CN106751501B - A kind of high tenacity, halogen-free flameproof vacuum diversion composition epoxy resin and preparation method thereof - Google Patents
A kind of high tenacity, halogen-free flameproof vacuum diversion composition epoxy resin and preparation method thereof Download PDFInfo
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- CN106751501B CN106751501B CN201611106116.9A CN201611106116A CN106751501B CN 106751501 B CN106751501 B CN 106751501B CN 201611106116 A CN201611106116 A CN 201611106116A CN 106751501 B CN106751501 B CN 106751501B
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- 0 CCc1ccc(C(C)(*)P(Oc2ccccc2)(Oc2ccccc2)=C)cc1 Chemical compound CCc1ccc(C(C)(*)P(Oc2ccccc2)(Oc2ccccc2)=C)cc1 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N COc1ccccc1 Chemical compound COc1ccccc1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 1
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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
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- 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
- C08G59/50—Amines
- C08G59/56—Amines together with other curing agents
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- 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
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
- C08K5/5333—Esters of phosphonic acids
- C08K5/5353—Esters of phosphonic acids containing also nitrogen
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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
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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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
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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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
- C08L2205/02—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
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a kind of high tenacity, halogen-free flameproof vacuum diversion composition epoxy resin and preparation method thereof, which includes component A and B component, and wherein component A is epoxy resin, reactive diluent, benzotriazole phosphonate ester, coupling agent;B component is amine curing agent, capric acid type benzotriazole phosphonate ester, the alpha-hydroxy benzotriazole phosphonate ester of quaternary carbon.Benzotriazole phosphonate ester is new and effective fire retardant, just shows high fire-retardance effect for composition epoxy resin for the first time.The epoxy resin cured product has high impact toughness and elongation at break, it can be used for the manufacture of various large-scale composite material components, meet the vacuum diversion moulding process requirement of fibre reinforced composites, integrate high tenacity, lightweight, fire-retardant, anti-corrosion, can be widely used in rail traffic, electrotechnical, electronic, aerospace, new energy, sports equipment etc. has the field that high flame-retardant property requires to material, is especially suitable for the vacuum diversion molding of railway air conditioner product and wind power generation blade.
Description
Technical field
The present invention relates to composition epoxy resin field more particularly to a kind of high tenacity, halogen-free flameproof vacuum diversion epoxies
Resin combination and preparation method thereof, more particularly to electrotechnical, electronic, aerospace, new energy, rail traffic, sports equipment etc.
There is the halogen-free flame retardant epoxy resin composition and preparation method thereof that high flame-retardant property requires to material.
Background technology
There is epoxide resin material good corrosion resistance, adhesive property, low-shrinkage to have compared with metal material
Have the advantages that light weight, intensity are high.But since the chemical constitution of epoxy resin itself determines its impact flexibility, elongation at break
It is poor with flame retardant property;It should be further noted that the composition epoxy resin gel time of domestic production at present is shorter,
And a large amount of solid metal hydroxide fire retardant of halogen-free fire-retardant epoxy resin generally use, this based flame retardant do not dissolve in resin
System, and the viscosity of resin system can be caused larger, it is only applicable to manual pasting forming process to limit it, is not met by big
The vacuum diversion forming requirements of type composite material, such as:The manufacture of wind turbine blade, railway air conditioner product, so scientific research personnel
By the modification to composition epoxy resin to obtaining better performance product.
To improve the flame retardant property of epoxy resin-base composite material, it usually needs be added in resin system and contain halogen flame retardant
Agent and/or halogen-free flame-retardant.Halogen-containing flame retardant will produce toxic, carcinogen in Pintsch process and burning.And Halogen
Fire retardant not will produce the carcinogens such as polybrominated dibenzo-furan and more bromo dibenzo dioxanes then in burning, be referred to as nothing
Public hazards fire retardant.It can be seen that a novel, strong mechanical performance of research and development, environment amenable halogen-free fire-retardant epoxy resin material
Material has very important realistic meaning.National 13 planning outlines are complied fully with for the research and development of such Halogen resin material
The Major Strategic Demands such as the environmentally protective industry of development of middle proposition, material.
