CN101225229B - Wet-heat cyanate ester/ composite material and preparation method thereof - Google Patents
Wet-heat cyanate ester/ composite material and preparation method thereof Download PDFInfo
- Publication number
- CN101225229B CN101225229B CN2008100184141A CN200810018414A CN101225229B CN 101225229 B CN101225229 B CN 101225229B CN 2008100184141 A CN2008100184141 A CN 2008100184141A CN 200810018414 A CN200810018414 A CN 200810018414A CN 101225229 B CN101225229 B CN 101225229B
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- micro
- composite
- capsule
- encapsulant
- 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.)
- Expired - Fee Related
Links
Abstract
The invention discloses a hydrothermal-resistant composite and a preparation method of the composite, in particular to a cyanate ester (CE)/micro encapsulant composite and a preparation method of the composite, belonging to the high performance resin matrix composite field. The mass ratios of the CE/micro encapsulant composite are 100 portions cyanate ester, 0 to 5 portions epoxy resin, 2 to 30 portions epoxy resin micro encapsulant, 0 to 600 portions fiber. The preparation method is characterized in that: the epoxy resin micro encapsulant coated by polyurea formaldehyde is filled into the CE to prepare CE/micro encapsulant resin system, and then the CE composite with high hydrothermal-resistant performance is obtained. The hydrothermal-resistant composite has the advantages that: compared with the CE system without micro encapsulant, the hydrothermal-resistant performance of the CE/micro encapsulant composite is improved greatly. The CE/micro encapsulant composite can be used for preparing printed circuit boards for high-speed digital and high frequency, high performance composite in aerospace.
Description
Technical field
The present invention relates to hot matrix material of a kind of moisture-proof and preparation method thereof, be particularly related to a kind of cyanate (CE)/microcapsule matrix material and preparation method thereof, be specially and adopt uramit coated epoxy resin microcapsules modification CE, belong to performance resins based composites field to improve the method for matrix material wet-hot aging performance.
Background technology
The performance resins based composites has many advantages such as specific tenacity height, heat-resisting good, light weight, is widely used in the leading-edge field of defense and commercial industry.The CE matrix material is as typical case's representative of performance resins based composites, and it has excellent mechanical property, high heat resistance, and good environment resistant and dielectric properties etc. are with a wide range of applications in fields such as aerospace, electronics.But one of disadvantage that the CE after solidifying exists is crisp, the poor toughness of performance, and is therefore more to the research of CE toughening modifying at present.That common method has is thermoplastic resin modified, modified rubber, copolymerization and blending and modifying etc.Because CE matrix material environment for use is very complicated, often be subjected to the effect of damp and hot, carrying etc., so the performance of material can reduce inevitably.For the CE after solidifying, because the singularity of its crosslinking structure itself has lower water absorbability.But consider performance such as the mechanical property of water absorbability to the CE material, influence such as thermal stability and dielectric properties is very big, and improves its anti-hygroscopic property and help keeping of material property, prolongs the work-ing life of material, the Application Areas of expansion material.Therefore, it is significant that how research improves the anti-hygroscopic property of CE matrix material.At present, the research report of relevant CE matrix material wet-hot aging performance raising is less.By adding epoxidised polysiloxane, thermoplastic resin such as polysulfones, small amount of epoxy resin and synthetic new CE monomer can improve the moisture resistance properties of CE matrix material.
Summary of the invention
The object of the present invention is to provide a kind of novel Wet-heat cyanate ester/composite material and preparation method thereof.
Realize a kind of Wet-heat cyanate ester/composite material that the object of the invention provided, its component is by weight:
Cyanate: 100 parts,
Resins, epoxy: 0～5 part,
Epoxy resin micro-capsule: 2～30 parts,
Fiber: 0～600 part.
The preparation method of above-mentioned Wet-heat cyanate ester/composite material, concrete steps are as follows:
(1) by weight, in 100 parts cyanate, add 0～5 part Resins, epoxy, in 130～140 ℃ of following pre-polymerization 40min, add 2～30 parts epoxy resin micro-capsule again behind heating and melting under 100 ℃ the temperature condition, stirring obtains containing the cyanate ester resin system of microcapsule;
(2) the fiber add-on is 0 o'clock, directly injects above-mentioned system through preheating and scribbles the mould of releasing agent, after vacuum outgas, is cured processing by 120 ℃ of technologies/1h+150 ℃/2h+180 ℃/2h+200 ℃/2h condition; The fiber add-on treats after the step (1) that resin system is cooled to 60 ℃ below the temperature during greater than 0～600 part, adds acetone and is made into glue, brush after stirring to glasscloth, treat that fugitive constituent less than after 1%, reduces prepreg, spread layer in mould, compression moulding on flat-bed press; Earlier at 120 ℃ of insulation 1h, add/release exits for several times during composite material forming, plus-pressure 1MPa then is cured processing by 150 ℃ of technologies/1h+180 ℃/2h+200 ℃/2h condition again.
