CN107033547A - Environmental protection flame retardant composition epoxy resin and its preparation method and application - Google Patents
Environmental protection flame retardant composition epoxy resin and its preparation method and application Download PDFInfo
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- CN107033547A CN107033547A CN201710335776.2A CN201710335776A CN107033547A CN 107033547 A CN107033547 A CN 107033547A CN 201710335776 A CN201710335776 A CN 201710335776A CN 107033547 A CN107033547 A CN 107033547A
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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
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4215—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof cycloaliphatic
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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
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The present invention relates to epoxide resin material technical field, more particularly to a kind of environmental protection flame retardant composition epoxy resin and its preparation method and application.The environmental protection flame retardant composition epoxy resin is made up of component A and component B, component A is bisphenol A type epoxy resin, glycolylurea epoxide resin, phosphonium flame retardant, core-shell tougheners, nitrile rubber toughener, the first dispersant, the first anti-settling agent and the first solid flame retardant, and B component is anhydride curing agent, chain extension modified anhydride, accelerator, the second dispersant, the second anti-settling agent and the second solid flame retardant.The environmental protection flame retardant composition epoxy resin of the present invention not only has environmentally friendly, fire-retardant performance, while also having excellent mechanical performance, heat resistance and sea water resistance energy.
Description
Technical field
The present invention relates to epoxide resin material technical field, more particularly to a kind of environmental protection flame retardant composition epoxy resin and its
Preparation method and application.
Background technology
Composition epoxy resin is the extremely wide material of purposes, except can be used as coating, adhesive etc., can also at sea be handed over
Applied in the maritime environments such as the containment vessel of logical field of tool and marine ships motor material.At present, at sea field of vehicles
In, although navigation demand and fire safety requirement are all being improved constantly, but (composite is used for for forming composite
Make maritime vehicles) though composition epoxy resin can meet mechanical requirement, typically do not have anti-flammability, especially
Perfusion, the epoxy resin of pouring technology are applied to hardly consistent with flame-retardancy requirements.If further requirement composition epoxy resin
There is seawater corrosion resistance and resistant to heat aging performance simultaneously, then such composition epoxy resin there's almost no.
In existing composition epoxy resin, in order to meet cast, instillation process condition, make composition epoxy resin with
The composite that reinforcing material is made has excellent mechanical performance, it is desirable to which epoxy resin has relatively low operation viscosity, good
Mechanical performance, and this performance and higher anti-flammability, preferable resistance to corrosion seawater are conflicting.This mainly by
Fire retardant employed in existing composition epoxy resin has certain drawback.For brominated epoxy resin based flame retardant, by
It is larger in the pollution of brominated system, environmental requirement is not met, therefore be gradually eliminated and do not use；For phosphorous epoxy resin
Based flame retardant, will reach that flame retardant rating just must be added to the substantial amounts of based flame retardant and could realize corresponding effect, but phosphorous ring
The viscosity of oxygen tree fat is larger, after being added largely in epoxy-resin systems, can lead to not realize the low viscous of epoxy-resin systems
Degree, and then do not meet cast, instillation process requirement；If using non-reacted phosphonium flame retardant, epoxy-resin systems can be made
Sea water resistance can decline to a great extent；If using solid flame retardant, though it is characterized in good flame-retarding characteristic, with making
The shortcoming that the mechanical performance of composite is substantially deteriorated.Therefore, existing composition epoxy resin is difficult to while taking into account excellent
Mechanical performance, good flame-retardance, good heat-resistant aging and good sea water resistance energy.
The content of the invention
It is existing to solve it is an object of the invention to provide a kind of environmental protection flame retardant composition epoxy resin and preparation method thereof
Composition epoxy resin is difficult to while taking into account very good mechanical properties, good flame-retardance, good heat-resistant aging and good resistance to sea
The problem of aqueous energy.
One side, the present invention provides a kind of environmental protection flame retardant composition epoxy resin, is made up of component A and component B, with
Being grouped in parts by weight meter, the component A is divided into：
In terms of parts by weight, being grouped in the component B is divided into：
The component A and component B ratio of weight and number is 100：80-120.
