CN106977717B - A kind of ester group compound containing alkenyl and preparation method thereof and the bimaleimide resin being modified using it - Google Patents
A kind of ester group compound containing alkenyl and preparation method thereof and the bimaleimide resin being modified using it Download PDFInfo
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Abstract
A kind of ester group compound containing alkenyl and preparation method thereof and the bimaleimide resin being modified using it the present invention relates to compound and preparation method thereof and utilize its modified bismaleimide resin.The invention solves existing bimaleimide resin, there are water absorption rate height, and high temperature is low with high damp and hot lower adhesive strength after solidification, the high problem of solidification temperature.General structure:Preparation method: terephthalyl chloride, 2- alkenyl phenol and catalyst being added in solvent, temperature reaction, cooling, filtering, precipitating, filtering, methanol washing and drying after reaction.It is prepared using the modified bimaleimide resin of ester group compound containing alkenyl by bismaleimide and ester group compound containing alkenyl.
Description
Technical field
The present invention relates to compound and preparation method thereof and utilize its modified bismaleimide resin.
Background technique
Thermosetting resin is widely used in the fields such as aerospace, electric, and bismaleimide (BMI) is current
The Typical Representative of high-performance thermosetting resin can satisfy the requirement of high speed, high frequency printed circuit boards substrate as matrix resin.
There is higher Tg after bimaleimide resin solidification, there is good mechanical performance, heat resistance, wet-heat resisting, solvent resistance etc.
Advantage.Therefore, bismaleimide, which becomes, uses resin used for printed circuit board more than temperature in epoxy resin.But its own is solid
Material fragility is big after change, and craftsmanship is poor, it is necessary to be modified.However, bismaleimide resin generallys use diallyl bisphenol and N,
The polymerization of N ' -4,4 '-diphenyl methane dimaleimide.But on the one hand, high density, the high multiple stratification stacking version being generally used
Bimaleimide resin, although excellent heat resistance, hygroscopicity is high, there are problems on cementability.Diallyl is double
Phenol A and N, 4,4 '-diphenyl methane dimaleimide resin system of N '-, water absorption rate is high after solidification.Generally reach 1% or so.Into
And temperature more higher than epoxy resin, longer time, the defects such as productivity is low for having that dilution influences are needed in stacking.
On the other hand, higher-strength and layers cementing performance are still maintained under applied at elevated temperature, high wet heat condition in order to meet, generallyd use
Diallyl bisphenol and N, 4,4 '-diphenyl methane dimaleimide of N '-, and not having heat-resisting in 250 degree or more of protrusion
Property and humidity resistance advantage, while solidification temperature is higher, reaches 230-250 degree, it is difficult to cope with continuous improvement material technology and
Application performance requirement.
For the above water imbibition, solidification temperature is high and high temperature, it is high it is damp and hot under bonding problem encountered, to bismaleimide resin
Modification mode it is very much, it is modified using multicomponent mixing match, it is not only complicated for operation, but also to craftsmanship, heat resistance and stabilization
Property has an impact.Such as by the way that catalyst, the epoxy resin of the low moisture absorption of high temperature resistant, thermoplastic resin (polyphenylene oxide, polyphenyl second is added
Alkene), cyanate ester resin, polyimide resin and compound special construction bimaleimide resin, be difficult to meet simultaneously low
Moisture absorption, low-temperature setting and high temperature (high damp and hot) adhesive property.Cause simultaneously sample preparation under polygamy side is difficult, hybrid technique is complicated,
The problems such as increasing prepolymerization step, increasing production processing cost.And the bismaleimide resin of other structures is used, in general, improve rigidity
With increase join section regularity, could to water imbibition and dilute it is heat-resisting helpful, but can bring resin cannot be dissolved in acetone,
In the common solvents such as methyl ethyl ketone, toluene, N.N- dimethylformamide, n,N-dimethylacetamide, so that resin can not be by wet
Method feeds molding in advance, so, the mode for not directlying adopt increase bismaleimide resin chain rigidity usually promotes water resistance.
Structure design simply is carried out to diallyl bisphenol, or chooses other solidification diluents of synthesis, is become prone to
It realizes and performance is stablized.In patent CN102134375, by introducing benzoxazine, material water imbibition is improved, but to then
No can be dissolved in low boiling point solvent is not described, and uses the resin modified span bigger than span brittleness, not
Effect such as propenyl compounds toughening modifying is good, and Tg relatively low (less than 210 degree) lacks and retouches to toughness and high-temperature behavior
It states.The use mentioned in other documents includes diallyl bisphenol S, chavicol, allyl phenolic aldehyde, diallyl diphenyl ether
The alkenyl modifying agent of equal spans there is no good resistance to moisture absorption, low-temperature setting and high temperature (high damp and hot) property modification effect or does not have
It refers to.
In addition, the dissolubility of prepolymer is formed for the above allyl compound and span, especially in low polar solvent
In dissolubility, generally show insoluble or seldom refer to it is few suitable for wet process so that in addition to diallyl bisphenol
The molding span prepreg of low boiling point (such as acetone).
In conclusion the prior art use bismaleimide and allylic compound prepolymer, using various kinds of resin,
Modifying agent and engineering plastic modification, though can partially solve temperature tolerance, for improving elevated temperature strength, wet-heat resisting simultaneously
And dissolubility, while water imbibition and solidification temperature are reduced, it can not meet simultaneously.And multicomponent addition will affect the property such as Tg
Can, also processing technology and cost can be brought uncontrollable.
Summary of the invention
The invention solves existing bimaleimide resins there are water absorption rate height, high temperature and high damp and hot lower bonding after solidification
Intensity is low, the high problem of solidification temperature, and provides a kind of ester group compound containing alkenyl and preparation method thereof and be modified using it
Bimaleimide resin.
A kind of general structure of the ester group compound containing alkenyl are as follows:
The R1For
The R2For-CH=CH-CH3Or-CH2- CH=CH2。
A kind of preparation method of the ester group compound containing alkenyl is to sequentially include the following steps:
Terephthalyl chloride is mixed with 2- alkenyl phenol, obtains mixture, then mixture and catalyst are added to solvent
Middle stirring 10h~20h, obtains reaction system, reaction system is warming up to 60 DEG C~80 DEG C, and be 60 DEG C~80 DEG C in temperature
Under the conditions of, 1h~5h is reacted, reaction system is then warming up to 100 DEG C~140 DEG C again, and is 100 DEG C~140 DEG C in temperature
Under the conditions of, 2h~6h is reacted, room temperature is down to after reaction, obtains crude product, crude product is shone into net filtration using 200 mesh~800 mesh,
Ethyl alcohol precipitating 3h~5h is added into filtrate, the solution after filtering precipitating obtains sediment, then washs sediment with methanol
It 3 times~5 times, finally dries to get ester group compound containing alkenyl is arrived；
The molar ratio of the terephthalyl chloride and 2- alkenyl phenol is 1:(2~2.5)；The terephthalyl chloride with urge
The molar ratio of agent is 1:(0.01~0.5)；The volume of the solvent and the mass ratio of mixture are (2~10) mL:1g.
Using the modified bimaleimide resin of ester group compound containing alkenyl in parts by weight by 100 parts of bismaleimides
Amine and 50 parts~120 parts ester group compounds containing alkenyl are prepared；
The preparation method of the modified bimaleimide resin of the utilization ester group compound containing alkenyl is according to following
What step carried out:
One, 100 parts of bismaleimide and 50 parts~120 parts ester group compounds containing alkenyl are weighed in parts by weight；
Two, 100 parts of bismaleimide and 50 parts~120 parts ester group compounds containing alkenyl are mixed, under agitation,
It is 110 DEG C~145 DEG C that reaction system, which is warming up to temperature, then under conditions of temperature is 110 DEG C~145 DEG C, keeps the temperature 5min
~30min, is cooled to room temperature after the reaction was completed, is utilized the modified bimaleimide resin of ester group compound containing alkenyl.