Chinese patent 201010602588.X discloses one kind by epoxy resin, reaction diluent and curing agent (amine and miaow
Azole compounds) composition epoxy-resin systems, the gel time at 23 DEG C is only 10-60min, is not suitable for hand paste and water conservancy diversion
Large component.It is to be noted that the toxicity of the accelerating agent phenolic compound described in the patent of invention is very big, with cell original
Protein chemically reacts in slurry, and then invades nerve center, stimulates spinal cord, eventually results in systemic toxicity profiles.
Chinese patent CN105315620A discloses a kind of epoxy resin enhancing lamination insulated type material.The fire retardant is big
Amount has used inorganic combustion inhibitor, therefore cannot achieve vacuum diversion.And it is using heat pressing process.Heat pressing process equipment at
This costliness, high processing costs, high energy consumption are not suitable for the rapid processing of short product of potential period.
Therefore, for a kind of solid metal hydroxide fire retardant and nontoxic or less toxic of capable of substituting completely of searching (1)
Sex flame retardant is applied to composition epoxy resin, and (2) have high impact toughness and the preferable epoxy of elongation at break, flame retardant property
Resin combination;(3) there is suitable gel time and exothermic peak temperature;(4) it is adapted to vacuum diversion moulding process, there is weight
The realistic meaning wanted.
Invention content
The technical problem to be solved by the present invention is to be directed to (1), the impact flexibility of epoxy resin-cured product and fracture are stretched at present
Long rate is relatively low;(2) gel time of composition epoxy resin is very fast, cannot be satisfied large-scale composite material manufacture and requires, such as large-scale
The manufacture of railway air conditioner product and wind power generation blade;(3) design is a kind of can substitute solid metal hydroxide fire retardant completely
And nontoxic or less toxic sex flame retardant, there is good compatibility with composition epoxy resin and vacuum diversion molding can be used for;
(4) in addition, some add the problems such as being unfavorable for health, raw material not environmentally in the prior art.For this purpose, we provide
A kind of raw material are cheap and easy to get, and product preparation method process is simple, clean manufacturing, and environmental protection is generated without " three wastes ", and final
Cured product has high impact toughness, fracture elongation and the good composition epoxy resin and preparation method thereof of flame retardant property.
In order to solve the above technical problems, the technical solution adopted by the present invention is:
A kind of high tenacity, halogen-free flameproof vacuum diversion composition epoxy resin, the epoxy resin include component A and B component,
By weight, the proportioning of component A and B component is 100:28-100:32, wherein
Component A is:Epoxy resin 61-66 parts by weight, reactive diluent 3-8 parts by weight, benzotriazole phosphonate ester 26-30
Parts by weight, coupling agent 0.1-1 parts by weight;
B component is:Amine curing agent 55-70 parts by weight, capric acid type benzotriazole phosphonate ester 22-30 parts by weight, quaternary carbon
Alpha-hydroxy benzotriazole phosphonate ester 5-20 parts by weight.
As limitation of the invention, epoxy resin of the present invention is bisphenol A type epoxy resin, bisphenol F type epoxy
Resin it is one or two kinds of.
As limitation of the invention, reactive diluent of the present invention be 1,6- hexanediol diglycidyl ethers or 1,
4- butanediol diglycidyl ethers.
As limitation of the invention further, benzotriazole phosphonate ester, capric acid type benzene described in component A of the present invention
And triazole phosphonate ester and the alpha-hydroxy benzotriazole phosphonate ester of quaternary carbon are efficient phosphonate fire retardant, structural formula point
Do not see that structure formula (I), (II), (III) are shown:
Structural formula I benzotriazole phosphonate ester;
II capric acid type benzotriazole phosphonate ester of structural formula;
The alpha-hydroxy benzotriazole phosphonate ester of formula II I quaternary carbons.
