CN112778696A - Maleimide group end-capped benzoxazine oligomer prepreg composition and preparation method thereof - Google Patents
Maleimide group end-capped benzoxazine oligomer prepreg composition and preparation method thereof Download PDFInfo
- Publication number
- CN112778696A CN112778696A CN202011606791.4A CN202011606791A CN112778696A CN 112778696 A CN112778696 A CN 112778696A CN 202011606791 A CN202011606791 A CN 202011606791A CN 112778696 A CN112778696 A CN 112778696A
- Authority
- CN
- China
- Prior art keywords
- maleimide group
- terminated
- benzoxazine oligomer
- oligomer
- prepreg
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 239000000203 mixture Substances 0.000 title claims abstract description 46
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 title claims description 15
- 238000002360 preparation method Methods 0.000 title claims description 8
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical group O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000000835 fiber Substances 0.000 claims abstract description 27
- 239000003822 epoxy resin Substances 0.000 claims abstract description 25
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 25
- 239000011159 matrix material Substances 0.000 claims abstract description 18
- 239000012745 toughening agent Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000004744 fabric Substances 0.000 claims abstract description 5
- 239000004014 plasticizer Substances 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 18
- 229920005989 resin Polymers 0.000 claims description 17
- 239000011347 resin Substances 0.000 claims description 17
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 6
- 239000004917 carbon fiber Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 238000007711 solidification Methods 0.000 claims description 6
- 230000008023 solidification Effects 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000004593 Epoxy Substances 0.000 claims description 4
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 4
- 150000005130 benzoxazines Chemical group 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000011258 core-shell material Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 229920002530 polyetherether ketone Polymers 0.000 claims description 4
- 150000008442 polyphenolic compounds Chemical class 0.000 claims description 4
- 235000013824 polyphenols Nutrition 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000004695 Polyether sulfone Substances 0.000 claims description 2
- 239000004697 Polyetherimide Substances 0.000 claims description 2
- 229920000297 Rayon Polymers 0.000 claims description 2
- 229920006231 aramid fiber Polymers 0.000 claims description 2
- 239000010426 asphalt Substances 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims description 2
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229920003208 poly(ethylene sulfide) Polymers 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920006393 polyether sulfone Polymers 0.000 claims description 2
- 229920001601 polyetherimide Polymers 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims 1
- 239000012943 hotmelt Substances 0.000 claims 1
- 229920006380 polyphenylene oxide Polymers 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 238000009776 industrial production Methods 0.000 abstract description 4
- 238000004132 cross linking Methods 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical group N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 1
- 235000003332 Ilex aquifolium Nutrition 0.000 description 1
- 235000002296 Ilex sandwicensis Nutrition 0.000 description 1
- 235000002294 Ilex volkensiana Nutrition 0.000 description 1
- 238000006683 Mannich reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- -1 o-hydroxyphenyl Chemical group 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C08L61/04, C08L61/18 and C08L61/20
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C08J2361/04, C08J2361/18, and C08J2361/20
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2461/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2461/16—Condensation polymers of aldehydes or ketones with phenols only of ketones with phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The invention relates to a maleimide group-terminated benzoxazine oligomer prepreg composition, which consists of maleimide group-terminated benzoxazine oligomers, epoxy resin and a plasticizer, wherein the maleimide group-terminated benzoxazine oligomers comprise the following components in percentage by weight: the mass fraction of the content of the maleimide group-terminated benzoxazine oligomer is 65-75%, the mass fraction of the content of the epoxy resin is 10-25%, and the mass fraction of the content of the toughening agent is 1-15%. By adopting the technical scheme, the maleimide group-terminated benzoxazine oligomer prepreg composition is prepared by adding and not limiting at least one epoxy resin to improve the process performance and enhance the bonding force between a maleimide group-terminated benzoxazine oligomer matrix and fibers, and adding at least one toughening agent to improve the toughness of the maleimide group-terminated benzoxazine oligomer matrix, so that the maleimide group-terminated benzoxazine oligomer matrix has good manufacturability for producing impregnated fibers/fabrics, and the maleimide group-terminated benzoxazine oligomer prepreg composition is excellent in performance, good in high-temperature resistance, easy to process and suitable for industrial production.
