CN106995582A - A kind of curable resin composition and its application containing benzoxazine and epoxy resin blend - Google Patents
A kind of curable resin composition and its application containing benzoxazine and epoxy resin blend Download PDFInfo
- Publication number
- CN106995582A CN106995582A CN201710341375.8A CN201710341375A CN106995582A CN 106995582 A CN106995582 A CN 106995582A CN 201710341375 A CN201710341375 A CN 201710341375A CN 106995582 A CN106995582 A CN 106995582A
- Authority
- CN
- China
- Prior art keywords
- benzoxazine
- epoxy resin
- composition
- composite
- curable resin
- 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
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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or 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
- 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
- C08J2461/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C08J2461/04, C08J2461/18, and C08J2461/20
-
- 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
- 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
- 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- 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)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The present invention relates to a kind of curable resin composition containing benzoxazine and epoxy resin blend, its composition at least includes following (1) to (3)：(1) a kind of cycloaliphatic epoxy resin, includes two or more epoxy radicals；(2) a kind of trifunctional benzoxazine compound；(3) a kind of phenolic compound is used as catalyst.Curable resin composition containing benzoxazine and epoxy resin blend can be used for manufacturing the high-performance composite materials with good Hygrothermal Properties, and its perforate compressive strength in space flight under the high temperature conditions equivalent to or better than applying using epoxy systems and span system as the composite of matrix；Using the curable resin composition containing benzoxazine/epoxy resin blend as composite matrix resin, the composite prepared has excellent perforate compression performance, 100 DEG C of high temperature ＞ under high temperature hygrometric state.
Description
Technical field
Contain benzoxazine and epoxy resin blend the present invention relates to a kind of technical field of composite materials, more particularly to one kind
Curable resin composition and its application.
Background technology
With the development of science and technology, due to polymer matrix composites high-strength light, gradually for alternative metals material,
It is widely used in high performance structures, such as Aero-Space, field of track traffic.Polymer matrix composite by reinforcing fiber such as
Carbon fiber, glass fibre and aramid fiber, and polymeric matrix composition.Thermosetting resin has excellent solvent resistance and hot
Can and be used primarily in the matrix resin for being used as polymer matrix composite, cross-linking formation three dimensional network after this kind of resin solidification
Network structure.
Because the caking property between epoxy resin and reinforcing fiber is good, and form after composite excellent mechanical strength and just
Property, epoxy resin is often used as polymeric matrix material.The polyfunctional group ring of many amine-type cures applied in aviation field
Oxygen tree fat needs to solidify under conditions of persistently overheating and pressurization.With thermoplastic resin and the rubber toughened epoxy systems of reactivity
The fragility under high crosslink density is improved, the model of composite fuselage application is had become.
Compared with other thermosetting resins, benzoxazine colophony has advantages below：Solidification need not add catalyst, no pair
Product is produced, and is shunk close to zero volume, low water absorption, high glass-transition temperature, high-modulus, and itself has FST performances, molecule
The flexibility of design, at room temperature with stability.However, the benzoxazine of polyfunctionality is solid below 120 DEG C, it is difficult to
The aeronautical technology of standard such as prepreg or liquid molding process machine-shaping.
The application design particularly space structure of composite needs to consider the Hygrothermal Properties of material.Spacecraft in a short time must
It must can bear extreme environmental conditions such as high temperature and high humility.Perforate compressive strength aviation composite wherein one under wet heat condition
Individual important performance, is generally exposed under humidity environment, the perforate compressive strength under high temperature can be reduced for a long time.It is a kind of
The training of standard is with bolt, rivet and other fasteners come the fuselage of assembling aircraft, and the hole for adapting to fastener and boring is considered aircraft
Shortcoming, can become under compressive stress failure point.The method of approved prediction Failure Analysis of Composite Materials is strong for perforate compression
The test of degree.
