CN106700549A - Modified bismaleimide resin, reinforced laminated board and preparation method thereof - Google Patents
Modified bismaleimide resin, reinforced laminated board and preparation method thereof Download PDFInfo
- Publication number
- CN106700549A CN106700549A CN201611034806.8A CN201611034806A CN106700549A CN 106700549 A CN106700549 A CN 106700549A CN 201611034806 A CN201611034806 A CN 201611034806A CN 106700549 A CN106700549 A CN 106700549A
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- CN
- China
- Prior art keywords
- resin
- bismaleimide resin
- modified bismaleimide
- modified
- adhesive plaster
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08L79/085—Unsaturated polyimide precursors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
- B32B37/1009—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure using vacuum and fluid pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/101—Glass fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2379/00—Other polymers having nitrogen, with or without oxygen or carbon only, in the main chain
- B32B2379/08—Polyimides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
Abstract
The invention relates to the technical field of polymer matrix composite materials and particularly discloses modified bismaleimide resin, a reinforced laminated board and a preparation method thereof. The bismaleimide resin is modified by cyanate ester resin, rubber, dicyandiamide and silicon dioxide to obtain the modified bismaleimide resin, the modified bismaleimide resin is used as an adhesive, glass fiber is used as a base material, and dip-coating, sizing, adhesive plaster drying and lamination pressing are performed to prepare the reinforced laminated board. The modified bismaleimide resin can meet the industrial production requirement, the reinforced laminated board is prepared by the modified bismaleimide resin and the glass fiber has good heat-resistant performance, the mechanical property of the board is also remarkably improved, the comprehensive performance is excellent, and the modified bismaleimide resin can be applied to the field of electrical insulation, aerospace and the like.
Description
Technical field
The present invention relates to polymer matrix composite technical field, particularly relate to a kind of modified bismaleimide resin,
Enhancing laminate and preparation method thereof.
Background technology
With the development of aerospace industry, to the performance requirement more and more higher of composite, high performance composite
Need high performance resin matrix.Composite with high performance resin as matrix is under the adverse circumstances such as high-temperature oxydation, corrosion
Used as structural material long-term use, the composite with epoxy resin, unsaturated polyester resin, phenolic resin as matrix is not
High performance requirement can be met.
Bimaleimide resin has the mobility and plasticity similar to typical thermosetting resin, is heating or is being catalyzed
In the presence of can have with excellent heat resistance and good mechanical property, dielectric properties, humidity resistance, anti-spoke with crosslinking curing
Penetrating property, chemical resistance etc., but general monomer bimaleimide resin fusing point is higher, dissolubility is poor and forming temperature
High, manufacture craft is poor, and cured product crosslink density is high, and fragility is very big, limits further application.
However, due to BMI poor toughness, have impact on it and further apply, the toughness reinforcing of bimaleimide resin
Modified is always the focus of researcher.The overwhelming majority is directed to the study on the modification of bimaleimide resin at present, and purpose is all
In order to improve its toughness, and all achieve certain achievement.But the shortcoming of its manufacturability difference is still difficult to solve, and changes utilizing
Property resin make laminate when, the glue of configuration is often difficult to be dissolved in conventional organic solvent, cause glue excessively sticky or
It is uneven, gluing quality is have impact on so as to influence the performance of laminate each side.
The content of the invention
The present invention is intended to provide a kind of modified bismaleimide resin, solves the part manufacture craft of composite not
Foot, improve resin stability, dissolubility and adhesiveness and with good dielectric properties and mechanical performance, so as to improve
Rough surface, poor glue phenomenon after resin solidification, the problems such as toughness is poor.
To achieve these goals, present invention employs following technical scheme：A kind of modified bismaleimide resin,
It is bimaleimide resin through cyanate ester resin, rubber, dicyandiamide, silica modified gained, the bismaleimide
Polyimide resin is 7 with the mass ratio of cyanate ester resin, rubber, dicyandiamide and silica：(2.5~3.5)：0.05：(1.2~
1.5)：0.01.
A kind of preparation method of modified bismaleimide resin, comprises the following steps：
1) bimaleimide resin, cyanate ester resin, rubber, dicyandiamide, silica are accurately weighed, the span comes
Imide resin is 7 with the mass ratio of cyanate ester resin, rubber, dicyandiamide and silica：(2.5~3.5)：0.05：(1.2
~1.5)：0.01；
2) mix under certain condition, stir, gained mixture is modified bismaleimide resin.
One kind enhancing laminate, it is with above-mentioned modified bismaleimide resin as adhesive, with glass fibre as base
Material, dries by dip-coating gluing, adhesive plaster, is laminated what is prepared.
