CN105585817B - 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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- CN105585817B CN105585817B CN201410566988.8A CN201410566988A CN105585817B CN 105585817 B CN105585817 B CN 105585817B CN 201410566988 A CN201410566988 A CN 201410566988A CN 105585817 B CN105585817 B CN 105585817B
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Abstract
The present invention relates to a kind of modified bismaleimide resin in the modified field of thermosetting resin and preparation method and its solidfied materials.The modified bismaleimide resin includes following components in parts by weight: 100 parts of bimaleimide resins, 80~120 parts of epoxy prepolymers, 50~100 parts of aromatic amine curing agents, 10~20 parts of rubber particles with cross-linked structure；The partial size 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 with the prior art, the technical method simple process that the present invention uses, and it is easily controllable, the dielectric loss of material is reduced, the dielectric properties of material are improved, and overcomes bimaleimide resin and the poor deficiency of fiber compatibility.
Description
Technical field
The present invention relates to the modified fields of thermosetting resin to be furtherly related to a kind of modified bismaleimide resin
And preparation method and its solidfied material.
Background technique
Bimaleimide resin (abbreviation BMI or bismaleimide resin) be derived from by polyimide resin system it is another kind of
Resin system 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, resin matrix, high temperature resistant copper-clad plate matrix and the high-temperature plastic of advanced composite material
Stick etc..
European Union's RoHS decree starts to execute on July 1st, 2006, the disabling of lead be on electronic field influence it is maximum,
Solder melt point is higher by nearly 50 DEG C than lead jointing when due to pb-free solder, this just needs PCB (printed circuit board) and CCL (to cover copper
Plate) heat resisting temperature to correspondingly increase, 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 field.On the other hand, electronic component is small
Type, it is integrated increase calorific value, basis material is put forward new requirements, high temperature resistant, but also the dielectric of itself are not only wanted
Loss also wants very low.The dielectric loss of medium is higher, and the loss of electric energy or signal is more, the dielectric loss height meeting of copper-clad plate
The ratio for making signal be converted into thermal energy in transmission process increases.And the dielectric loss of bismaleimide is to be improved.
Summary 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.Modified bismaleimide resin of the invention has dielectric properties outstanding and processing performance.
An object of the present invention is to provide a kind of modified bismaleimide resin.The modified bismaleimide tree
Rouge, includes following components in parts by weight: 100 parts of bimaleimide resins, 80~120 parts of epoxy prepolymers, and 50
~100 parts of aromatic amine curing agents, 10~20 parts of rubber particles with cross-linked structure；The rubber granule with cross-linked structure
The partial size of son is 0.02 μm~2 μm, and for gel content up to 60% weight or higher, more excellent is 75% weight or higher.
The bimaleimide resin can be selected from N.N ' -4.4 '-diphenyl methane dimaleimide, N, N'-4,4'- bis-
At least one of phenylate bismaleimide, preferably N.N ' -4.4 '-diphenyl methane dimaleimide.
The aromatic amine curing agent can be selected from as 4,4- diaminodiphenylsulfone, 4,4'- diaminodiphenyl ethers, and 4,4'- bis-
At least one of diaminodiphenylmethane.
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 during the 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 carboxy nitrile rubber etc..Preferably Vulcanized Powdered Nitrile Rubber and complete
Sulfide powder carboxy nitrile rubber, more preferably form of finely divided powder, mehtod carboxy nitrile rubber.This kind of fully vulcanized powder rubber refers to solidifying
For glue content up to 60% weight or higher, more excellent is 75% weight or higher, it is dry after without plus interleaving agent, that is, free flowable
Rubber micro mist.The partial size of the powdered rubber is 0.02 μm~2 μm, preferably 0.05 μm~1.5 μm.In the fully vulcanized powder rubber
Each particle be it is homogeneous, i.e., single particle is all homogeneous in composition, micro- under the observation of existing microtechnic
Intragranular does not find the not homogeneous phenomenon such as layering, split-phase.The powdered rubber is by by corresponding rubber latex cross-linking radiation
And rubber particles partial size is fixed.In this preparation method, need fully vulcanized powder rubber with dry crosslinking according to processing
Powder morphology is added.
Epoxy prepolymer of the present invention primarily to improve bismaleimide resin toughness and improve processing performance,
Make powdered rubber dispersion wherein as decentralized medium simultaneously.Fully vulcanized powder rubber can play the work for reducing dielectric material loss
With.
The second object of the present invention is to providing the preparation method of the modified bismaleimide resin.
