CN110283289A - A kind of phosphorous benzoxazine resin of high flame retardant and its preparation method and application - Google Patents
A kind of phosphorous benzoxazine resin of high flame retardant and its preparation method and application Download PDFInfo
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- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
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- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
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- B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
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- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
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- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
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- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/021—Fibrous or filamentary layer
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- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—Synthetic resin
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
- B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
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Abstract
A kind of preparation method of the phosphorous benzoxazine resin of high flame retardant, phosphorous bis-phenol intermediate, primary amine and aldehyde compound is uniformly mixed in organic solvent, then add amines catalyst, is carried out reaction and is synthesized phosphorous benzoxazine resin；The chemical structural formula of the phosphorous benzoxazine resin is shown in formula I:
Description
Technical field
The present invention relates to the preparation technical fields of benzoxazine resin, and in particular to a kind of phosphorous benzoxazine of high flame retardant
Resin and its preparation method and application.
Background technique
Ring-opening polymerisation occurs under heating or catalyst action for benzoxazine, and generating has nitrogenous and similar phenolic resin net
The polybenzoxazine of shape structure, therefore also known as novel phenolic resins.Benzoxazine resin has been widely applied to largely at present
In industrial products, such as high temperature resistant composite, high performance copper clad laminate, high-quality plastic packaging material.It can also with other resins or
Additive (catalyst, toughener etc.) is compound to further increase performance；Benzoxazine resin performance is than traditional phenolic resin, ring
Oxygen resin wants excellent, and Costco Wholesale is moderate, and future can play in some middle- and high-end applications and do use.Benzoxazine resin and other
The compatibility of resin can also compound the heat resistance for increasing material with other resins, improve the functions such as dimension stability.
The common synthetic method of benzoxazine resin has solwution method, solventless method, suspension method etc. at present.Solwution method is will be anti-
It answers object to be dissolved in temperature reaction after mixing in suitable solvent, is removing solvent after reactive polymeric, this method is a little
It is uniformly mixed between solid reactant solution, heat release incrementally increase with reaction, and product yield is higher.The disadvantage is that
It needs using a large amount of first benzene kind solvent, solvent can be carcinogenic, and a large amount of use costs are high；No-solvent synthesis process, reaction monomers
It is solid, molten condition is heated into after mechanical mixture and starts to react, starts to react at a certain temperature, the method is without using molten
Agent can effectively avoid environmental pollution and reduce cost, but also result in exothermic heat of reaction and be not easily controlled, and reaction part is put
Popular drama is strong, influences product yield；Suspension method is using water as decentralized medium, and under the action of suspending agent, high-speed stirred cools down after being granulated
Cleaning product.For suspension method using water as decentralized medium, avoiding reduces environmental pollution using organic solvent, further reduced into
This, but since the direct dissolubility of reactant is bad, cause reaction speed slow, product purity is not high, and yield is low.
And with laminate, the requirement of refractory material, interior trim prepreg to Flame Retardancy energy is increasingly increased, and is proposed
A kind of benzoxazine resin polymer of the high flame retardant of phosphorous hot book structure.Common benzoxazine resin glass cloth laminated board
V-0 can be can achieve by the flame retardant rating of material after the fire retardants such as the inorganic aluminium hydroxide of addition, polysilane, methyl phosphorodithioate
Grade, but to the electricity of material, Effect on Mechanical Properties is very serious, and additive amount is all in 10%-20% or more.Such as add six benzene oxygen
After three phosphorus eyeball of basic ring, the flame retardant rating of laminate reaches V-0 grades, but the complete intensity of laminate is dropped to by 484Mpa
410Mpa, 5% thermal weight loss also have 420 DEG C of pure benzoxazine resin to drop to 290 DEG C, also will affect the outer of product when in addition solidifying
The property seen.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of phosphorous benzoxazine resin of high flame retardant and its preparation sides
Method and purposes, overcome the deficiencies in the prior art, change benzoxazine resin monomer structure by chemic modified method, increase
Phosphorous-containing monomers have designed and synthesized out phosphorous ring-like benzoxazine monomer, have effectively improved in the molecular structure of benzoxazine
The heat resistance and anti-flammability of polybenzoxazine resin, and mechanical property, electric property do not have much affect；And it is preparing
It can be improved product purity and yield in technique；It can be suitble to be mass produced.
