CN105038224A - Benzoxazine prepreg composite and preparation method - Google Patents
Benzoxazine prepreg composite and preparation method Download PDFInfo
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- CN105038224A CN105038224A CN201510438489.5A CN201510438489A CN105038224A CN 105038224 A CN105038224 A CN 105038224A CN 201510438489 A CN201510438489 A CN 201510438489A CN 105038224 A CN105038224 A CN 105038224A
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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
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- 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
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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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
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/53—Core-shell polymer
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention relates to a benzoxazine prepreg composite. The benzoxazine prepreg composite is composed of, by mass, 65-75% of benzoxazine resin, 5-20% of epoxy resin and 5-15% of flexibilizer. By means of the technical scheme, through benzoxazine compound components with at least one monofunctional/polyfunctional group, by adding the epoxy resin not limited to one type, processing properties are improved, and the binding force of benzoxazine resin base bodies and fiber is enhanced; the flexibilizer is selected from at least one type of flexibilizer, the rigidity of the benzoxazine resin base bodies is improved, and therefore fiber/fabric produced and impregnated through the benzoxazine resin base bodies has high manufacturability, and the benzoxazine prepreg composite long in room temperature storage life and high in performance is obtained.
Description
Technical field
The present invention relates to technical field of composite materials, particularly a kind of benzoxazine prepreg composition.
Background technology
Benzoxazine colophony is a kind of novel phenolic resins newly developed, the class being Material synthesis with phenolic compound, aldehydes and aminated compounds is containing the intermediate of oxygen, nitrogen heterocyclic structure, the reticulated structure that ring-opening polymerization forms similar resol is there is under heating/catalyst action, due to polymerization discharge without small molecules, the cure shrinkage of goods is little, porosity is low, has excellent mechanical property, electric property and flame retardant properties.
Prepreg is that matrix resin is combined the matrix material intermediateness product formed with strongthener, the matrix material of certain structural shape, mechanical property is formed, the matrix resin mainly thermosetting resin of current matrix material by certain lay-up process and curing process.Benzoxazine colophony has auto-polymerization ability, but polymerization temperature is more than 200 DEG C and fragility is large, be difficult to be applied in the field of compound material of main force support structure, so usually add catalyzer (promotor) to reduce solidification value, shorten set time, improve urethane cure degree, reach reduction energy consumption, cost-saving, improve the object of product properties, catalyzer (promotor) adds in the middle of matrix resin in advance, by heating, pressurization final molding goods, utilize the latent of catalyzer (promotor), prepreg is made to have certain storage period, but resin matrix is through heating mixing, film, the thermal history operations such as impregnation, its latent reduces greatly, so prepreg transports under cryogenic, storage, considerably increase cost like this to drop into.
Therefore, need now to develop and be a kind ofly suitable for room temperature prolonged storage and the not impaired benzoxazine prepreg composition material of performance.
Summary of the invention
The technical problem to be solved in the present invention is, is suitable for room temperature prolonged storage and the not impaired benzoxazine prepreg composition material of performance.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is, this benzoxazine prepreg composition is made up of benzoxazine colophony, epoxy resin and toughner; The massfraction of the content of described benzoxazine colophony is 60 ~ 79%, and the massfraction of the content of described epoxy resin is 1 ~ 20%, and the massfraction of the content of described toughner is 1 ~ 20%.
Adopt technique scheme, because prepreg working life is by determining the working life of matrix resin to a great extent, so reduce benzoxazine colophony matrix room temperature activity to play key effect to the prolongation benzoxazine colophony matrix prepreg room temperature storage phase, by comprising at least one list/many (containing two) functional group benzoxazine compound component, add and be not limited to a kind of epoxy resin and improve processing performance and strengthen benzoxazine colophony matrix and fibrous binding force, toughner is selected from above-mentioned at least one toughner, improve benzoxazine colophony matrix toughness, thus make the production of benzoxazine colophony matrix and impregnation fiber/fabric have good manufacturability, and obtain there is room temperature storage phase long and high performance benzoxazine prepreg composition.