The beneficial effects of the present invention are: one kind ester group compound containing alkenyl prepared by the present invention.Firstly, diallyl bis-phenol
A and span polymerization can first carry out ENE addition and " Diels-Alder " react.Since there are resistance in diallyl bisphenol structure
Hot poor weak link, such as-C (CH3)2, lower thermal decomposition temperature and glass transition temperature have seriously affected span
Applied at elevated temperature effect.The presence of terminal hydroxy group simultaneously, greatly increases the water imbibition of material.The ester-containing based compound of alkenyl phenyl
Have after span polymerization reaction, in strand ester group in height phenylating and high structural symmetry and molecular structure (-
COO-), the introducing of fluorine side group increases the charge-transfer interaction of molecule interchain, so that polymer is with excellent
Thermal stability, by avoid introduce hydroxyl, reduce water absorption rate, and it is unexpected show excellent dilution heat resistance,
This may be since high crosslink density and good interface cohesion effect (polar group) cause jointly.In addition, carbon-on alkene end group
Under the conjugation of carbon double bond and phenyl ring, reaction work can be improved by reacting electron rich double bond with bismaleimide electron-deficient double bond
Property and stability, and then reduce curing reaction temperature and time；In addition, the ester group sucting electronic effect in main chain can further decrease
The cloud density of monoene body is more advantageous to and further increases curing reaction rate with span polyenoid body, thus not drawing
Under conditions of entering organic micromolecule catalyst, being really achieved reduces resin cure temperature effect.
In addition, how to dissolve prepolymer under the premise of keeping excellent moisture absorption property, heat resistance and low-temperature setting
It is the necessity for realizing wet forming prepreg in common solvent, such as acetone.Usually, simply increase chain rigidity, it can band
Carry out prepolymer dissolution difficulty, usual alkenyl class aromatic compound can not provide good dissolubility after span pre-polymerization.This hair
Involved structure not only provides good material property in bright, but also unexpected reduces and pre-polymerization after span pre-polymerization
The problems such as crystallinity of object, the Solvent Induced Crystallization that avoid usually will appear in a solvent is precipitated.It is molten to realize
The combination of Xie Xingyu application performance.
Resin combination of the invention has highly dissoluble, and the present invention relates to a kind of ester group compound containing alkenyl and its preparations
Method and the bimaleimide resin being modified using it, are applied to printed circuit board field.More specifically, using above-mentioned resin
The laminate of the rich metal foil layer of the prepreg of preparation is suitable for cope with lead-free solder reflux, the printing of high-frequency and high multilayer
Circuit board is encapsulated for motherboard and to contain the plastic semiconductor of semiconductor chip.
The present invention is for a kind of ester group compound containing alkenyl and preparation method thereof and the bismaleimide being modified using it
Resin.
Detailed description of the invention
Fig. 1 is the infrared spectrum of 4,4 '-two [2- (1- allyl) ester group] biphenyl prepared by embodiment 1；
Fig. 2 is the efficient liquid phase figure of 4,4 '-two [2- (1- allyl) ester group] biphenyl prepared by embodiment 1；
Fig. 3 is the infrared spectrum of 4,4 '-two [2- (1- allyl) ester group] bisphenol-A phenyl diether prepared by embodiment 3；
Fig. 4 is the efficient liquid phase figure of 4,4 '-two [2- (1- allyl) ester group] bisphenol-A phenyl diether prepared by embodiment 3；
Fig. 5 is DSC test chart, the 1 bismaleimide tree being modified for ester group compound containing alkenyl prepared by embodiment 1
Rouge, 2 bimaleimide resins being modified for ester group compound containing alkenyl prepared by embodiment 2,3 containing for prepared by embodiment 3
The modified bimaleimide resin of alkenyl ester group compound, 4 pairs being modified for ester group compound containing alkenyl prepared by embodiment 4
Maleimide resin, 5 bimaleimide resins prepared for comparative experiments 1.
Specific embodiment
Specific embodiment 1: a kind of general structure of ester group compound containing alkenyl of present embodiment are as follows:
The R1For
The R2For-CH=CH-CH3Or-CH2- CH=CH2。
The beneficial effect of present embodiment is: one kind ester group compound containing alkenyl of present embodiment preparation.Firstly, diene
Propyl bisphenol-A and span polymerization can first carry out ENE addition and " Diels-Alder " react.Due to diallyl bisphenol structure
The middle weak link poor there are heat resistance, such as-C (CH3)2, lower thermal decomposition temperature and the serious shadow of glass transition temperature
The applied at elevated temperature effect of span is rung.The presence of terminal hydroxy group simultaneously, greatly increases the water imbibition of material.Alkenyl phenyl is ester-containing
After based compound and span polymerization reaction, there is height phenylating and high structural symmetry and molecular structure in strand
The introducing of middle ester group (- COO-), fluorine side group, increases the charge-transfer interaction of molecule interchain, so that polymer has
There is excellent thermal stability, introduces hydroxyl by avoiding, reduce water absorption rate, and unexpected show excellent dilution
Heat resistance, this may be since high crosslink density and good interface cohesion effect (polar group) cause jointly.In addition, alkene end
On base under the conjugation of carbon-to-carbon double bond and phenyl ring, electron rich double bond is made to react and can mention with bismaleimide electron-deficient double bond
High reaction activity and stability, and then reduce curing reaction temperature and time；In addition, ester group sucting electronic effect in main chain can be into
One step reduces the cloud density of monoene body, is more advantageous to and further increases curing reaction rate with span polyenoid body, from
And under conditions of not introducing organic micromolecule catalyst, being really achieved reduces resin cure temperature effect
In addition, how to dissolve prepolymer under the premise of keeping excellent moisture absorption property, heat resistance and low-temperature setting
It is the necessity for realizing wet forming prepreg in common solvent, such as acetone.Usually, simply increase chain rigidity, it can band
Carry out prepolymer dissolution difficulty, usual alkenyl class aromatic compound can not provide good dissolubility after span pre-polymerization.This reality
Apply in mode involved structure and good material property be not only provided, and it is unexpected reduce with after span pre-polymerization
The problems such as crystallinity of prepolymer, the Solvent Induced Crystallization that avoid usually will appear in a solvent is precipitated.To realize
Dissolubility and application performance combination.
The resin combination of present embodiment has highly dissoluble, and present embodiment is related to a kind of ester group compound containing alkenyl
And preparation method thereof and using its be modified bimaleimide resin, be applied to printed circuit board field.More specifically, using
The laminate of the rich metal foil layer of the prepreg of above-mentioned resin preparation is suitable for cope with lead-free solder reflux, high-frequency and Gao Duo
The printed circuit board of layer is encapsulated for motherboard and to contain the plastic semiconductor of semiconductor chip.