In order to achieve the above object, the present invention is achieved by the following technical programs:
A kind of phosphorous benzoxazine resin of high flame retardant, the chemical structural formula of phosphorous benzoxazine resin are such as Formulas I institute
Show:
Wherein,For any one in having structure:
The invention also discloses the preparation methods of phosphorous benzoxazine resin, specifically includes the following steps:
(1) benzoxazine monomer is prepared, is sequentially added in the organic solvent into self-priming exhaust gas heat exchanging reactor phosphorous
Bis-phenol intermediate, primary amine, aldehyde compound and amines catalyst open Mixing Machine and are stirred mixing, and use gradient increased temperature
It to 100 DEG C~110 DEG C, reacts 1.5-2.5 hours, when system becomes transparence, leads to condensed water cooling, terminate reaction；It obtains
Benzoxazine monomer mixture.
(2) aqueous slkali is added in the obtained benzoxazine monomer mixture in step (1) and is stirred for purification process
1-2 hours, the oligomer generated in removing system and other impurities, then washing 3 times makes system close to neutrality.
(3) it removes solvent: the system after step (2) purification process being heated to 90-100 DEG C, is rapidly removed under vacuum
Solvent and residual moisture in system obtain benzoxazine monomer.
(4) compound solidifies: benzoxazine monomer obtained in step (3) being placed in stainless steel mould, in electric heating
In air dry oven after pumping 30min, start program heating.Solidify temperature program: 1 hour under the conditions of 160 DEG C, 180 DEG C of conditions
Under the conditions of lower 1 hour, 200 DEG C 1 hour under the conditions of 1 hour, 240 DEG C, obtain solidifying phosphorous benzoxazine resin product.
Preferably, the molar ratio of phosphorous bis-phenol intermediate, primary amine and aldehyde compound is 1:1:2 in the step (1).
Preferably, the chemical structural formula of the phosphorous bis-phenol intermediate in the step (1) is as shown in formula II:
Preferably, the synthetic reaction equation of the phosphorous bis-phenol intermediate is as shown in formula III:
Its synthesis step are as follows:
A. acetic acid and a hydration sodium hypophosphite are added in three mouthfuls of reaction flasks, initiator benzoyl peroxide is added after its dissolution
Formyl and to allyloxy phenol, after 100 DEG C of reaction 4h, is cooled to room temperature, obtains light yellow liquid.
B. yellow liquid is transferred in single necked round bottom flask and rotates out solvent and recycles, remaining solid is with two in bottle
Chloromethanes washing removes organic impurities, and phosphorous bis-phenol intermediate is obtained after draining.
Preferably, the organic solvent in the step (1) is methanol, ethyl alcohol, ethyl acetate, methylene chloride, chloroform, first
Benzene, dimethylbenzene, acetone, butanone, methylisobutylketone, glycol monoethyl ether, glycol dimethyl ether, propylene glycol monomethyl ether, dioxy six
One or more of ring, dimethyl sulfoxide compound.
Preferably, the aldehyde compound in the step (1) is formalin or paraformaldehyde.
Preferably, being added in the step (2) is aqueous slkali for sodium hydroxide or potassium hydroxide, and is combined with phase turn
Shifting catalyst.
The invention also discloses a kind of manufacture craft of glass cloth laminated board, step includes: by above-mentioned preparation method institute
Obtained phosphorous benzoxazine resin monomer is uniformly mixed with curing agent, bisphenol A type epoxy resin, butanone, is added certain
Aluminium hydroxide obtains non-antiflaming property benzoxazine resin liquid after high speed dispersion；Above-mentioned benzoxazine resin liquid is impregnated into nothing again
Alkali glass cloth, and prepreg is prepared on gluing machine, prepreg amount containing benzoxazine resin is 37%-42%；It again will preimpregnation
Required size is made in material, according to the thickness that product needs, takes several prepreg overlapping layers and is placed in smooth stainless
On steel plate, wherein being coated with release agent；It is hot-forming on press again, control gradient increased temperature, 10-20 DEG C of set temperature/
30min gradually heats up and pressurizes, and temperature 30min is kept after rising to 220 DEG C, increases pressure to 5Mpa, hot-forming 2h, demoulding
Product can be obtained.
The present invention provides a kind of preparation methods of the phosphorous benzoxazine resin of high flame retardant.Have it is following the utility model has the advantages that
Benzoxazine resin monomer structure is changed by chemic modified method, increases phosphorous-containing monomers in the molecular structure of benzoxazine,
Phosphorous ring-like benzoxazine monomer has been designed and synthesized out, has effectively improved polybenzoxazine by improving phosphorus content in monomer
The heat resistance and anti-flammability of resin, and mechanical property, electric property do not have much affect；And it can in preparation process
Improve product purity and yield.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with the attached drawing in the present invention, to this
Technical solution in invention is clearly and completely described.
