CN110054757A - A kind of synthetic method of improved high-efficiency flame retardant type epoxy vinyl ester resin - Google Patents
A kind of synthetic method of improved high-efficiency flame retardant type epoxy vinyl ester resin Download PDFInfo
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- CN110054757A CN110054757A CN201910345368.4A CN201910345368A CN110054757A CN 110054757 A CN110054757 A CN 110054757A CN 201910345368 A CN201910345368 A CN 201910345368A CN 110054757 A CN110054757 A CN 110054757A
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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
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
- C08G59/1461—Unsaturated monoacids
- C08G59/1466—Acrylic or methacrylic acids
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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
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1488—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing phosphorus
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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
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1494—Polycondensates modified by chemical after-treatment followed by a further chemical treatment thereof
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- Emergency Medicine (AREA)
- Macromonomer-Based Addition Polymer (AREA)
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Abstract
The invention discloses a kind of synthetic methods of improved high-efficiency flame retardant type epoxy vinyl ester resin, synthesis material uses bisphenol A type epoxy resin in method provided by the invention, in addition, further including the ingredients such as chain extender binary acid, unsaturated monoacid, flame retardant, catalyst, polymerization inhibitor, antioxidant and crosslinking agent containing halogen in the synthesis material.Synthetic method provided by the invention is compounded by introducing chain extender and addition solvent type organophosphorus compounds flame retardant of the response type containing ignition-proof element, gives full play to flame retardant synergism between the two, highly effective flame-retardant type epoxy vinyl ester resin is made.
Description
Technical field
The invention belongs to organic high molecular compounds to synthesize field, more particularly to a kind of improved high-efficiency flame retardant type epoxy
The synthetic method of vinyl ester resin.
Background technique
Vinyl ester resin is chemically reacted and is made by open loop addition by epoxy resin and unsaturated monoacid.It is protected
The basic segment of epoxy resin has been stayed, and has had the good process performance of unsaturated polyester resin, has adhered to the excellent of epoxy resin
It is more outstanding in terms of good characteristic, curability and mouldability, styrene and acrylic monomer can be dissolved in.Due to having both epoxy
With unsaturated advantage, application field constantly expands, and it is severe to be mainly used in the requirement conditions such as resistant to chemical etching, acid and alkali-resistance
The chemical field at quarter, such as in new energy wind-power electricity generation, the manufacture of environmental protection industry (epi) desulphurization denitration equipment, paper industry blow-off line
The application of the high-end fields such as preparation and pleasure boat, high-speed rail.With the expansion of vinyl ester resin application field, in some spies
The application in different field is needed with flame retarding function, such as in flue gas desulfurization field.Common flame-retardant vinyl ester resin it is fire-retardant etc.
Grade is not reached requirement or is produced thick smoke and poison gas causes environment and personal injury, and higher cost, Yi Jitian in burning
Add inorganic fire-retarded filler that the performance of product is caused the factors such as to decline.
In the synthesis of flame-retardant vinyl ester resin disclosed above, majority is filled out using by adding inorganic/organic fire-resisting
Expect the mode mixed with resin matrix, antimony oxide, three hydrated aluminum hydroxides, ten bromines two are added such as into resin matrix
The fire-retardant fillers such as vinylbenzene, hexabromocyclododecane, and certain fire-retardant fillers are because having harmfulness by " Convention of Stockholm "
Limitation uses, or adds low viscosity solvent type organophosphorus ester based flame retardant or introduce reaction-type flame-retarding element to molecular skeleton
It is middle to generate permanent flame retardant effect.That reports in patent introduces the more of response type halogen, and often compounds with antimony oxide
It uses, effect is ideal, but the transparency and mechanical property of product are influenced when additive amount is more.Therefore certain special
Application field such as glass reinforced plastic wet process electrostatic precipitator equipment requires have stronger acid-alkali-corrosive-resisting at high temperature, and has
Excellent mechanical property and efficient flame retardant property only fails using only the preparation method of the flame-retarded resin of the above patent report
Reach comprehensive expected ideal effect.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of conjunctions of improved high-efficiency flame retardant type epoxy vinyl ester resin
At method.