The perforate compressive strength of many polymer matrix composites is typical definite value or under definite value at room temperature, but full
Largely decline with being had under high temperature after moisture absorption.The compressive strength reduction of composite is under usual high temperature and hygrometric state condition
It is well-known.Commercialization bismaleimide resin system Cycom977-3 and Cycom5250-4 have developed into high performance turbine and are combined
Material.Composite based on these resins has excellent hot wet perforate compression performance, is adapted to hold as the master of aircraft
Power structure.Although having many study on the synthesis, application reports on benzoxazine compound, under wet heat condition (149
DEG C, the temperature in use of conventional span system) it is seldom as the perforate compression performance of the composite of matrix report using benzoxazine.
Compared with the epoxy systems under high crosslink density and span system, (100 DEG C of ＞) has all to come with body benzoxazine at high temperature
Excellent compression performance.
Therefore, the present invention provides a kind of curable resin composition containing benzoxazine and epoxy resin blend and can be used for
High-performance composite materials of the manufacture with good Hygrothermal Properties, its perforate compressive strength is under the high temperature conditions equivalent to or better than preceding
What face was mentioned apply in space flight using epoxy systems and span system as the composite of matrix.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of curable composition mixed containing benzoxazine and epoxy resin
Thing, with its dipping or perfusion reinforcing fiber, solidification prepares composite, composite is had excellent damp and hot perforate compressibility
Energy.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is：This contains benzoxazine and epoxy resin is common
The composition of the curable resin composition of mixed thing at least includes following (1) to (4)：
(1) a kind of cycloaliphatic epoxy resin, includes two or more epoxy radicals；
(2) a kind of trifunctional benzoxazine compound；
(3) a kind of phenolic compound is used as catalyst.
Wherein epoxy component selects alicyclic epoxy, compared with other kinds of epoxy resin, and alicyclic epoxy can be disconnected
The balance provided in toughness, glass transition temperature and manufacturability is provided；Suitable alicyclic epoxide compound is generally each
A cycloaliphatic ring and at least two epoxy radicals are comprised at least on strand.Impregnated by matrix resin of this curable resin composition
Carbon fiber, the composite prepared is under wet heat condition, with excellent perforate compression performance.
The present invention further improvement is that, this contains the curable resin composition of benzoxazine and epoxy resin blend
Composition also includes a kind of (4) difunctional benzoxazine compound；(4) structure of difunctional benzoxazine compound is such as
Under：
Wherein：R1, R2For alkyl, cycloalkyl, aryl；
Z1For-C (R3) (R4) ,-C (R3) (aryl) ,-C (O)-,-S- ,-O- ,-S (O)-,-S (O) 2-, bivalent heterocyclic
Compound and-[C (R3) (R4)] x- arlydene-[C (R5) (R6)] y-；R3, R4, R5, R6 are hydrogen, alkyl, halogenated alkyl；X and y are
0 or 1；Z1Group is linear or nonlinear.Curable resin combination also includes (4) difunctional benzo in the present invention
Oxazine compounds；Wherein the addition of benzoxazine component (2) and (4) exceedes the 50% of total composition.Difunctional benzo
Oxazine compounds are defined as containing Liang oxazine ring.The chemical constitution of suitable difunctional benzoxazine is as follows：
Wherein：Z1For-C (R3) (R4) ,-C (R3) (aryl) ,-C (O)-,-S- ,-O- ,-S (O)-,-S (O) 2-, divalence is miscellaneous
Cycle compound and-[C (R3) (R4)] x- arlydene-[C (R5) (R6)] y-；R1 and R2 is alkyl, cycloalkyl, aryl；R3, R4,
R5 is hydrogen, alkyl, halogenated alkyl；X and y independently are 0 or 1.
Group Z1But linear and nonlinear, typically linear, specific difunctional benzoxazine structure
It is as follows：
Difunctional benzoxazine in the present invention can be anti-by polyhydric phenols, particularly bis-phenol, aromatic amine and paraformaldehyde
Answer and obtain, the difunctional benzoxazine of commercialization mainly has bisphenol-A and bisphenol-f type benzoxazine and diaminourea two
Methane type benzoxazine.