As preferred version of the present invention, the massfraction of the content of described benzoxazine colophony is 60 ~ 75%, and the massfraction of the content of described epoxy resin is 5 ~ 20%, and the massfraction of the content of described toughner is 5 ~ 20%.
As preferred version of the present invention, the massfraction of the content of described benzoxazine colophony is 65 ~ 75%, and the massfraction of the content of described epoxy resin is 10 ~ 20%, and the massfraction of the content of described toughner is 5 ~ 15%.
Further improvement of the present invention is, described benzoxazine colophony is that polyphenol type benzoxazine colophony is or/and two amine type benzoxazines; The molecular structural formula of described polyphenol type benzoxazine colophony is:
Wherein, O is 1-4; When O is 1, X=alkyl ,-SH-; When O is 2, X=-,-S-,-SO
2-,-CO-,-CH
2-,-C (CH
3)
2-, polyurethane molecular compliant section; When O is 2 ~ 4, X=alkylidene group, R
1=methyl, ethyl, propyl group, butyl, aryl; The molecular structural formula of described two amine type benzoxazines is:
Wherein, P is 1 ~ 2; When P is 1, Y=alkyl, aryl; When P is 2, Y=phenylbenzene (methane/isopropyl alkane/sulfoxide/sulfone); R
4=hydrogen, halogen, alkyl, unsaturated group, cyano group, aldehyde radical.
As the preferred version of embodiments of the invention, the molecular structure of described benzoxazine colophony at least comprises following molecular structure:
Wherein: X is methylene radical, sec.-propyl, carbonyl, thioether, sulfoxide, sulfuryl, long chain molecule soft segment, R
1and R
2identical or different, being selected from hydrogen is alkyl, aryl, unsaturated group, R
4for hydrogen, halogen, alkyl, unsaturated group.
Further improvement of the present invention is, described epoxy resin is one or more mixing of bisphenol A-type or polyphenol type or mixed type epoxy resin; Described bisphenol A type epoxy resin at least comprises the one of the molecular structural formula of (I) or (II);
Wherein: R
5and R
6identical or different, be hydrogen or oxygen or methyl; The molecular structural formula of described many phenol-type epoxy resins is:
Wherein, R
7for hydrogen or methyl; Described mixed type epoxy resin at least comprises the one of the molecular structural formula of (A) or (B).
Further improvement of the present invention is, described toughner is one or more mixing of PES or polyether-ether-ketone or polyphenylene oxide or polyetherimide or fluid rubber or core-shell polymer or nano silicon.
The technical problem that the present invention also will solve is, provides a kind of and is suitable for room temperature prolonged storage and the preparation method of the not impaired benzoxazine prepreg composition material of performance.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is, the preparation method of this benzoxazine prepreg composition, and concrete steps are as follows:
(1) in vacuum environment, and vacuum tightness >=0.95, in the temperature range of 60 ~ 90 DEG C, heat benzoxazine colophony make its melting and can flow, and stir 30 ~ 60min, and do not cause solidification, obtain even benzoxazine colophony melts;
(2) by the even benzoxazine colophony melts of gained in step (1), at the temperature of 80 ~ 100 DEG C, add toughner, and stirring is dissolved, churning time is 60 ~ 90min, make it mix, and do not cause solidification, obtain a homogeneous mixture;
(3) by gained uniform mixture in step (2), first make it be cooled to 50 ~ 65 DEG C, add epoxy resin, and stir 45 ~ 80min, make it stir, obtain benzoxazine prepreg composition.
Another problem that the present invention also will solve is, provides a kind of method utilizing benzoxazine prepreg composition to produce prepreg.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is, this method utilizing benzoxazine prepreg composition to produce prepreg produces prepreg for adopting heat melting method, and concrete steps are as follows:
The preparation of (a) raw material: preparation layer of fibers and the present invention prepare benzoxazine prepreg composition;
B benzoxazine prepreg composition and described layer of fibers combine by (), and form prepreg by certain lay-up process, and curing process prepreg being placed in certain temperature and pressure is cured, and forms fiber reinforced resin based body material.
As preferred version of the present invention, described layer of fibers is cut fiber by continuous unidirectional fibre, fabric, chopped strand or length and is formed successively; Fiber is selected from carbon fiber, glass fibre, aramid fiber, quartz fibre; Described carbon fiber is selected from polyacrylonitrile-radical, viscose base, asphaltic base.