Coupling agent of the present invention is the one or two of titanate coupling agent, silane coupling agent.
Amine curing agent in B component of the present invention be isophorone diamine, polyetheramine D230, polyetheramine T403 two
Kind is two or more.
It is limited as another step to the present invention, capric acid type benzotriazole phosphonate ester and quaternary carbon α-hydroxyl of the present invention
The benzotriazole phosphonate ester of base is the phosphonate ester of response type, can promote epoxy resin cure.
Moreover, benzotriazole phosphonate ester dissolves each other with reactive diluent in the component A, epoxy resin can be completely dissolved in
Composition.
The preparation method of the halogen-free flameproof vacuum diversion composition epoxy resin, follows the steps below:
(1) preparation of component A
By epoxy resin 61-66 parts by weight, reactive diluent 3-8 parts by weight, benzotriazole phosphonate ester 26-30 weight
Part, coupling agent 0.1-1 parts by weight are put into reaction kettle, are heated up to 50-80 DEG C, are stirred with the mixing speed of 80-100r/min
0.5-1h stops stirring after vacuumizing 15-30min, continues to vacuumize 5-30min postcoolings, resin is packed into pail pack one;
(2) preparation of B component
By amine curing agent 55-70 parts by weight, capric acid type benzotriazole phosphonate ester 22-30 parts by weight, quaternary carbon Alpha-hydroxy
Benzotriazole phosphonate ester 5-20 parts by weight input reaction kettle in, at room temperature with the mixing speed of 50-80r/min stir 1-
2h stops stirring after vacuumizing 5-10min, opens nitrogen valve, lead to nitrogen release, curing agent is packed into pail pack two;
(3) by two component of A, B in mass ratio 100:28-100:32 are stirred at room temperature uniformly mixed, injection mold, through room
The lower gel of temperature, after heat release for a period of time, the molding of room temperature precuring for 24 hours, finally in the environment of 50-80 DEG C, constant temperature 4-8h
Obtain rear cured finished product.
As the restriction to above-mentioned preparation method, the gel time is 270-320min, exothermic peak temperature 65-80
℃。
High tenacity of the present invention, halogen-free flame retardant epoxy resin composition can be used for various large-scale composite material components
Manufacture requires, and can be widely used in rail traffic, new energy, electrotechnical, electronic, aerospace, sports equipment etc. has high resistant to material
The field for firing characteristic requirements is particularly suitable for the vacuum diversion molding of large-scale railway air conditioner product and wind power generation blade.
The present invention introduces novel phosphonate ester containing benzotriazole in epoxy-resin systems component A and component B, is added this kind of
The phosphonate ester of the group containing benzotriazole can substitute solid metal hydroxide fire retardant completely (such as:Aluminium hydroxide and hydrogen-oxygen
Change magnesium etc.), this is because the phosphonate compound of (1) this kind of group containing benzotriazole itself is a kind of nitrogenous and phosphorous height
Effect, the fire retardant stablized;(2) the N-P cooperative flame retardants effect generated in system can further enhance the flame retardant property of resin, therefore
Final cured halogen-free flame retardant epoxy resin composition has outstanding flame retardant effect.It should be pointed out that due to this kind of novel
Fire retardant can be completely dissolved in composition epoxy resin, and novel capric acid type benzotriazole phosphonate ester of the present invention and season
The alpha-hydroxy benzotriazole phosphonate ester of carbon can also further participate in reaction, and the reactive hydrogen atom obtained can be to some extent
It collectively promotes epoxy resin to react with amine curing agent, when ensure that the epoxy resin has suitable for gel time and solidification
Between.In addition, after composition epoxy resin is added in novel capric acid type benzotriazole phosphonate ester, cured resin has higher
Impact flexibility and elongation at break.Moreover, since such phosphonate compound with functionalization group is organic phosphatization
Object is closed, and has good compatibility with composition epoxy resin, therefore the effect of highly effective flame-retardant can also be played in system.
