CN105585846B - A kind of modified bismaleimide resin and preparation method and its solidfied material - Google Patents
A kind of modified bismaleimide resin and preparation method and its solidfied material Download PDFInfo
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- CN105585846B CN105585846B CN201410569414.6A CN201410569414A CN105585846B CN 105585846 B CN105585846 B CN 105585846B CN 201410569414 A CN201410569414 A CN 201410569414A CN 105585846 B CN105585846 B CN 105585846B
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Abstract
The present invention relates to thermosetting resin to be modified field, furtherly, is related to a kind of modified bismaleimide resin and preparation method and its solidfied material.The modified bismaleimide resin, include following components in parts by weight：100 parts of bimaleimide resins, 30~90 parts of liquid end ene compounds and 1~10 part have the rubber particles of cross-linked structure；The liquid end ene compound is containing double-key end group (CH2=CH) liquid compound；The particle diameter of the rubber particles with cross-linked structure is 0.02 μm~2 μm, and for gel content up to 60% weight or higher, more excellent is 75% weight or higher.Compared to prior art, the preparation method technique that the present invention uses is simple and easily controllable.The dielectric loss of modified bismaleimide resin solidfied material prepared by the present invention is greatly reduced, and dielectric properties are obviously improved, and gel time significantly shortens.
Description
Technical field
The present invention relates to thermosetting resin to be modified field, furtherly, is related to a kind of modified bismaleimide resin
And preparation method and its solidfied material.
Background technology
Bimaleimide resin (abbreviation BMI or bismaleimide resin) be derived from by polyimide resin system it is another kind of
Resin system, it is the bifunctional compound with maleimide (MI) for active end group.Bismaleimide resin is excellent heat-resisting with its
Property, electrical insulating property, wave, radiation hardness, anti-flammability, good mechanical property and dimensional stability, be widely used in aviation,
In the industrial circles such as space flight, machinery, electronics, the resin matrix of advanced composite material, high-end copper-clad plate matrix and adhesive etc..
European Union's RoHS decrees start to perform on July 1st, 2006, and the disabling of lead is to influence maximum to electronic applications,
Solder melt point is higher by nearly 50 DEG C than lead jointing during due to pb-free solder, and this just needs PCB (printed circuit board (PCB)) and CCL (to cover copper
Plate) heat resisting temperature accordingly to improve, this is that conventional resins matrix is difficult to reach.The high-fire resistance of bimaleimide resin
This requirement can be conformed exactly to, therefore it is had an optimistic view of extensively in the application prospect of electronic applications.On the other hand, electronic component is small
Type, it is integrated increase caloric value, new requirement is proposed to matrix material, not only wants high temperature resistant, and the dielectric of itself
Loss is also very low.The dielectric loss of medium is higher, and the loss of electric energy or signal is more, the high meeting of dielectric loss of copper-clad plate
Signal is set to be converted into the ratio rise of heat energy in transmitting procedure.And the dielectric loss of BMI has much room for improvement.
The content of the invention
In order to solve the above-mentioned problems in the prior art, the present invention propose a kind of modified bismaleimide resin and
Preparation method and its solidfied material.The modified bismaleimide resin of the present invention has prominent dielectric properties and processing characteristics.
An object of the present invention is to provide a kind of modified bismaleimide resin.The modified bismaleimide tree
Fat, include following components in parts by weight：100 parts of bimaleimide resins, 30~90 parts of liquid end ene compounds and 1~
10 parts of rubber particles with cross-linked structure；
The liquid end ene compound is containing double-key end group (CH2=CH-) liquid compound；It is described that there is cross-linked structure
Rubber particles particle diameter be 0.02 μm~2 μm, for gel content up to 60% weight or higher, more excellent is 75% weight or higher.
The BMI is selected from N.N ' -4.4 '-diphenyl methane dimaleimide, N, N'-4,4'- diphenyl ether pair
At least one of maleimide, preferably N.N ' -4.4 '-diphenyl methane dimaleimide.
Described liquid end ene compound can be selected from pi-allyl cresols and/or diallyl bisphenol, preferably two allyls
Base bisphenol-A.Liquid end ene compound plays toughening effect, while it is also curing agent (the span tree of bimaleimide resin
Fat do not have to curing agent can also autohemagglutination, but it is especially crisp).