Specific embodiment 2: a kind of preparation method of the ester group compound containing alkenyl described in present embodiment is by following
Step carries out:
Terephthalyl chloride is mixed with 2- alkenyl phenol, obtains mixture, then mixture and catalyst are added to solvent
Middle stirring 10h~20h, obtains reaction system, reaction system is warming up to 60 DEG C~80 DEG C, and be 60 DEG C~80 DEG C in temperature
Under the conditions of, 1h~5h is reacted, reaction system is then warming up to 100 DEG C~140 DEG C again, and is 100 DEG C~140 DEG C in temperature
Under the conditions of, 2h~6h is reacted, room temperature is down to after reaction, obtains crude product, crude product is shone into net filtration using 200 mesh~800 mesh,
Ethyl alcohol precipitating 3h~5h is added into filtrate, the solution after filtering precipitating obtains sediment, then washs sediment with methanol
It 3 times~5 times, finally dries to get ester group compound containing alkenyl is arrived；
The molar ratio of the terephthalyl chloride and 2- alkenyl phenol is 1:(2~2.5)；The terephthalyl chloride with urge
The molar ratio of agent is 1:(0.01~0.5)；The volume of the solvent and the mass ratio of mixture are (2~10) mL:1g.
Specific embodiment 3: present embodiment is unlike specific embodiment two: the terephthalyl chloride is It is other to be identical with embodiment two.
Specific embodiment 4: unlike one of present embodiment and specific embodiment two or three: the 2- alkene
Base phenol is 2- chavicol or 2- acrylic phenol.It is other identical as specific embodiment two or three.
Specific embodiment 5: unlike one of present embodiment and specific embodiment two to four: the catalysis
Agent is the mixture of acid compound and alkali compounds；The mass ratio of the acid compound and alkali compounds is 1:
(1.2~5)；The acid compound is oxalic acid；The alkali compounds is tri-n-butylamine.Other and specific embodiment two
It is identical to four.
Specific embodiment 6: unlike one of present embodiment and specific embodiment two to five: the solvent
For the mixture of solvent A and solvent B；The mass ratio of the solvent A and solvent B is 10:(1~5)；The solvent A is γ-
One of the lactone solvent of butyrolactone, the esters solvent of methyl benzoate class and ether solvent of triglyme class
Or in which several mixture；The solvent B is the solvent that can remove the water of dehydration and imidizate generation.It is other with it is specific
Embodiment two to five is identical.
Specific embodiment 7: unlike one of present embodiment and specific embodiment two to six: the solvent A
For methyl benzoate or butyl benzoate；The solvent B is toluene or dimethylbenzene.It is other with two to six phase of specific embodiment
Together.
Specific embodiment 8: the bimaleimide resin that the utilization ester group compound containing alkenyl of present embodiment is modified
It is prepared in parts by weight by 100 parts of bismaleimide and 50 parts~120 parts ester group compounds containing alkenyl；
The preparation method of the modified bimaleimide resin of the utilization ester group compound containing alkenyl is according to following
What step carried out:
One, 100 parts of bismaleimide and 50 parts~120 parts ester group compounds containing alkenyl are weighed in parts by weight；
Two, 100 parts of bismaleimide and 50 parts~120 parts ester group compounds containing alkenyl are mixed, under agitation,
It is 110 DEG C~145 DEG C that reaction system, which is warming up to temperature, then under conditions of temperature is 110 DEG C~145 DEG C, keeps the temperature 5min
~30min, is cooled to room temperature after the reaction was completed, is utilized the modified bimaleimide resin of ester group compound containing alkenyl.
The beneficial effect of present embodiment is: one kind ester group compound containing alkenyl of present embodiment preparation.Firstly, diene
Propyl bisphenol-A and span polymerization can first carry out ENE addition and " Diels-Alder " react.Due to diallyl bisphenol structure
The middle weak link poor there are heat resistance, such as-C (CH3)2, lower thermal decomposition temperature and the serious shadow of glass transition temperature
The applied at elevated temperature effect of span is rung.The presence of terminal hydroxy group simultaneously, greatly increases the water imbibition of material.Alkenyl phenyl is ester-containing
After based compound and span polymerization reaction, there is height phenylating and high structural symmetry and molecular structure in strand
The introducing of middle ester group (- COO-), fluorine side group, increases the charge-transfer interaction of molecule interchain, so that polymer has
There is excellent thermal stability, introduces hydroxyl by avoiding, reduce water absorption rate, and unexpected show excellent dilution
Heat resistance, this may be since high crosslink density and good interface cohesion effect (polar group) cause jointly.In addition, alkene end
On base under the conjugation of carbon-to-carbon double bond and phenyl ring, electron rich double bond is made to react and can mention with bismaleimide electron-deficient double bond
High reaction activity and stability, and then reduce curing reaction temperature and time；In addition, ester group sucting electronic effect in main chain can be into
One step reduces the cloud density of monoene body, is more advantageous to and further increases curing reaction rate with span polyenoid body, from
And under conditions of not introducing organic micromolecule catalyst, being really achieved reduces resin cure temperature effect.
In addition, how to dissolve prepolymer under the premise of keeping excellent moisture absorption property, heat resistance and low-temperature setting
It is the necessity for realizing wet forming prepreg in common solvent, such as acetone.Usually, simply increase chain rigidity, it can band
Carry out prepolymer dissolution difficulty, usual alkenyl class aromatic compound can not provide good dissolubility after span pre-polymerization.This reality
Apply in mode involved structure and good material property be not only provided, and it is unexpected reduce with after span pre-polymerization
The problems such as crystallinity of prepolymer, the Solvent Induced Crystallization that avoid usually will appear in a solvent is precipitated.To realize
Dissolubility and application performance combination.
The resin combination of present embodiment has highly dissoluble, and present embodiment is related to a kind of ester group compound containing alkenyl
And preparation method thereof and using its be modified bimaleimide resin, be applied to printed circuit board field.More specifically, using
The laminate of the rich metal foil layer of the prepreg of above-mentioned resin preparation is suitable for cope with lead-free solder reflux, high-frequency and Gao Duo
The printed circuit board of layer is encapsulated for motherboard and to contain the plastic semiconductor of semiconductor chip.
The bimaleimide resin that the utilization ester group compound containing alkenyl of present embodiment preparation is modified solidifies work
Skill are as follows: solidify 1h at being 130 DEG C in temperature, solidify 120min at being then 230 DEG C in temperature.
The modified bimaleimide resin of the utilization ester group compound containing alkenyl of present embodiment preparation is available to be had
Solvent reduces the viscosity of resin combination, improves operability, and improves immersion with glass cloth.As in resin varnish
The organic solvent used, as long as the solvent of dissolution maleimide resin.Such as acetone, methyl ethyl ketone, methyl-isobutyl
The ketones such as ketone, cyclohexanone, benzene,toluene,xylene etc. is aromatic hydrocarbon, the amides such as dimethylformamide, dimethyl acetamide
Deng but not limited to this.In addition, these organic solvents can be used alone or by two or more appropriately combined use.
Prepreg:
The bimaleimide resin that the utilization ester group compound containing alkenyl of present embodiment preparation is modified is added to
It is diluted in acetone solvent, obtains resin solution, be then impregnated or coated resin solution to substrate, be then in temperature
10min~30min is heated in 100 DEG C~200 DEG C of drying machine, is made resin semi-solid preparation, is obtained prepreg.It, can be with as substrate
Use the well known materials for various printed circuit board materials.For example, E glass, D glass, S glass, NE glass, T glass, Q glass
The glass fibres such as glass.In these substrates, more preferably using the coefficient of expansion of in-plane and drill processability balancing good
E glass these glass fibres.Relative to whole prepregs, the modified bismaleimide tree of ester group compound containing alkenyl is utilized
Rouge is preferably the 20%~90% of mass percentage to the adhesion amount of substrate.
Laminate:
Prepreg is from top to bottom successively stacked, stacking the number of plies is 1 or 2 or more, the prepreg after being stacked, root
According to the metal foils such as the required prepreg single side after stacking or upper and lower surface fitting copper, aluminium, (solidification) is formed, to manufacture
Laminate obtains metal-coated laminated board, as the condition of laminating molding, pressurizes usually using multistage pressuring machine, multi-stage vacuum, is continuous
Forming, autoclave forming machine etc. are 100 DEG C~300 DEG C in temperature, pressure 2kgf/cm2~100kgf/cm2, heating time is
1min~180min.