Described Resins, epoxy is bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, bisphenol-A epoxy resin and linear phenolic epoxy resin; Described bisphenol A epoxide resin is E-55, E-51, E-44, E-42, E-33 and E-20; Described linear phenolic epoxy resin is F-44, F-51, F-48, F-46, JF-45 and JF-43.
Described microcapsule are the epoxy resin micro-capsule that uramit coats, and its particle size range is 10～900 μ m.
Described fiber is carbon fiber and glass fibre; Described carbon fiber comprises T300, T400H, T700, T800, IM6, IM7, IM8 and high modulus carbon fiber M40, M40J, M55J, M60J; Described glass fibre comprises EW-210, EW240, SW220, SW100A, CWR200-90, CWR300-90, CW100E-100, CW120D-100, EW210, EW240, SW220, SW100A, CWR200-90, CWR300-90, CW100E-100 and CW120D-100.
Above, described uramit coated epoxy resin microcapsules is a disclosed technology among the Chinese invention patent CN1927187 " dicyclopentadiene microcapsule with melamine methyl aldehyde coating and preparation method thereof ", and its component is: trimeric cyanamide, formaldehyde solution, dicyclopentadiene, stopper, water, tensio-active agent and defoamer.Preparation process is: trimeric cyanamide, formaldehyde solution, water are put into bottle, and heating is also adopted the alkali lye regulator solution, is obtained the melamino-formaldehyde prepolymer solution; With DCPD and aqueous solution, inject the reaction flask stirring and add the melamino-formaldehyde prepolymer solution, add the aqueous solution that contains emulsifying agent and defoamer again and stir; The temperature rise rate of control reaction system, insulation also finishes reaction; Product is washed with water for several times, obtain microcapsule product through suction filtration and drying.
The present invention is filled among the CE by the epoxy resin micro-capsule that uramit is coated, and the hot CE/ microcapsule of a kind of novel moisture-proof matrix material is provided.The raising of this advanced composite material wet-hot aging performance, major cause is: (1) microcapsule add the shrinking percentage that resin matrix has improved matrix, have reduced the defective of matrix inside; (2) penetrate the reaction of capsule-core Resins, epoxy and cyanate group or triazine ring on a small quantity, Sheng Cheng oxazolidine ring forms one deck supple buffer layer at the interfacial layer of microcapsule and matrix, helps the raising of material wet-hot aging performance; (3) microcapsule have bigger volume, thereby its existence can make the evolving path of water molecules increase the infiltration rate that slows down water molecules, helps improving the wet-hot aging performance of material.The matrix material that is obtained can be used for production high-speed figure and high frequency printed circuit board, aerospace high performance structures matrix material etc.
Embodiment
The invention will be further elaborated below in conjunction with embodiment.
Embodiment one:
Take by weighing 100g 4,4 '-two cyanate ester based diphenyl propanes and 5g bisphenol A type epoxy resin (E-51) mixture are in the 250ml beaker, behind heating and melting under 100 ℃ of temperature in 130～140 ℃ of following pre-polymerization 40min, adding median size respectively is the uramit coated epoxy resin microcapsules 2,5,8 of 330 μ m, 10,15,20g, stirring obtains containing the CE system of different amount microcapsule.Described uramit coated epoxy resin microcapsules component is: trimeric cyanamide, formaldehyde solution, dicyclopentadiene, stopper, water, tensio-active agent and defoamer.Preparation process is: trimeric cyanamide, formaldehyde solution, water are put into bottle, and heating is also adopted the alkali lye regulator solution, is obtained the melamino-formaldehyde prepolymer solution; With DCPD and aqueous solution, inject the reaction flask stirring and add the melamino-formaldehyde prepolymer solution, add the aqueous solution that contains emulsifying agent and defoamer again and stir; The temperature rise rate of control reaction system, insulation also finishes reaction; Product is washed with water for several times, obtain microcapsule product through suction filtration and drying.
