CN102408419B - Preparation method of benzoxazine resin - Google Patents
Preparation method of benzoxazine resin Download PDFInfo
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- CN102408419B CN102408419B CN201110228773.1A CN201110228773A CN102408419B CN 102408419 B CN102408419 B CN 102408419B CN 201110228773 A CN201110228773 A CN 201110228773A CN 102408419 B CN102408419 B CN 102408419B
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Abstract
The invention relates to a preparation method of a benzoxazine resin. The invention is to solve the problem that the current nitrogen, silicon and boron flame retardant epoxy resin has poor usability and high cost and the toxic substance is easily exuded by the phosphorus flame retardant to pollute environment. The benzoxazine resin is prepared by formaldehyde, alkali regulator, tripolycyanamide, solvent and bis-functional phenol compound. The method comprises the following steps of: taking the formaldehyde, regulating pH value by the alkali regulator, adding the tripolycyanamide, stirring and reacting; adding the bis-functional phenol compound and the solvent, heating and reacting to obtain resin solution; and decompressing and distilling the resin solution, and stopping decompression until no water is discharged so as to obtain the benzoxazine resin. The benzoxazine resin provided by the invention has high nitrogen content so that the flame retardance of the resin can be improved; and the benzoxazine resin has no phosphorus and will not cause pollution to environment. The benzoxazine resin is used for preparation of flame retardant product.
Description
Technical field
The present invention relates to a kind of method of benzoxazine colophony.
Background technology
The fire-retardant copper-clad plate of copper-clad plate manufacturer production technology comparative maturity is by introducing and contain the flame retardant resistance that the environmentally harmful flame-retardant compounds such as halogen, antimony element improve sheet material in resin mostly.European Union came into effect RoHS standard in 2006, and the electrical and electronic product that contains the fire retardants such as heavy metal, polybromodiphenyl ether and Polybrominated biphenyl will not allow to enter EU market.Therefore, research and development halogen-free flame retardants becomes very urgent task.
In recent years, though the research that nitrogen, silicon, boron are fire retarding epoxide resin make some progress, yet at the aspects such as fire-retardant application of flame retardant epoxy range of product and copper-clad plate, internal and overseas industry advanced country still exists sizable gap.All there is high cost and the poor shortcoming of use properties in all multi-products of report at present, substantially there is no and realize suitability for industrialized production.At present the focus of research is synthetic to phosphonium flame retardant, and phosphorus flame retardant is high molecular fire-retardant very effective to polycondensation, has the features such as low toxicity, lasting, inexpensive, Heat stability is good.But the perishable mould of phosphorus flame retardant, reduces the processability of polymkeric substance, and toxic substance easily oozes out and causes secondary pollution from resin matrix.
Summary of the invention
The present invention is that will to solve existing nitrogen, silicon, boron be that the use properties of fire retarding epoxide resin is poor, cost is high, and phosphorus flame retardant easily oozes out toxic substance and the problem of contaminate environment, and the method for benzoxazine colophony is provided.
Benzoxazine colophony of the present invention is made by the formaldehyde of 650～820 parts, the alkaline conditioner of 0.1～2.5 part, the trimeric cyanamide of 120～190 parts, the solvent of 0～600 part and the two functionality phenolic compounds of 100～200 parts by ratio of weight and the number of copies; Wherein said alkaline conditioner is a kind of in sodium hydroxide, triethylamine, ammoniacal liquor or several mixture wherein; Described solvent is a kind of in dioxane, toluene, dimethylbenzene, methyl alcohol, ethanol, ethylene glycol, trichloromethane or several mixture wherein; Described two functionality phenolic compounds are dihydroxybiphenyl compounds, dihydroxy naphthlene compounds or bisphenol compound, and facing in a carbon atom of the phenolic hydroxyl group place carbon atom of two functionality phenolic compounds has at least a hydrogen atom facing on a carbon atom by other groups, not replaced.
The preparation method of above-mentioned benzoxazine colophony, carry out according to the following steps: one, getting the formaldehyde of 650～820 parts, is 8～9 with the alkaline conditioner adjust pH of 0.1～2.5 part, then adds the trimeric cyanamide of 120～190 parts, under 68～72 ℃ of conditions, stir to clarify, react afterwards 20～30 minutes; Two, then in reaction system, add the two functionality phenolic compounds of 100～200 parts and the solvent of 0～600 part, make reaction system be warming up to 80～120 ℃, react 2～3 hours, obtain resin liquid; Three, by resin liquid underpressure distillation, when anhydrous, stop decompression while deviating from, obtain benzoxazine colophony; Wherein said alkaline conditioner is a kind of in sodium hydroxide, triethylamine, ammoniacal liquor or several mixture wherein; Described solvent is a kind of in dioxane, toluene, dimethylbenzene, methyl alcohol, ethanol, ethylene glycol, trichloromethane or several mixture wherein; Described two functionality phenolic compounds are dihydroxybiphenyl compounds, dihydroxy naphthlene compounds or bisphenol compound, and facing in a carbon atom of the phenolic hydroxyl group place carbon atom of two functionality phenolic compounds has at least a hydrogen atom facing on a carbon atom by other groups, not replaced.