The rubber particles with cross-linked structure can be used according to the applicant in the China submitted on December 3rd, 1999
Fully vulcanized powder rubber prepared by patent application 99125530.5.Preferential select includes following full vulcanization powder in preparation process
At least one of last rubber：Form of finely divided powder, mehtod natural rubber, form of finely divided powder, mehtod butadiene-styrene rubber, form of finely divided powder, mehtod polybutadiene rubber
Glue, Vulcanized Powdered Nitrile Rubber or form of finely divided powder, mehtod XNBR etc..This kind of fully vulcanized powder rubber refers to that gel contains
For amount up to 60% weight or higher, more excellent is 75% weight or higher, and interleaving agent need not be added to be free flowable rubber after drying
Micro mist.The particle diameter of the powdered rubber is 0.02 μm~2 μm, preferably 0.05 μm~1.5 μm.It is every in the fully vulcanized powder rubber
One particulate is all homogeneous, i.e., single particulate is all homogeneous in composition, under the observation of existing microtechnic in particulate
The not homogeneous phenomenon such as layering, split-phase is not found.The powdered rubber is by the way that corresponding rubber latex cross-linking radiation is incited somebody to action
What rubber particles particle diameter was fixed.In this preparation method, fully vulcanized powder rubber is needed with dry cross-linked powder according to processing
Form adds.Powdered rubber for the present invention is preferably Vulcanized Powdered Nitrile Rubber and form of finely divided powder, mehtod carboxyl butyronitrile rubber
Glue, more preferably form of finely divided powder, mehtod XNBR.
The two of the object of the invention are to provide the preparation method of described modified bismaleimide resin.
The preparation method comprises the following steps：By the liquid end ene compound and the rubber with cross-linked structure
Mix particles, then obtained mixture and bimaleimide resin blending are heated, vacuumize, obtain described modification
Bimaleimide resin.
Specifically, comprise the following steps：
Step 1)：The liquid end ene compound is mixed with the rubber particles with cross-linked structure；
Step 2)：The bimaleimide resin is mixed with the mixture obtained by step 1), heats up, is being kept stirring for
Under conditions of carry out curing reaction, after vacuum takes bubble away, obtain modified bismaleimide resin.
Wherein,
Liquid end ene compound described in the step 1) can be adopted after being mixed with the rubber particles with cross-linked structure
Disperseed in three times with three-roll grinder；
In the step 2)：After the bimaleimide resin is mixed with the mixture obtained by step 1), it is warming up to
130 DEG C~150 DEG C, reacted 15~30 minutes under conditions of being kept stirring for.
The three of the object of the invention are to provide a kind of solidfied material of modified bismaleimide resin.The solidfied material by comprising
It is made after the cured processing of described modified bismaleimide resin, or described modification span is included in its preparation method
The preparation method and curing process of bismaleimide resin.
I.e. its preparation process includes：The liquid end ene compound and the rubber particles with cross-linked structure are used
Three-roll grinder is mixed, then obtained mixture and bimaleimide resin blending are heated, and is vacuumized, is solidified
Processing obtains the solidfied material of the modified bismaleimide resin, i.e. modified bismaleimide solidified resin.
Wherein, the curing process include 150 DEG C/2h, 180 DEG C/2h and 200 DEG C/2h.
Solidify afterwards processing is may also include after the curing process, solidify afterwards processing includes 240 DEG C/2h.
A kind of modified bismaleimide resin proposed by the present invention and preparation method and its solidfied material, compared to existing skill
Art, the preparation method technique that the present invention uses are simple and easily controllable.Modified bismaleimide resin prepared by the present invention
The dielectric loss of solidfied material is greatly reduced, and dielectric properties are obviously improved, and gel time significantly shortens.
Brief description of the drawings
Fig. 1 is the modified bismaleimide resin of the invention being modified by the rubber particles with cross-linked structure
The transmission electron microscope picture (TEM) of solidfied material.It can be seen that favorable dispersibility.
Embodiment
With reference to embodiment, the present invention is further illustrated.
Raw material sources
Form of finely divided powder, mehtod XNBR：Beijing Chemical Research Institute produces, trade mark VP-501；
Vulcanized Powdered Nitrile Rubber：Beijing Chemical Research Institute produces, trade mark VP-401；
Diallyl bisphenol：Hubei Province Honghu bismaleimide resin factory produces；
N, N'-4,4'- diphenyl methane dimaleimide：Hubei Province Honghu bismaleimide resin factory produces；
Other raw materials are commercially available.