To sum up, electrotechnical, electronic, aviation boat can be widely used for after the epoxy resin composition that patent of the present invention proposes
It, new energy, rail traffic, sports equipment etc. have the field that high flame-retardant property requires to material.It is particularly suitable for railway air conditioner
The vacuum diversion of product and wind power generation blade is molded.
After above-mentioned technical solution, the advantageous effect that the present invention obtains is:
(1) phosphonate ester of the capric acid group described in patent of the present invention is not only a kind of new flame retardant, but also is one
Kind can effectively improve the compound of resin toughness.It epoxy resin toughened composition, obtained epoxy resin cure can be produced well
Object has stable quality and product excellent storage stability, is tested through related experiment, and gained epoxy resin product has good comprehensive
Mechanical property, especially preferable impact flexibility and elongation at break are closed, suitable for having higher want to curing degree and impact property
The railway air conditioner product and wind power generating blade sheet articles asked.
(2) patent of the present invention devises the novel halogen-free flame retardants of several moneys first, including novel benzotriazole phosphonate ester,
The novel capric acid type benzotriazole phosphonate ester of response type and the alpha-hydroxy benzotriazole phosphonate ester of novel quaternary carbon are used for epoxy
Resin system largely improves research shows that the flame retardant property of epoxy resin has.
(3) patent of the present invention by be added the group containing functionalization fire retardant, as hydroxyl, capric acid can adjust resin jointly
Gel time and hardening time so that epoxy-resin systems obtain suitable gel and hardening time.
(4) patent of the present invention provides a kind of composition epoxy resin that can meet vacuum diversion moulding process and its preparation
Method.The mechanical properties such as the tensile strength and bending strength of resin-base glass fibre (unidirectional cloth) composite material are higher, draw
It stretches intensity and bending strength and is up to 890MPa and 997MPa respectively.
Specific implementation mode
The present invention will be described further with regard to following embodiment, however, it should be noted that these embodiments are only to illustrate
It is used, and is not necessarily to be construed as the limitation that the present invention is implemented.
Embodiment 1
A kind of high tenacity, halogen-free flameproof vacuum diversion composition epoxy resin have following operating procedure:
(1) preparation of component A
By 40 parts by weight of bisphenol A type epoxy resin, 21 parts by weight of bisphenol f type epoxy resin, 1,6- hexylene glycol two shrinks sweet
8 parts by weight of oily ether, novel 30 parts by weight of benzotriazole phosphonate ester, 0.5 parts by weight of titanate coupling agent, silane coupling agent 0.5
Parts by weight are put into reaction kettle, are heated up to 50 DEG C, are stirred 0.5h with the mixing speed of 100r/min, are stopped after vacuumizing 30min
Stirring, continues to vacuumize 5min postcoolings, and resin is packed into pail pack one;
(2) preparation of B component
By 20 parts by weight of isophorone diamine, 35 parts by weight of polyetheramine D230,30 weight of capric acid type benzotriazole phosphonate ester
Part is measured, alpha-hydroxy 15 parts by weight of benzotriazole phosphonate ester of quaternary carbon are put into reaction kettle, at room temperature with the stirring of 50r/min speed
Degree stirring 2h, stops stirring after vacuumizing 5min, opens nitrogen valve, lead to nitrogen release, curing agent is packed into pail pack two;
(3) by two component of A, B in mass ratio 100:28 at room temperature manually or mechanical agitation be uniformly mixed, inject mould
Tool.Through gel at room temperature, room temperature precuring for 24 hours be molded, then in the environment of 80 DEG C, constant temperature 4h can be obtained it is rear it is cured at
Product.