The halogen-free phosphorus-free inflaming retarding copper-clad plate that the above-mentioned benzoxazine colophony of take is made as raw material is made by the benzoxazine colophony of 20～90 parts, the epoxy resin of 10～80 parts, the epoxy curing agent of 0～30 part, the curing catalyst of 0.1～5 part, the mixed solvent of 30～100 parts and the inorganic combustion inhibitor of 5～50 parts by ratio of weight and the number of copies with dipping glue; Wherein epoxy resin is a kind of in E-51, E-44, F-44, F-51 or several mixture wherein; Epoxy curing agent is a kind of in aliphatie diamine, aromatic diamine, modified aliphatic diamines or several mixture wherein; Curing catalyst is benzylamine or imidazoles, mixed solvent by component A and B component in mass ratio 1～3:1 form, wherein component A is N, dinethylformamide, N, a kind of in N-N,N-DIMETHYLACETAMIDE, acetone, pimelinketone, toluene, dimethylbenzene or wherein several mixture, B component is methyl alcohol, ethanol, a kind of in ethylene glycol or wherein several mixture; Inorganic combustion inhibitor is a kind of in magnesium hydroxide, aluminium hydroxide, magnesium borate crystal whisker, aluminium borate whisker or several mixture wherein.
The reaction process of benzoxazine colophony of the present invention is as follows, and wherein R1 is two functionality phenolic compounds, and R2 is benzoxazine colophony.
Advantage of the present invention is as follows:
1, benzoxazine colophony of the present invention has high nitrogen content, can obviously improve the flame retardant resistance of resin; Not phosphorous in benzoxazine colophony, can be to environment;
2, benzoxazine colophony of the present invention is according to the test of GB/T4722-92-26 vertical combustion method, and its cured article has self-extinguishing;
3, after the polymerization of benzoxazine colophony own, there is self-extinguishing; When itself and epoxy resin, when mixing, can obviously improve the inflammable resin such as resol the flame retardant resistance of resin; When its solidifying agent as epoxy resin, not only the phenolic hydroxyl group after open loop can with epoxy reaction, and methylol also can react with epoxy resin, between unnecessary methylol, self also can polycondensation.Benzoxazine colophony has polyfunctionality, self can open loop crosslinking reaction and polycondensation, and when its solidifying agent as epoxy resin reacts with epoxy resin, cross-linking density is large, and can improve its mechanical property and resistance toheat.
4, in dipping glue of the present invention, the consumption of solvent is low, has saved cost, and dipping glue, prepreg and baseplate material is not halogen-containing and phosphorus, meets environmental requirement.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: present embodiment benzoxazine colophony is made by the formaldehyde of 650～820 parts, the alkaline conditioner of 0.1～2.5 part, the trimeric cyanamide of 120～190 parts, the solvent of 0～600 part and the two functionality phenolic compounds of 100～200 parts by ratio of weight and the number of copies; Wherein said alkaline conditioner is a kind of in sodium hydroxide, triethylamine, ammoniacal liquor or several mixture wherein; Described solvent is a kind of in dioxane, toluene, dimethylbenzene, methyl alcohol, ethanol, ethylene glycol, trichloromethane or several mixture wherein; Described two functionality phenolic compounds are dihydroxybiphenyl compounds, dihydroxy naphthlene compounds or bisphenol compound, and facing in a carbon atom of the phenolic hydroxyl group place carbon atom of two functionality phenolic compounds has at least a hydrogen atom facing on a carbon atom by other groups, not replaced.
When described in present embodiment, alkaline conditioner is mixture, between each component, mix in any proportion; When solvent is mixture, between each component, mix in any proportion.
Embodiment two: what present embodiment was different from embodiment one is that: benzoxazine colophony is made by the formaldehyde of 650 parts, the alkaline conditioner of 0.1 part, the trimeric cyanamide of 120 parts and the two functionality phenolic compounds of 100 parts by ratio of weight and the number of copies.Other is identical with embodiment one.
Embodiment three: what present embodiment was different from embodiment one is that: benzoxazine colophony is made by the formaldehyde of 820 parts, the alkaline conditioner of 2.5 parts, the trimeric cyanamide of 190 parts, the solvent of 600 parts and the two functionality phenolic compounds of 200 parts by ratio of weight and the number of copies.Other is identical with embodiment one.