Embodiment 1
Ground after 100 parts of diallyl bisphenols are tentatively mixed with 15 parts of form of finely divided powder, mehtod XNBRs with three rollers
Machine disperses, and grinds in three times, per minor tick 24h, obtains the mixture of powdered rubber and diallyl bisphenol.By 100 parts of N,
N'-4,4'- diphenyl methane dimaleimides and the mixture of 70 parts of powdered rubbers and diallyl bisphenol are added to flask
In, 140 DEG C are warming up to, vacuum suction, is reacted 20 minutes under conditions of being kept stirring for, reactant is then poured into 120 DEG C
In the mould of preheating.By solidification of the obtained modified bismaleimide resin through 150 DEG C/2h, 180 DEG C/2h and 200 DEG C/2h
After the processing of processing and 240 DEG C/2h solidify afterwards, modified bismaleimide solidified resin is obtained.
Comparative example 1
By 100 parts of N, the mixture of N'-4,4'- diphenyl methane dimaleimides and 60.8 parts of diallyl bisphenols adds
Enter into flask, be warming up to 140 DEG C, vacuum suction, react 20 minutes under conditions of being kept stirring for, then pour into a mould reactant
Into the mould of 120 DEG C of preheatings.By obtained modified bismaleimide resin through 150 DEG C/2h, 180 DEG C/2h and 200 DEG C/2h
Curing process and 240 DEG C/2h solidify afterwards processing after, obtain unmodified BMI solidified resin.
Embodiment 2
By the diallyl bisphenol in pi-allyl cresols alternate embodiment 1, remaining is same as Example 1, prepares and is modified
BMI solidified resin.
Embodiment 3
By N, the N in N'-4,4'- Diphenyl Ether Bismaleimides alternate embodiment 1, N'-4,4'- diphenyl-methanes span comes
Acid imide, remaining is same as Example 1, prepares modified bismaleimide solidified resin.
Embodiment 4
By the form of finely divided powder, mehtod XNBR in Vulcanized Powdered Nitrile Rubber alternate embodiment 1, remaining with reality
It is identical to apply example 1, prepares modified bismaleimide solidified resin.
Embodiment 5
Three-roll grinder is used after 100 parts of diallyl bisphenols are tentatively mixed with 5 parts of form of finely divided powder, mehtod XNBRs
It is scattered, grind in three times, per minor tick 24h, obtain the mixture of powdered rubber and diallyl bisphenol.By 100 parts of N, N'-
4,4'- diphenyl methane dimaleimides and the mixture of 31.5 parts of powdered rubbers and diallyl bisphenol are added in flask,
140 DEG C are warming up to, vacuum suction, is reacted under conditions of being kept stirring for 20 minutes, reactant is then poured into 120 DEG C of preheatings
Mould in.By curing process of the obtained modified bismaleimide resin through 150 DEG C/2h, 180 DEG C/2h and 200 DEG C/2h
And after 240 DEG C/2h solidify afterwards processing, obtain modified bismaleimide solidified resin.
Embodiment 6
Three-roll grinder is used after 90 parts of diallyl bisphenols are tentatively mixed with 10 parts of form of finely divided powder, mehtod XNBRs
It is scattered, grind in three times, per minor tick 24h, obtain the mixture of powdered rubber and diallyl bisphenol.By 100 parts of N, N'-
4,4'- diphenyl methane dimaleimides and the mixture of 100 parts of powdered rubbers and diallyl bisphenol are added in flask,
140 DEG C are warming up to, vacuum suction, is reacted under conditions of being kept stirring for 20 minutes, reactant is then poured into 120 DEG C of preheatings
Mould in.By curing process of the obtained modified bismaleimide resin through 150 DEG C/2h, 180 DEG C/2h and 200 DEG C/2h
And after 240 DEG C/2h solidify afterwards processing, obtain modified bismaleimide solidified resin.
By modified bismaleimide solidified resin that embodiment 1~6 obtains and comparative example 1 obtain without adding powder rubber
The main performance for the BMI solidified resin that glue is modified is compared, as a result as shown in table 1.The survey of gel time
Test-object standard is carried out according to HB 7736.7-2004, and dielectric loss angle tangent value is carried out according to standard GB/T 5594.4-1985.