Specific embodiment 9: present embodiment is unlike specific embodiment eight: span described in step 1
Carrying out acid imide is 4,4 '-diaminodiphenylmethane type bismaleimide and 3,3 '-dimethyl -5,5 '-diethyl -4,4 '-two
The mixture of one or both of phenylmethane bismaleimide.It is other identical as specific embodiment eight.
Beneficial effects of the present invention are verified using following embodiment:
Embodiment 1:
A kind of ester group compound containing alkenyl and preparation method thereof and the bimaleimide resin being modified using it:
A kind of preparation method of the ester group compound containing alkenyl is to sequentially include the following steps:
4,4 '-biphenyl acyl chlorides are mixed with 2- chavicol, obtain mixture, then mixture and catalyst are added to
10h is stirred in solvent, obtains reaction system, reaction system is warming up to 60 DEG C, and under conditions of temperature is 60 DEG C, reaction
Then reaction system is warming up to 120 DEG C again by 3h, and under conditions of temperature is 120 DEG C, reacts 5h, be down to room temperature after reaction,
Crude product is obtained, crude product is shone into net filtration using 300 mesh, ethyl alcohol precipitating 5h is added into filtrate, the solution after filtering precipitating,
Sediment is obtained, then washs sediment 3 times with methanol, is finally dried to get to 4,4 '-two [2- (1- allyl) ester groups]
Biphenyl；
The molar ratio of described 4,4 '-biphenyl acyl chlorides and 2- chavicol is 1:2；Described 4,4 '-biphenyl acyl chlorides with
The molar ratio of catalyst is 1:0.1；The volume of the solvent and the mass ratio of mixture are 3mL:1g；
The catalyst is the mixture of acid compound and alkali compounds；The acid compound and alkalization
The mass ratio for closing object is 1:3；The acid compound is oxalic acid；The alkali compounds is tri-n-butylamine；
The solvent is methyl benzoate and toluene, and the mass ratio of the methyl benzoate and toluene is 3:1.
Using the modified bimaleimide resin of ester group compound containing alkenyl in parts by weight by 100 part of 4,4 '-diamino
Base diphenyl-methane type bismaleimide and 90 part of 4,4 '-two [2- (1- allyl) ester group] biphenyl are prepared；
The preparation method of the modified bimaleimide resin of the utilization ester group compound containing alkenyl is according to following
What step carried out:
One, 100 part of 4,4 '-diaminodiphenylmethane type bismaleimide and 90 part 4,4 '-two are weighed in parts by weight
[2- (1- allyl) ester group] biphenyl；
Two, by 100 part of 4,4 '-diaminodiphenylmethane type bismaleimide and 90 part of 4,4 '-two [2- (1- allyl)
Ester group] biphenyl mixing, under agitation, it is 110 DEG C that reaction system, which is warming up to temperature, the item for being then 110 DEG C in temperature
Under part, 30min is kept the temperature, is cooled to room temperature after the reaction was completed, is utilized the modified bismaleimide of ester group compound containing alkenyl
Polyimide resin.
The yield of 4,4 '-two [2- (1- allyl) ester group] biphenyl manufactured in the present embodiment is 93.8%.
Fig. 1 is the infrared spectrum of 4,4 '-two [2- (1- allyl) ester group] biphenyl prepared by embodiment 1, and test uses Fu
In leaf infrared spectrometer, it follows that from the point of view of structure, 3004cm-1~3072cm-1There is moderate strength absorption peak, this is attributed to
(C=CH) stretching vibration absworption peak hydrocarbon in carbon-carbon double bond, it was demonstrated that the presence of allyl, in 1728cm-1Be ester carbonyl it is strong
Absorption peak.In 1216cm-1It is the vibration peak of the C-O key of ester；Demonstrate the generation of esterification.The presence of these characteristic absorption peaks
Show to successfully synthesize monomer.1559cm-1、1452cm-1、1427cm-1Place is phenyl ring skeletal vibration absorption peak, it was demonstrated that biphenyl knot
Structure exists.
Fig. 2 is the efficient liquid phase figure of 4,4 '-two [2- (1- allyl) ester group] biphenyl prepared by embodiment 1, as seen from the figure,
Product purity is very high.
Table 1 is the peak result of Fig. 2
| Title | Retention time (minute) | Area (microvolt second) | Highly (microvolt) | Content | Unit | % area | |
| 1 | 12.944 | 3182965 | 163732 | 100.00 |
Therefore, it is to require structural formula that provable the present embodiment, which prepares 4,4 '-two [2- (1- allyl) ester group] biphenyl, are as follows:
Embodiment 2: the present embodiment unlike the first embodiment: using the modified span of ester group compound containing alkenyl come acyl
Imide resin is in parts by weight by 100 part of 3,3 '-dimethyl -5,5 '-diethyl -4,4 '-diphenyl methane bismaleimide
And 90 part of 4,4 '-two [2- (1- allyl) ester group] biphenyl is prepared；
The preparation method of the modified bimaleimide resin of the utilization ester group compound containing alkenyl is according to following
What step carried out:
One, 100 part of 3,3 '-dimethyl -5,5 '-diethyl -4,4 '-diphenyl methane span is weighed in parts by weight carrys out acyl
Imines and 90 part of 4,4 '-two [2- (1- allyl) ester group] biphenyl；
Two, by 100 part of 3,3 '-dimethyl -5,5 '-diethyl -4,4 '-diphenyl methane bismaleimide and 90 part 4,
The mixing of 4 '-two [2- (1- allyl) ester group] biphenyl, under agitation, it is 110 DEG C that reaction system, which is warming up to temperature, then
Under conditions of temperature is 110 DEG C, 30min is kept the temperature, is cooled to room temperature after the reaction was completed, is utilized ester group compound containing alkenyl
Modified bimaleimide resin.It is other same as Example 1.
Embodiment 3:
A kind of ester group compound containing alkenyl and preparation method thereof and the bimaleimide resin being modified using it:
A kind of preparation method of the ester group compound containing alkenyl is to sequentially include the following steps:
Bisphenol-A diether diacid chloride is mixed with 2- chavicol, obtains mixture, then mixture and catalyst are added
10h is stirred into solvent, obtains reaction system, reaction system is warming up to 60 DEG C, and under conditions of temperature is 60 DEG C, reaction
Then reaction system is warming up to 120 DEG C again by 3h, and under conditions of temperature is 120 DEG C, reacts 5h, be down to room temperature after reaction,
Crude product is obtained, crude product is shone into net filtration using 300 mesh, ethyl alcohol precipitating 5h is added into filtrate, the solution after filtering precipitating,
Sediment is obtained, then washs sediment 3 times with methanol, is finally dried to get to 4,4 '-two [2- (1- allyl) ester groups]
Bisphenol-A phenyl diether；
The molar ratio of the bisphenol-A diether diacid chloride and 2- chavicol is 1:2；Two acyl of bisphenol-A diether
The molar ratio of chlorine and catalyst is 1:0.1；The volume of the solvent and the mass ratio of mixture are 3mL:1g；
The catalyst is the mixture of acid compound and alkali compounds；The acid compound and alkalization
The mass ratio for closing object is 1:3；The acid compound is oxalic acid；The alkali compounds is tri-n-butylamine；
The solvent is methyl benzoate and toluene, and the mass ratio of the methyl benzoate and toluene is 3:1.