Adopt technical scheme of the present invention, its beneficial effect produced is: benzoxazine prepreg composition of the present invention can keep the high-performance of benzoxazine colophony based composites to have again the quite long room temperature storage phase, greatly reduce the storage of benzoxazine prepreg, transportation cost like this, be more conducive to widespread use.
Accompanying drawing explanation
In order to make content of the present invention more easily be clearly understood, below according to specific embodiment also by reference to the accompanying drawings, the present invention is further detailed explanation:
Fig. 1 is the curing process schema of benzoxazine prepreg composition of the present invention;
Embodiment
Embodiment 1
The component of benzoxazine prepreg composition is: B-A type benzoxazine, glycidyl amine epoxy mixture as resin body, wherein benzoxazine colophony/epoxy resin=3/1, its total mass mark 90wt%; Core-shell rubber particles toughner selected by toughner, and its massfraction is at 10wt%.
(1) in vacuum environment, vacuum tightness >=0.95, heating benzoxazine colophony, Heating temperature is 75 DEG C, makes its melting and can flow, and churning time 30min, and do not cause solidification, obtain even benzoxazine colophony melts;
(2) by the even benzoxazine melts of gained in step (1), Heating temperature is risen to 90 DEG C, add Core-shell rubber particles toughner, and stirring is dissolved, churning time is 80min, mixes, do not cause solidification, obtain a homogeneous mixture;
(3) by gained uniform mixture in step (2), be cooled to 55 DEG C, add epoxy resin, churning time is 60min, stirs, and obtains benzoxazine prepreg composition.
Embodiment 2
The component of benzoxazine prepreg composition is: B-A type benzoxazine, and alicyclic epoxy mixture is as resin body, and wherein benzoxazine/epoxy resin=5/1, its total mass mark 85wt%, fluid rubber selected by toughner, and its massfraction is at 15wt%.
(1) in vacuum environment, vacuum tightness >=0.95, heating benzoxazine colophony, Heating temperature is 70 DEG C, makes its melting and can flow, and stirring 45min, and not causing solidification, obtains even benzoxazine colophony melts;
(2) by the even benzoxazine melts of gained in step (1), Heating temperature is risen to 85 DEG C, add liquid rubber toughening agent, and stirring is dissolved, churning time is 100min, mixes, do not cause solidification, obtain a homogeneous mixture;
(3) by gained uniform mixture in step (2), be cooled to 70 DEG C, add epoxy resin, churning time is 60min, stirs, and obtains benzoxazine prepreg composition.
Hot melt process dipping standard modulus carbon fiber benzoxazine prepreg composition obtained in embodiment 1 and embodiment 2 is adopted to produce Fabric prereg, wherein resin content 40%, fiber areal densities 220g/m
2, weave construction 2/2 twill, through Lay up design, prepreg is cured through technique as shown in Figure 1, obtains carbon fiber enhancement resin base body material.
Fiber reinforced resin based for gained body material is carried out interlayer shear (with reference to ASTMD2344), Tg (DMTA method, E curve judges), prepreg viscosity (HB7736.8-2004) test, test as shown in table 1; Benzoxazine colophony matrix pour mass impact property (with reference to GB/T2567-2008).
The performance test results of the fiber reinforced resin based body material of table 1
| Sequence number | Embodiment 1 | Embodiment 2 |
| Pour mass shock strength/KJm -2 | 24 | 30 |
| Interlaminar shear strength/MPa | 76 | 81 |
| Tg/℃ | 195 | 186 |
| (grade 3 grades) viscosity/moon | >3 | ＞3 |
Known by table 1, compare benzoxazine colophony, the fragility of carbon fiber enhancement resin base body material obtains improvement to a certain degree, the T of carbon fiber enhancement resin base body material
ghigher than solidification value (180 DEG C), prepreg viscosity room temperature storage, apparently higher than epoxy resin-matrix prepreg, can be applied in the every field of commercial market and military markets.
Finally, it is also to be noted that what enumerate above is only several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be had.All distortion that those of ordinary skill in the art can directly derive from content disclosed by the invention or associate, all should think protection scope of the present invention.