Table 1
The above-mentioned data of table 1 show that the BMI solidified resin prepared compared to comparative example 1 is provided by the invention to change
The dielectric properties of property BMI solidified resin have significant raising, referring to Fig. 1.Shown from gel time data, this
Invention offer modified bismaleimide solidified resin has more preferable reactivity.
Claims (11)
1. a kind of modified bismaleimide resin, include following components in parts by weight：100 parts of BMI trees
Fat, 30~90 parts of liquid end ene compounds and 1~10 part have the rubber particles of cross-linked structure；The liquid end ene compound is
Liquid compound containing double-key end group；The particle diameter of the rubber particles with cross-linked structure is 0.02~2 μm, and gel content reaches
60% weight is higher.
2. modified bismaleimide resin according to claim 1, it is characterised in that：The rubber with cross-linked structure
The particle diameter of micelle is 0.05~1.5 μm.
3. modified bismaleimide resin according to claim 1, it is characterised in that：Gel content up to 75% weight or
It is higher.
4. modified bismaleimide resin according to claim 1, it is characterised in that：The BMI is selected from
At least one of N, N'-4,4'- diphenyl methane dimaleimide, N, N'-4,4'- Diphenyl Ether Bismaleimides.
5. modified bismaleimide resin according to claim 1, it is characterised in that：Described liquid end ene compound
Selected from pi-allyl cresols and/or diallyl bisphenol.
6. modified bismaleimide resin according to claim 1, it is characterised in that：
The rubber particles with cross-linked structure are equal phase structure.
7. modified bismaleimide resin according to claim 1, it is characterised in that：The rubber with cross-linked structure
Micelle is selected from least one of following fully vulcanized powder rubber：Form of finely divided powder, mehtod natural rubber, form of finely divided powder, mehtod butadiene-styrene rubber,
Form of finely divided powder, mehtod polybutadiene rubber, Vulcanized Powdered Nitrile Rubber or form of finely divided powder, mehtod XNBR.
8. according to any described modified bismaleimide resin of claim 1~7, it is characterised in that its described modification is double
Maleimide resin is prepared by following methods：By the liquid end ene compound and the rubber particles with cross-linked structure
Mixing, then obtained mixture and bimaleimide resin blending heating are vacuumized, obtain described modification span
Bismaleimide resin.
9. according to the preparation method of any described modified bismaleimide resin of claim 1~8, it is characterised in that bag
Include：
Step 1)：The liquid end ene compound is mixed with the rubber particles with cross-linked structure；
Step 2)：The bimaleimide resin is mixed with the mixture obtained by step 1), heated up, in the bar being kept stirring for
Curing reaction is carried out under part, after vacuum takes bubble away, obtains modified bismaleimide resin.
10. the preparation method of modified bismaleimide resin according to claim 9, it is characterised in that including：
In the step 2)：After the bimaleimide resin is mixed with the mixture obtained by step 1), 130 DEG C are warming up to
~150 DEG C, reacted 15~30 minutes under conditions of being kept stirring for.
11. a kind of solidfied material of modified bismaleimide resin, it is characterised in that by any institute comprising claim 1~8
It is made after the cured processing of modified bismaleimide resin stated.
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| CN201410569414.6A CN105585846B (en) | 2014-10-22 | 2014-10-22 | A kind of modified bismaleimide resin and preparation method and its solidfied material |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1412244A (en) * | 2001-10-12 | 2003-04-23 | 中国石油化工股份有限公司 | Toughened thermosetting resin and its preparation method |
| CN103467987A (en) * | 2013-09-30 | 2013-12-25 | 黑龙江省科学院石油化学研究院 | Toughening modification method for bismaleimide resin |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100240811A1 (en) * | 2009-03-18 | 2010-09-23 | He Yufang | Thermosetting Resin Composition and Application Thereof |
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2014
- 2014-10-22 CN CN201410569414.6A patent/CN105585846B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1412244A (en) * | 2001-10-12 | 2003-04-23 | 中国石油化工股份有限公司 | Toughened thermosetting resin and its preparation method |
| CN103467987A (en) * | 2013-09-30 | 2013-12-25 | 黑龙江省科学院石油化学研究院 | Toughening modification method for bismaleimide resin |
Non-Patent Citations (1)
| Title |
|---|
| "端羧基丁腈橡胶对双马来酰亚胺树脂体系性能的影响";王汝敏等;《玻璃钢/复合材料》;19911231(第6期);第6-8页及第14页 * |
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