Embodiment four: what present embodiment was different from embodiment one is that: benzoxazine colophony is made by the formaldehyde of 700～800 parts, the alkaline conditioner of 0.5～2 part, the trimeric cyanamide of 130～180 parts, the solvent of 100～500 parts and the two functionality phenolic compounds of 120～180 parts by ratio of weight and the number of copies.Other is identical with embodiment one.
Embodiment five: what present embodiment was different from embodiment one is that: benzoxazine colophony is made by the formaldehyde of 730～770 parts, the alkaline conditioner of 1～1.5 part, the trimeric cyanamide of 140～170 parts, the solvent of 200～400 parts and the two functionality phenolic compounds of 140～160 parts by ratio of weight and the number of copies.Other is identical with embodiment one.
Embodiment six: what present embodiment was different from embodiment one is that: benzoxazine colophony is made by the formaldehyde of 750 parts, the alkaline conditioner of 1.2 parts, the trimeric cyanamide of 160 parts, the solvent of 300 parts and the two functionality phenolic compounds of 150 parts by ratio of weight and the number of copies.Other is identical with embodiment one.
Embodiment seven: the preparation method of present embodiment benzoxazine colophony, carry out according to the following steps: one, get the formaldehyde of 650～820 parts, with the alkaline conditioner adjust pH of 0.1～2.5 part, be 8～9, then the trimeric cyanamide that adds 120～190 parts, under 68～72 ℃ of conditions, stir to clarify, react afterwards 20～30 minutes; Two, then in reaction system, add the two functionality phenolic compounds of 100～200 parts and the solvent of 0～600 part, make reaction system be warming up to 80～120 ℃, react 2～3 hours, obtain resin liquid; Three, by resin liquid underpressure distillation, when anhydrous, stop decompression while deviating from, obtain benzoxazine colophony; Wherein said alkaline conditioner is a kind of in sodium hydroxide, triethylamine, ammoniacal liquor or several mixture wherein; Described solvent is a kind of in dioxane, toluene, dimethylbenzene, methyl alcohol, ethanol, ethylene glycol, trichloromethane or several mixture wherein; Described two functionality phenolic compounds are dihydroxybiphenyl compounds, dihydroxy naphthlene compounds or bisphenol compound, and facing in a carbon atom of the phenolic hydroxyl group place carbon atom of two functionality phenolic compounds has at least a hydrogen atom facing on a carbon atom by other groups, not replaced.
When described in present embodiment, alkaline conditioner is mixture, between each component, mix in any proportion; When solvent is mixture, between each component, mix in any proportion.
Embodiment eight: present embodiment is different from embodiment seven: be 8 with alkaline conditioner adjust pH in step 1.Other is identical with embodiment seven.
Embodiment nine: present embodiment is different from embodiment seven: be 9 with alkaline conditioner adjust pH in step 1.Other is identical with embodiment seven.
Embodiment ten: present embodiment is different from embodiment seven: be 8.5 with alkaline conditioner adjust pH in step 1.Other is identical with embodiment seven.
Embodiment 11: present embodiment is different from one of embodiment seven to ten: stir under 68 ℃ of conditions in step 1.Other is identical with one of embodiment seven to ten.
Embodiment 12: present embodiment is different from one of embodiment seven to ten: stir under 72 ℃ of conditions in step 1.Other is identical with one of embodiment seven to ten.
Embodiment 13: present embodiment is different from one of embodiment seven to ten: stir under 70 ℃ of conditions in step 1.Other is identical with one of embodiment seven to ten.
Embodiment 14: present embodiment is different from one of embodiment seven to 13: react in step 1 20 minutes.Other is identical with one of embodiment seven to 13.
Embodiment 15: present embodiment is different from one of embodiment seven to 13: react in step 1 30 minutes.Other is identical with one of embodiment seven to 13.
Embodiment 16: present embodiment is different from one of embodiment seven to 13: react in step 1 25 minutes.Other is identical with one of embodiment seven to 13.
Embodiment 17: present embodiment is different from one of embodiment seven to 16: be warming up to 80 ℃ in step 2.Other is identical with one of embodiment seven to 16.
Embodiment 18: present embodiment is different from one of embodiment seven to 16: be warming up to 120 ℃ in step 2.Other is identical with one of embodiment seven to 16.
Embodiment 19: present embodiment is different from one of embodiment seven to 16: be warming up to 100 ℃ in step 2.Other is identical with one of embodiment seven to 16.
Embodiment 20: present embodiment is different from one of embodiment seven to 19: react in step 22 hours.Other is identical with one of embodiment seven to 19.
Embodiment 21: present embodiment is different from one of embodiment seven to 19: react in step 23 hours.Other is identical with one of embodiment seven to 19.
Embodiment 22: present embodiment is different from one of embodiment seven to 19: react in step 2 2.5 hours.Other is identical with one of embodiment seven to 19.