Embodiment 2
A kind of high tenacity, halogen-free flameproof vacuum diversion composition epoxy resin have following operating procedure:
(the preparation of (1) component A
By 66 parts by weight of bisphenol A type epoxy resin, 3.5 parts by weight of 1,4-butanediol diglycidyl ether, novel benzo three
30 parts by weight of nitrogen azoles phosphonate ester, 0.5 parts by weight of silane coupling agent are put into reaction kettle, 80 DEG C are heated up to, with the stirring of 80r/min
Speed stirs 1h, stops stirring after vacuumizing 15min, continues to vacuumize 20min postcoolings, resin is packed into pail pack one;
(2) preparation of B component
By 24 parts by weight of isophorone diamine, 20 parts by weight of polyetheramine T403,26 parts by weight of polyetheramine D230, capric acid type
25 parts by weight of benzotriazole phosphonate ester, alpha-hydroxy 5 parts by weight of benzotriazole phosphonate ester of quaternary carbon are put into reaction kettle, room temperature
Under 1h stirred with the mixing speed of 80r/min, stop stirring after vacuumizing 10min, open nitrogen valve, lead to nitrogen release, will consolidate
Agent is packed into pail pack two;
(3) by two component of A, B in mass ratio 100:28 at room temperature manually or mechanical agitation be uniformly mixed, inject mould
Tool.Through gel at room temperature, the molding of room temperature precuring for 24 hours, then in the environment of 80 DEG C, constant temperature 4h can be obtained it is rear it is cured at
Product.
Embodiment 3
A kind of high tenacity, halogen-free flameproof vacuum diversion composition epoxy resin have following operating procedure:
(1) preparation of component A
By 64 parts by weight of bisphenol A type epoxy resin, 1,6- hexanediol diglycidyl ether, 6.9 parts by weight, quaternary carbon Alpha-hydroxy
29 parts by weight of benzotriazole phosphonate ester, 0.1 parts by weight of silane coupling agent put into reaction kettle in, 60 DEG C are heated up to, with 90r/
The mixing speed of min stirs 0.7h, stops stirring after vacuumizing 20min, continues to vacuumize 30min postcoolings, resin is packed into
In pail pack one;
(2) preparation of B component
By 20 parts by weight of isophorone diamine, 40 parts by weight of polyetheramine T403,25 weight of capric acid type benzotriazole phosphonate ester
Part is measured, alpha-hydroxy 15 parts by weight of benzotriazole phosphonate ester of quaternary carbon are put into reaction kettle, at room temperature with the stirring of 60r/min speed
Degree stirring 1.5h, stops stirring after vacuumizing 8min, opens nitrogen valve, lead to nitrogen release, curing agent is packed into pail pack two;
(3) by two component of A, B in mass ratio 100:29 at room temperature manually or mechanical agitation be uniformly mixed, inject mould
Tool.Through gel at room temperature, the molding of room temperature precuring for 24 hours, then in the environment of 50 DEG C, constant temperature 8h can be obtained it is rear it is cured at
Product.
Embodiment 4
A kind of high tenacity, halogen-free flameproof vacuum diversion composition epoxy resin have following operating procedure:
(1) preparation of component A
By 66 parts by weight of bisphenol A type epoxy resin, 1,6- hexanediol diglycidyl ether, 7 parts by weight, three nitrogen of novel benzo
26 parts by weight of azoles phosphonate ester, 1 parts by weight of titanate coupling agent are put into reaction kettle, are heated up to 80 DEG C, with the stirring speed of 80r/min
Degree stirring 0.5h, stops stirring after vacuumizing 15min, continues to vacuumize 15min postcoolings, resin is packed into pail pack one;
(2) preparation of B component
By 22 parts by weight of isophorone diamine, 43 parts by weight of polyetheramine D230,22 weight of capric acid type benzotriazole phosphonate ester
Part is measured, alpha-hydroxy 13 parts by weight of benzotriazole phosphonate ester of quaternary carbon stir 1h with the mixing speed of 70r/min at room temperature, take out
Stop stirring after vacuum 10min, open nitrogen valve, lead to nitrogen release, curing agent is packed into pail pack two;
(3) by two component of A, B in mass ratio 100:32 at room temperature manually or mechanical agitation be uniformly mixed, inject mould
Tool.Through gel at room temperature, the molding of room temperature precuring for 24 hours, then in the environment of 60 DEG C, constant temperature 7h can be obtained it is rear it is cured at
Product.