Alternatively, the phosphonium flame retardant is phosphorous epoxy resin or methyl-phosphoric acid dimethyl ester.
Alternatively, first solid flame retardant and second solid flame retardant using aluminium hydroxide, magnesium hydroxide or
One or more in aluminum carbonate basic.
Alternatively, the anhydride curing agent in the component B be selected from methyl tetrahydro phthalic anhydride, HHPA, methyl hexahydrophthalic anhydride,
One or more in maleic anhydride or methylnadic anhydride.
Alternatively, the chain extension modified anhydride is neopentyl glycol modified methyl THPA.
Further, the preparation method of the neopentyl glycol modified methyl THPA comprises the following steps：
Amount ratio according to material is 2:1 weighs after THPA and neopentyl glycol, heating response, by reacted reactant
It is dissolved in methyl tetrahydro phthalic anhydride, obtains the neopentyl glycol modified methyl THPA.
Further, in the preparation method of the neopentyl glycol modified methyl THPA, heating-up temperature is 140-160
DEG C, the reaction time is 2-4 hours；In dissolving step, the mass ratio of reacted reactant and methyl tetrahydro phthalic anhydride is 1:0.5-
2。
Alternatively, one or more of the accelerator in the component B in benzyl dimethylamine, imidazoles, DMP-30.
Further, first dispersant and second dispersant are phosphoric acid polyester, first anti-settling agent and institute
The second anti-settling agent is stated for bentonite.
Second aspect, a kind of preparation method of above-mentioned environmental protection flame retardant composition epoxy resin of present invention offer, including with
Lower step：
Prepare the component A：Parts by weight according to each component in the component A take the bisphenol A type epoxy resin, institute
Glycolylurea epoxide resin, the phosphonium flame retardant, the core-shell tougheners and the nitrile rubber toughener are stated, at 40-60 DEG C
Stirring 0.8-2 hour to be well mixed；First dispersant and first anti-settling agent are added according still further to parts by weight, is continued
Stirring 0.8-2 hours；First solid flame retardant is added according still further to parts by weight, is deaerated 0.8-2 hours under vacuum,
Obtain the component A；
Prepare the component B：Parts by weight according to each component in the component B take the anhydride curing agent, the expansion
Chain modified acid anhydrides and the accelerator, heat at 40-60 DEG C；Second dispersant is added according still further to parts by weight and described
Second anti-settling agent, continues to stir 0.8-2 hours；The second solid flame retardant is added according still further to parts by weight, is taken off under vacuum
Gas 0.8-2 hours, obtains the component B；
Prepare the fire retarded epoxy resin composition：The obtained component A and the component are taken according to ratio of weight and number
B, is separately heated to 40-60 DEG C；Stirred under 40-60 DEG C of vacuum condition to well mixed, obtain the environmental protection flame retardant asphalt mixtures modified by epoxy resin
Oil/fat composition.
Further, when preparing the component A, first solid flame retardant is added to be slowly added to, described first is treated
After solid flame retardant is all added, then vacuum outgas；When preparing the component B, it is slow to add second solid flame retardant
Add, after second solid flame retardant is all added, then vacuum outgas.
3rd aspect, the present invention provides a kind of application of above-mentioned environmental protection flame retardant composition epoxy resin, the environmental protection resistance
Combustion composition epoxy resin is used to make outside maritime vehicles, clamp plate of ship and exterior trim or interior trim, marine ships motor material
The composite of shell, marine engineering building.
Compared with prior art, the present invention possesses following beneficial effect：
The present invention is added with the first solid flame retardant and glycolylurea epoxide resin in resin Composition A, is hindered by the first solid
The good heat aging property of the flame-retarding characteristic and glycolylurea epoxide resin that fire agent is acted synergistically, and has composition epoxy resin
Good heat aging property can be kept by having while fire resistance, be unlikely to make its heat aging property reduce a lot, in spy
Ageing-resistant degree is poor when determining to work at temperature, along with the second solid flame retardant added in curing agent component B, can fully protect
Demonstrate,prove the anti-flammability of composition epoxy resin.In addition, the primary solids fire retardant employed in the present invention is aluminium hydroxide, hydroxide
The class solid flame retardant of magnesium one, does not both use halogen system fire retardant, also not no containing with phosphorous epoxy resin or non-reactive
Based on phosphorus fire retardant, the pollution problem because being brought using halogen system fire retardant is thus avoided, phosphorous asphalt mixtures modified by epoxy resin is it also avoid
Fire retardant based on fat can cause the problem of composition epoxy resin viscosity is big, and it also avoid non-reactive phosphonium flame retardant can lead
Cause the problem of sea water resistance can decline by a big margin.