Embodiment one, a kind of phosphorous benzoxazine resin of high flame retardant, the chemical structural formula of phosphorous benzoxazine resin
It is shown in formula I:
Wherein,For any one in having structure:
The invention also discloses the preparation methods of phosphorous benzoxazine resin, specifically includes the following steps:
(1) benzoxazine monomer is prepared, in the organic solvent into self-priming exhaust gas heat exchanging reactor successively in molar ratio
Phosphorous bis-phenol intermediate, primary amine, aldehyde compound is added for the ratio of 1:1:2, and amines catalyst is added, open Mixing Machine into
Row is stirred, and using gradient increased temperature to 80 DEG C~120 DEG C, is reacted 2-8 hours, when system becomes transparence, leads to condensation
Water cooling, terminates reaction；Obtain benzoxazine monomer mixture.Wherein amines catalyst can preferably reduce the residual of unhindered amina
It is remaining, increase reactivity, accelerates reaction speed.Wherein the chemical structural formula of phosphorous bis-phenol intermediate is as shown in formula II:
(2) sodium hydroxide or hydrogen are added in the obtained benzoxazine monomer mixture in step (1) for purification process
The aqueous slkali of potassium oxide is stirred 1-2 hours, the oligomer generated in removing system and other impurities, then is washed 3 times and made body
It is close to neutrality.Wherein the aqueous slkali of sodium hydroxide or potassium hydroxide needs to be added a small amount of phase transfer catalysis (PTC) when preparing
Agent is primarily used to wash off unreacted phenolic substances.
(3) it removes solvent: the system after step (2) purification process being heated to 90-100 DEG C, is rapidly removed under vacuum
Solvent and residual moisture in system obtain benzoxazine monomer.
(4) compound solidifies: benzoxazine monomer obtained in step (3) being placed in stainless steel mould, in electric heating
In air dry oven after pumping 30min, start program heating.Solidify temperature program: 1 hour under the conditions of 160 DEG C, 180 DEG C of conditions
Under the conditions of lower 1 hour, 200 DEG C 1 hour under the conditions of 1 hour, 240 DEG C, obtain solidifying phosphorous benzoxazine resin product.
Embodiment two
It is as follows using solwution method preparation benzoxazine resin reaction equation:
Its experimental procedure are as follows: at room temperature, add in the 100mL three neck round bottom flask equipped with reflux condensing tube and thermometer
Enter the aniline of 0.1mol, the toluene of 30mL and 0.2mol paraformaldehyde, the lower phosphorous bis-phenol intermediate of addition 0.05mol is sufficiently stirred
After A, it is warming up to 80 DEG C and reacts 4 hours.After being cooled to room temperature, reactant is washed three times, and vacuum distillation removes solvent and residual water
Get target benzoxazine resin BZ-1 about 26.5g, yield 85%.Resulting composition is subjected to 31P NMR test, gained
As a result as shown in Figure 1；It is as shown in Figure 2 that DSC tests acquired results；It is as shown in Figure 3 that TGA tests acquired results.
Embodiment three
It is as follows using solwution method preparation benzoxazine resin reaction equation:
Its experimental procedure are as follows: at room temperature, add in the 100mL three neck round bottom flask equipped with reflux condensing tube and thermometer
Enter the methylamine of 0.1mol, the dioxane of 30mL and 0.2mol paraformaldehyde, is sufficiently stirred in the phosphorous bis-phenol of lower addition 0.05mol
After mesosome A, it is warming up to 60 DEG C and reacts 8 hours.After being cooled to room temperature, reactant is washed three times, and vacuum distillation removes solvent and residual
Moisture is stayed to obtain target benzoxazine resin BZ-2 about 19.4g, yield 78%.
Example IV
It is as follows using solwution method preparation benzoxazine resin reaction equation:
Its experimental procedure are as follows: at room temperature, add in the 100mL three neck round bottom flask equipped with reflux condensing tube and thermometer
Enter the n-butylamine of 0.1mol, the dioxane of 30mL and 0.2mol paraformaldehyde, the phosphorous bis-phenol of lower addition 0.05mol is sufficiently stirred
After intermediate A, it is warming up to 100 DEG C and reacts 6 hours.After being cooled to room temperature, reactant wash three times, vacuum distillation remove solvent and
Residual moisture obtains target benzoxazine resin BZ-3 about 23.9g, yield 82%.