Embodiment 5
A kind of high tenacity, halogen-free flameproof vacuum diversion composition epoxy resin have following operating procedure:
(1) preparation of component A
By 66 parts by weight of bisphenol A type epoxy resin, 1,6- hexanediol diglycidyl ether, 3 parts by weight, three nitrogen of novel benzo
30 parts by weight of azoles phosphonate ester, 1 parts by weight of titanate coupling agent are put into reaction kettle, 60 DEG C are heated up to, with the stirring of 100r/min
Speed stirs 0.5h, stops stirring after vacuumizing 30min, continues to vacuumize 30min postcoolings, and resin is packed into pail pack one
It is interior;
(2) preparation of B component
By 20 parts by weight of isophorone diamine, 35 parts by weight of polyetheramine D230,25 weight of capric acid type benzotriazole phosphonate ester
Part is measured, alpha-hydroxy 20 parts by weight of benzotriazole phosphonate ester of quaternary carbon stir 2h with the mixing speed of 80r/min at room temperature, take out
Stop stirring after vacuum 5min, open nitrogen valve, lead to nitrogen release, curing agent is packed into pail pack two;
(3) by two component of A, B in mass ratio 100:31 at room temperature manually or mechanical agitation be uniformly mixed, inject mould
Tool.Through gel at room temperature, the molding of room temperature precuring for 24 hours, then in the environment of 70 DEG C, constant temperature 8h can be obtained it is rear it is cured at
Product.
Embodiment 6
A kind of high tenacity, halogen-free flameproof vacuum diversion composition epoxy resin have following operating procedure:
(1) preparation of component A
By 62 parts by weight of bisphenol A type epoxy resin, 1,6- hexanediol diglycidyl ether, 7 parts by weight, three nitrogen of novel benzo
30 parts by weight of azoles phosphonate ester, 1 parts by weight of silane coupling agent are put into reaction kettle, 60 DEG C are heated up to, with the mixing speed of 80r/min
1h is stirred, stops stirring after vacuumizing 30min, continues to vacuumize 30min postcoolings, resin is packed into pail pack one;
(2) preparation of B component
By 23 parts by weight of isophorone diamine, 37 parts by weight of polyetheramine D230,28 weight of capric acid type benzotriazole phosphonate ester
Part is measured, alpha-hydroxy 12 parts by weight of benzotriazole phosphonate ester of quaternary carbon are put into reaction kettle, at room temperature with the stirring of 80r/min speed
Degree stirring 2h, stops stirring after vacuumizing 10min, opens nitrogen valve, lead to nitrogen release, curing agent is packed into pail pack two;
(3) by two component of A, B in mass ratio 100:32 at room temperature manually or mechanical agitation be uniformly mixed, inject mould
Tool.Through gel at room temperature, the molding of room temperature precuring for 24 hours, then in the environment of 80 DEG C, constant temperature 4h can be obtained it is rear it is cured at
Product.
Comparative example 1
A kind of halogen-free flameproof vacuum diversion composition epoxy resin has following operating procedure:
(1) preparation of component A
By 40 parts by weight of bisphenol A type epoxy resin, 21 parts by weight of bisphenol f type epoxy resin, 1,6- hexylene glycol two shrinks sweet
8 parts by weight of oily ether, novel 30 parts by weight of benzotriazole phosphonate ester, 0.5 parts by weight of titanate coupling agent, silane coupling agent 0.5
Parts by weight are put into reaction kettle, are heated up to 50 DEG C, are stirred 0.5h with the mixing speed of 100r/min, are stopped after vacuumizing 30min
Stirring, continues to vacuumize 5min postcoolings, and resin is packed into pail pack one;
(2) preparation of B component
By 50 parts by weight of isophorone diamine, 35 parts by weight of polyetheramine D230, the alpha-hydroxy benzotriazole phosphonic acids of quaternary carbon
15 parts by weight of ester are put into reaction kettle, stir 2h at room temperature with the mixing speed of 50r/min, stop stirring after vacuumizing 5min,
Nitrogen valve is opened, nitrogen release is led to, curing agent is packed into pail pack two;
(3) by two component of A, B in mass ratio 100:28 at room temperature manually or mechanical agitation be uniformly mixed, inject mould
Tool.Through gel at room temperature, the molding of room temperature precuring for 24 hours, then in the environment of 80 DEG C, constant temperature 4h can be obtained it is rear it is cured at
Product.