Embodiment 23: the preparation method of present embodiment benzoxazine colophony, carry out according to the following steps: one, to the formaldehyde that adds 700 parts in there-necked flask, with the triethylamine adjust pH of 0.5 part, be 8, then the trimeric cyanamide that adds 136 parts, under 70 ℃ of conditions, stir to clarify, react afterwards 20 minutes; Two, then to the dihydroxyphenyl propane that adds 123 parts in reaction system, make reaction system be warming up to 98 ℃, react 2 hours, obtain resin liquid; Three, by resin liquid underpressure distillation, when anhydrous, stop decompression while deviating from, obtain benzoxazine colophony.
The structure of the benzoxazine colophony that present embodiment makes is as follows:
Embodiment 24: the preparation method of present embodiment benzoxazine colophony, carry out according to the following steps: one, to the formaldehyde that adds 700 parts in there-necked flask, with the sodium hydroxide adjust pH of 1 part, be 8.5, then the trimeric cyanamide that adds 100 parts, under 68 ℃ of conditions, stir to clarify, react afterwards 25 minutes; Two, then to add in reaction system 133 parts 2, the dioxane of 2'-dihydroxybiphenyl and 130 parts, makes reaction system be warming up to 80 ℃, reacts 2 hours, obtains resin liquid; Three, by resin liquid underpressure distillation, when anhydrous, stop decompression while deviating from, obtain benzoxazine colophony.
The structure of the benzoxazine colophony that present embodiment makes is as follows:
Embodiment 25: the preparation method of present embodiment benzoxazine colophony, carry out according to the following steps: one, to the formaldehyde that adds 700 parts in there-necked flask, with the ammoniacal liquor adjust pHs of 2 parts, be 8.5, then the trimeric cyanamide that adds 30 parts, under 72 ℃ of conditions, stir to clarify, react afterwards 25 minutes; Two, then in reaction system, add the 2,7 dihydroxy naphthalene of 115 parts and the dimethylbenzene of 200 parts, make reaction system be warming up to 120 ℃, react 3 hours, obtain resin liquid; Three, by resin liquid underpressure distillation, when anhydrous, stop decompression while deviating from, obtain benzoxazine colophony.
The structure of the benzoxazine colophony that present embodiment makes is as follows:
Embodiment 26: the preparation method of present embodiment benzoxazine colophony, carry out according to the following steps: one, to the formaldehyde that adds 800 parts in there-necked flask, with the sodium hydroxide of 0.5 part and 0.2 part of triethylamine adjust pH, be 8.5, then the trimeric cyanamide that adds 100 parts, under 68 ℃ of conditions, stir to clarify, react afterwards 25 minutes; Two, then to add in reaction system 130 parts 4, the dimethylbenzene of 4-dihydroxybiphenyl and 150 parts, makes reaction system be warming up to 100 ℃, reacts 2 hours, obtains resin liquid; Three, by resin liquid underpressure distillation, when anhydrous, stop decompression while deviating from, obtain benzoxazine colophony.
The structure of the benzoxazine colophony that present embodiment makes is as follows:
Embodiment 27: the preparation method of present embodiment benzoxazine colophony, carry out according to the following steps: one, to the formaldehyde that adds 810 parts in there-necked flask, with 0.8 part of triethylamine adjust pH, be 9.0, then the trimeric cyanamide that adds 110 parts, under 70 ℃ of conditions, stir to clarify, react afterwards 30 minutes; Two, then to the 5' that adds 133 parts in reaction system, 5-diallyl-2,2'-'-biphenyl diphenol, dimethylbenzene and 50 parts of ethanol of 100 parts, make reaction system be warming up to 120 ℃, reacts 3 hours, obtains resin liquid; Three, by resin liquid underpressure distillation, when anhydrous, stop decompression while deviating from, obtain benzoxazine colophony.
The structure of the benzoxazine colophony that present embodiment makes is as follows:
Embodiment 28: the preparation method of present embodiment benzoxazine colophony, carry out according to the following steps: one, to the formaldehyde that adds 820 parts in there-necked flask, with 0.5 part of triethylamine and 1.5 parts of ammoniacal liquor adjust pHs, be 9.0, then the trimeric cyanamide that adds 110 parts, under 72 ℃ of conditions, stir to clarify, react afterwards 30 minutes; Two, then to the 5' that adds 110 parts in reaction system, 5-diallyl-2,2'-'-biphenyl diphenol, dimethylbenzene and 50 parts of ethanol of 100 parts, make reaction system be warming up to 120 ℃, reacts 3 hours, obtains resin liquid; Three, by resin liquid underpressure distillation, when anhydrous, stop decompression while deviating from, obtain benzoxazine colophony.