Description
[ technical field ] A method for producing a semiconductor device
The invention relates to the technical field of composite materials, in particular to a maleimide group end-capped benzoxazine oligomer impregnating compound.
[ technical background ] A method for producing a semiconductor device
Since the discovery of benzoxazine compounds by the Mannich reaction synthesized by Holly and Cope from o-hydroxyphenyl, methylamine and formaldehyde in 1944, the benzoxazine compounds have attracted much attention due to their excellent thermo-mechanical properties, weather resistance and electrical insulation. But also causes difficulty in processing and forming due to higher curing temperature, and limits the application of the resin in certain aspects.
The preparation of prepregs plays an important role in the application of polymer-based composites. In order to adapt to modern low-cost high-performance industrial production, a maleimide group-terminated benzoxazine is applied to the production of prepregs. The benzoxazine resin introduces maleimide group at the molecular chain end, so that the synthesis time of benzoxazine can be shortened, and the production efficiency of the benzoxazine can be improved. Meanwhile, when the epoxy resin is cured at high temperature and/or in the presence of a catalyst, besides ring-opening crosslinking of an oxazine ring, crosslinking reaction can further occur on a maleimide group, so that a more compact double-crosslinking three-dimensional network system is obtained. Thus, the thermal stability of the resin can be greatly improved, the processability of the resin is improved, and the subsequent processing and forming are facilitated. The prepreg taking the maleimide group-terminated benzoxazine oligomer as the matrix has excellent performance, good high-temperature resistance, easy processing and suitability for industrial production. In addition, no report is made to the synthesis and performance of maleimide group-terminated benzoxazine oligomer prepreg.
[ summary of the invention ]
The invention aims to solve the technical problem of obtaining the maleimide group-terminated benzoxazine oligomer prepreg composition which has excellent performance, good high-temperature resistance, easy processing and suitability for industrial production.
In order to solve the problems, the invention adopts the technical scheme that the maleimide group-terminated benzoxazine oligomer prepreg composition consists of a maleimide group-terminated benzoxazine oligomer, epoxy resin and a plasticizer; the mass fraction of the content of the maleimide group-terminated benzoxazine oligomer is 65-75%, the mass fraction of the content of the epoxy resin is 10-25%, and the mass fraction of the content of the toughening agent is 1-15%.
By adopting the scheme, the prepreg consists of the matrix resin and the reinforcing material, and the dosage of the matrix resin is far greater than that of the reinforcing material, so that the processability and high temperature resistance of the matrix resin have decisive influence on the performance of a prepreg product. The maleimide group-terminated benzoxazine oligomer just meets the requirements, has good processing formability, can carry out secondary crosslinking when the maleimide group is heated, and can effectively improve the high-temperature resistance of the prepreg. The maleimide group-terminated benzoxazine oligomer composition has the advantages that the maleimide group-terminated benzoxazine oligomer resin component is added and is not limited to epoxy resin to improve the process performance and enhance the bonding force between a maleimide group-terminated benzoxazine oligomer matrix and fibers, and a toughening agent is selected to improve the toughness of the maleimide group-terminated benzoxazine oligomer matrix, so that the maleimide group-terminated benzoxazine oligomer matrix has good manufacturability for producing impregnated fibers/fabrics, and the maleimide group-terminated prepreg benzoxazine oligomer composition with good process performance, high temperature resistance, high crosslinking density and low cost is obtained.
As a preferable scheme of the invention, the preferable mass fraction of the content of the maleimide group terminated benzoxazine oligomer is 70-75%, the preferable mass fraction of the content of the epoxy resin is 15-20%, and the preferable mass fraction of the content of the toughening agent is 5-10%.