The product that embodiment obtains is tested for the property, concrete outcome is shown in Tables 1 and 2.
Pour mass performance data after 1 resin physicochemical property of table, gel time and solidification
It can be obtained by 1 data of table to draw a conclusion:
Under (1) 25 ± 2 DEG C of environment, it is only 180-260mPas that two component of A, B, which mixes viscosity, is suitble to vacuum diversion technique.
(2) embodiment 1-6 has been separately added into the phosphonate compound of the group containing capric acid of different weight part, which can be with
Have a good compatibility with the composition epoxy resin, and the compound of the group containing capric acid can with epoxy resin toughened system,
It can be proved from the data of table 1.Wherein, the impact flexibility of embodiment 1 and elongation at break highest, and be not added containing the last of the ten Heavenly stems
The impact flexibility and elongation at break of the comparative example 1 of the phosphonate ester of acid groups are respectively down to 51kJ/m2With 4.4%.
2 epoxy laminate of table (unidirectional cloth) performance data
It can be obtained by 2 data of table to draw a conclusion:
(1) flame retardant rating that the embodiment 1-6 of a certain amount of phosphonate fire retardant is added reaches UL94V-0.Due to comparative example 1
In suitable phosphonate ester is not added, so affecting its flame retardant property, flame retardant rating can only achieve UL94V-1.
(2) high tenacity of patent proposition of the present invention, halogen-free flame retardant epoxy resin composition embodiment 1-6 are due to adding foot
The novel phosphonate fire retardant enough measured, therefore DIN5510-2 can be met:S4 in 2009 standards, SR2, the fire protection requirement of ST2.
(3) high tenacity of patent proposition of the present invention, halogen-free flame retardant epoxy resin composition can be used for vacuum diversion technique.Its
The density of manufactured resin-base glass fibre (unidirectional cloth) composite material is usually less than the epoxy resin lamination insulation that filler is added
Proximate matter, also well below the density of steel.It can be seen that there is light weight according to laminate made of patent of the present invention, use
The advantages that more convenient.
(4) epoxy resin (unidirectional cloth) composite materials property made of patent of the present invention is higher, tensile strength and curved
Qu Qiangdu is up to 890MPa and 997MPa respectively.It can be seen that much according to laminate mechanical property made of patent of the present invention
Higher than steel.
It is enlightenment with above-mentioned desirable embodiment according to the present invention, through the above description, relevant staff is complete
Various changes and amendments can be carried out without departing from the scope of the technological thought of the present invention' entirely.The technology of this invention
Property range is not limited to the contents of the specification, it is necessary to determine its technical scope according to right.
Claims (10)
1. a kind of high tenacity, halogen-free flameproof vacuum diversion composition epoxy resin, it is characterised in that:The epoxy resin includes A groups
Point and B component, by weight, the proportioning of component A and B component is 100:28-100:32, wherein
Component A is:Epoxy resin 61-66 parts by weight, reactive diluent 3-8 parts by weight, benzotriazole phosphonate ester 26-30 weight
Part, coupling agent 0.1-1 parts by weight;
B component is:Amine curing agent 55-70 parts by weight, response type capric acid type benzotriazole phosphonate ester 22-30 parts by weight, instead
Answer the alpha-hydroxy benzotriazole phosphonate ester 5-20 parts by weight of type quaternary carbon.