The present invention further improvement is that, (2) trifunctional benzoxazine compound that the composition includes and
(4) the content sum of difunctional benzoxazine compound accounts for more than the 50% of total composition；(1) ring in the composition
The part by weight of the benzoxazine compound of oxygen tree fat and (2) trifunctional is 5:95~90:10；And in the composition
(1) the content sum of the benzoxazine compound of epoxy resin and (2) trifunctional accounts for the 50%~80% of total composition；Institute
The content for stating in composition (3) phenolic compound is no more than the 15% of total composition.
The present invention further improvement is that, the structure of (2) trifunctional benzoxazine compound in the composition
It is as follows：
Wherein：R1, R2And R3For alkyl, cycloalkyl, aryl；R4For hydrogen, halogen, alkyl and alkylene.
The present invention further improvement is that, the alicyclic epoxy of (1) cycloaliphatic epoxy resin is 3', 4'- epoxycyclohexyls
Methyl -3,4- epoxycyclohexyl formic acid esters.
The present invention further improvement is that, (3) phenolic compound is the sub- isopropyl of thiodiphenol (TDP) or 4,4'-
Base -2,6- xylenols or 4,4'- cyclohexylenes biphenol or 4,4'- ethylenebis phenol.
Its epoxy resin (1) is 5 relative to the part by weight of the benzoxazine of (2) trifunctional:95~90:10,
It is 20 in some instantiations:80~70:30；By embodiment in the parts by weight that constitute of component (1) and (2) more than 50%, or
Person's component (1) and the parts by weight of (2) composition are more than 80%.Why epoxy component selects alicyclic epoxy, and other kinds of
Epoxy resin is compared, the balance that alicyclic epoxy can be provided in fracture toughness, glass transition temperature and manufacturability.Properly
Alicyclic epoxide compound generally on each strand comprise at least a cycloaliphatic ring and at least two epoxy radicals.At one
In reference example, aliphatic epoxy resin is 3', 4'- epoxycyclohexyl-methyl -3,4- epoxycyclohexyl formic acid esters, and structure is such as
Under：
Such epoxy commercialization has the Hensel to step advanced materialCY179；EPONEX epoxy resin, is such as stepped
The EPONEX1510 of figure special chemical article；Epoxy resin such as YDH 184, (the Aditya Birla of YDH 3000
Chemicals)；Tao Shi ERLTM4421.
The structure of the benzoxazine compound of trifunctional is as follows：
Wherein：R1, R2And R3For alkyl, cycloalkyl, aryl；R4For hydrogen, halogen, alkyl and alkylene.
Trifunctional benzoxazine preferably includes following compound：
Trifunctional benzoxazine disclosed herein can be by trisphenol, aromatic amine and formaldehyde with traditional solvent method or nothing
Solvent method is synthesized.Especially, the trifunctional benzoxazine of aniline type can by 1,1,1- tri- (4- hydroxy benzenes) ethane and aniline,
Polyformaldehyde reaction is obtained；P- tri- benzoxazines are synthesized by 1,1,1- tri- (4- hydroxy benzenes) ethane and para-totuidine, paraformaldehyde,
M- tri- benzoxazines are synthesized by (4- hydroxy benzenes) ethane of 1,1,1- tri- and meta-aminotoluene and paraformaldehyde.
In the present invention, phenolic compound is the effective catalyst of benzoxazine/epoxy-resin systems.One of which is adapted to
Phenolic compound be thiodiphenol (TDP), structure is as follows：
Other phenolic compounds that can be added include 4,4'- isopropylidene -2,6- xylenols, 4,4'- cyclohexylenes
Biphenol, 4,4'- ethylenebis phenol etc., the addition of phenolic compound is no more than the 15% of total composition.
The technical problem to be solved in the present invention be to provide it is a kind of using containing benzoxazine and epoxy resin mix it is curable
Composition is as the method for preparing composite of matrix material, and with its dipping or perfusion reinforcing fiber, solidification prepares composite wood
Material, makes composite have excellent damp and hot perforate compression performance.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is：This is using containing benzoxazine and asphalt mixtures modified by epoxy resin
The curable compositions of fat mixing comprise the following steps as the method for preparing composite of matrix material：(a) with containing benzo
The curable resin composition of oxazine and epoxy resin blend is increased as the matrix resin of composite using dipping or perfusion
Strong fiber formation prepreg, its reinforcing fiber is chopped fiber or continuous fiber or monofilament or tow；(b) prepreg is solidified
Obtain composite.