The invention has the further improvement that the benzoxazine oligomer is maleimide group-terminated benzoxazine oligomer resin; the structural formula of the maleimide group-terminated benzoxazine oligomer is as follows:
the maleimide group is at the ortho, meta or para position of the benzoxazine epoxy atom.
Wherein, -R1-is one of the following:
-R2-is one of the following:
the further improvement of the invention is that the epoxy resin is one or more of bisphenol A type or polyphenol type or mixed type epoxy resin: the bisphenol A epoxy resin at least comprises one of the following two molecular structural formulas (I) and (II):
wherein, R3 and R4 are the same or different and are hydrogen or methyl. The molecular structural formula of the polyphenol epoxy resin is as follows:
wherein R5 is hydrogen or methyl. The mixed epoxy resin at least comprises one of the molecular structural formulas of (A) or (B).
The invention is further improved in that the toughening agent is one or a mixture of PES or polyether ether ketone or polyphenyl ether or polyetherimide or liquid rubber or core-shell polymer or nano silicon dioxide.
In order to solve the problems, the invention adopts the technical scheme that the preparation method of the benzoxazole prepreg composition of the main chain type benzoxazine comprises the following specific steps:
(1) heating the maleimide group-terminated benzoxazine oligomer in a vacuum environment with the vacuum degree of more than or equal to 0.95 at the temperature of 65-80 ℃ to melt and flow, stirring for 40-65min, and curing to obtain uniform maleimide group-terminated benzoxazine oligomer melt;
(2) adding a toughening agent into the uniform maleimide group-terminated benzoxazine oligomer melt obtained in the step (1) at the temperature of 85-100 ℃, stirring for dissolving, wherein the stirring time is 70-100min, so that the uniform mixture is uniformly mixed without causing solidification, and obtaining a uniform mixture;
(3) and (3) cooling the uniform mixture obtained in the step (2) to 45-60 ℃, adding epoxy resin, and stirring for 60-80min to obtain the maleimide group-terminated benzoxazine oligomer prepreg composition.
Another problem to be solved by the present invention is to provide a method for producing a prepreg using a maleimide group-terminated benzoxazine oligomer prepreg composition.
In order to solve the problems, the invention adopts the technical scheme that a hot melting method is adopted to produce the prepreg, and the method comprises the following specific steps:
(a) preparation of raw materials: preparing a fiber layer and the prepared maleimide group-terminated benzoxazine oligomer prepreg composition;
(b) combining the benzoxazole prepreg composition with the fiber layer, forming a prepreg through a certain layering process, and curing the prepreg through a curing process at a certain temperature and pressure to form the fiber reinforced resin matrix material.
In a preferred embodiment of the present invention, the fiber layer is formed of continuous unidirectional fibers, a fiber fabric, chopped fibers or long-cut fibers in this order; the fiber is selected from carbon fiber, glass fiber, aramid fiber and quartz fiber; the carbon fiber is selected from polyacrylonitrile base, viscose base and asphalt base.
By adopting the technical scheme, the main maleimide group-terminated benzoxazine oligomer prepreg composition has the advantages of good processing performance, high temperature resistance, high crosslinking density, low cost and the like. Therefore, the service performance of the benzoxazole prepreg composition is greatly improved, and the benzoxazole prepreg composition is more beneficial to wide application.
[ detailed description ] embodiments
Example 1
The maleimide group terminated benzoxazine oligomer prepreg composition comprises the following components: the structural formula of the adopted maleimide group-terminated benzoxazine oligomer is shown as the following formula, a glycidylamine epoxy mixture is used as a resin matrix, wherein the maleimide group-terminated benzoxazine oligomer/epoxy resin is 5/2, and the total mass fraction is 90 wt%; the toughening agent is polyether-ether-ketone toughening agent with the mass fraction of 10 wt%.