2. a kind of high tenacity according to claim 1, halogen-free flameproof vacuum diversion composition epoxy resin, it is characterised in that
The epoxy resin be bisphenol A type epoxy resin, bisphenol f type epoxy resin it is one or two kinds of.
3. a kind of high tenacity according to claim 1, halogen-free flameproof vacuum diversion composition epoxy resin, feature exist
In the reactive diluent be 1,6 hexanediol diglycidylether or 1,4-butanediol diglycidyl ethers.
4. a kind of high tenacity according to claim 1, halogen-free flameproof vacuum diversion composition epoxy resin, it is characterised in that
Benzotriazole phosphonate ester, capric acid type benzotriazole phosphonate ester described in B component and the alpha-hydroxy benzotriazole of quaternary carbon
Phosphonate ester is efficient phosphonate fire retardant, and structural formula is shown in structural formula respectively(I)Benzotriazole phosphonate ester,(II)Capric acid
Type benzotriazole phosphonate ester,(III)Shown in the alpha-hydroxy benzotriazole phosphonate ester of quaternary carbon:
Structural formula I;
Structural formula II;
Structural formula III.
5. a kind of high tenacity according to claim 1, halogen-free flameproof vacuum diversion composition epoxy resin, feature exist
In:Benzotriazole phosphonate ester dissolves each other with reactive diluent in the component A, can be completely dissolved in composition epoxy resin.
6. a kind of high tenacity according to claim 1, halogen-free flameproof vacuum diversion composition epoxy resin, it is characterised in that
The coupling agent is the one or two of titanate coupling agent, silane coupling agent.
7. a kind of high tenacity according to claim 1, halogen-free flameproof vacuum diversion composition epoxy resin, feature exist
In:The amine curing agent be isophorone diamine, polyetheramine D230, polyetheramine T403 two or more.
8. according to claim 1-7 any one of them high tenacity, halogen-free flame retardant epoxy resin composition, it is characterised in that be made
Finished product can be widely used for material have high flame-retardant property require rail traffic, new energy, electrotechnical, electronic, aerospace or fortune
Dynamic clothing arts.
9. according to a kind of claim 1-7 any one of them high tenacity, halogen-free flameproof vacuum diversion composition epoxy resin
Preparation method, it is characterised in that this method has following steps:
(1)The preparation of component A
By epoxy resin 61-66 parts by weight, reactive diluent 3-8 parts by weight, benzotriazole phosphonate ester 26-30 parts by weight are even
Join in agent 0.1-1 parts by weight input reaction kettle, be heated up to 50-80 DEG C, 0.5-1h is stirred with the mixing speed of 80-100r/min,
Stop stirring after vacuumizing 15-30min, continue to vacuumize 5-30min postcoolings, resin is packed into pail pack one;
(2)The preparation of B component
By amine curing agent 55-70 parts by weight, capric acid type benzotriazole phosphonate ester 22-30 parts by weight, the alpha-hydroxy benzene of quaternary carbon
And in triazole phosphonate ester 5-20 parts by weight input reaction kettle, 1-2 h is stirred with the mixing speed of 50-80r/min at room temperature, are taken out
Stop stirring after vacuum 5-10 min, open nitrogen valve, lead to nitrogen release, curing agent is packed into pail pack two;
(3)By two component of A, B in mass ratio 100: 28-100:32 are stirred at room temperature uniformly mixed, injection mold, through room temperature
Lower gel, after heat release for a period of time, the molding of room temperature precuring for 24 hours, finally in the environment of 50-80 DEG C, constant temperature 4-8h can be obtained
To rear cured finished product.
10. the preparation side of a kind of high tenacity according to claim 9, halogen-free flameproof vacuum diversion composition epoxy resin
Method, it is characterised in that the gel time is 270-320min, and exothermic peak temperature is 65-80 DEG C.
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