Using the modified bimaleimide resin of ester group compound containing alkenyl in parts by weight by 100 part of 4,4 '-diamino
Base diphenyl-methane type bismaleimide and 90 part of 4,4 '-two [2- (1- allyl) ester group] bisphenol-A phenyl diether are prepared；
The preparation method of the modified bimaleimide resin of the utilization ester group compound containing alkenyl is according to following
What step carried out:
One, 100 part of 4,4 '-diaminodiphenylmethane type bismaleimide and 90 part 4,4 '-two are weighed in parts by weight
[2- (1- allyl) ester group] bisphenol-A phenyl diether；
Two, by 100 part of 4,4 '-diaminodiphenylmethane type bismaleimide and 90 part of 4,4 '-two [2- (1- allyl)
Ester group] mixing of bisphenol-A phenyl diether, under agitation, it is 110 DEG C that reaction system, which is warming up to temperature, is then in temperature
Under conditions of 110 DEG C, 30min is kept the temperature, is cooled to room temperature after the reaction was completed, is utilized modified pair of ester group compound containing alkenyl
Maleimide resin.
The yield of manufactured in the present embodiment 4,4 '-two [2- (1- allyl) ester group] bisphenol-A phenyl diether is 96.8%, is led to
Crossing HPLC measurement purity is 97.8%.
Fig. 3 is the infrared spectrum of 4,4 '-two [2- (1- allyl) ester group] bisphenol-A phenyl diether prepared by embodiment 3, is surveyed
Fourier infrared spectrograph is used, it follows that from the point of view of structure, 2976cm-1~3068cm-1There is moderate strength absorption peak,
This is attributed to (C=CH) hydrocarbon in carbon-carbon double bond and methyl stretching vibration absworption peak, it was demonstrated that the presence of allyl and methyl,
1726cm-1It is the carbonyl strong absworption peak of ester.In 1235cm-1And 1065cm-1It is the symmetrical and asymmetric stretching vibration of ehter bond respectively
Peak, in 1209cm-1It is the vibration peak of the C-O key of ester；Demonstrate the generation of esterification.The presence of these characteristic absorption peaks shows
Successfully synthesize monomer.
Fig. 4 is the efficient liquid phase figure of 4,4 '-two [2- (1- allyl) ester group] bisphenol-A phenyl diether prepared by embodiment 3,
As seen from the figure, product purity is very high.
Table 2 is the peak result of Fig. 4
| Title | Retention time (minute) | Area (microvolt second) | Highly (microvolt) | Content | Unit | % area | |
| 1 | 3.702 | 89740 | 11075 | 1.22 | |||
| 2 | 3.928 | 14677 | 1875 | 0.20 | |||
| 3 | 9.460 | 18006 | 1321 | 0.25 | |||
| 4 | 12.288 | 7226727 | 391930 | 98.33 |
Therefore, provable the present embodiment prepares 4,4 '-two [2- (1- allyl) ester group] bisphenol-A phenyl diether to require
Structural formula are as follows:
Embodiment 4: the present embodiment as different from Example 3: using the modified span of ester group compound containing alkenyl come acyl
Imide resin is in parts by weight by 100 part of 4,4 '-diaminodiphenylmethane type bismaleimide and 70 part of 4,4 '-two [2- (1-
Allyl) ester group] bisphenol-A phenyl diether is prepared；
The preparation method of the modified bimaleimide resin of the utilization ester group compound containing alkenyl is according to following
What step carried out:
One, 100 part of 4,4 '-diaminodiphenylmethane type bismaleimide and 70 part 4,4 '-two are weighed in parts by weight
[2- (1- allyl) ester group] bisphenol-A phenyl diether；
Two, by 100 part of 4,4 '-diaminodiphenylmethane type bismaleimide and 70 part of 4,4 '-two [2- (1- allyl)
Ester group] mixing of bisphenol-A phenyl diether, under agitation, it is 110 DEG C that reaction system, which is warming up to temperature, is then in temperature
Under conditions of 110 DEG C, 30min is kept the temperature, is cooled to room temperature after the reaction was completed, is utilized modified pair of ester group compound containing alkenyl
Maleimide resin.It is other same as Example 3.
Comparative experiments 1:
This comparative experiments is the comparative experiments of embodiment 1 to 4, and bimaleimide resin prepared by this comparative experiments 1 is pressed
Parts by weight are prepared by 100 parts of N, N ' -4,4 '-diphenyl methane dimaleimide and 90 parts of diallyl bisphenols；
The preparation method of the bimaleimide resin follows the steps below:
One, 100 parts of N are weighed in parts by weight, and N ' -4,4 '-diphenyl methane dimaleimide and 90 parts of diallyls are double
Phenol A；
Two, it by 100 parts of N, 4,4 '-diphenyl methane dimaleimide of N '-and 90 parts of diallyl bisphenol mixing, is stirring
Under the conditions of mixing, it is 110 DEG C that reaction system, which is warming up to temperature, then under conditions of temperature is 110 DEG C, keeps the temperature 30min, reaction
It is cooled to room temperature after the completion, obtains bimaleimide resin；
Comparative experiments 2:
This comparative experiments is the comparative experiments of embodiment 1 to 4, and bimaleimide resin prepared by this comparative experiments 2 is pressed
Parts by weight are prepared by 100 parts of N, N ' -4,4 '-diphenyl methane dimaleimide and 90 parts of diallyl bisphenol Ss；
The preparation method of the bimaleimide resin follows the steps below:
One, 100 parts of N are weighed in parts by weight, and N ' -4,4 '-diphenyl methane dimaleimide and 90 parts of diallyls are double
Phenol S；
Two, it by 100 parts of N, 4,4 '-diphenyl methane dimaleimide of N '-and 90 parts of diallyl bisphenol S mixing, is stirring
Under the conditions of mixing, it is 110 DEG C that reaction system, which is warming up to temperature, then under conditions of temperature is 110 DEG C, keeps the temperature 30min, reaction
It is cooled to room temperature after the completion, obtains maleimide resin.
Comparative experiments 3:
This comparative experiments is the comparative experiments of embodiment 1 to 4, and bimaleimide resin prepared by this comparative experiments 3 is pressed
Parts by weight are by 100 parts of N, N ' -4,4 '-diphenyl methane dimaleimide, 40 parts of naphthalene skeleton epoxy resin, 5 parts of amino triazines
Novolac resin and 30 parts of phenolic cyanates are prepared；
The preparation method of the bimaleimide resin follows the steps below:
One, 100 parts of N, N ' -4,4 '-diphenyl methane dimaleimide, 40 parts of naphthalene skeleton asphalt mixtures modified by epoxy resin are weighed in parts by weight
Rouge, 5 parts of amino triazine novolac resins and 30 parts of phenolic cyanates；
Two, by 100 parts of N, N ' -4,4 '-diphenyl methane dimaleimide, 30 parts of phenolic cyanates and 40 parts of naphthalene skeleton rings
The mixing of oxygen resin, under agitation, it is 110 DEG C that reaction system, which is warming up to temperature, the condition for being then 110 DEG C in temperature
Under, 30min is kept the temperature, Bismaleimide prepolymer is obtained；
Three, 5 parts of amino triazine novolac resins are added to Bismaleimide prepolymer, are then 70 DEG C in temperature
And under stirring condition, 10min is reacted, is cooled to room temperature after the reaction was completed, obtains bimaleimide resin.
The bimaleimide resin and comparison be modified to utilization ester group compound containing alkenyl prepared by embodiment 1 to 4 is real
The bimaleimide resin for testing 1 to 3 preparation is solidified, curing process are as follows: is solidified 1h at being 130 DEG C in temperature, is then existed
Temperature is to solidify 120min at 230 DEG C.