(1) Heating maleimide group-terminated benzoxazine oligomers to 75 ℃ in a vacuum environment with the vacuum degree being more than or equal to 0.95, melting and flowing the maleimide group-terminated benzoxazine oligomers, and stirring for 55min without causing solidification to obtain uniform maleimide group-terminated benzoxazine oligomer melts;
(2) heating the uniform maleimide group-terminated benzoxazine oligomer melt obtained in the step (1) to 90 ℃, adding a core-shell rubber particle toughening agent, stirring for dissolving, wherein the stirring time is 80min, uniformly mixing the materials without causing solidification, and obtaining a uniform mixture;
(3) and (3) cooling the uniform mixture obtained in the step (2) to 55 ℃, adding epoxy resin, stirring for 60min, and stirring uniformly to obtain the maleimide group-terminated benzoxazine oligomer prepreg composition.
Example 2
The maleimide group terminated benzoxazine oligomer prepreg composition comprises the following components: the structural formula of the adopted maleimide group-terminated benzoxazine oligomer is shown as the following formula, a glycidylamine epoxy mixture is used as a resin matrix, wherein the maleimide group-terminated benzoxazine oligomer/epoxy resin is 4/1.5, and the total mass fraction is 85 wt%; the toughening agent is polyether-ether-ketone toughening agent with the mass fraction of 15 wt%.
(1) Heating maleimide group-terminated benzoxazine oligomers to 75 ℃ in a vacuum environment with the vacuum degree being more than or equal to 0.95, melting and flowing the maleimide group-terminated benzoxazine oligomers, and stirring for 45min without causing solidification to obtain uniform maleimide group-terminated benzoxazine oligomer melts;
(2) heating the uniform maleimide group-terminated benzoxazine oligomer melt obtained in the step (1) to 90 ℃, adding a core-shell rubber particle toughening agent, stirring for dissolving, wherein the stirring time is 80min, uniformly mixing the materials without causing solidification, and obtaining a uniform mixture;
(3) and (3) cooling the uniform mixture obtained in the step (2) to 55 ℃, adding epoxy resin, stirring for 60min, and stirring uniformly to obtain the maleimide group-terminated benzoxazine oligomer prepreg composition.
The maleimide group-terminated benzoxazine oligomer prepreg compositions prepared in the embodiments 1 and 2 are used for impregnating standard modulus carbon fiber to produce fabric prepreg by adopting a hot melting method, wherein the resin content is 40%, the fiber surface density is 220g/m2, and the weave structure is 2/2 twill, and the carbon fiber reinforced resin matrix material is obtained by carrying out layering design and curing the prepreg through a process.
The obtained fiber reinforced resin matrix material was subjected to interlaminar shear (refer to ASTM D2344), Tg (DMTA method, determination of E curve), prepreg tack (HB 7736.8-2004) tests as shown in table 1; impact performance of the maleimide group-terminated benzoxazine oligomer matrix casting (refer to GB/T2567-2008).
TABLE 1 Performance test results of fiber reinforced resin matrix materials
| Serial number | Example 1 | Example 2 |
| Impact Strength of cast body/KJ.m 2 | 32 | 36 |
| Interlaminar shear strength/MPa | 85 | 84 |
| Tg/℃ | 410 | 413 |
| (class 3) viscosity/month | ＞3 | ＞3 |
It is to be noted that: the above examples are only for further illustration of the present invention and are not to be construed as limiting the scope of the present invention. After reading the present invention, those skilled in the art can make various improvements and modifications without departing from the spirit of the present invention, and such improvements and modifications are within the scope of the present invention as claimed.
Claims (8)
1. A maleimide group-terminated benzoxazine oligomer prepreg composition is characterized by comprising maleimide group-terminated benzoxazine oligomers, epoxy resin and a plasticizer; the mass fraction of the content of the maleimide group-terminated benzoxazine oligomer is 65-75%, the mass fraction of the content of the epoxy resin is 10-25%, and the mass fraction of the content of the toughening agent is 1-15%.