But the solid flame retardant based on aluminium hydroxide, magnesium hydroxide easily makes the mechanical performance of composition epoxy resin
It is greatly reduced, to solve this problem, the present invention is added with core-shell tougheners in component A, or even can further add butyronitrile
Rubber toughening agent, the mechanical performance of composition epoxy resin is lifted by above-mentioned toughener, but be unlikely to make flame-retarding characteristic, it is resistance to
Heat aging performance is a greater impact.
The environmental protection flame retardant composition epoxy resin of the present invention passes through from specific resin Composition A's and curing agent component B
Constituent species and its proportioning, by the synergy between each component, can be had concurrently good fire resistance simultaneously (fire-retardant
Property be V-0 grade), heat aging property, excellent mechanical performance, sea water resistance energy composition epoxy resin.
Embodiment
The technical scheme in the embodiment of the present invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of embodiment of the invention, rather than whole embodiments.Based on the embodiment in the present invention, the common skill in this area
The every other embodiment that art personnel are obtained under the premise of creative work is not made, belongs to the model that the present invention is protected
Enclose.
It should be noted that the term " comprising " and " having " of the embodiment of the present invention and their any deformation, it is intended that
Be to cover it is non-exclusive include, for example, containing process, method, system, product or the equipment of series of steps or unit not
Be necessarily limited to those steps or the unit clearly listed, but may include not list clearly or for these processes, side
The intrinsic other steps of method, product or equipment or unit.
In the present invention, bisphenol A type epoxy resin, glycolylurea epoxide resin, phosphonium flame retardant, core-shell tougheners, butyronitrile rubber
The raw material components such as glue toughener, dispersant, anti-settling agent, solid flame retardant, anhydride curing agent, accelerator can be by commercially available
Obtain.
Embodiment one
The present embodiment provides a kind of environmental protection flame retardant composition epoxy resin, is made up of component A and component B, each group in component A
Divide and parts by weight are：
Component and parts by weight are in component B：
It is used in mixed way condition：Component A and component B ratio of weight and number is 100：90.
The preparation method of above-mentioned environmental protection flame retardant composition epoxy resin, comprises the following steps：
Prepare component A：Parts by weight according to each component in component A take bisphenol A type epoxy resin (E51), hydantoin epoxy
Resin and core-shell tougheners, stir 1 hour to well mixed at 40-60 DEG C；According still further to parts by weight add phosphoric acid polyester and
Bentonite, continues to stir 1 hour；Be slowly added to aluminium hydroxide (duration is about 0.5 hour) according still further to parts by weight, after adding
Deaerated 1 hour under vacuum condition, component A is obtained, by component A running into tank sealing preserves；
Prepare component B：Parts by weight according to each component in component B take methylnadic anhydride and benzyl dimethylamine,
Heated at 40-60 DEG C；Phosphoric acid polyester and bentonite are added according still further to parts by weight, continues to stir 1 hour；According still further to parts by weight
Aluminium hydroxide (duration is about 0.5 hour) is slowly added to, is deaerated under vacuum after adding 1 hour, obtains component B, by group
Divide B running into tank sealing preserves；
Prepare environmental protection flame retardant composition epoxy resin：Obtained component A and component B is taken according to ratio of weight and number, is added respectively
It is added to after hot to 40-60 DEG C in reactor；Stirred under 40-60 DEG C of vacuum condition to well mixed, obtain environmental protection flame retardant ring
Epoxy resin composition.The environmental protection flame retardant composition epoxy resin can be poured into a mould, irrigated and used, and condition of cure is：Successively 80
Solidify 6 hours at DEG C, solidify 4 hours, solidification 12 hours at 130 DEG C at 100 DEG C.