Embodiment five
It is as follows using solwution method preparation benzoxazine resin reaction equation:
Its experimental procedure are as follows: at room temperature, add in the 100mL three neck round bottom flask equipped with reflux condensing tube and thermometer
Enter the n-butylamine of 0.1mol, the dimethylbenzene of 30mL and 0.2mol paraformaldehyde, is sufficiently stirred in the phosphorous bis-phenol of lower addition 0.05mol
After mesosome A, it is warming up to 120 DEG C and reacts 2 hours.After being cooled to room temperature, reactant is washed three times, and vacuum distillation removes solvent and residual
Moisture is stayed to obtain target benzoxazine resin BZ-4 about 29.6g, yield 88%.
Embodiment six
The invention also discloses one kind to make glass fabric layer by the phosphorous benzoxazine resin monomer of above-mentioned high flame retardant
The manufacture craft of pressing plate, step include: by the obtained phosphorous benzoxazine resin monomer of above-mentioned preparation method and curing agent,
Bisphenol A type epoxy resin, butanone are proportionally uniformly mixed, and add the aluminium hydroxide of different quality containing, after high speed dispersion
Obtain non-antiflaming property benzoxazine resin liquid；Above-mentioned benzoxazine resin liquid is impregnated into alkali-free glass cloth again, and according to the rules
Technique is prepared into prepreg on gluing machine, and prepreg amount containing benzoxazine resin is 37%-42%；Institute is made in prepreg again
The size needed takes several prepreg overlapping layers and is placed on smooth stainless steel plate according to the thickness that product needs,
In be coated with release agent；It is hot-forming on press again, gradient increased temperature is controlled, 10-20 DEG C of set temperature/30min gradually heats up
And pressurization, holding temperature 30min after rising to 220 DEG C, increase pressure to 5Mpa, hot-forming 2h, demoulding can obtain product.
It is as follows to above-mentioned obtained benzoxazine resin fire block articles test experiments:
It is tested according to UL94V-0 vertical combustion standard, taking 5 a length of 125 ± 5mm, width is 13.0 ± 0.5mm, thick
Degree is the batten of 3mm, is tested after polishing, being dried.The flame height of UL-94 Vertical combustion instrument is adjusted to
2cm high, batten one end perpendicular to 10s is lighted on flame, flame of having opened fire, record batten burns away to self-extinguishing time；Each
Batten is lighted twice, records 10 times the duration after lighting altogether.Its test result is as shown in table 1:
The relationship of table 1 aluminium hydroxide additive amount and flame retardant rating
In upper table 1: V-0 grades were expressed as the maximum sustained combustion time no more than 10 seconds, averagely continued the right time for 10 times and did not surpassed
5 seconds are spent, without dripping off object；
V-1 grades of UL94 were expressed as the maximum sustained combustion time no more than 30 seconds, and the average burning time is no more than 25 seconds, nothing
Dropping；
V-2 grades of UL94 were expressed as the maximum sustained combustion time no more than 30 seconds, and the average burning time is no more than 25 seconds, has
Dropping.
Product typical performance after solidifying to above-mentioned benzoxazine resin is shown in the following table 2:
Product typical performance after table 2 solidifies
By above-mentioned experiment it is found that preparing phosphorous benzoxazine resin polymer, with common bisphenol A type resin, diamine type benzene
And oxazines resin increases phosphor-containing structure in paradigmatic structure, by effectively being improved after adding fire retardant aluminium hydroxide on a small quantity
The heat resistance and anti-flammability of polybenzoxazine resin, and mechanical property, electric property do not have much affect.
The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although with reference to the foregoing embodiments
Invention is explained in detail, those skilled in the art should understand that: it still can be to aforementioned each implementation
Technical solution documented by example is modified or equivalent replacement of some of the technical features；And these modification or
Replacement, the spirit and scope for technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution.