The present invention further improvement is that, additive is added during composite is prepared；The additive includes
Toughener and functional additive；The content of the additive is less than or equal to the 15% of total composition.Because itself is more crisp, group
Need addition toughening agent modified in compound.Suitable toughener includes but is not limited to thermoplastic resin such as polyether sulfone, polyether sulfone and gathers
The copolymer of ether ether sulfone, elastomer such as reactive fluid rubber, special toughener such as thermoplastic particles, rubber particles and nucleocapsid rubber
Micelle；In order that composite possesses certain feature, some functional additives can be added and control its rheological behavior, electrically
Energy, optical property, anti-flammability and hot property；Functional additive includes but is not limited to, filler, pigment, thixotropic agent, tackifier, conductive
Additive, fire retardant, ultraviolet protective agent etc.；The form of these additives includes but is not limited to particle, thin slice, strip etc..
The present invention further improvement is that, the functional additive be filler or pigment or thixotropic agent or tackifier or conduction
Additive or fire retardant or ultraviolet protective agent.
The present invention further improvement is that, the mass content of the reinforcing fiber in the composite is 60%~70%；
Wherein after the prepreg by being formed comprising benzoxazine and epoxy resin blend using impregnating reinforcing fiber, using autoclave
Solidification, the pressure of solidification process is 6~7.5bar, and solidification temperature is more than 140 DEG C；Cure cycle is the heating speed with 2 DEG C/min
Rate is incubated 120min from room temperature to 140~180 DEG C, then proceedes to be cooled to room temperature after being warming up to 200 DEG C of insulation 2h；When
It is molded using resin infusion, includes resin transfer moulding (RTM) and vacuum assisted resin transfer molding (VARTM)；It will increase first
The precast body of definite shape is made in strong fiber, then curable resin composition is directly injected into fiber preform, then
Solidification.The mass content of reinforcing fiber in the composite is in 60%~70%, typically at least 68%.In industry and AEROSPACE APPLICATION
In high performance structures, be more likely to continuous fiber manufacture, such as glass or aramid fiber or carbon are fine, and its content is arrived 30%
70%, its special volume content is 50%~70%；Forming composite can impregnate curable resin composition or irrigate
Reinforcing fiber, but it is not limited to dipping or resin infusion；Wherein preimpregnation refers to curable matrix resin being incorporated into reinforcing fiber,
So that partly or entirely fiber is infiltrated by resin.Matrix resin is general first to paint resin film on device for coating, then with fiber
It is combined under certain temperature and pressure and forms prepreg；Prepreg after impregnation is a kind of curable or partially cured flexible
State, prepreg is layered on to be formed after solidification on mould according to specific direction applies certain pressure in laminate, solidification process,
Solidification of hot-press tank is generally used as high performance structural member；Solidification temperature is more than 140 DEG C, suitably at 160 DEG C~220 DEG C.Than
Comparatively ideal cure cycle is, from room temperature to 180 DEG C, to be incubated 120min with 2 DEG C/min heating rate, then proceedes to rise
Temperature is incubated to be cooled in room temperature, solidification process after 2h to 200 DEG C needs pressurized exhaust gas to reduce the formation of hole, generally Jia 6
~7.5bar pressure；Composite material component can include resin transfer moulding (RTM) and vacuum aided using resin infusion shaping
Resin transfer moulding (VARTM)；By resin infusion such as RTM or VARTM, fiber is made to the precast body of definite shape first,
Then curable resin is directly injected into fiber preform, is then solidified.When curable resin combination is used for resin
During method for filling, it is accordingly required in particular to add phenolic compound as catalyst.
