolymer thereof, xylene formaldehyde resin, and is at least a in aralkyl ethers such as methoxyl group phenyl ether monomer and oligopolymer thereof, the diphenyl ether.
6. according to claim 2 or the 3 described preparation methods that contain the benzoxazine resin of aralkyl structure, it is characterized in that: described binary amine compound is quadrol, butanediamine, hexanediamine, the decamethylene diamine in the aliphatic diamine, in the aromatic diamine 4,4 ' diaminodiphenylmethane, 4,4 ' diaminodiphenylsulfone(DDS), 4,4 ' diaminodiphenyl oxide, and the diamine compound that contains aralkyl structure of structure such as figure below is at least a:
n＝1～3 m＝1～3
R＝-O-、-OC
2H
5、-OCH
3、-CH
3
7. according to claim 2 or the 3 described preparation methods that contain the benzoxazine resin of aralkyl structure, it is characterized in that: described basic catalyst is sodium hydroxide, ammoniacal liquor, urotropine or potassium hydroxide.
8. according to the described preparation method who contains the benzoxazine resin of aralkyl structure of claim 2, it is characterized in that: 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.
9. according to claim 2 or the 3 described preparation methods that contain the benzoxazine resin of aralkyl structure, it is characterized in that: described solvent is that toluene, alcohol, acetone, butanone are or/and methane amide.
10. according to the described benzoxazine resin that contains aralkyl structure of claim 1, it is characterized in that: this resin is that tackiness agent is used to prepare high performance structures material, electrically insulating material or the second-order transition temperature of the use more than 180 ℃ with stable electrical insulation properties and higher mechanical properties and halogen-free flame-retardance at the glass fabric layer more than 175 ℃, moulding material as matrix resin.
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