Claims (9)
1. a kind of phosphorous benzoxazine resin of high flame retardant, it is characterised in that: the chemical structural formula of its phosphorous benzoxazine resin
It is shown in formula I:
Wherein,For any one in having structure:
2. a kind of preparation method of the phosphorous benzoxazine resin of high flame retardant according to claim 1, it is characterised in that: packet
Include following steps:
(1) benzoxazine monomer is prepared, sequentially adds phosphorous bis-phenol in the organic solvent into self-priming exhaust gas heat exchanging reactor
Intermediate, primary amine, aldehyde compound and amines catalyst open Mixing Machine and are stirred mixing, and using gradient increased temperature to 80
DEG C~120 DEG C, it reacts 2-8 hours, when system becomes transparence, leads to condensed water cooling, terminate reaction；Obtain benzoxazine list
Body mixture.
(2) aqueous slkali is added in the obtained benzoxazine monomer mixture in step (1) and is stirred 1-2 for purification process
Hour, the oligomer and other impurities generated in removing system, then washing 3 times makes system close to neutrality.
(3) it removes solvent: the system after step (2) purification process being heated to 90-100 DEG C, rapidly removes system under vacuum
In solvent and residual moisture obtain benzoxazine monomer.
(4) compound solidifies: benzoxazine monomer obtained in step (3) being placed in stainless steel mould, in electric heating air blast
In drying box after pumping 30min, start program heating；Solidify temperature program: 1 small under the conditions of 1 hour, 180 DEG C under the conditions of 160 DEG C
When, under the conditions of 200 DEG C 1 hour under the conditions of 1 hour, 240 DEG C, obtain solidifying phosphorous benzoxazine resin product.
3. a kind of preparation method of the phosphorous benzoxazine resin of high flame retardant according to claim 2, it is characterised in that: institute
The molar ratio for stating phosphorous bis-phenol intermediate, primary amine and aldehyde compound in step (1) is 1:1:2.
4. a kind of preparation method of the phosphorous benzoxazine resin of high flame retardant according to claim 2, it is characterised in that: institute
The chemical structural formula for stating the phosphorous bis-phenol intermediate in step (1) is as shown in formula II:
5. a kind of preparation method of the phosphorous benzoxazine resin of high flame retardant according to claim 4, which is characterized in that institute
The synthetic reaction equation of phosphorous bis-phenol intermediate is stated as shown in formula III:
Its synthesis step are as follows:
A. acetic acid and a hydration sodium hypophosphite are added in three mouthfuls of reaction flasks, initiator benzoyl peroxide is added after its dissolution
With to allyloxy phenol, after 100 DEG C of reaction 4h, it is cooled to room temperature, obtains light yellow liquid；
B. yellow liquid is transferred in single necked round bottom flask and rotates out solvent and recycles, remaining solid dichloromethane in bottle
Alkane washing removes organic impurities, and phosphorous bis-phenol intermediate is obtained after draining.
6. a kind of preparation method of the phosphorous benzoxazine resin of high flame retardant according to claim 2, it is characterised in that: institute
Stating the organic solvent in step (1) is methanol, ethyl alcohol, ethyl acetate, methylene chloride, chloroform, toluene, dimethylbenzene, acetone, fourth
Ketone, methylisobutylketone, glycol monoethyl ether, glycol dimethyl ether, propylene glycol monomethyl ether, dioxane, in dimethyl sulfoxide
One or more of compounds.
7. a kind of preparation method of the phosphorous benzoxazine resin of high flame retardant according to claim 2, it is characterised in that: institute
Stating the aldehyde compound in step (1) is formalin or paraformaldehyde.
8. a kind of preparation method of the phosphorous benzoxazine resin of high flame retardant according to claim 2, it is characterised in that: institute
It states that be added in step (2) be aqueous slkali for sodium hydroxide or potassium hydroxide, and is combined with phase transfer catalyst.
9. a kind of manufacture craft of glass cloth laminated board, it is characterised in that: by phosphorous benzoxazine resin described in claim 1
Monomer is uniformly mixed with curing agent, bisphenol A type epoxy resin, butanone, is added certain aluminium hydroxide, is obtained after high speed dispersion
Non-antiflaming property benzoxazine resin liquid；Above-mentioned benzoxazine resin liquid is impregnated into alkali-free glass cloth again, and is made on gluing machine
For at prepreg, prepreg amount containing benzoxazine resin is 37%-42%；Prepreg is made to required size again, according to system
The thickness that product need, takes several prepreg overlapping layers and is placed on smooth stainless steel plate, wherein being coated with release agent；
It is hot-forming on press again, gradient increased temperature is controlled, 10-20 DEG C of set temperature/30min gradually heats up and pressurizes, rises to 220
Holding temperature 30min after DEG C, increase pressure to 5Mpa, hot-forming 2h, demoulding can obtain product.
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