Utilization ester group compound containing alkenyl prepared by embodiment 1 to 4 modified bimaleimide resin and comparison is real
The bimaleimide resin for testing 1 to 3 preparation carries out adhesives and solidifies, and shear strength test is then carried out, to embodiment 1
Bimaleimide resin after solidification prepared by bimaleimide resin and comparative experiments 1 to 3 after to the solidification of 4 preparations
Glass transition temperature, thermal stability, peel strength and water imbibition test, as shown in table 3, the test-strips of properties are carried out
Part is referring to following standard (method):
1, thermal stability: test uses thermal gravimetric analyzer (TGA).Heating rate: 10 DEG C/min；Measurement atmosphere: air.
2, carry out glass transition temperature and elasticity modulus to obtaining resin: test is using dynamic thermomechanical analysis apparatus
(DMA).Heating rate: 5 DEG C/min；Measurement atmosphere: air.
3, shear strength: test is referring to GB/T7124-2008 adhesive tensile shear strength test method.Material:
LY12CZ aluminium alloy.
4, water absorption rate: in pressure cooker, 121 DEG C, handle 5 hours under 2 air pressures after water absorption rate.
5, differential scanning calorimeter, 10 DEG C/min of heating rate solidification temperature: are utilized.
Table 3
Embodiment 1 to 4 is compared to comparative experiments 1 to 3:
1, with 600 DEG C of carbon yields under good heat resistance, especially air, it is real that embodiment is much higher than comparison
It tests；
2, more importantly, comparative experiments is higher than at the high temperature bonding intensity of embodiment, especially 250 DEG C, and pass through
It improves rigidity and linear chain structure, water absorption rate is reduced to 0.15~0.20.Far below common span/allyl compound.Using more
Kind filler combination addition, is difficult to promote hot property, water absorption resistance and solidification temperature simultaneously, embodiment 1 to 4 can be used as high-frequency line
High performance resin in the plate of road, and it is not limited to the embodiment enumerated.
3, the bimaleimide resin modified to the ester group compound containing alkenyl of embodiment 1 to embodiment 4 preparation and right
Bimaleimide resin than 1 preparation of experiment carries out DSC test；Fig. 5 is DSC test chart, and 1 contains alkene for prepared by embodiment 1
The modified bimaleimide resin of base ester based compound, 2 spans being modified for ester group compound containing alkenyl prepared by embodiment 2
Bismaleimide resin, 3 bimaleimide resins being modified for ester group compound containing alkenyl prepared by embodiment 3,4 be embodiment
The modified bimaleimide resin of the ester group compound containing alkenyl of 4 preparations, 5 bismaleimide prepared for comparative experiments 1
Resin；Wherein haircut represents heat release upwards, and as seen from the figure, embodiment 1 to 4 is different containing alkenyl being added compared to comparative experiments
In the DSC figure of the modified different bismaleimide of ester group compound, faster curing reaction rate is all had, hence it is evident that reduce solidification
Summit temperature and curing exotherm tail of the peak temperature, can be effectively reduced the solidification temperature of resin.It is solid to solidify bind temperature and starting
Change temperature and compare comparative experiments, reduces by 55 DEG C, modified effect is more preferably.
The bimaleimide resin and comparison that the utilization ester group compound containing alkenyl prepared using embodiment 1 to 4 is modified
The bimaleimide resin of 1 to 2 preparation of experiment prepares copper clad laminate, and concrete operations are as follows:
Embodiment 5:
Acetone will be added to using the modified bimaleimide resin of ester group compound containing alkenyl prepared by embodiment 1
It is diluted in solvent, obtains the resin solution that weight percent is 55%, then put the resin solution that weight percent is 55%
It sets overnight to no Precipitation, is impregnated using the solution after standing overnight to a thickness of the E-glass cloth of 0.1mm,
Under conditions of temperature is 140 DEG C, 20min is heated, obtains the prepreg that weight resin percentage composition is 55%；
The preparation of metal-coated laminated board: the prepreg that weight resin percentage composition is 55% is from top to bottom successively stacked,
Stacking the number of plies is 8, the prepreg after being stacked, the electrolysis that the prepreg upper and lower surface coating thickness after stacking is 12 μm
Copper foil is 30kgf/cm in pressure2And solidify 2h molding at 230 DEG C of temperature, obtain the metal-clad that thickness of insulating layer is 0.8mm
Pressing plate.
Embodiment 6: the present embodiment as different from Example 5: will be prepared by embodiment 2 using the chemical combination of ester group containing alkenyl
The modified bimaleimide resin of object, which is added in acetone solvent, to be diluted, and the resin solution that weight percent is 55% is obtained.
It is other same as Example 5.
Embodiment 7: the present embodiment as different from Example 5: will be prepared by embodiment 3 using the chemical combination of ester group containing alkenyl
The modified bimaleimide resin of object, which is added in acetone solvent, to be diluted, and the resin solution that weight percent is 55% is obtained.
It is other same as Example 5.
Embodiment 8: the present embodiment as different from Example 5: will be prepared by embodiment 4 using the chemical combination of ester group containing alkenyl
The modified bimaleimide resin of object, which is added in acetone solvent, to be diluted, and the resin solution that weight percent is 55% is obtained.
It is other same as Example 5.
Embodiment 9: the present embodiment as different from Example 5: by bimaleimide resin prepared by comparative experiments 1
It is added in acetone solvent and dilutes, obtain the resin solution that weight percent is 55%.It is other same as Example 5.
Embodiment 10: the present embodiment as different from Example 5: by bismaleimide tree prepared by comparative experiments 2
Rouge, which is added in acetone solvent, to be diluted, and the resin solution that weight percent is 55% is obtained.It is other same as Example 5.
Embodiment 11:
It adds mixture in acetone solvent and dilutes, obtain mixture solution, then stand overnight mixture solution
To no Precipitation, is impregnated using the solution after standing overnight to a thickness of the E-glass cloth of 0.1mm, be in temperature
Under conditions of 140 DEG C, 20min is heated, obtains the prepreg that weight resin percentage composition is 55%；
The weight percent of mixture is 55% in the mixture solution, and the mixture is in parts by weight by 70
The modified bimaleimide resin of utilization ester group compound containing alkenyl, 1.5 parts of infiltration dispersion liquids prepared by part embodiment 1,
0.02 part of zinc octoate and 100 parts of silica mix；
The preparation of metal-coated laminated board: the prepreg that weight resin percentage composition is 55% is from top to bottom successively stacked,
Stacking the number of plies is 8, the prepreg after being stacked, the electrolysis that the prepreg upper and lower surface coating thickness after stacking is 12 μm
Copper foil is 30kgf/cm in pressure2And solidify 2h molding at 230 DEG C of temperature, obtain the metal-clad that thickness of insulating layer is 0.8mm
Pressing plate.
Embodiment 12: the present embodiment as different from Example 11: the mixture in parts by weight by 70 parts implement
Prepared by example 1 using the modified bimaleimide resin of ester group compound containing alkenyl, 1.5 parts of infiltration dispersion liquids, 120 parts suddenly
Nurse stone and 0.02 part of zinc octoate mix.It is other identical as embodiment 11.
Embodiment 13: the present embodiment as different from Example 11: the mixture in parts by weight by 70 parts implement
The modified bimaleimide resin of utilization ester group compound containing alkenyl, 20 parts of phenol biphenyl aralkyl epoxies prepared by example 1,
5 parts of ammonia amino triazine phenolic aldehyde, 15 parts of bisphenol A cyanate esters and 0.01 part of imidazoles mix.It is other identical as embodiment 11.