Inject above-mentioned system through preheating and scribble the mould of releasing agent,, be cured processing by 120 ℃ of technologies/1h+150 ℃/2h+180 ℃/2h+200 ℃/2h in 90～100 ℃ of following vacuum outgas 30min.The casting matrix for preparing is being cut into desired size sample test performance behind poach 100h on the cutting machine.The relevant performance data of casting matrix sees Table 1 behind the poach.
Table 1
As can be seen from Table 1, behind the epoxy resin micro-capsule that adding 330 μ m uramits coat in CE, the water-intake rate of material reduces, and the mechanical property conservation rate of material is also higher behind the poach, illustrates that CE/ microcapsule casting matrix has good wet-hot aging performance.
Embodiment 2
Take by weighing 100g 4,4 '-two cyanate ester based diphenyl propanes and 5g bisphenol A type epoxy resin (E-51) mixture are in the 250ml beaker, behind 100 ℃ of following heating and meltings in 130～140 ℃ of following pre-polymerization 40min, adding median size is the uramit coated epoxy resin microcapsules 2 of 140 μ m, 5,8,10,15g, stirring obtains containing the CE system of different amount microcapsule.
Inject above-mentioned system through preheating and scribble the mould of releasing agent,, be cured by 120 ℃ of technologies/1h+150 ℃/2h+180 ℃/2h+200 ℃/2h in 90～100 ℃ of following vacuum outgas 30min.The casting matrix for preparing is being cut into desired size sample test performance behind poach 100h on the cutting machine.The relevant performance data of casting matrix sees Table 2 behind the poach.
Table 2
As can be seen from Table 2, behind the epoxy resin micro-capsule that adding 140 μ m uramits coat in CE, the water-intake rate of material obviously reduces, and the mechanical property conservation rate of material is also higher behind the poach, illustrates that CE/ microcapsule casting matrix has good wet-hot aging performance.
Embodiment 3
Take by weighing 100g 4,4 '-two cyanate ester based diphenyl propanes and 5g bisphenol A type epoxy resin (E-51) mixture are in the 250ml beaker, behind 100 ℃ of following heating and meltings in 130～140 ℃ of following pre-polymerization 40min, adding median size is the uramit coated epoxy resin microcapsules 2,5,8 of 86 μ m, 10,15,20g, stirring obtains containing the CE system of different amount microcapsule.
Inject above-mentioned system through preheating and scribble the mould of releasing agent,, be cured by 120 ℃ of technologies/1h+150 ℃/2h+180 ℃/2h+200 ℃/2h in 90～100 ℃ of following vacuum outgas 30min.The casting matrix for preparing is being cut into desired size sample test performance behind poach 100h on the cutting machine.The relevant performance data of casting matrix sees Table 3 behind the poach.
Table 3
[0035]
As can be seen from Table 3, behind the epoxy resin micro-capsule that adding 86 μ m uramits coat in CE, the water-intake rate of material reduces, and the mechanical property conservation rate of material is also higher behind the poach, illustrates that CE/ microcapsule casting matrix has good wet-hot aging performance.
Embodiment 4
Take by weighing 100g 4,4 '-two cyanate ester based diphenyl propanes and 5g bisphenol A type epoxy resin (E-51) mixture are in the 250ml beaker, behind 100 ℃ of following heating and meltings in 130～140 ℃ of following pre-polymerization 40min, adding median size is the uramit coated epoxy resin microcapsules 2 of 140 μ m, 5,8,10,15g, stirring obtains containing the CE system of different amount microcapsule.
Treat that resin system is cooled to below 60 ℃, add an amount of acetone and be made into glue, brush after stirring to glasscloth (EW210), treat that fugitive constituent less than after 1%, reduces prepreg, the shop layer in mould, compression moulding on flat-bed press.Earlier at 120 ℃ of insulation 1h, add/release exits for 5～10 times during composite material forming, plus-pressure 1MPa then is cured by 150 ℃/1h+180 ℃/2h+200 ℃/2h again.The matrix material for preparing is being cut into desired size sample test performance behind poach 100h on the cutting machine.The relevant performance data of matrix material sees Table 4 behind the poach.
Table 4
As can be seen from Table 4, after in CE, adding the epoxy resin micro-capsule of 140 μ m uramits coating, the water-intake rate of the fibre-reinforced CE/ microencapsulation material of preparation reduces, the mechanical property conservation rate of material obviously improves behind the poach, illustrates that fiber reinforcement CE/ microcapsule matrix material has good wet-hot aging performance.