The present invention further improvement is that, the reinforcing fiber is that glass fibre or carbon fiber or aramid fiber or quartz are fine
Dimension or polyethylene fibre or polyester fiber or one or both of pbo fiber or graphite fibre and two or more combinations；Institute
It is unidirectional or polyaxial fiber or woven fabric or non-woven to state continuous fiber.By curable resin combination and reinforcing fiber
Combine to form composite, wherein the form of reinforcing fiber can be chopped fiber, continuous fiber, monofilament, tow, sheet material etc..
Continuous fiber is using unidirectional, polyaxial, woven fabric, non-woven etc., the combination from different fibers, obtained composite
Can be different；Fibrous material may include but be not limited to glass fibre, carbon fiber, aramid fiber, quartz fibre, polyethylene fibre, poly-
Ester fiber, the application after pbo fiber, graphite fibre and combination；The composite of high intensity is manufactured, is such as applied in spacecraft and vapour
Car field, the tensile strength of reinforcing fiber is expected to reach more than 3000MPa.
Compared with prior art, the invention has the advantages that：What the present invention was described contains benzoxazine and asphalt mixtures modified by epoxy resin
The curable resin composition of resin blends can be used for manufacturing the high-performance composite materials with good Hygrothermal Properties, its perforate pressure
Contracting intensity under the high temperature conditions equivalent to or better than it is above-mentioned applied in space flight using epoxy systems and span system as
The composite of matrix；It regard the curable resin composition containing benzoxazine/epoxy resin blend as composite material base
Body resin, the composite prepared has excellent perforate compression performance at high temperature, and 100 DEG C of high temperature ＞ especially exists
121~149 DEG C.
Embodiment
In order to deepen the understanding of the present invention, the present invention is described in further detail below in conjunction with embodiment, the reality
Apply example to be only used for explaining the present invention, protection scope of the present invention is not constituted and limited.
Embodiment：It is prepared for the different curable resin combinations containing benzoxazine and epoxy resin blend of 8 kinds of components
Thing, as shown in table 1, all numerical value in table are mass percent to each component ratio.
The composition of the different ratio of table 1
| Numbering | 1# | 2# | 3# | 4# | 5# | 6# | 7# | 8# |
| Ba-Boz | 65 | 55 | 50 | 40 | 50 | 25 | ||
| m-bis-Boz | 75 | 30 | ||||||
| Alicyclic epoxy | 25 | 25 | 20 | 20 | 25 | 25 | ||
| Pa-Boz | 25 | 25 | ||||||
| tris-Boz | 10 | 35 | 65 | |||||
| m-tris-Boz | 20 | |||||||
| p-tris-Boz | 20 | 10 | ||||||
| TDP | 10 | 10 | 10 | 10 | 10 | 10 |
Remarks：Ba-Boz is bisphenol-A-aniline type benzoxazine, and TDP is thiodiphenol, and Pa-Boz is phenol-aniline type
Simple function group benzoxazine.
Using the curable resin composition system containing benzoxazine and epoxy resin blend of the formula system in upper table 1
Resin film, unidirectional pre-immersion material is prepared using T700 grade carbon fibers, and resin content is 35%, and fiber areal densities are 130gsm；It is multiple
Condensation material laminate presses [+45/0/-45/90] by 32 layers of prepreg4sLaying is carried out, every 4 layers of progress is once pre- during laying
Compacting, 10min；Accomplish fluently vacuum bag after having spread in autoclave by 180 DEG C/3h to solidify, whole process plus 6.5bar pressure；Layer after solidification
Pressing plate tests perforate compressive strength by ASTM D6484, and specimen size is all hygrometric state processing in 4mm × 36mm × 300mm, table 2
Condition be 71 DEG C at water boil 14 days, perforate compression result is shown in Table 2.