The structure of the benzoxazine colophony that present embodiment makes is as follows:
Embodiment 29: the preparation method of present embodiment benzoxazine colophony, carry out according to the following steps: one, to the formaldehyde that adds 710 parts in there-necked flask, with 0.5 part of triethylamine adjust pH, be 8.5, then the trimeric cyanamide that adds 100 parts, under 68 ℃ of conditions, stir to clarify, react afterwards 25 minutes; Two, then in reaction system, add the Bisphenol F of 140 parts and the dimethylbenzene of 200 parts, make reaction system be warming up to 98 ℃, react 2 hours, obtain resin liquid; Three, by resin liquid underpressure distillation, when anhydrous, stop decompression while deviating from, obtain benzoxazine colophony.
The structure of the benzoxazine colophony that present embodiment makes is as follows:
Embodiment 30: the preparation method of present embodiment benzoxazine colophony, carry out according to the following steps: one, to the formaldehyde that adds 740 parts in there-necked flask, with 2 parts of ammoniacal liquor adjust pHs, be 8.5, then the trimeric cyanamide that adds 110 parts, under 70 ℃ of conditions, stir to clarify, react afterwards 25 minutes; Two, then in reaction system, add the bisphenol S of 115 parts and the toluene of 100 parts, make reaction system be warming up to 98 ℃, react 2 hours, obtain resin liquid; Three, by resin liquid underpressure distillation, when anhydrous, stop decompression while deviating from, obtain benzoxazine colophony.
The structure of the benzoxazine colophony that present embodiment makes is as follows:
Embodiment 31: present embodiment benzoxazine colophony is that the halogen-free phosphorus-free inflaming retarding copper-clad plate that raw material is made is made by the benzoxazine colophony of 20～90 parts, the epoxy resin of 10～80 parts, the epoxy curing agent of 0～30 part, the curing catalyst of 0.1～5 part, the mixed solvent of 30～100 parts and the inorganic combustion inhibitor of 5～50 parts by ratio of weight and the number of copies with dipping glue; Wherein epoxy resin is a kind of in E-51, E-44, F-44, F-51 or several mixture wherein; Epoxy curing agent is a kind of in aliphatie diamine, aromatic diamine, modified aliphatic diamines or several mixture wherein; Curing catalyst is benzylamine or imidazoles, mixed solvent by component A and B component in mass ratio 1～3:1 form, wherein component A is N, dinethylformamide, N, a kind of in N-N,N-DIMETHYLACETAMIDE, acetone, pimelinketone, toluene, dimethylbenzene or wherein several mixture, B component is methyl alcohol, ethanol, a kind of in ethylene glycol or wherein several mixture; Inorganic combustion inhibitor is a kind of in magnesium hydroxide, aluminium hydroxide, magnesium borate crystal whisker, aluminium borate whisker or several mixture wherein.
When described in present embodiment, epoxy resin is mixture, between each component, mix in any proportion; When epoxy curing agent is mixture, between each component, mix in any proportion; When curing catalyst is mixture, between each component, mix in any proportion; When the component A in mixed solvent is mixture, between each component, mix in any proportion; When the B component in mixed solvent is mixture, between each component, mix in any proportion; When inorganic combustion inhibitor is mixture, between each component, mix in any proportion.
Embodiment 32: what present embodiment was different from embodiment 31 is that: benzoxazine colophony is that the halogen-free phosphorus-free inflaming retarding copper-clad plate that raw material is made is made by the benzoxazine colophony of 20 parts, the epoxy resin of 10 parts, the curing catalyst of 0.1 part, the mixed solvent of 30 parts and the inorganic combustion inhibitor of 5 parts by ratio of weight and the number of copies with dipping glue.Other is identical with embodiment 31.
Embodiment 33: what present embodiment was different from embodiment 31 is that: benzoxazine colophony is that the halogen-free phosphorus-free inflaming retarding copper-clad plate that raw material is made is made by the benzoxazine colophony of 90 parts, the epoxy resin of 80 parts, the epoxy curing agent of 30 parts, the curing catalyst of 5 parts, the mixed solvent of 100 parts and the inorganic combustion inhibitor of 50 parts by ratio of weight and the number of copies with dipping glue.Other is identical with embodiment 31.
Embodiment 34: what present embodiment was different from embodiment 31 is that: benzoxazine colophony is that the halogen-free phosphorus-free inflaming retarding copper-clad plate that raw material is made is made by the benzoxazine colophony of 30～70 parts, the epoxy resin of 20～70 parts, the epoxy curing agent of 5～25 parts, the curing catalyst of 0.5～4 part, the mixed solvent of 40～90 parts and the inorganic combustion inhibitor of 10～40 parts by ratio of weight and the number of copies with dipping glue.Other is identical with embodiment 31.