The preparation method includes: to mix the epoxy prepolymer and the rubber particles with cross-linked structure
It closes, then heating is blended with the bismaleimide in obtained mixture, the aromatic amine curing agent is added, vacuumizes,
Obtain the modified bismaleimide resin.
Specifically, comprising the following steps:
Step 1): divide in three times after the epoxy prepolymer is mixed with the rubber particles with cross-linked structure
It dissipates；Specifically available three-roll grinder is dispersed.
Step 2): the bimaleimide resin is mixed with the resulting mixture of step 1), and heating is being kept stirring
Under conditions of react, after vacuum takes bubble away, add the aromatic amine curing agent, continue heating stirring, be evacuated, obtain simultaneously
To the modified bismaleimide resin.
In the step 2), resulting epoxy prepolymer is mixed with powdered rubber mixture, be warming up to 130 DEG C~
It 150 DEG C, is reacted 15~30 minutes under conditions of being kept stirring.
The three of the object of the invention are to provide a kind of solidfied material of modified bismaleimide resin.It is described by comprising described
Be made after the cured processing of modified bismaleimide resin or preparation method in comprising the modified bismaleimide
The preparation method and curing process of polyimide resin.
I.e. its preparation step includes: to use the epoxy prepolymer and the rubber particles with cross-linked structure
Three-roll grinder is mixed, then heating is blended with the bimaleimide resin for obtained mixture, and aromatic amine is added
Class curing agent, vacuumizes, and curing process obtains the solidfied material of the modified bismaleimide resin.
The curing process includes 150 DEG C/2h, 180 DEG C/2h and 200 DEG C/2h.
It may also include the rear curing process of 220 DEG C/2h after the curing process.
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 simple process that the present invention uses, and also it is easily controllable, the dielectric loss of material is reduced, material is improved
Dielectric properties, and overcome bimaleimide resin and the poor deficiency of fiber compatibility.Using method system of the invention
Standby bimaleimide resin has good dissolubility in acetone and other organic solvent, this is compound for production high-performance
Material is highly beneficial.In addition, the additive amount of modifying agent is lower, cost control is preferable, and the rubber particles with cross-linked structure also make
The gel time of bimaleimide resin substantially shortens.
Detailed description of the invention
Fig. 1 is the of the invention modified bismaleimide resin solidification modified by the rubber particles with cross-linked structure
The transmission electron microscope picture (TEM) of object.
Specific embodiment
Below with reference to embodiment, the present invention is further illustrated.
Raw material sources
CYD-128 type epoxy prepolymer: Sinopec Ba Ling petrochemical industry branch company production；
Vulcanized Powdered Nitrile Rubber: Beijing Chemical Research Institute's production, trade mark VP-401；
Form of finely divided powder, mehtod carboxy nitrile rubber: Beijing Chemical Research Institute's production, trade mark VP-501；
N, N'-4,4'- diphenyl methane dimaleimide: Hubei Province Honghu bismaleimide resin factory production；
4,4- diaminodiphenylsulfone: Suzhou Yin Sheng Chemical Co., Ltd. production；
Other raw materials used in embodiment are commercially available.
Embodiment 1
With three after 100 parts of CYD-128 type epoxy prepolymers are tentatively mixed with 15 parts of Vulcanized Powdered Nitrile Rubbers
Roller mill dispersion, grinds, every minor tick for 24 hours, obtains the mixture of powdered rubber and epoxy prepolymer in three times.It will
The mixture of 100g N, N'-4,4'- diphenyl methane dimaleimide and 115g powdered rubber and epoxy prepolymer is added
Into flask, 140 DEG C, vacuum suction 10min are warming up to, adds 50g 4,4- diaminodiphenylsulfone continues heating stirring, together
When be evacuated, after 15min by reactant be poured into 120 DEG C preheating mold in.
Curing process by obtained modified bismaleimide resin through 150 DEG C/2h, 180 DEG C/2h and 200 DEG C/2h with
And after the rear curing process of 220 DEG C/2h, obtain modified bismaleimide solidified resin.
Comparative example 1
By 100g N, N'-4,4'- diphenyl methane dimaleimide adds with 100g CYD-128 type epoxy prepolymer
Entering into flask, be warming up to 140 DEG C, vacuum suction 10min, adds 50g 4,4- diaminodiphenylsulfone continues heating stirring,
It is evacuated, reactant is poured into the mold of 120 DEG C of preheatings simultaneously after 15min.The modified bismaleimide resin that will be obtained
Through 150 DEG C/2h, 180 DEG C/2h and 200 DEG C/2h curing process and 220 DEG C/2h after after curing process, obtain modified double
Maleimide solidified resin.