The laminate Tg of table 2 and perforate compressive strength
Find out from the result of table 2, aliphatic epoxy and trifunctional benzoxazine (3#, 4#, 6#, 8#) are contained in resin system
The compressive strength of perforate is higher at 121 DEG C and 149 DEG C of high temperature after being handled through hygrometric state, and four systems dry state glass transition temperature
Degree and wet glass transition temperature are above other systems.Test Tg by dynamic mechanical analysis, containing alicyclic epoxy and
The system Tg of trifunctional benzoxazine is higher, and in the system without alicyclic epoxy, trifunctional benzoxazine plus
Enter to reduce the Tg (5#) of system.
The present invention is not limited to above-mentioned particular implementation, is made on the premise of above-mentioned basic fundamental thought is not departed from
Various deformations or amendments, all fall within the row of rights protection scope of the present invention.
Claims (10)
1. a kind of curable resin composition containing benzoxazine and epoxy resin blend, it is characterised in that this contains Ben Bing Evil
The composition of the curable resin composition of piperazine and epoxy resin blend at least includes following (1) to (3)：
(1) a kind of cycloaliphatic epoxy resin, includes two or more epoxy radicals；
(2) a kind of trifunctional benzoxazine compound；
(3) a kind of phenolic compound is used as catalyst.
2. the curable resin composition according to claim 1 containing benzoxazine and epoxy resin blend, its feature
It is, it is a kind of double that the composition for containing the curable resin composition of benzoxazine and epoxy resin blend also includes (4)
Functional group's benzoxazine compound；(4) structure of difunctional benzoxazine compound is as follows：
Wherein：R1, R2For alkyl, cycloalkyl, aryl；
Z1For-C (R3) (R4) ,-C (R3) (aryl) ,-C (O)-,-S- ,-O- ,-S (O)-,-S (O) 2-, bivalent heterocyclic compound
With-[C (R3) (R4)] x- arlydene-[C (R5) (R6)] y-；R3, R4, R5, R6 are hydrogen, alkyl, halogenated alkyl；X and y be 0 or
1；Z1Group is linear or nonlinear.
3. the curable resin composition according to claim 1 or 2 containing benzoxazine and epoxy resin blend, it is special
Levy and be, the structure of (2) trifunctional benzoxazine compound in the composition is as follows：
Wherein：R1, R2And R3For alkyl, cycloalkyl, aryl；R4For hydrogen, halogen, alkyl and alkylene.
4. the curable resin composition according to claim 3 containing benzoxazine and epoxy resin blend, its feature
It is, (2) trifunctional benzoxazine compound that the composition includes and (4) difunctional benzoxazine compound
Content sum account for more than the 50% of total composition；The benzo of (1) epoxy resin and (2) trifunctional in the composition
The part by weight of oxazine compounds is 5:95~90:10；And (1) epoxy resin and (2) trifunctional in the composition
The content sum of benzoxazine compound accounts for the 50%~80% of total composition；(3) phenolic compound in the composition
Content be no more than total composition 15%.
5. the curable resin composition according to claim 4 containing benzoxazine and epoxy resin blend, its feature
It is, the alicyclic epoxy of (1) cycloaliphatic epoxy resin in the composition is 3', 4'- epoxycyclohexyl-methyls -3,4-
Epoxycyclohexyl formic acid esters；(3) phenolic compound in the composition is thiodiphenol (TDP) or the sub- isopropyls of 4,4'-
Base -2,6- xylenols or 4,4'- cyclohexylenes biphenol or 4,4'- ethylenebis phenol.
6. the curable resin group containing benzoxazine and epoxy resin blend described in a kind of utilization claim any one of 1-5
The method that compound prepares composite, it is characterised in that comprise the following steps：(a) with containing benzoxazine and epoxy blend
The curable resin composition of thing forms prepreg as the matrix resin of composite using impregnating or irrigating reinforcing fiber,
Its reinforcing fiber is chopped fiber or continuous fiber or monofilament or tow；(b) prepreg solidify obtaining composite.
7. according to claim 6 prepared using the curable resin composition containing benzoxazine and epoxy resin blend
The method of composite, it is characterised in that additive is added during composite is prepared；The additive includes toughness reinforcing
Agent and functional additive；The content of the additive is less than or equal to the 15% of total composition.