Embodiment 35: what present embodiment was different from embodiment 31 is that: benzoxazine colophony is that the halogen-free phosphorus-free inflaming retarding copper-clad plate that raw material is made is made by the benzoxazine colophony of 40～60 parts, the epoxy resin of 30～60 parts, the epoxy curing agent of 10～20 parts, the curing catalyst of 1～3 part, the mixed solvent of 50～80 parts and the inorganic combustion inhibitor of 20～30 parts by ratio of weight and the number of copies with dipping glue.Other is identical with embodiment 31.
Embodiment 36: what present embodiment was different from embodiment 31 is that: benzoxazine colophony is that the halogen-free phosphorus-free inflaming retarding copper-clad plate that raw material is made is made by the benzoxazine colophony of 50 parts, the epoxy resin of 45 parts, the epoxy curing agent of 15 parts, the curing catalyst of 2 parts, the mixed solvent of 65 parts and the inorganic combustion inhibitor of 25 parts by ratio of weight and the number of copies with dipping glue.Other is identical with embodiment 31.
Embodiment 37: present embodiment benzoxazine colophony is that the halogen-free phosphorus-free inflaming retarding copper-clad plate that raw material is made is made by the benzoxazine colophony of 40 parts, the epoxy resin E-51 of 60 parts, the dimethyl benzylamine of 0.325 part, the DMF of 25 parts, the methyl alcohol of 25 parts and the magnesium hydroxide of 30 parts by ratio of weight and the number of copies with dipping glue; Wherein benzoxazine colophony is the benzoxazine colophony that embodiment 23 makes.
The copper-clad plate of present embodiment halogen-free phosphorus-free inflaming retarding by the preparation method of dipping glue is: 40 parts of benzoxazine colophonies and 60 parts of epoxy resin E-51 are joined in reactor, and add 25 parts of N, dinethylformamide and 25 parts of methyl alcohol, then add 0.325 part of dimethyl benzylamine, at 85 ℃, stir slaking 2 hours, sampling and measuring molding time, 80～100s/160 ℃ when the molding, adds 30 parts of magnesium hydroxides, then stirs 3 hours, sampling and measuring molding time, molding time 80～100s/160 ℃.
Embodiment 38: present embodiment benzoxazine colophony is that the halogen-free phosphorus-free inflaming retarding copper-clad plate that raw material is made is made by the benzoxazine colophony of 40 parts, the epoxy resin F-44 of 40 parts, the epoxy resin E-44 of 20 parts, the glyoxal ethyline of 0.6 part, the N,N-dimethylacetamide of 25 parts, the ethanol of 25 parts and the magnesium borate crystal whisker of 6 parts by ratio of weight and the number of copies with dipping glue; Wherein benzoxazine colophony is the benzoxazine colophony mixture that 1:1 forms in mass ratio that the benzoxazine colophony that makes of embodiment 24 and embodiment 25 make.
The copper-clad plate of present embodiment halogen-free phosphorus-free inflaming retarding by the preparation method of dipping glue is: 40 parts of benzoxazine colophonies, 40 parts of epoxy resin F-44 and 20 parts of epoxy resin E-44s are joined in reactor, and add 25 parts of N, N-N,N-DIMETHYLACETAMIDE and 25 parts of ethanol, add again 0.6 part of glyoxal ethyline, at 80 ℃, stir slaking 3 hours, survey molding time 100～130s/160 ℃, add 6 parts of magnesium borate crystal whiskers, stir again sampling and measuring molding time, gel time 100～130s/160 ℃ 4 hours
Embodiment 39: to be the raw material halogen-free phosphorus-free inflaming retarding copper-clad plate of making made by the benzoxazine colophony of 30 parts, the epoxy resin E-51 of 40 parts, the epoxy resin F-51 of 30 parts, the 2-phenylimidazole of 0.2 part, the toluene of 25 parts, the methyl alcohol of 25 parts, magnesium hydroxide and 10 parts of aluminium hydroxides of 30 parts with dipping glue present embodiment benzoxazine colophony by ratio of weight and the number of copies; Wherein benzoxazine colophony is the benzoxazine colophony that embodiment 25 makes.
The copper-clad plate of present embodiment halogen-free phosphorus-free inflaming retarding by the preparation method of dipping glue is: 30 parts of benzoxazine colophonies, 40 parts of epoxy resin E-51 and 30 parts of epoxy resin F-51 are joined in reactor, and add 25 parts of toluene and 25 parts of methyl alcohol, the 2-phenylimidazole that adds again 0.2 part, at 83 ℃, stir slaking 4 hours, survey molding time 100～130s/160 ℃, add 20 parts of magnesium hydroxides and 10 parts of aluminium hydroxides, stir again 5 hours, sampling and measuring molding time, gel time 100～130s/160 ℃.