In order to achieve the above objectives, the technical scheme is that
A kind of synthetic method of improved high-efficiency flame retardant type epoxy vinyl ester resin, comprising the following steps:
(1) prepare include bisphenol A type epoxy resin, the chain extender binary acid containing halogen, polymerization inhibitor, catalyst,
Antioxidant, unsaturated monoacid, crosslinking agent and flame retardant synthesis material, by weight ratio successively, accurately weigh each synthesis
Raw material, wherein the molar ratio of bisphenol A type epoxy resin and chain extender binary acid is 1:0.5~1:0.8, reviews and validate and sets
Whether standby, electric appliance, instrument, valve and raw material are normal；
(2) by first throw liq material, the rear sequence for throwing solid material successively puts into bisphenol A type epoxy resin into reaction kettle, expands
Chain agent binary acid, polymerization inhibitor, catalyst and antioxidant, reaction temperature are to slowly warm up to 75-85 DEG C, keep the temperature 2h, reaction acid value drop
To 2mgKOH/g or less；
(3) unsaturated monoacid is added dropwise into reaction kettle, rate of addition is controlled in 50ml/h, slowly heating after being added dropwise
To 110-115 DEG C, 4-5h is kept the temperature, is down to 15mgKOH/g or less to acid value；
(4) it is diluted, is sufficiently stirred with crosslinking agent, flame retardant is then added, material temperature is down to 45 DEG C hereinafter, stopping stirring
It mixes, close cooling water, pack.
Further, the chain extender binary acid be include HET acid, tetrachlorophthalic acid and tetrabromophthalate
In one or more of them mixture.
Further, the polymerization inhibitor in step (1) be hydroquinone, methylnaphthohydroquinone, 1,4-benzoquinone 2- tert-butyl hydroquinone,
One or more of them mixture in p-hydroxyanisole, tert-butyl catechol and copper naphthenate.
Further, the catalyst in step (1) is tetraethylammonium bromide, tetrabutylammonium bromide and N, N- dimethyl benzyl
One or more of them mixture in ammonium chloride.
Further, antioxidant is in triphenyl phosphite, 2,5- di-tert-butyl hydroquinone and hypophosphorous acid in step (1)
One or more of them mixture.
Further, unsaturated monoacid is acrylic acid, methacrylic acid, the one of which in butenoic acid in step (1)
Or a variety of mixtures.
Further, crosslinking agent is styrene, methyl styrene, methyl acrylate, methyl methacrylate in step (1)
In one or more of them mixture.
Further, flame retardant is triethyl phosphate, in tricresyl phosphate isopropyl ester, trichloroethyl phosphate in step (1)
One or more of them mixture, adding proportion accounts for the 3-5% that raw material always puts into quality.
After adopting the above technical scheme, a kind of synthesis side of improved high-efficiency flame retardant type epoxy vinyl ester resin of the present invention
Method, have the advantages that the experiment proved that, the present invention by introduce chain extender be the binary acid framework containing ignition-proof element
Into molecular skeleton, achieve the effect that high-efficient and lasting is fire-retardant, halogenated flame retardant mainly plays fire retardation in the gas phase.Because of halogen
Compound decomposes the hydrogen halide generated, is non-flammable gases, there is dilution effect.Its specific gravity is larger, forms one layer of air film, covers
It covers in high molecular material solid phase surface, air and heat can be completely cut off, play blanketing effect.Halogenation Hydrogen Energy inhibits high molecular material burning
Chain reaction plays a part of to remove free radical.And the skeleton of epoxy resin itself also promotes the mechanical property of resin entirety, with
And it introduces chain extension binary acid and can also be improved mechanical strength and heat-and corrosion-resistant performance.By introducing different reaction ratios
Different grades of flame retardant products are prepared, meet the needs of different levels user, and it is fire-retardant to introduce solvent type organophosphorus compounds
Chain extender of the agent with response type containing ignition-proof element compounds, and gives full play to the synergistic effect of the two, reaches optimal flame retardant effect, full
The flame-retardancy requirements of the certain special dimensions of foot.
Specific embodiment
In order to further explain the technical solution of the present invention, being explained in detail below by specific embodiment the present invention
It states.