2. The maleimide group-terminated benzoxazine oligomer prepreg composition according to claim 1, wherein the preferable mass fraction of the content of the maleimide group-terminated benzoxazine oligomer is 70-75%, the preferable mass fraction of the content of the epoxy resin is 15-20%, and the preferable mass fraction of the content of the toughening agent is 5-10%.
3. The maleimide group-terminated benzoxazine oligomer prepreg composition according to claim 1, wherein the benzoxazine oligomer is a maleimide group-terminated benzoxazine oligomer, and the structural formula of the maleimide group-terminated benzoxazine oligomer is as follows:
the maleimide group is at the ortho, meta or para position of the benzoxazine epoxy atom.
Wherein, -R1-is one of the following:
-R2-is one of the following:
4. the maleimide group-terminated benzoxazine oligomer prepreg composition according to claim 1, wherein the epoxy resin is one or more of bisphenol a type or polyphenol type or mixed epoxy resin: the bisphenol A epoxy resin at least comprises one of the following two molecular structural formulas (I) and (II):
wherein, R3 and R4 are the same or different and are hydrogen or methyl. The molecular structural formula of the polyphenol epoxy resin is as follows:
wherein R5 is hydrogen or methyl. The mixed epoxy resin at least comprises one of the molecular structural formulas of (A) or (B).
5. The maleimide group-terminated benzoxazine oligomer prepreg composition according to claim 1, wherein the toughening agent is one or more of PES or polyetheretherketone or polyphenylene oxide or polyetherimide or liquid rubber or core-shell polymer or nano-silica.
6. A preparation method of the maleimide group-terminated benzoxazine oligomer prepreg composition according to any one of claims 1 to 5 comprises the following specific steps:
(1) heating the maleimide group-terminated benzoxazine oligomer in a vacuum environment with the vacuum degree of more than or equal to 0.95 at the temperature of 65-80 ℃ to melt and flow, stirring for 40-65min, and curing to obtain uniform maleimide group-terminated benzoxazine oligomer melt;
(2) adding a toughening agent into the uniform maleimide group-terminated benzoxazine oligomer melt obtained in the step (1) at the temperature of 85-100 ℃, stirring for dissolving, wherein the stirring time is 70-100min, so that the uniform mixture is uniformly mixed without causing solidification, and obtaining a uniform mixture;
(3) and (3) cooling the uniform mixture obtained in the step (2) to 45-60 ℃, adding epoxy resin, and stirring for 60-80min to obtain the maleimide group-terminated benzoxazine oligomer prepreg composition.
7. A method for preparing a prepreg by using the maleimide group terminated benzoxazine oligomer prepreg composition according to any one of claims 1-5, wherein the prepreg is prepared by a hot-melt method, and comprises the following specific steps:
(a) preparation of raw materials: preparing a fiber layer and the prepared maleimide group-terminated benzoxazine oligomer prepreg composition;
(b) and combining the benzoxazine oligomer prepreg composition with the fiber layer, forming a prepreg through a certain layering process, and curing the prepreg through a curing process at a certain temperature and pressure to form the fiber reinforced resin matrix material.