8. according to claim 7 prepared using the curable resin composition containing benzoxazine and epoxy resin blend
The method of composite, it is characterised in that the functional additive is that filler or pigment or thixotropic agent or tackifier or conduction add
Plus agent or fire retardant or ultraviolet protective agent.
9. according to claim 7 prepared using the curable resin composition containing benzoxazine and epoxy resin blend
The method of composite, it is characterised in that the mass content of the reinforcing fiber in the composite is 60%~70%；Wherein
It is solid using autoclave after by using the prepreg that impregnating reinforcing fiber is formed comprising benzoxazine and epoxy resin blend
Change, the pressure of solidification process is 6~7.5bar, and solidification temperature is more than 140 DEG C；Cure cycle is with 2 DEG C/min heating rate
From room temperature to 140~180 DEG C, 120min is incubated, then proceedes to be cooled to room temperature after being warming up to 200 DEG C of insulation 2h；When adopting
It is molded with resin infusion, includes resin transfer moulding (RTM) and vacuum assisted resin transfer molding (VARTM)；First will enhancing
The precast body of definite shape is made in fiber, and then curable resin composition is directly injected into fiber preform, Ran Hougu
Change.
10. according to claim 7 utilize the curable resin composition system containing benzoxazine and epoxy resin blend
The method of standby composite, it is characterised in that the reinforcing fiber is that glass fibre or carbon fiber or aramid fiber or quartz are fine
Dimension or polyethylene fibre or polyester fiber or one or both of pbo fiber or graphite fibre and two or more combinations；Institute
It is unidirectional or polyaxial fiber or woven fabric or non-woven to state continuous fiber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710341375.8A CN106995582A (en) | 2017-05-16 | 2017-05-16 | A kind of curable resin composition and its application containing benzoxazine and epoxy resin blend |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710341375.8A CN106995582A (en) | 2017-05-16 | 2017-05-16 | A kind of curable resin composition and its application containing benzoxazine and epoxy resin blend |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106995582A true CN106995582A (en) | 2017-08-01 |
Family
ID=59434506
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710341375.8A Pending CN106995582A (en) | 2017-05-16 | 2017-05-16 | A kind of curable resin composition and its application containing benzoxazine and epoxy resin blend |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106995582A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108504290A (en) * | 2018-05-10 | 2018-09-07 | 江苏地基工程有限公司 | A kind of water resistant resin anchor fixing agent and preparation method thereof |
| CN111086281A (en) * | 2019-12-31 | 2020-05-01 | 浙江林境新材料科技有限公司 | Anti-static halogen-free flame-retardant circulating packaging box and preparation method thereof |
| CN111902465A (en) * | 2018-03-30 | 2020-11-06 | 东丽株式会社 | Benzoxazine resin composition, prepreg and fiber-reinforced composite material |
| CN112210106A (en) * | 2019-07-12 | 2021-01-12 | 航天材料及工艺研究所 | Preparation method of hot-melt benzoxazine composition capable of being cured at medium temperature |
| WO2022168815A1 (en) * | 2021-02-02 | 2022-08-11 | Ｅｎｅｏｓ株式会社 | Composition for curable resins, cured product of said composition, method for producing said composition, method for producing said cured product, and semiconductor device |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1115772A (en) * | 1994-07-29 | 1996-01-31 | 四川联合大学 | Open-loop polymerized phenolic resin and relevant composite fibre-reinforced material |
| CN1451679A (en) * | 2003-04-30 | 2003-10-29 | 四川大学 | Modified benzoxazine resin capable of using for RTM and process for preparing same |
| CN102173153A (en) * | 2010-12-13 | 2011-09-07 | 中国航空工业集团公司北京航空材料研究院 | Preparation method of fiber reinforced composite material |
| CN102421824A (en) * | 2009-05-14 | 2012-04-18 | 亨斯迈先进材料美国有限责任公司 | Liquid monobenzoxazine based resin system |