Embodiment 14: the present embodiment as different from Example 11: the mixture in parts by weight by 70 parts implement
The modified bimaleimide resin of utilization ester group compound containing alkenyl, 20 parts of phenol biphenyl aralkyl epoxies prepared by example 1,
0.02 part of zinc octoate and 15 parts of Novolac Cyanate Eater Resins mix.It is other identical as embodiment 11.
Embodiment 15: the present embodiment as different from Example 11: the mixture in parts by weight by 70 parts implement
The modified bimaleimide resin of utilization ester group compound containing alkenyl, 20 parts of phenol biphenyl aralkyl epoxies prepared by example 1,
0.02 part of zinc octoate and 15 parts of biphenyl aralkyl cyanates mix.It is other identical as embodiment 11.
Embodiment 16: the present embodiment as different from Example 11: the mixture in parts by weight by 24 parts implement
The modified bimaleimide resin of utilization ester group compound containing alkenyl, 50 parts of phenol biphenyl aralkyl epoxies prepared by example 1,
0.04 part of zinc octoate and 50 parts of bisphenol A cyanate esters mix.It is other identical as embodiment 11.
Embodiment 17: the present embodiment as different from Example 11: the mixture in parts by weight by 24 parts implement
The modified bimaleimide resin of utilization ester group compound containing alkenyl, 50 parts of phenol biphenyl aralkyl epoxies prepared by example 1,
0.04 part of zinc octoate and 50 parts of Novolac Cyanate Eater Resins mix.It is other identical as embodiment 11.
Embodiment 18: the present embodiment as different from Example 11: the mixture in parts by weight by 70 parts implement
The modified bimaleimide resin of utilization ester group compound containing alkenyl, 20 parts of phenol biphenyl aralkyl epoxies prepared by example 3,
0.02 part of zinc octoate, 5 parts of bisphenol A cyanate esters and 5 parts of phenol aralkyl phenolic aldehyde mix.It is other identical as embodiment 11.
Embodiment 19: the present embodiment as different from Example 11: the mixture in parts by weight by 70 parts implement
The modified bimaleimide resin of utilization ester group compound containing alkenyl, 20 parts of phenol novolac epoxies prepared by example 3,
0.02 part of zinc octoate and 15 parts of Novolac Cyanate Eater Resins mix.It is other identical as embodiment 11.
Embodiment 20: the present embodiment as different from Example 11: the mixture in parts by weight by 24 parts implement
The modified bimaleimide resin of utilization ester group compound containing alkenyl, 30 parts of phenol biphenyl aralkyl epoxies prepared by example 3,
24 parts of phenol aldehyde type bimaleimide resins, 0.04 part of zinc octoate and 50 parts of Novolac Cyanate Eater Resins mix.Other and implementation
Example 11 is identical.
Comparative experiments 4: the present embodiment as different from Example 11: the mixture is in parts by weight by 50 parts of phenol
Biphenyl aralkyl epoxy, 0.04 part of zinc octoate, 100 parts of silica and 50 parts of biphenyl aralkyl cyanates mix.It is other
It is identical as embodiment 11.
Comparative experiments 5: the present embodiment as different from Example 11: the mixture is in parts by weight by 50 parts of phenol
Biphenyl aralkyl epoxy, 0.04 part of zinc octoate, 50 parts of bisphenol A cyanate esters and 100 parts of silica mix.It is other with it is real
It is identical to apply example 11.
Comparative experiments 6: the present embodiment as different from Example 11: the mixture is in parts by weight by 50 parts of phenol
Biphenyl aralkyl epoxy, 0.04 part of zinc octoate, 100 parts of silica and 50 parts of Novolac Cyanate Eater Resins mix.It is other with it is real
It is identical to apply example 11.
Comparative experiments 7: the present embodiment as different from Example 11: the mixture is in parts by weight by 40 parts of phenol
Biphenyl aralkyl epoxy, 24 part of 3 '-dimethyl -5,5 '-diethyl -4,4 '-diphenyl methane bismaleimide, 1 part of infiltration
Dispersion liquid, 120 parts of boehmites, 0.02 part of zinc octoate and 36 parts of biphenyl aralkyl cyanates mix.Other and embodiment 11
It is identical.
Comparative experiments 8: the present embodiment as different from Example 11: the mixture is in parts by weight by 26 part 3 '-
Dimethyl -5,5 '-diethyl -4,4 '-diphenyl methane bismaleimide, 1 part of infiltration dispersion liquid, 120 parts of boehmites, 15 parts
Phenol novolac epoxy, 0.02 part of zinc octoate and 39 parts of biphenyl aralkyl cyanates mix.It is other with 11 phase of embodiment
Together.
Comparative experiments 9: the present embodiment as different from Example 11: the mixture is in parts by weight by 15 part 3 '-
Dimethyl -5,5 '-diethyl -4,4 '-diphenyl methane bismaleimide, 1.5 parts of infiltration dispersion liquids, 120 parts of boehmites, 45
Part phenol novolac epoxy, 5 parts of ammonia amino triazine phenolic aldehyde, 15 parts of biphenyl aralkyl cyanates, 0.01 part of imidazoles and 20 parts of benzene
Phenol aralkyl phenolic aldehyde mixes.It is other identical as embodiment 11.
Comparative experiments 10: the present embodiment as different from Example 11: the mixture is in parts by weight by 15 part 3 '-
Dimethyl -5,5 '-diethyl -4,4 '-diphenyl methane bismaleimide, 20 parts of phenol aldehyde type bimaleimide resins, 45
Part phenol novolac epoxy, 0.01 part of imidazoles and 20 parts of phenol aralkyl phenolic aldehyde mix.It is other identical as embodiment 11.
Above-mentioned raw material are selected from:
The phenol biphenyl aralkyl epoxy: NC-3000, Japanese chemical drug company；
Described 3,3 '-dimethyl -5,5 '-diethyl -4,4 '-diphenyl methane bismaleimide: BMI-70, Japan
Big and chemical conversion company；
The infiltration dispersion liquid: Disperbyk-161, Japanese BYK chemistry；
The boehmite: APYRALAOH60Nabalte company；
The phenol aldehyde type bimaleimide resin: BMI-2300, Japan is big and is melted into；
Described 4,4 '-diaminodiphenylmethane type bismaleimide: Honghu bismaleimide resin factory；
The phenol novolac epoxy: EPICLON 770, Japanese DIC company；
The diallyl bisphenol: Japanese DIC company；
The diallyl bisphenol S: TCI company；
The bisphenol A cyanate ester: BA3000, Lonza company, Switzerland；
The silica: SC2050MR, Admatechs company；
The Novolac Cyanate Eater Resin: PT30, Lonza company, Switzerland；
The biphenyl aralkyl cyanate: MEH-7852, Japan is bright and is melted into company；
The amino triazine phenolic aldehyde: PHENOLITE LA-3018-50P, Dainippon Ink Chemicals's manufacture；
The imidazoles: four countries, 2P4MZ Japan chemical conversion；
The phenol aralkyl phenolic aldehyde: KAYAHRAD GPH-103, Japanese chemical drug；
The naphthalene skeleton epoxy resin (HP-4032D, Nippon kayaku company).
To the modified bimaleimide resin of ester group compound containing alkenyl described in embodiment 5 to 8, embodiment 9 and 10
Mixture described in the bimaleimide resin, embodiment 11 to 20 and comparative experiments 4 to 10 carries out dissolubility test,
Room temperature and high temperature peel strength, water suction have been carried out to metal-coated laminated board prepared by embodiment 5 to 20 and comparative experiments 4 to 10
Rate, moisture absorption heat resistance, T-288 generate the time of splitting, thermal expansion coefficient (CTE) test, as shown in table 4 and 5, Ge Xiangxing
The test condition of energy is referring to following standard (method):
1, dissolubility: the solubility property of test resin in a solvent, 55g can be dissolved in 100g solvent, and in 10 days
Whether precipitation is to judge deliquescent standard.