The environmental protection flame retardant composition epoxy resin that the present embodiment is obtained has good mechanical performance, heat-resistant aging, resistance to
Seawater performance and anti-flammability, its specific performance parameter are as follows：
Embodiment two
The present embodiment provides a kind of environmental protection flame retardant composition epoxy resin, is made up of component A and component B, each group in component A
Divide and parts by weight are：
Component and parts by weight are in component B：
It is used in mixed way condition：Component A and component B ratio of weight and number is 100：90.
The preparation method of above-mentioned environmental protection flame retardant composition epoxy resin, comprises the following steps：
Prepare component A：Parts by weight according to each component in component A take bisphenol A type epoxy resin (E51), hydantoin epoxy
Resin, core-shell tougheners and nitrile rubber toughener, stir 1 hour to well mixed at 40-60 DEG C；According still further to parts by weight
Phosphoric acid polyester and bentonite are added, continues to stir 1 hour；Being slowly added to aluminium hydroxide according still further to parts by weight, (duration is about 0.5
Hour), deaerated under vacuum after adding 1 hour, obtain component A, by component A running into tank sealing preserves；
Prepare component B：Parts by weight according to each component in component B take methyl tetrahydro phthalic anhydride and benzyl dimethylamine, in 40-
Heated at 60 DEG C；Phosphoric acid polyester and bentonite are added according still further to parts by weight, continues to stir 1 hour；It is slow according still further to parts by weight
It is slow to add aluminium hydroxide (duration is about 0.5 hour), deaerated under vacuum after adding 1 hour, obtain component B, by component B
Running into tank sealing preserve；
Prepare environmental protection flame retardant composition epoxy resin：Obtained component A and component B is taken according to ratio of weight and number, is added respectively
It is added to after hot to 40-60 DEG C in reactor；Stirred under 40-60 DEG C of vacuum condition to well mixed, obtain environmental protection flame retardant ring
Epoxy resin composition.The environmental protection flame retardant composition epoxy resin can be poured into a mould, irrigated and used, and condition of cure is：Successively 80
Solidify 6 hours at DEG C, solidify 4 hours, solidification 12 hours at 130 DEG C at 100 DEG C.
The environmental protection flame retardant composition epoxy resin that the present embodiment is obtained has good mechanical performance, heat-resistant aging, resistance to
Seawater performance and anti-flammability, its specific performance parameter are as follows：
Compared with embodiment one, in the present embodiment on the basis of added with core-shell tougheners, further added with fourth
Nitrile rubber toughener, by the test result of the present embodiment, in guarantee and the same good every mechanicalness of embodiment one
On the basis of energy index, the elongation at break of the present embodiment environmental protection flame retardant composition epoxy resin is higher than embodiment one, that is, has
There is more preferable toughness, be difficult brittle failure.But still ensure that simultaneously the good flame-retardance of composition epoxy resin, heat aging property and
Sea water corrosion resistant.
Embodiment three
The present embodiment provides a kind of environmental protection flame retardant composition epoxy resin, is made up of component A and component B, each group in component A
Divide and parts by weight are：
Component and parts by weight are in component B：
It is used in mixed way condition：Component A and component B ratio of weight and number is 100：100.