Claims (10)
1. a benzoxazine prepreg composition, is characterized in that, this benzoxazine prepreg composition is made up of benzoxazine colophony, epoxy resin and toughner; The massfraction of the content of described benzoxazine colophony is 60 ~ 79%, and the massfraction of the content of described epoxy resin is 1 ~ 20%, and the massfraction of the content of described toughner is 1 ~ 20%.
2. benzoxazine prepreg composition according to claim 1, it is characterized in that, the massfraction of the content of described benzoxazine colophony is 60 ~ 75%, and the massfraction of the content of described epoxy resin is 5 ~ 20%, and the massfraction of the content of described toughner is 5 ~ 20%.
3. benzoxazine prepreg composition according to claim 2, it is characterized in that, the massfraction of the content of described benzoxazine colophony is 65 ~ 75%, and the massfraction of the content of described epoxy resin is 10 ~ 20%, and the massfraction of the content of described toughner is 5 ~ 15%.
4. the benzoxazine prepreg composition according to any one of claim 1-3, is characterized in that, described benzoxazine colophony is that polyphenol type benzoxazine colophony is or/and two amine type benzoxazines; The molecular structural formula of described polyphenol type benzoxazine colophony is:
Wherein, O is 1-4; When O is 1, X=alkyl ,-SH-; When O is 2, X=-,-S-,-SO
2-,-CO-,-CH
2-,-C (CH
3)
2-, polyurethane molecular compliant section; When O is 2 ~ 4, X=alkylidene group, R
1=methyl, ethyl, propyl group, butyl, aryl; The molecular structural formula of described two amine type benzoxazines is:
Wherein, P is 1 ~ 2; When P is 1, Y=alkyl, aryl; When P is 2, Y=phenylbenzene (methane/isopropyl alkane/sulfoxide/sulfone); R
4=hydrogen, halogen, alkyl, unsaturated group, cyano group, aldehyde radical.
5. benzoxazine prepreg composition according to claim 4, is characterized in that, the molecular structure of described benzoxazine colophony at least comprises following molecular structure:
Wherein: X is methylene radical, sec.-propyl, carbonyl, thioether, sulfoxide, sulfuryl, long chain molecule soft segment, R
1and R
2identical or different, for hydrogen is alkyl, aryl, unsaturated group, R
4for hydrogen, halogen, alkyl, unsaturated group.
6. benzoxazine prepreg composition according to claim 5, is characterized in that, described epoxy resin is one or more mixing of bisphenol A-type or polyphenol type or mixed type epoxy resin; Described bisphenol A type epoxy resin at least comprises the one of the molecular structural formula of (I) or (II);
Wherein: R
5and R
6identical or different, be hydrogen or oxygen or methyl; The molecular structural formula of described many phenol-type epoxy resins is:
Wherein, R
7for hydrogen or methyl; Described mixed type epoxy resin at least comprises the one of the molecular structural formula of (A) or (B).
。
7. benzoxazine prepreg composition according to claim 6, is characterized in that, described toughner is one or more mixing of PES or polyether-ether-ketone or polyphenylene oxide or polyetherimide or fluid rubber or core-shell polymer or nano silicon.
8. a preparation method for the benzoxazine prepreg composition as described in any one of claim 1-7, concrete steps are as follows:
(1) in vacuum environment, and vacuum tightness >=0.95, in the temperature range of 60 ~ 90 DEG C, heat benzoxazine colophony make its melting and can flow, and stir 30 ~ 60min, and do not cause solidification, obtain even benzoxazine colophony melts;
(2) by the even benzoxazine colophony melts of gained in step (1), at the temperature of 80 ~ 100 DEG C, add toughner, and stirring is dissolved, churning time is 60 ~ 90min, make it mix, and do not cause solidification, obtain a homogeneous mixture;
(3) by gained uniform mixture in step (2), first make it be cooled to 50 ~ 65 DEG C, add epoxy resin, and stir 45 ~ 80min, make it stir, obtain benzoxazine prepreg composition.