2, room temperature and high temperature peel strength: according to the peel strength of JIS C6481 test copper foil.
3, moisture absorption heat resistance: after metal-coated laminated board is cut into 50mm × 50mm, production eliminates single side by etching
The copper-plated samples of more than half.The sample is handled into 3h, 4h and 5h with pressure cooker test machine with 121 DEG C, 2 atmospheric pressure respectively
Afterwards, it is impregnated 30 seconds in 260 DEG C of solder bath, visually whether there is or not cosmetic variations for observation.4 samples are tested, for each
Zhang Jilu variation, statistics have bubble to generate plate number.
4, T-288 generates the time of splitting: sample being heated up with 10 DEG C/min of TMA equipment instrument according to IPC TM-650
To 288 DEG C.288 DEG C of holding is constant, measures the time for generating splitting at 288 DEG C, is considered as lower than 10min unqualified.
5, thermal expansion coefficient (CTE): after metal-coated laminated board is handled copper foil in corrosive liquid, with TMA test 50 to 200
DEG C face direction thermal expansion coefficient.Measurement direction is the longitudinal direction of the glass fabric of metal-coated laminated board.
Table 4
Table 5
Moisture absorption heat resistance tests 4 samples in table, and 0/4 to represent in 4 samples bubble to generate plate number be 0, and 1/4
Representing in 4 samples bubble and generating plate number be 1, and 2/4 to represent bubble generation plate number in 4 samples be 2, and 3/4 represents 4 samples
It is 3 that bubble, which generates plate number, in product, and 4/4 to represent in 4 samples bubble to generate plate number be 4.
Other commercially available structure diluent such as two allyls in addition to diallyl bisphenol are used it can be seen from the comparison of table 4 and 5
Base bisphenol S or other structures bismaleimide resin such as phenolic aldehyde span etc. can not be dissolved in low boiling-point and polarity solvent, in higher boiling
Though can dissolve in solvent, high-temperature solvent removal is not clean, will lead to the problems such as bubble between laminate layer is more, can not survey
Examination.So can seldom obtain deliquescent span prepolymer (including span and diluent).Using embodiment 5 to 7, implement
The modified bimaleimide resin of utilization ester group compound containing alkenyl prepared by example 11 to 20, can be dissolved in acetone isopolarity
In solvent, and the good copper clad laminate of surface quality can be obtained with hot pressing after being prepared into prepreg.
Secondly, compared with embodiment 5 to 7, embodiment 11 to 20, comparative experiments linear expansion coefficient with higher (CTE),
Higher water absorption rate, 288 degree of reflux-resisting welded, moisture absorption heat resistances and lower elevated temperature strength are kept.High temperature and height are seriously affected
Damp and hot lower using effect.As known from the above, the advantage using alkenyl ester group compound is embodied.Join in addition, being combined using ester group
Benzene, ehter bond etc. greatly reduce the water absorption rate of material unexpectedly, obtain better moisture absorption heat resistance.
Embodiment 5 to 7, using the span prepolymer of embodiment 1 to 4, has better high temperature compared with embodiment 8 to 20
Bonding, higher glass transition temperature and wet-hot aging performance.And embodiment 9 and 10, dissolubility is poor, high temperature and height are damp and hot
Property is poor.Using the embodiment 11 to 20 of 1 to 4 resin of section Example, water resistance can be greatly improved, dilute the stripping of heat-resisting and high temperature
From intensity.
Claims (8)
1. a kind of ester group compound containing alkenyl, which is characterized in that a kind of general structure of the ester group compound containing alkenyl are as follows:
The R1For
The R2For-CH=CH-CH3Or-CH2- CH=CH2。
2. a kind of preparation method of the ester group compound containing alkenyl as described in claim 1, which is characterized in that one kind contains alkenyl esters
The preparation method of based compound is to sequentially include the following steps:
Terephthalyl chloride is mixed with 2- alkenyl phenol, obtains mixture, then mixture and catalyst are added in solvent and stirred
10h~20h is mixed, reaction system is obtained, reaction system is warming up to 60 DEG C~80 DEG C, and the condition for being 60 DEG C~80 DEG C in temperature
Under, 1h~5h is reacted, reaction system is then warming up to 100 DEG C~140 DEG C, and the condition for being 100 DEG C~140 DEG C in temperature again
Under, 2h~6h is reacted, room temperature is down to after reaction, obtains crude product, crude product is used into 200 mesh~800 mesh net filtrations, to filter
Ethyl alcohol precipitating 3h~5h is added in liquid, the solution after filtering precipitating obtains sediment, then washs sediment 3 times with methanol
It~5 times, finally dries to get ester group compound containing alkenyl is arrived；
The molar ratio of the terephthalyl chloride and 2- alkenyl phenol is 1:(2~2.5)；The terephthalyl chloride and catalyst
Molar ratio be 1:(0.01~0.5)；The volume of the solvent and the mass ratio of mixture are (2~10) mL:1g；
The terephthalyl chloride is
3. a kind of preparation method of ester group compound containing alkenyl according to claim 2, which is characterized in that the 2- alkene
Base phenol is 2- chavicol or 2- acrylic phenol.
4. a kind of preparation method of ester group compound containing alkenyl according to claim 2, which is characterized in that the catalysis
Agent is the mixture of acid compound and alkali compounds；The mass ratio of the acid compound and alkali compounds is 1:
(1.2~5)；The acid compound is oxalic acid；The alkali compounds is tri-n-butylamine.
5. a kind of preparation method of ester group compound containing alkenyl according to claim 2, which is characterized in that the solvent
For the mixture of solvent A and solvent B；The mass ratio of the solvent A and solvent B is 10:(1~5)；The solvent A is benzene
Methyl formate or butyl benzoate；The solvent B is the solvent that can remove the water of dehydration and imidizate generation.
6. a kind of preparation method of ester group compound containing alkenyl according to claim 5, which is characterized in that the solvent
B is toluene or dimethylbenzene.
7. utilizing the modified bimaleimide resin of ester group compound containing alkenyl described in claim 1, which is characterized in that benefit
With the modified bimaleimide resin of ester group compound containing alkenyl in parts by weight by 100 parts of bismaleimide and 50 parts~
120 parts of ester group compounds containing alkenyl are prepared；
The preparation method of the modified bimaleimide resin of the utilization ester group compound containing alkenyl is according to the following steps
It carries out:
One, 100 parts of bismaleimide and 50 parts~120 parts ester group compounds containing alkenyl are weighed in parts by weight；
Two, 100 parts of bismaleimide and 50 parts~120 parts ester group compounds containing alkenyl are mixed, it under agitation, will be anti-
Answering system to be warming up to temperature is 110 DEG C~145 DEG C, then under conditions of temperature is 110 DEG C~145 DEG C, heat preservation 5min~
30min is cooled to room temperature after the reaction was completed, is utilized the modified bimaleimide resin of ester group compound containing alkenyl.
8. the bimaleimide resin modified using ester group compound containing alkenyl according to claim 7, feature exist
In bismaleimide described in step 1 is 4,4 '-diaminodiphenylmethane type bismaleimide and 3,3 '-diformazans
The mixture of one or both of base -5,5 '-diethyl -4,4 '-diphenyl methane bismaleimide.
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| CN112694451B (en) * | 2020-12-24 | 2023-03-07 | 广东盈骅新材料科技有限公司 | Modified allyl compound, bismaleimide prepolymer and application thereof |
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