The preparation method of above-mentioned environmental protection flame retardant composition epoxy resin, comprises the following steps：
Prepare component A：Parts by weight according to each component in component A take bisphenol A type epoxy resin (E51), hydantoin epoxy
Resin, phosphorous epoxy resin and core-shell tougheners, stir 1 hour to well mixed at 40-60 DEG C；According still further to parts by weight plus
Enter phosphoric acid polyester, continue to stir 1 hour；Aluminium hydroxide (duration is about 0.5 hour) is slowly added to according still further to parts by weight, is added
Deaerate 1 hour under vacuum afterwards, component A is obtained, by component A running into tank sealing preserves；
Prepare component B：Parts by weight according to each component in component B take methylnadic anhydride, neopentyl glycol to be modified first
Base THPA and benzyl dimethylamine, are heated at 40-60 DEG C；Phosphoric acid polyester and bentonite are added according still further to parts by weight, after
Continuous stirring 1 hour；Aluminium hydroxide (duration is about 0.5 hour) is slowly added to according still further to parts by weight, in vacuum condition after adding
Lower degassing 1 hour, obtains component B, by component B running into tank sealing preserves；
Prepare environmental protection flame retardant composition epoxy resin：Obtained component A and component B is taken according to ratio of weight and number, is added respectively
It is added to after hot to 40-60 DEG C in reactor；Stirred under 40-60 DEG C of vacuum condition to well mixed, obtain environmental protection flame retardant ring
Epoxy resin composition.The environmental protection flame retardant composition epoxy resin can be poured into a mould, irrigated and used, and condition of cure is：Successively 80
Solidify 6 hours at DEG C, solidify 4 hours, solidification 12 hours at 130 DEG C at 100 DEG C.
The preparation method of neopentyl glycol modified methyl THPA in the present embodiment comprises the following steps：According to material
Amount is than being 2:1 weighs THPA and neopentyl glycol, heating response 2-4 hours at 140-160 DEG C, by reacted reactant
It is dissolved in methyl tetrahydro phthalic anhydride, and the mass ratio of reacted reactant and methyl tetrahydro phthalic anhydride is 1 during dissolving:0.5-2, is obtained
Neopentyl glycol modified methyl THPA.
The environmental protection flame retardant composition epoxy resin that the present embodiment is obtained has good mechanical performance, heat-resistant aging, resistance to
Seawater performance and anti-flammability, its specific performance parameter are as follows：
Compared with embodiment one, in the present embodiment on the basis of added with core-shell tougheners, solidification is being played
Chain extension modified anhydride is added with component B.By the test result of the present embodiment, in guarantee and the every machinery of embodiment one
On the basis of performance indications remain basically stable, the elongation at break and impact strength of the present embodiment environmental protection flame retardant composition epoxy resin
Embodiment one will be higher than, i.e., with more preferable toughness, be difficult brittle failure.But the good of composition epoxy resin is still ensure that simultaneously
Anti-flammability, heat aging property and sea water corrosion resistant.
Example IV
The present embodiment provides a kind of environmental protection flame retardant composition epoxy resin, is made up of component A and component B, each group in component A
Divide and parts by weight are：
Component and parts by weight are in component B：
It is used in mixed way condition：Component A and component B ratio of weight and number is 100：100.
The preparation method of above-mentioned environmental protection flame retardant composition epoxy resin, comprises the following steps：
Prepare component A：Parts by weight according to each component in component A take bisphenol A type epoxy resin (E51), hydantoin epoxy
Resin, methyl-phosphoric acid dimethyl ester and core-shell tougheners, stir 1 hour to well mixed at 40-60 DEG C；According still further to parts by weight
Phosphoric acid polyester and bentonite are added, continues to stir 1 hour；Being slowly added to aluminium hydroxide according still further to parts by weight, (duration is about 0.5
Hour), deaerated under vacuum after adding 1 hour, obtain component A, by component A running into tank sealing preserves；
Prepare component B：Parts by weight according to each component in component B take methylnadic anhydride and benzyl dimethylamine,
Heated at 40-60 DEG C；Phosphoric acid polyester and bentonite are added according still further to parts by weight, continues to stir 1 hour；According still further to parts by weight
Aluminium hydroxide (duration is about 0.5 hour) is slowly added to, is deaerated under vacuum after adding 1 hour, obtains component B, by group
Divide B running into tank sealing preserves；
Prepare environmental protection flame retardant composition epoxy resin：Obtained component A and component B is taken according to ratio of weight and number, is added respectively
It is added to after hot to 40-60 DEG C in reactor；Stirred under 40-60 DEG C of vacuum condition to well mixed, obtain environmental protection flame retardant ring
Epoxy resin composition.The environmental protection flame retardant composition epoxy resin can be poured into a mould, irrigated and used, and condition of cure is：Successively 80
Solidify 6 hours at DEG C, solidify 4 hours, solidification 12 hours at 130 DEG C at 100 DEG C.