The method for preparing enhancing laminate, comprises the following steps：
1) lotion is prepared：Modified bismaleimide resin powder is dissolved in DMF, is soaked
Masking liquid；
2) gluing is impregnated：The lotion is evenly applied to use in advance on the good glass fibre of coupling agent treatment, and
It is impregnated with glass fibre, as adhesive plaster；
3) adhesive plaster is dried：By step 2) gained adhesive plaster is placed in 40~50 DEG C of temperature ranges and is dried；
4) lamination compacting：By step 3) the dried adhesive plaster of gained suppressed after overlapping layer by layer, and press temperature is 230~
235 DEG C, pressure is 1.5~2.5MPa, and soaking time is 1.5~2 hours, and enhancement layer pressing plate is obtained after cooling.
The beneficial effects of the present invention are：Using the technical program, fracture toughness increases；Make its solidfied material water absorption rate
There is reduction trend；Modified resin has good wellability；Preferably, manufacturability is good for BMI viscosity after improvement
It is good, fiber surface is coated in without glue branch non-uniform phenomenon, part solidifies out, and surface roughness is preferable, without poor glue phenomenon,
Meet outward appearance use requirement.
Specific embodiment
Below in conjunction with the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described,
Obviously, described embodiment is only a part of embodiment of the invention, rather than whole embodiments.Based in the present invention
Embodiment, the every other embodiment that those of ordinary skill in the art are obtained under the premise of creative work is not made, all
Belong to the scope of protection of the invention.
Embodiment 1
A kind of modified bismaleimide resin, comprises the steps of：It is bimaleimide resin through cyanate resin
Fat, rubber, dicyandiamide, silica modified gained, wherein being by mass bimaleimide resin 70g, cyanate ester resin
25g, rubber 0.5g, dicyandiamide 12g and silica 0.1g.
A kind of preparation method of modified bismaleimide resin, comprises the following steps：
1) bimaleimide resin 70g, cyanate ester resin 25g, rubber 0.5g, dicyandiamide 12g and dioxy accurately are weighed
SiClx 0.1g, bimaleimide resin is 7 with the mass ratio of cyanate ester resin, rubber, dicyandiamide and silica：2.5：
0.05：1.2：0.01；
2) mix under certain condition, stir, gained mixture is modified bismaleimide resin.
One kind enhancing laminate, it is with above-mentioned modified bismaleimide resin as adhesive, with glass fibre as base
Material, dries by dip-coating gluing, adhesive plaster, is laminated what is prepared.
The method for preparing enhancing laminate, comprises the following steps：
1) lotion is prepared：Modified bismaleimide resin powder is dissolved in DMF, is soaked
Masking liquid；
2) gluing is impregnated：The lotion is evenly applied to use in advance on the good glass fibre of coupling agent treatment, and
It is impregnated with glass fibre, as adhesive plaster；
3) adhesive plaster is dried：By step 2) gained adhesive plaster is placed in 40 DEG C of temperature ranges and is dried；
4) lamination compacting：By step 3) the dried adhesive plaster of gained suppressed after overlapping layer by layer, and press temperature is 230
DEG C, pressure is 1.5MPa, and soaking time is 1.5 hours, and enhancement layer pressing plate is obtained after cooling.
Embodiment 2
A kind of modified bismaleimide resin, comprises the steps of：It is bimaleimide resin through cyanate resin
Fat, rubber, dicyandiamide, silica modified gained, wherein being by mass bimaleimide resin 70g, cyanate ester resin
35g, rubber 0.5g, dicyandiamide 15g and silica 0.1g.
A kind of preparation method of modified bismaleimide resin, comprises the following steps：
1) bimaleimide resin 70g, cyanate ester resin 35g, rubber 0.5g, dicyandiamide 15g and dioxy accurately are weighed
SiClx 0.1g, bimaleimide resin is 7 with the mass ratio of cyanate ester resin, rubber, dicyandiamide and silica：3.5：
0.05：1.5：0.01；
2) mix under certain condition, stir, gained mixture is modified bismaleimide resin.
One kind enhancing laminate, it is with above-mentioned modified bismaleimide resin as adhesive, with glass fibre as base
Material, dries by dip-coating gluing, adhesive plaster, is laminated what is prepared.
The method for preparing enhancing laminate, comprises the following steps：
1) lotion is prepared：Modified bismaleimide resin powder is dissolved in DMF, is soaked
Masking liquid；
2) gluing is impregnated：The lotion is evenly applied to use in advance on the good glass fibre of coupling agent treatment, and
It is impregnated with glass fibre, as adhesive plaster；
3) adhesive plaster is dried：By step 2) gained adhesive plaster is placed in 50 DEG C of temperature ranges and is dried；
4) lamination compacting：By step 3) the dried adhesive plaster of gained suppressed after overlapping layer by layer, and press temperature is 235
DEG C, pressure is 2.5MPa, and soaking time 2 hours obtains enhancement layer pressing plate after cooling.