Embodiment 5
Take by weighing 100g 4,4 '-two cyanate ester based diphenyl propanes and 5g bisphenol A type epoxy resin (E-51) mixture are in the 250ml beaker, behind 100 ℃ of following heating and meltings in 130～140 ℃ of following pre-polymerization 40min, adding median size is the uramit coated epoxy resin microcapsules 2 of 86 μ m, 5,8,10,15g, stirring obtains containing the CE system of different amount microcapsule.
Treat that resin system is cooled to below 60 ℃, add an amount of acetone and be made into glue, brush after stirring to glasscloth (EW210), treat that fugitive constituent less than after 1%, reduces prepreg, the shop layer in mould, compression moulding on flat-bed press.Earlier at 120 ℃ of insulation 1h, add/release exits for 5 ~ 10 times during composite material forming, plus-pressure 1MPa then is cured by 150 ℃/1h+180 ℃/2h+200 ℃/2h again.The matrix material for preparing is being cut into desired size sample test performance behind poach 100h on the cutting machine.The relevant performance data of matrix material sees Table 5 behind the poach.
Table 5
As can be seen from Table 5, after in CE, adding the epoxy resin micro-capsule of 86 μ m uramits coating, the water-intake rate of the fibre-reinforced CE/ microencapsulation material of preparation reduces, the mechanical property conservation rate of material obviously improves behind the poach, illustrates that fiber reinforcement CE/ microcapsule matrix material has good wet-hot aging performance.
Claims (2)
1. Wet-heat cyanate ester/composite material, it is characterized in that: its component is by weight:
Cyanate: 100 parts,
Resins, epoxy: 0～5 part,
Epoxy resin micro-capsule: 2～30 parts,
Fiber: 0～600 part,
Described epoxy resin micro-capsule is the epoxy resin micro-capsule that uramit coats.
2. the preparation method of a Wet-heat cyanate ester/composite material is characterized in that concrete steps are as follows:
(1) by weight, in 100 parts cyanate, add 0～5 part Resins, epoxy, behind heating and melting under 100 ℃ the temperature condition in 130～140 ℃ of following pre-polymerization 40min, the epoxy resin micro-capsule that adds 2～30 parts again, stirring obtains containing the cyanate ester resin system of microcapsule, and described epoxy resin micro-capsule is the epoxy resin micro-capsule that uramit coats;
(2) the fiber add-on is 0 o'clock, directly injects above-mentioned system through preheating and scribbles the mould of releasing agent, after vacuum outgas, is cured processing by 120 ℃ of technologies/1h+150 ℃/2h+180 ℃/2h+200 ℃/2h condition; The fiber add-on is greater than 0 and during smaller or equal to 600 parts, treat after the step (1) that resin system is cooled to 60 ℃ below the temperature, add acetone and be made into glue, brush after stirring to glasscloth, treat that fugitive constituent is less than after 1%, prepreg is reduced, spread layer in mould, compression moulding on flat-bed press; Earlier at 120 ℃ of insulation 1h, add/release exits for several times during composite material forming, plus-pressure 1MPa then is cured processing by 150 ℃ of technologies/1h+180 ℃/2h+200 ℃/2h condition again.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100184141A CN101225229B (en) | 2008-02-04 | 2008-02-04 | Wet-heat cyanate ester/ composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100184141A CN101225229B (en) | 2008-02-04 | 2008-02-04 | Wet-heat cyanate ester/ composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101225229A CN101225229A (en) | 2008-07-23 |
| CN101225229B true CN101225229B (en) | 2010-11-10 |
Family
ID=39857443
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100184141A Expired - Fee Related CN101225229B (en) | 2008-02-04 | 2008-02-04 | Wet-heat cyanate ester/ composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101225229B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102675825A (en) * | 2011-12-03 | 2012-09-19 | 西北工业大学 | High-performance wave-transmitting composite material based on PBO (poly-p-phenylene benzobisthiazole) fiber and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0414461B1 (en) * | 1989-08-24 | 1995-07-12 | Amoco Corporation | Resin compositions comprising aromatic cyanate esters, polyepoxide compounds and thermoplastic polymers and prepreg made therefrom |