Embodiment 40: present embodiment benzoxazine colophony is that the halogen-free phosphorus-free inflaming retarding copper-clad plate that raw material is made is made by the benzoxazine colophony of 35 parts, the epoxy resin E-44 of 75 parts, the dimethyl benzylamine of 0.15 part, the pimelinketone of 30 parts, ethanol and 30 parts of aluminium hydroxides of 30 parts by ratio of weight and the number of copies with dipping glue; Wherein benzoxazine colophony is the benzoxazine colophony that embodiment 29 makes.
The copper-clad plate of present embodiment halogen-free phosphorus-free inflaming retarding by the preparation method of dipping glue is: the epoxy resin E-44 of 35 parts of benzoxazine colophonies and 75 parts is joined in reactor, and add the pimelinketone of 30 parts and the ethanol of 30 parts, the dimethyl benzylamine that adds again 0.15 part, at 70 ℃, stir slaking 3 hours, survey molding time 80～100s/160 ℃, add 30 parts of aluminium hydroxides, then stir 4 hours, sampling and measuring molding time, gel time 80～100s/160 ℃.
Embodiment 41: present embodiment benzoxazine colophony be the raw material halogen-free phosphorus-free inflaming retarding copper-clad plate made from dipping glue by ratio of weight and the number of copies by the benzoxazine colophony of 30 parts, 70 parts epoxy resin E-51,6 parts 4,4' diaminodiphenylsulfone(DDS), the dimethyl benzylamine of 1.5 parts, the acetone of 40 parts, the ethanol of 20 parts, the magnesium borate crystal whisker of 2 parts and the aluminium borate whisker of 2.5 parts are made; Wherein benzoxazine colophony is the benzoxazine colophony that embodiment 28 makes.
The copper-clad plate of present embodiment halogen-free phosphorus-free inflaming retarding by the preparation method of dipping glue is: the epoxy resin E-51 of 30 parts of benzoxazine colophonies and 70 parts is joined in reactor, and add the acetone of 40 parts and the ethanol of 20 parts, add again 6 parts 4, the dimethyl benzylamine of 4' diaminodiphenylsulfone(DDS) and 1.5 parts, at 70 ℃, stir slaking 3 hours, survey molding time 80～100s/160 ℃, add 2 parts of magnesium borate crystal whiskers and 2.5 parts of aluminium borate whiskers, stir again 4 hours, sampling and measuring molding time, gel time 80～100s/160 ℃.
The dipping glue that embodiment 37～embodiment 41 is made is impregnated glass-fiber cloth respectively, in the baking oven of 130～140 ℃, dries 3～5min, makes prepreg.Recording soluble resin content is 85～92wt%, and volatile content is less than 2wt%.
Prepared prepreg is according to certain size cutting, superimposed by certain number, and initial temperature is 120～130 ℃, and initial pressure is 1～2Mpa, and outlet temperature is 170 ℃, and final pressure is 8～9Mpa, and compacting 150min obtains copper clad laminate material.
Copper clad laminate material is carried out to the test of electric property, mechanical property and the flame retardant properties of sheet material according to < < printed electronic circuit with copper-clad laminate test method > > GB/T4722-92.Utilize the performance of halogen-free phosphorus-free inflaming retarding copper clad laminate material prepared by dipping glue that embodiment 37～embodiment 41 obtains as shown in table 1.
Table 1
From table, result is known, and halogen-free phosphorus-free inflaming retarding copper clad laminate material meets the industry standard that FR-4 copper-clad plate is produced.
Claims (3)
1. the preparation method of benzoxazine colophony, the preparation method who it is characterized in that benzoxazine colophony, carry out according to the following steps: one, get the formaldehyde of 650～820 parts, with the alkaline conditioner adjust pH of 0.1～2.5 part, be 8～9, then the trimeric cyanamide that adds 120～190 parts, under 68～72 ℃ of conditions, stir to clarify, react afterwards 20～30 minutes; Two, then in reaction system, add the two functionality phenolic compounds of 100～200 parts and the solvent of 0～600 part, make reaction system be warming up to 100 ℃, react 2～3 hours, obtain resin liquid; Three, by resin liquid underpressure distillation, when anhydrous, stop decompression while deviating from, obtain benzoxazine colophony; Wherein said alkaline conditioner is a kind of in sodium hydroxide, triethylamine, ammoniacal liquor or several mixture wherein; Described solvent is a kind of in dioxane, toluene, dimethylbenzene, methyl alcohol, ethanol, ethylene glycol, trichloromethane or several mixture wherein; Described two functionality phenolic compounds are dihydroxybiphenyl compounds, dihydroxy naphthlene compounds or bisphenol compound, and facing in a carbon atom of the phenolic hydroxyl group place carbon atom of two functionality phenolic compounds has at least a hydrogen atom facing on a carbon atom by other groups, not replaced.