This mixture shrinkage factor is 0.85%~0.93%, and bending strength increases with cyanate, rubber ratio increase,
Fragility is gradually reduced, and meets the defect of material needs improvement.Improve its material technology operability, product is improved in manufacturing process
Range of application.
Modified bismaleimide resin is mainly used in aircraft radome, machine components, interior structure part and resistant to elevated temperatures gluing
Agent.
Presently preferred embodiments of the present invention is the foregoing is only, is not intended to limit the invention, it is all in essence of the invention
Within god and principle, any modification, equivalent substitution and improvements made etc. should be included within the scope of the present invention.
Claims (4)
1. a kind of modified bismaleimide resin, it is characterised in that it is bimaleimide resin through cyanate ester resin, rubber
Glue, dicyandiamide, silica modified gained, the bimaleimide resin and cyanate ester resin, rubber, dicyandiamide and dioxy
The mass ratio of SiClx is 7：(2.5~3.5)：0.05：(1.2~1.5)：0.01.
2. the preparation method of a kind of modified bismaleimide resin according to claim 1, it is characterised in that including with
Lower step：
1) bimaleimide resin, cyanate ester resin, rubber, dicyandiamide, silica, the bismaleimide are accurately weighed
Polyimide resin is 7 with the mass ratio of cyanate ester resin, rubber, dicyandiamide and silica：(2.5~3.5)：0.05：(1.2~
1.5)：0.01；
2) mix under certain condition, stir, gained mixture is modified bismaleimide resin.
It is 3. a kind of to strengthen laminate, it is characterised in that：It is with above-mentioned modified bismaleimide resin as adhesive, with glass
Fiber is base material, is dried by dip-coating gluing, adhesive plaster, is laminated what is prepared.
4. the method for preparing a kind of enhancing laminate described in claim 3, it is characterised in that comprise the following steps：
1) lotion is prepared：Modified bismaleimide resin powder is dissolved in DMF, lotion is obtained；
2) gluing is impregnated：The lotion is evenly applied to use in advance on the good glass fibre of coupling agent treatment, and is impregnated with
Glass fibre, as adhesive plaster；
3) adhesive plaster is dried：By step 2) gained adhesive plaster is placed in 40~50 DEG C of temperature ranges and is dried；
4) lamination compacting：By step 3) the dried adhesive plaster of gained suppressed after overlapping layer by layer, and press temperature is 230~235
DEG C, pressure is 1.5~2.5MPa, and soaking time is 1.5~2 hours, and enhancement layer pressing plate is obtained after cooling.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611034806.8A CN106700549A (en) | 2016-11-23 | 2016-11-23 | Modified bismaleimide resin, reinforced laminated board and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611034806.8A CN106700549A (en) | 2016-11-23 | 2016-11-23 | Modified bismaleimide resin, reinforced laminated board and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106700549A true CN106700549A (en) | 2017-05-24 |
Family
ID=58941270
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611034806.8A Pending CN106700549A (en) | 2016-11-23 | 2016-11-23 | Modified bismaleimide resin, reinforced laminated board and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115972711A (en) * | 2022-12-13 | 2023-04-18 | 南京理工大学 | Fire-resistant explosion-proof composite board and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6060147A (en) * | 1996-11-27 | 2000-05-09 | Korea Advanced Institute Of Science And Technology | Process for preparing a carbon fiber-reinforced composite material having a morphology gradient |
| CN101220160A (en) * | 2007-12-07 | 2008-07-16 | 广东生益科技股份有限公司 | Prepreg applied for multi-layer board of printed electronic circuit |
| CN101343412A (en) * | 2007-07-12 | 2009-01-14 | 三菱瓦斯化学株式会社 | Prepreg and laminate |
| CN105601924A (en) * | 2016-03-17 | 2016-05-25 | 武汉理工大学 | Modified bismaleimide resin, modified bismaleimide resin/carbon fiber reinforced laminated board and preparation method thereof |
-
2016
- 2016-11-23 CN CN201611034806.8A patent/CN106700549A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6060147A (en) * | 1996-11-27 | 2000-05-09 | Korea Advanced Institute Of Science And Technology | Process for preparing a carbon fiber-reinforced composite material having a morphology gradient |
| CN101343412A (en) * | 2007-07-12 | 2009-01-14 | 三菱瓦斯化学株式会社 | Prepreg and laminate |
| CN101220160A (en) * | 2007-12-07 | 2008-07-16 | 广东生益科技股份有限公司 | Prepreg applied for multi-layer board of printed electronic circuit |
| CN105601924A (en) * | 2016-03-17 | 2016-05-25 | 武汉理工大学 | Modified bismaleimide resin, modified bismaleimide resin/carbon fiber reinforced laminated board and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115972711A (en) * | 2022-12-13 | 2023-04-18 | 南京理工大学 | Fire-resistant explosion-proof composite board and preparation method thereof |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170524 |
|
| RJ01 | Rejection of invention patent application after publication |