The environmental protection flame retardant composition epoxy resin that the present embodiment is obtained has good mechanical performance, heat-resistant aging, resistance to
Seawater performance and anti-flammability, its specific performance parameter are as follows：
Comparative example one
The present embodiment provides a kind of composition epoxy resin, is made up of component A and component B, each component and weight in component A
Number is：
Component and parts by weight are in component B：
It is used in mixed way condition：Component A and component B ratio of weight and number is 100：90.
The preparation method of above-mentioned composition epoxy resin, comprises the following steps：
Prepare component A：Parts by weight according to each component in component A take bisphenol A type epoxy resin (E51), hydantoin epoxy
Resin, phosphorous epoxy resin and core-shell tougheners, stir 1 hour to well mixed at 40-60 DEG C；Component A is obtained, by component
A running into tank sealing preserves；
Prepare component B：Parts by weight according to each component in component B take methylnadic anhydride and benzyl dimethylamine, obtain
To component B, by component B running into tank sealing preserves；
Prepare composition epoxy resin：Obtained component A and component B is taken according to ratio of weight and number, 40-60 is separately heated to
It is added to after DEG C in reactor；Stirred under 40-60 DEG C of vacuum condition to well mixed, obtain composition epoxy resin.
The specific performance parameter for the composition epoxy resin that this comparative example is obtained is as follows：
The main distinction of this comparative example and embodiment one is in this comparative example using phosphorous epoxy resin as fire retardant, no longer
Use aluminium hydroxide.It can be seen from upper table information, substantial amounts of phosphorous epoxy resin is added in this comparative example of fire resistance to reach,
But this component can only ensure that anti-flammability reaches V-1 grades, and cause the viscosity of composition epoxy resin to increase a lot, be unfavorable for
Subsequently poured into a mould, instillation process is operated, and heat aging property is decreased.
Comparative example two
The present embodiment provides a kind of composition epoxy resin, is made up of component A and component B, each component and weight in component A
Number is：
Component and parts by weight are in component B：
It is used in mixed way condition：Component A and component B ratio of weight and number is 100：90.
The preparation method of above-mentioned composition epoxy resin, comprises the following steps：
Prepare component A：Parts by weight according to each component in component A take bisphenol A type epoxy resin (E51) and nucleocapsid toughness reinforcing
Agent, stirs 1 hour to well mixed at 40-60 DEG C；Phosphoric acid polyester and bentonite are added according still further to parts by weight, continues to stir
1 hour；Aluminium hydroxide (duration is about 0.5 hour) is slowly added to according still further to parts by weight, 1 is deaerated after adding under vacuum
Hour, component A is obtained, by component A running into tank sealing preserves；
Prepare component B：Parts by weight according to each component in component B take methylnadic anhydride and benzyl dimethylamine,
Heated at 40-60 DEG C；Phosphoric acid polyester and bentonite are added according still further to parts by weight, continues to stir 1 hour；According still further to parts by weight
Aluminium hydroxide (duration is about 0.5 hour) is slowly added to, is deaerated under vacuum after adding 1 hour, obtains component B, by group
Divide B running into tank sealing preserves；
Prepare composition epoxy resin：Obtained component A and component B is taken according to ratio of weight and number, 40-60 is separately heated to
It is added to after DEG C in reactor；Stirred under 40-60 DEG C of vacuum condition to well mixed, obtain composition epoxy resin.
The specific performance parameter for the composition epoxy resin that this comparative example is obtained is as follows：
The main distinction of this comparative example and embodiment one is in this comparative example no longer to add glycolylurea epoxide resin.According to upper
Knowable to table information, the synergy without glycolylurea epoxide resin, the heat aging property and fire resistance of composition epoxy resin
All decline more.
Comparative example three
The present embodiment provides a kind of composition epoxy resin, is made up of component A and component B, each component and weight in component A
Number is：
Component and parts by weight are in component B：
It is used in mixed way condition：Component A and component B ratio of weight and number is 100：90.