| CN1970627A (en) * | 2006-10-11 | 2007-05-30 | 苏州大学 | Cyanate resin/ carbon fiber composite material and its preparing process |
-
2008
- 2008-02-04 CN CN2008100184141A patent/CN101225229B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0414461B1 (en) * | 1989-08-24 | 1995-07-12 | Amoco Corporation | Resin compositions comprising aromatic cyanate esters, polyepoxide compounds and thermoplastic polymers and prepreg made therefrom |
| CN1970627A (en) * | 2006-10-11 | 2007-05-30 | 苏州大学 | Cyanate resin/ carbon fiber composite material and its preparing process |
Non-Patent Citations (8)
| Title |
|---|
| JP昭56-18615A 1981.02.21 |
| JP特开2003-213019A 2003.07.30 |
| 秦华宇等.改性氰酸酯树脂基复合材料的研究.玻璃钢/复合材料 1.2000,(1),36-38. |
| 秦华宇等.改性氰酸酯树脂基复合材料的研究.玻璃钢/复合材料 1.2000,(1),36-38. * |
| 赵磊等.环氧树脂改性氰酸酯树脂基复合材料.工程塑料应用28 3.2000,28(3),7-9. |
| 赵磊等.环氧树脂改性氰酸酯树脂基复合材料.工程塑料应用28 3.2000,28(3),7-9. * |
| 赵磊等.环氧树脂改性氰酸酯树脂玻璃布层压板的研制.玻璃钢/复合材料 4.2000,(4),32-34. |
| 赵磊等.环氧树脂改性氰酸酯树脂玻璃布层压板的研制.玻璃钢/复合材料 4.2000,(4),32-34. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101225229A (en) | 2008-07-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102660874B (en) | Thermoplasticity sizing agent for carbon fiber and preparation and usage thereof | |
| JP5808057B2 (en) | Modified resin system for liquid resin injection applications and related processing methods | |
| CN101891957B (en) | Organic silicon resin-based heat-resisting wave-penetrating composite material and preparation method thereof | |
| CN105367793A (en) | Cyanate ester resin prepolymer with excellent space environment property, and prepreg, preparation method and application thereof | |
| CN100575421C (en) | The hot bismaleimides of high moisture-proof/microcapsule matrix material and preparation method thereof | |
| CN102675825A (en) | High-performance wave-transmitting composite material based on PBO (poly-p-phenylene benzobisthiazole) fiber and preparation method thereof | |
| CN109082117A (en) | It is a kind of with low-k, low-dielectric loss and can intermediate temperature setting Penetrating and preparation method thereof | |
| CN101597371A (en) | High-ductility co-cured resin of cyanate and preparation method thereof, application | |
| RU2318666C2 (en) | Method of manufacture of the fibers reinforced articles on the basis of the epoxy resin | |
| CN106995582A (en) | A kind of curable resin composition and its application containing benzoxazine and epoxy resin blend | |
| CN110879018A (en) | Fiber-reinforced composite plastic for motorcycle helmet and preparation method thereof | |
| CN101225229B (en) | Wet-heat cyanate ester/ composite material and preparation method thereof | |
| CN103012790A (en) | Bisphthalonitrile-amino phenoxy phthalonitrile copolymer and condensate, and glass fiber composite material and preparation method thereof | |
| CN108384234B (en) | A kind of wave-penetrating composite material and preparation method thereof | |
| CN1213084C (en) | Preparation method and application of modified double maleimide resin | |
| CN104194264A (en) | High-thermal-resisting POSS-based epoxy resin nano composite material for PCBs and preparation method of high-thermal-resisting POSS-based epoxy resin nano composite material | |
| CN104448711A (en) | Epoxy resin/carbon fiber/halloysite nanotube composite material and preparation method thereof | |
| CN101570600B (en) | Resin matrix for resin transfer molding process, and preparation method thereof | |
| CN104861422A (en) | Novel epoxy resin laminated composite for snowboard and preparation method of novel epoxy resin laminated composite | |
| Hou et al. | Double‐vacuum‐bag technology for volatile management in composite fabrication | |
| CN102863634A (en) | Process for preparing poly-p-phenylenebenzobisthiazole (PBO) fiber/benzoxazine composite material | |
| CN114539956A (en) | Preparation method of formaldehyde-free wave-absorbing lignin modified phenolic resin adhesive | |
| CN103724931B (en) | A kind of phenol-formaldehyde resin modified, wave-penetrating composite material and preparation method | |
| CN103172858B (en) | Preparation method of electronic material for transmitting high-frequency signals | |
| CN112048085A (en) | Preparation process of biodegradable resin-based composite material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20101110 Termination date: 20130204 |