Embodiment 2
By N, N in N'-4,4'- Diphenyl Ether Bismaleimide alternate embodiment 1, N'-4,4'- diphenyl-methane span comes
Acid imide, remaining is same as Example 1, prepares modified bismaleimide solidified resin.
Embodiment 3
By the Vulcanized Powdered Nitrile Rubber in form of finely divided powder, mehtod carboxy nitrile rubber alternate embodiment 1, remaining with reality
It is identical to apply example 1, prepares modified bismaleimide solidified resin.
Embodiment 4
By 4, the 4- diaminodiphenylsulfone in 4,4'- diaminodiphenyl ether alternate embodiment 1, remaining with 1 phase of embodiment
Together, modified bismaleimide solidified resin is prepared.
Embodiment 5
By 4, the 4- diaminodiphenylsulfone in 4,4'- diaminodiphenylmethane alternate embodiment 1, remaining with embodiment 1
It is identical, prepare modified bismaleimide solidified resin.
Embodiment 6
It is used after 100 parts of CYD-128 type epoxy prepolymers are tentatively mixed with 12.5 parts of Vulcanized Powdered Nitrile Rubbers
Three-roll grinder dispersion, grinds, every minor tick for 24 hours, obtains the mixture of powdered rubber and epoxy prepolymer in three times.It will
The mixture of 100g N, N'-4,4'- diphenyl methane dimaleimide and 90g powdered rubber and epoxy prepolymer is added
Into flask, 140 DEG C, vacuum suction 10min are warming up to, adds 50g 4,4- diaminodiphenylsulfone continues heating stirring, together
When be evacuated, after 15min by reactant be poured into 120 DEG C preheating mold in.Obtained modified bismaleimide resin is passed through
150 DEG C/2h, after the rear curing process of the curing process of 180 DEG C/2h and 200 DEG C/2h and 220 DEG C/2h, obtain modified span
Carry out acid imide solidified resin.
Embodiment 7
It is used after 100 parts of CYD-128 type epoxy prepolymers are tentatively mixed with 12.5 parts of Vulcanized Powdered Nitrile Rubbers
Three-roll grinder dispersion, grinds, every minor tick for 24 hours, obtains the mixture of powdered rubber and epoxy prepolymer in three times.It will
100g N, N'-4,4'- diphenyl methane dimaleimide and the mixture of 133.3g powdered rubber and epoxy prepolymer add
Enter into flask, be warming up to 140 DEG C, vacuum suction 10min, add 100g 4,4- diaminodiphenylsulfone continues heating and stirs
It mixes, is evacuated simultaneously, reactant is poured into the mold of 120 DEG C of preheatings after 15min.The modified bismaleimide tree that will be obtained
Rouge through 150 DEG C/2h, 180 DEG C/2h and 200 DEG C/2h curing process and 220 DEG C/2h after after curing process, be modified
Bismaleimide solidified resin.
Embodiment 8
With three after 100 parts of CYD-128 type epoxy prepolymers are tentatively mixed with 25 parts of Vulcanized Powdered Nitrile Rubbers
Roller mill dispersion, grinds, every minor tick for 24 hours, obtains the mixture of powdered rubber and epoxy prepolymer in three times.It will
The mixture of 100g N, N'-4,4'- diphenyl methane dimaleimide and 100g powdered rubber and epoxy prepolymer is added
Into flask, 140 DEG C, vacuum suction 10min are warming up to, adds 50g 4,4- diaminodiphenylsulfone continues heating stirring, together
When be evacuated, after 15min by reactant be poured into 120 DEG C preheating mold in.Obtained modified bismaleimide resin is passed through
150 DEG C/2h, after the rear curing process of the curing process of 180 DEG C/2h and 200 DEG C/2h and 220 DEG C/2h, obtain modified span
Carry out acid imide solidified resin.
By the modified bismaleimide resin that Examples 1 to 8 obtains and the modified bismaleimide that comparative example 1 obtains
The main performance of resin is compared, and the results are shown in Table 1.The testing standard of gel time according to HB 7736.7-2004 into
Row, dielectric loss angle tangent value are carried out according to standard GB/T 5594.4-1985.
Table 1
Above-mentioned 1 data of table show that, compared to the bimaleimide resin for individually using epoxy resin modification, embodiment 1 provides
The dielectric loss of modified bismaleimide resin be greatly reduced, dielectric properties have obtained significant raising.From gel time
Data show that present invention offer modified bismaleimide resin has better reactivity.