The preparation method of above-mentioned composition epoxy resin, comprises the following steps：
Prepare component A：Parts by weight according to each component in component A take bisphenol A type epoxy resin (E51), hydantoin epoxy
Resin, stirs 1 hour to well mixed at 40-60 DEG C；Phosphoric acid polyester and bentonite are added according still further to parts by weight, continues to stir
Mix 1 hour；Aluminium hydroxide (duration is about 0.5 hour) is slowly added to according still further to parts by weight, is taken off under vacuum after adding
Gas 1 hour, obtains component A, by component A running into tank sealing preserves；
Prepare component B：Parts by weight according to each component in component B take methylnadic anhydride and benzyl dimethylamine,
Heated at 40-60 DEG C；Phosphoric acid polyester and bentonite are added according still further to parts by weight, continues to stir 1 hour；According still further to parts by weight
Aluminium hydroxide (duration is about 0.5 hour) is slowly added to, is deaerated under vacuum after adding 1 hour, obtains component B, by group
Divide B running into tank sealing preserves；
Prepare composition epoxy resin：Obtained component A and component B is taken according to ratio of weight and number, 40-60 is separately heated to
It is added to after DEG C in reactor；Stirred under 40-60 DEG C of vacuum condition to well mixed, obtain composition epoxy resin.
The specific performance parameter for the composition epoxy resin that this comparative example is obtained is as follows：
The main distinction of this comparative example and embodiment one is in this comparative example no longer to add core-shell tougheners.According to upper table
Information is not it is recognized that while when having core-shell tougheners, and composition epoxy resin can still keep anti-flammability, but its mechanical performance can be by
To considerable influence, especially toughness declines serious, makes to utilize the easy embrittlement of product made from composition epoxy resin, cracking
The problem of.
In summary, environmental protection flame retardant composition epoxy resin of the invention is by selecting specific resin Composition A and solidification
Agent component B constituent species and its proportioning, by the synergy between each component, can be had concurrently good fire-retardant simultaneously
Performance (anti-flammability is V-0 grades), heat aging property, excellent mechanical performance, the composition epoxy resin of sea water resistance energy.
Above to a kind of environmental protection flame retardant composition epoxy resin and its preparation method and application disclosed in the embodiment of the present invention
It is described in detail, specific case used herein is set forth to the principle and embodiment of the present invention, and the above is real
The explanation for applying example is only intended to the method and its core concept for helping to understand the present invention；Simultaneously for the general technology of this area
Personnel, according to the thought of the present invention, will change in specific embodiments and applications, in summary, this theory
Bright book content should not be construed as limiting the invention.
Claims (10)
1. a kind of environmental protection flame retardant composition epoxy resin, it is characterised in that：It is made up of component A and component B, in terms of parts by weight,
Being grouped in the component A is divided into：
In terms of parts by weight, being grouped in the component B is divided into：
The component A and component B ratio of weight and number is 100：80-120.
2. environmental protection flame retardant composition epoxy resin according to claim 1, it is characterised in that：First solid flame retardant
The one or more in aluminium hydroxide, magnesium hydroxide or aluminum carbonate basic are used with second solid flame retardant.
3. environmental protection flame retardant composition epoxy resin according to claim 1, it is characterised in that：Acid anhydrides in the component B
The one kind of curing agent in methyl tetrahydro phthalic anhydride, HHPA, methyl hexahydrophthalic anhydride, maleic anhydride or methylnadic anhydride
Or it is several.
4. environmental protection flame retardant composition epoxy resin according to claim 1, it is characterised in that：The chain extension modified anhydride is
Neopentyl glycol modified methyl THPA.
5. environmental protection flame retardant composition epoxy resin according to claim 4, it is characterised in that the neopentyl glycol is modified first
The preparation method of base THPA comprises the following steps：
Amount ratio according to material is 2:1 is weighed after THPA and neopentyl glycol, heating response, and reacted reactant is dissolved in
In methyl tetrahydro phthalic anhydride, the neopentyl glycol modified methyl THPA is obtained.