| US20160185907A1 (en) * | 2014-12-29 | 2016-06-30 | Cytec Industries Inc. | Trifunctional benzoxazine |
| US20160362554A1 (en) * | 2015-06-12 | 2016-12-15 | Cytec Industries Inc. | Curable compositions containing benzoxazine epoxy blend and use thereof |
-
2017
- 2017-05-16 CN CN201710341375.8A patent/CN106995582A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1115772A (en) * | 1994-07-29 | 1996-01-31 | 四川联合大学 | Open-loop polymerized phenolic resin and relevant composite fibre-reinforced material |
| CN1451679A (en) * | 2003-04-30 | 2003-10-29 | 四川大学 | Modified benzoxazine resin capable of using for RTM and process for preparing same |
| CN102421824A (en) * | 2009-05-14 | 2012-04-18 | 亨斯迈先进材料美国有限责任公司 | Liquid monobenzoxazine based resin system |
| CN102173153A (en) * | 2010-12-13 | 2011-09-07 | 中国航空工业集团公司北京航空材料研究院 | Preparation method of fiber reinforced composite material |
| US20160185907A1 (en) * | 2014-12-29 | 2016-06-30 | Cytec Industries Inc. | Trifunctional benzoxazine |
| US20160362554A1 (en) * | 2015-06-12 | 2016-12-15 | Cytec Industries Inc. | Curable compositions containing benzoxazine epoxy blend and use thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111902465A (en) * | 2018-03-30 | 2020-11-06 | 东丽株式会社 | Benzoxazine resin composition, prepreg and fiber-reinforced composite material |
| CN108504290A (en) * | 2018-05-10 | 2018-09-07 | 江苏地基工程有限公司 | A kind of water resistant resin anchor fixing agent and preparation method thereof |
| CN112210106A (en) * | 2019-07-12 | 2021-01-12 | 航天材料及工艺研究所 | Preparation method of hot-melt benzoxazine composition capable of being cured at medium temperature |
| CN112210106B (en) * | 2019-07-12 | 2023-04-14 | 航天材料及工艺研究所 | Preparation method of hot-melt benzoxazine composition capable of being cured at medium temperature |
| CN111086281A (en) * | 2019-12-31 | 2020-05-01 | 浙江林境新材料科技有限公司 | Anti-static halogen-free flame-retardant circulating packaging box and preparation method thereof |
| WO2022168815A1 (en) * | 2021-02-02 | 2022-08-11 | Ｅｎｅｏｓ株式会社 | Composition for curable resins, cured product of said composition, method for producing said composition, method for producing said cured product, and semiconductor device |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106995582A (en) | A kind of curable resin composition and its application containing benzoxazine and epoxy resin blend | |
| CA2511571C (en) | Manufacture of void-free laminates and use thereof | |
| US10836118B2 (en) | Modified resin systems for liquid resin infusion applications and process methods related thereto | |
| CN105108929B (en) | Curable composition, method for preparing composite material using the composition and method for preparing composite material with excellent surface smoothness and high fiber consolidation | |
| CN100418720C (en) | Preparation method of liquid state shaping composite material preshaped body | |
| US10792871B2 (en) | Moulding | |
| CN108276578B (en) | High-temperature-resistant high-toughness bismaleimide resin and preparation method and application thereof | |
| CN107353594A (en) | A kind of curable resin blend composition and its application | |
| CN105907040B (en) | Composition epoxy resin that a kind of suitable low temperature uses and preparation method thereof | |
| EP3233960B1 (en) | Epoxy-based resin composition for composite materials | |
| CN108384188A (en) | A kind of prepreg and its application based on engineering plastics non-woven cloth | |
| AU2018300733B2 (en) | Improvements in resin curative systems | |
| KR101848280B1 (en) | Cold hardening epoxy resin using the composition and prepreg, and prepreg to make it into a layer of polymer composite | |
| JPS63218325A (en) | Rim manufacture of thermosetting fiber-reinforced composite body | |
| KR20210025383A (en) | Light-weight prepreg and method for producing the same | |
| KR20200071120A (en) | Resin composition and resin injection process |
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 |
Application publication date: 20170801 |
|
| RJ01 | Rejection of invention patent application after publication |