9. utilize the benzoxazine prepreg composition as described in any one of claim 1-7 to produce a method for prepreg, adopt heat melting method to produce prepreg, concrete steps are as follows:
The preparation of (a) raw material: preparation layer of fibers and the present invention prepare benzoxazine prepreg composition;
B benzoxazine prepreg composition and described layer of fibers combine by (), and form prepreg by certain lay-up process, and curing process prepreg being placed in certain temperature and pressure is cured, and forms fiber reinforced resin based body material.
10. benzoxazine prepreg composition according to claim 9 produces the method for prepreg, it is characterized in that, described layer of fibers is cut fiber by continuous unidirectional fibre, fabric, chopped strand or length and formed successively; Fiber is selected from carbon fiber, glass fibre, aramid fiber, quartz fibre; Described carbon fiber is selected from polyacrylonitrile-radical, viscose base, asphaltic base.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105733468A (en) * | 2016-04-28 | 2016-07-06 | 国网山东省电力公司济南市长清区供电公司 | Insulating tape |
| CN106167599A (en) * | 2016-07-13 | 2016-11-30 | 吉林瀛豪工贸有限公司 | A kind of epoxy phenolics prepreg and preparation method thereof |
| CN107903581A (en) * | 2017-12-19 | 2018-04-13 | 广西信和新合成材料有限公司 | Square particle benzoxazine moulding compound |
| CN108587060A (en) * | 2018-05-02 | 2018-09-28 | 江苏恒神股份有限公司 | A kind of benzoxazine colophony constituent and its prepreg suitable for microwave curing process |
| CN108794785A (en) * | 2017-04-26 | 2018-11-13 | 深圳光启高等理工研究院 | prepreg 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 |
| CN111892728A (en) * | 2020-06-23 | 2020-11-06 | 航天特种材料及工艺技术研究所 | Preparation method of benzoxazine resin hot-melt prepreg for autoclave molding process |
| CN112239586A (en) * | 2020-06-23 | 2021-01-19 | 航天特种材料及工艺技术研究所 | Curable resin composition containing benzoxazine and preparation method thereof |
| CN112442158A (en) * | 2019-08-27 | 2021-03-05 | 中国石油化工股份有限公司 | Bio-based degradable benzoxazine resin, preparation method thereof, cured resin thereof, compound thereof and degradation method |
| CN114230832A (en) * | 2021-12-21 | 2022-03-25 | 长春长光宇航复合材料有限公司 | Preparation method of benzoxazine prepreg by hot melting method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105733468A (en) * | 2016-04-28 | 2016-07-06 | 国网山东省电力公司济南市长清区供电公司 | Insulating tape |
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| CN107903581A (en) * | 2017-12-19 | 2018-04-13 | 广西信和新合成材料有限公司 | Square particle benzoxazine moulding compound |
| CN108587060A (en) * | 2018-05-02 | 2018-09-28 | 江苏恒神股份有限公司 | A kind of benzoxazine colophony constituent and its prepreg suitable for microwave curing process |
| CN112442158A (en) * | 2019-08-27 | 2021-03-05 | 中国石油化工股份有限公司 | Bio-based degradable benzoxazine resin, preparation method thereof, cured resin thereof, compound thereof and degradation method |
| 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 |
| CN111892728A (en) * | 2020-06-23 | 2020-11-06 | 航天特种材料及工艺技术研究所 | Preparation method of benzoxazine resin hot-melt prepreg for autoclave molding process |
| CN112239586A (en) * | 2020-06-23 | 2021-01-19 | 航天特种材料及工艺技术研究所 | Curable resin composition containing benzoxazine and preparation method thereof |
| CN111892728B (en) * | 2020-06-23 | 2022-09-23 | 航天特种材料及工艺技术研究所 | Preparation method of benzoxazine resin hot-melt prepreg for autoclave molding process |
| CN114230832A (en) * | 2021-12-21 | 2022-03-25 | 长春长光宇航复合材料有限公司 | Preparation method of benzoxazine prepreg by hot melting method |
| CN114230832B (en) * | 2021-12-21 | 2024-02-20 | 长春长光宇航复合材料有限公司 | Preparation method of benzoxazine prepreg by hot melting method |
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Application publication date: 20151111 |