8. The preparation method for producing the prepreg by using the maleimide group terminated benzoxazine oligomer prepreg composition according to claim 7, wherein the fiber layer is formed by sequentially arranging continuous unidirectional fibers, fiber fabrics, chopped fibers or long-cut fibers; the fiber is selected from carbon fiber, glass fiber, aramid fiber and quartz fiber; the carbon fiber is selected from polyacrylonitrile base, viscose base and asphalt base.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011606791.4A CN112778696A (en) | 2020-12-30 | 2020-12-30 | Maleimide group end-capped benzoxazine oligomer prepreg composition and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011606791.4A CN112778696A (en) | 2020-12-30 | 2020-12-30 | Maleimide group end-capped benzoxazine oligomer prepreg composition and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112778696A true CN112778696A (en) | 2021-05-11 |
Family
ID=75753482
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011606791.4A Pending CN112778696A (en) | 2020-12-30 | 2020-12-30 | Maleimide group end-capped benzoxazine oligomer prepreg composition and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112778696A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113337077A (en) * | 2021-07-29 | 2021-09-03 | 吉林大学 | High-thermal-conductivity electromagnetic shielding polyether-ether-ketone composite material with isolation structure and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106750289A (en) * | 2016-12-20 | 2017-05-31 | 江苏大学 | A kind of benzoxazine oligomer of maleimide base group end-sealed type and preparation method thereof |
| CN110818932A (en) * | 2019-09-18 | 2020-02-21 | 常州市宏发纵横新材料科技股份有限公司 | Norbornene-based end-capped benzoxazine oligomer prepreg composition, and preparation method and application method thereof |
-
2020
- 2020-12-30 CN CN202011606791.4A patent/CN112778696A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106750289A (en) * | 2016-12-20 | 2017-05-31 | 江苏大学 | A kind of benzoxazine oligomer of maleimide base group end-sealed type and preparation method thereof |
| CN110818932A (en) * | 2019-09-18 | 2020-02-21 | 常州市宏发纵横新材料科技股份有限公司 | Norbornene-based end-capped benzoxazine oligomer prepreg composition, and preparation method and application method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113337077A (en) * | 2021-07-29 | 2021-09-03 | 吉林大学 | High-thermal-conductivity electromagnetic shielding polyether-ether-ketone composite material with isolation structure and preparation method and application thereof |
| CN113337077B (en) * | 2021-07-29 | 2022-05-17 | 吉林大学 | High-thermal-conductivity electromagnetic shielding polyether-ether-ketone composite material with isolation structure and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1734069B1 (en) | Composite material | |
| CN100523087C (en) | Thermostable benzoxazine resin compound and its preparation method and uses | |
| CN102850545A (en) | High-toughness high-heat-resistant poly-benzoxazine/ bismaleimide blending resin and preparation method thereof | |
| CN110818932A (en) | Norbornene-based end-capped benzoxazine oligomer prepreg composition, and preparation method and application method thereof | |
| AU2015374285A1 (en) | Benzoxazines and compositions containing the same | |
| CN1207325C (en) | Modified benzoxazine resin capable of using for RTM and process for preparing same | |
| TWI692474B (en) | Trifunctional benzoxazine | |
| CN112778696A (en) | Maleimide group end-capped benzoxazine oligomer prepreg composition and preparation method thereof | |
| CN101864076A (en) | Cyanate resin modified by phenylacetylene base silane resin and preparation method thereof | |
| CN104045978A (en) | Polyarylether nitrile/epoxy resin copolymerized modified composition and preparation method and application thereof | |
| CN111875793A (en) | Phthalonitrile resin for composite material and preparation method thereof | |
| CN111295407B (en) | Resin composition and resin infusion method | |
| CN109096753B (en) | Nitrile resin composite material and preparation method thereof | |
| CN101570599B (en) | Cyanate/bisoxazoline co-cured resin and preparation method and application thereof | |
| CN113861362B (en) | Method for rapidly curing and toughening benzoxazine resin | |
| CN109096488B (en) | Phthalonitrile resin composition and preparation method thereof | |
| CN111574712B (en) | Low-melting-point bismaleimide resin monomer eutectic and preparation method thereof, bismaleimide resin composition and preparation method of bismaleimide resin | |
| CN115584625B (en) | Organic fiber, fiber composite material, preparation method and application thereof | |
| CN114474778B (en) | Preparation method of modified high-silicon-content aryne resin and composite material thereof | |
| CN116535821A (en) | Preparation method of epoxy resin composition and preparation method of composite material | |
| CN115651356A (en) | Benzoxazine resin system, preparation method thereof and method for preparing composite material | |
| CN117700926A (en) | Resin material system for mold and preparation method and application thereof | |
| CN114015197A (en) | Matrix resin suitable for non-autoclave molding and preparation method thereof | |
| GB2521636A (en) | Improvements in or relating to fibre reinforced composites | |
| CN117021711A (en) | Fiber reinforced resin matrix composite material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210511 |