6. environmental protection flame retardant composition epoxy resin according to claim 5, it is characterised in that：It is modified in the neopentyl glycol
In the preparation method of methyl tetrahydro phthalic anhydride, heating-up temperature is 140-160 DEG C, and the reaction time is 2-4 hours；In dissolving step, instead
The mass ratio of reactant and methyl tetrahydro phthalic anhydride after answering is 1:0.5-2.
7. environmental protection flame retardant composition epoxy resin according to claim 1, it is characterised in that：Promotion in the component B
One or more of the agent in benzyl dimethylamine, imidazoles, DMP-30.
8. a kind of preparation method of environmental protection flame retardant composition epoxy resin as described in claim any one of 1-7, its feature exists
In comprising the following steps：
Prepare the component A：Parts by weight according to each component in the component A take the bisphenol A type epoxy resin, the sea
Because of epoxy resin, the phosphonium flame retardant, the core-shell tougheners and the nitrile rubber toughener, stirred at 40-60 DEG C
0.8-2 hours to well mixed；First dispersant and first anti-settling agent are added according still further to parts by weight, continues to stir
0.8-2 hours；First solid flame retardant is added according still further to parts by weight, deaerates 0.8-2 hours, obtains under vacuum
The component A；
Prepare the component B：Parts by weight according to each component in the component B take the anhydride curing agent, the chain extension to change
Property the acid anhydrides and accelerator, heated at 40-60 DEG C；Second dispersant and described second are added according still further to parts by weight
Anti-settling agent, continues to stir 0.8-2 hours；The second solid flame retardant is added according still further to parts by weight, is deaerated under vacuum
0.8-2 hours, obtain the component B；
Prepare the fire retarded epoxy resin composition：The obtained component A and component B is taken according to ratio of weight and number, point
40-60 DEG C is not heated to it；Stirred under 40-60 DEG C of vacuum condition to well mixed, obtain the environmental protection flame retardant epoxy resin group
Compound.
9. preparation method according to claim 8, it is characterised in that：When preparing the component A, first solid is added
Fire retardant is is slowly added to, after first solid flame retardant is all added, then vacuum outgas；When preparing the component B, plus
Enter second solid flame retardant to be slowly added to, after second solid flame retardant is all added, then vacuum outgas.
10. a kind of application of environmental protection flame retardant composition epoxy resin as described in claim any one of 1-7, it is characterised in that：
The environmental protection flame retardant composition epoxy resin is used to make maritime vehicles, clamp plate of ship and exterior trim or interior trim, marine ships
The composite of motor material shell, marine engineering building.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108504253A (en) * | 2018-05-08 | 2018-09-07 | 冯蕾萍 | A kind of nanocomposite applied to shipbuilding |
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| CN1554701A (en) * | 2003-12-22 | 2004-12-15 | 中国石化集团巴陵石油化工有限责任公 | Epoxy resin special material of compressed nazural gas cylinder |
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| CN102675826A (en) * | 2012-04-25 | 2012-09-19 | 北京化工大学常州先进材料研究院 | Temperature-resistant high-strength high-toughness composite epoxy resin and manufacturing method thereof |
| CN103146148A (en) * | 2013-03-07 | 2013-06-12 | 明珠电气有限公司 | Halogen-free flame retardant epoxy resin composition and dry type transformer poured by same |
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| CN1554701A (en) * | 2003-12-22 | 2004-12-15 | 中国石化集团巴陵石油化工有限责任公 | Epoxy resin special material of compressed nazural gas cylinder |
| CN102276959A (en) * | 2011-06-22 | 2011-12-14 | 天津市凯华绝缘材料有限公司 | Halogen-free non-phosphorization flame-retardant epoxy resin composition and preparation method thereof |
| CN102675826A (en) * | 2012-04-25 | 2012-09-19 | 北京化工大学常州先进材料研究院 | Temperature-resistant high-strength high-toughness composite epoxy resin and manufacturing method thereof |
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| CN108504253A (en) * | 2018-05-08 | 2018-09-07 | 冯蕾萍 | A kind of nanocomposite applied to shipbuilding |
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