2. the preparation method of benzoxazine colophony according to claim 1, is characterized in that in step 1 being 8.5 with alkaline conditioner adjust pH.
3. the preparation method of benzoxazine colophony according to claim 1 and 2, is characterized in that under 70 ℃ of conditions, stirring in step 1.
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| CN103951808B (en) * | 2014-01-21 | 2015-12-02 | 哈尔滨理工大学 | Water-soluble benzoxazine colophony and preparation method thereof |
| CN104927353B (en) * | 2015-06-12 | 2017-07-11 | 四川东材科技集团股份有限公司 | Fire-retardant non-halogen non-phosphate resin combination and application thereof and for prepreg, laminate, copper-clad plate preparation method |
| CN109748279A (en) * | 2019-02-21 | 2019-05-14 | 南京大学 | One kind is based on poromeric micro-pore carbon material of benzoxazine and its preparation method and application |
| CN113956750B (en) * | 2021-11-12 | 2022-10-11 | 中国林业科学研究院林产化学工业研究所 | Benzoxazine/epoxy resin composite flame-retardant anticorrosive coating and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4436853A (en) * | 1982-08-20 | 1984-03-13 | The Goodyear Tire & Rubber Company | Phenol-melamine resins for improving rubber to metal adhesion |
| CN1723243A (en) * | 2002-11-08 | 2006-01-18 | 阿克苏诺贝尔公司 | Epoxy resin composition containing reactive flame retardant phosphonate oligomer and filler |
| CN101376735A (en) * | 2008-09-26 | 2009-03-04 | 广东生益科技股份有限公司 | Halogen-free flame-proof epoxy resin composition and bonding sheet and copper clad laminate prepared thereby |
| CN101381506A (en) * | 2008-09-26 | 2009-03-11 | 广东生益科技股份有限公司 | Halogen and phosphor-free flame-proof epoxy resin composition and bonding sheet and copper clad laminate prepared thereby |
-
2011
- 2011-08-10 CN CN201110228773.1A patent/CN102408419B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4436853A (en) * | 1982-08-20 | 1984-03-13 | The Goodyear Tire & Rubber Company | Phenol-melamine resins for improving rubber to metal adhesion |
| CN1723243A (en) * | 2002-11-08 | 2006-01-18 | 阿克苏诺贝尔公司 | Epoxy resin composition containing reactive flame retardant phosphonate oligomer and filler |
| CN101376735A (en) * | 2008-09-26 | 2009-03-04 | 广东生益科技股份有限公司 | Halogen-free flame-proof epoxy resin composition and bonding sheet and copper clad laminate prepared thereby |
| CN101381506A (en) * | 2008-09-26 | 2009-03-11 | 广东生益科技股份有限公司 | Halogen and phosphor-free flame-proof epoxy resin composition and bonding sheet and copper clad laminate prepared thereby |
Non-Patent Citations (7)
| Title |
|---|
| Condensation of Substituted Phenols with Hexakis(methoxymethyl)melamine:Synthesis, Characterization, and Properties of Substituted 2,4,6-Tris[3,4-dihydro-1,3-(2H)-benzoxazin-3-yl]-s-triazine Derivatives;Ramachandran P. Subrayan,等;《Chem. Mater.》;19981017;第10卷(第11期);第3507页左栏Synthesis of 1,3-benzoxazines * |
| Hann-Jang Hwang，等.Flame Retardancy and Dielectric Properties of Dicyclopentadiene-Based Benzoxazine Cured with a phosphorus-containing phenolic resin.《Journal of applied polymer science》.2008,第110卷(第4期),2413-2423. * |
| Jeng-Yueh Shieh，等.Synthesis and Characterization of Novel Dihydrobenzoxazine Resins.《Journal of Applied Polymer Science》.2006,第101卷(第1期),342-347. * |
| Ramachandran P. Subrayan,等.Condensation of Substituted Phenols with Hexakis(methoxymethyl)melamine:Synthesis, Characterization, and Properties of Substituted 2,4,6-Tris[3,4-dihydro-1,3-(2H)-benzoxazin-3-yl]-s-triazine Derivatives.《Chem. Mater.》.1998,第10卷(第11期),3506-3512. * |
| 宋小平，等.三聚氰胺甲醛胶黏剂.《胶黏剂实用配方与生产工艺》.中国纺织出版社,2010,(第1版),248-249. * |
| 欧育湘.三嗪系阻燃剂.《阻燃剂：制造、性能及应用》.兵器工业出版社,1997,(第1版),139-140. * |
| 王永红，等.阻燃热固性树脂及其材料国外研究进展.《热固性树脂》.2006,第21卷57-79. * |
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