Claims (9)
1. a kind of modified bismaleimide resin is made of following components in parts by weight: 100 parts of bismaleimide trees
Rouge, 80~120 parts of epoxy prepolymers, 50~100 parts of aromatic amine curing agents, 10~20 parts of rubber with cross-linked structure
Particle；The partial size of the rubber particles with cross-linked structure is 0.02~2 μm, and gel content is up to 60% weight or higher；Institute
It states modified bismaleimide resin to be prepared by following methods: the epoxy prepolymer step 1): being had into friendship with described
It is coupled the rubber particles mixing of structure；Step 2): the bimaleimide resin is mixed with the resulting mixture of step 1), is risen
Temperature after vacuum takes bubble away, adds the aromatic amine curing agent, heating stirring is taken out simultaneously under conditions of being kept stirring
Gas obtains the modified bismaleimide resin.
2. modified bismaleimide resin according to claim 1, it is characterised in that: the rubber with cross-linked structure
The partial size of micelle is 0.05~1.5 μm.
3. modified bismaleimide resin according to claim 1, it is characterised in that: the rubber with cross-linked structure
The gel content of micelle is 75% weight or higher.
4. modified bismaleimide resin according to claim 1, it is characterised in that: the bimaleimide resin
Selected from N, 4,4 '-diphenyl methane dimaleimide of N '-, N, N'-4, at least one in 4'- Diphenyl Ether Bismaleimide
Kind.
5. modified bismaleimide resin according to claim 1, it is characterised in that: the aromatic amine curing agent choosing
From 4,4- diaminodiphenylsulfone, 4,4'- diaminodiphenyl ethers, at least one of 4,4'- diaminodiphenylmethane.
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 be selected from following fully vulcanized powder rubber at least one: 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 carboxy nitrile rubber.
8. the preparation method of modified bismaleimide resin described in one of -7 according to claim 1, it is characterised in that:
In the step 2), after the bimaleimide resin is mixed with the resulting mixture of step 1), it is warming up to 130 DEG C
It~150 DEG C, is reacted 15~30 minutes under conditions of being kept stirring.
9. a kind of solidfied material of modified bismaleimide resin, it is characterised in that by any described comprising claim 1~7
The cured processing of modified bismaleimide resin after be made.
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| KR102187162B1 (en) | 2017-12-14 | 2020-12-04 | 주식회사 엘지화학 | Thermosetting composition for coating metal thin film and thin metal film laminate using the same |
| CN112341850A (en) * | 2019-08-09 | 2021-02-09 | 金鹏节能科技有限公司 | Aluminum alloy door and window coating and preparation method thereof |
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| CN1402752A (en) * | 1999-12-03 | 2003-03-12 | 中国石油化工集团公司 | Full vulcanized powdered rubber with controllable particle diameter, preparing method thereof |
| 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 |
| CN1845949A (en) * | 2003-09-18 | 2006-10-11 | 株式会社钟化 | Process for producing rubbery polymer particle and process for producing resin composition containing the same |
| CN101935435A (en) * | 2009-07-03 | 2011-01-05 | 中国石油化工股份有限公司 | Toughened epoxy resin composition and preparation method thereof |
| CN102268174A (en) * | 2010-06-04 | 2011-12-07 | 中国石油化工股份有限公司 | Epoxy resin composition with high thermal resistance and high ductility, and preparation method thereof |
| CN102558861A (en) * | 2011-12-27 | 2012-07-11 | 广东生益科技股份有限公司 | Halogen-free phosphate-free high-heat-resistance thermosetting resin composition as well as bonding sheet and copper clad laminate prepared from same |
-
2014
- 2014-10-22 CN CN201410566988.8A patent/CN105585817B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1402752A (en) * | 1999-12-03 | 2003-03-12 | 中国石油化工集团公司 | Full vulcanized powdered rubber with controllable particle diameter, preparing method thereof |
| 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 |
| CN1845949A (en) * | 2003-09-18 | 2006-10-11 | 株式会社钟化 | Process for producing rubbery polymer particle and process for producing resin composition containing the same |
| CN101935435A (en) * | 2009-07-03 | 2011-01-05 | 中国石油化工股份有限公司 | Toughened epoxy resin composition and preparation method thereof |
| CN102268174A (en) * | 2010-06-04 | 2011-12-07 | 中国石油化工股份有限公司 | Epoxy resin composition with high thermal resistance and high ductility, and preparation method thereof |
| CN102558861A (en) * | 2011-12-27 | 2012-07-11 | 广东生益科技股份有限公司 | Halogen-free phosphate-free high-heat-resistance thermosetting resin composition as well as bonding sheet and copper clad laminate prepared from same |
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