One, composition of raw materials and synthetic method
Embodiment 1
A kind of synthetic method of improved high-efficiency flame retardant type epoxy vinyl ester resin of the present invention, synthesis material include such as
Lower component: bisphenol A type epoxy resin 370Kg, HET acid 116Kg, unsaturated unitary acid acrylic acid 80Kg, three chloroethene of flame retardant
Base phosphate 42.6Kg, catalyst tetraethylammonium bromide 5Kg, triphenyl phosphite 2.0Kg, hydroquinone of polymerization retarder 500g, resistance
Poly- agent copper naphthenate 600g and crosslinking styrene 450Kg, wherein the molar ratio of bisphenol A type epoxy resin and HET acid is
1:0.3, trichloroethyl phosphate account for 3~5% that raw material always puts into quality, are specially 4% in the present embodiment.
A kind of synthetic method of improved high-efficiency flame retardant type epoxy vinyl ester resin of the present invention, synthetic method include such as
Lower step:
(1) by weight ratio successively, accurately weigh each synthesis material component, review and validate equipment, electric appliance, instrument, valve
Whether door and raw material are normal；
(2) by first throw liq material, the rear sequence for throwing solid material successively puts into double bisphenol A type epoxy resin resins into reaction kettle,
HET acid, polymerization inhibitor (i.e. hydroquinone and copper naphthenate), catalyst (i.e. tetraethylammonium bromide) and antioxidant, reaction temperature liter
Temperature keeps the temperature 2h to 75 DEG C, and reaction acid value is down to 1.5mgKOH/g；
(3) unsaturated monoacid (i.e. acrylic acid) is added dropwise into reaction kettle, rate of addition is controlled in 50ml/h, and pays attention to seeing
Reaction temperature situation of change is examined, should not heat up too fast, lead to gelatin phenomenon；110 DEG C are to slowly warm up to after being added dropwise, heat preservation
4.5h is down to 14.8mgKOH/g to acid value.
(4) it is diluted, is sufficiently stirred with crosslinking agent (i.e. styrene), flame retardant is then added, material temperature is down to 45 DEG C
Hereinafter, stop stirring, close cooling water, packaging.
It should be noted that chain extender binary acid is the binary acid containing ignition-proof element halogen in the present invention, in addition to
Individually using outside above-mentioned HET acid, also can be used in HET acid, tetrachlorophthalic acid and tetrabromophthalate wherein one
Kind or a variety of mixtures.
Flame retardant in addition to individually use trichloroethyl phosphate other than, also can be used triethyl phosphate, tricresyl phosphate isopropyl ester,
One or more of them mixture in trichloroethyl phosphate.
Hydroquinone, aphthenic acids also can be used other than the combination using above-mentioned hydroquinone and copper naphthenate in polymerization inhibitor
Copper, methylnaphthohydroquinone, 1,4-benzoquinone 2- tert-butyl hydroquinone, p-hydroxyanisole and one of which in tert-butyl catechol or
A variety of mixtures.
Tetraethylammonium bromide, tetrabutyl phosphonium bromide also can be used other than individually using above-mentioned tetraethylammonium bromide in catalyst
Ammonium and N, the one or more of them mixture in N- dimethyl benzyl ammonium chloride.
Crosslinking agent in addition to individually use above-mentioned styrene other than, also can be used styrene, methyl styrene, methyl acrylate,
One or more of them mixture in methyl methacrylate.
Other than individually using acrylic acid acrylic acid, methacrylic acid also can be used, in butenoic acid in unsaturated monoacid
One or more of them mixture.
Triphenyl phosphite can be used in antioxidant, one or more of them in 2,5- di-tert-butyl hydroquinone and hypophosphorous acid
Mixture.
Embodiment 2
A kind of synthetic method of improved high-efficiency flame retardant type epoxy vinyl ester resin of the present invention, synthesis material include such as
Lower component: bisphenol A type epoxy resin 370Kg, chain extender binary acid tetrachlorophthalic acid 151Kg, unsaturated unitary acid propylene
Sour 100Kg, flame retardant trichloroethyl phosphate 45Kg, catalyst tetraethylammonium bromide 6.0Kg, triphenyl phosphite 2Kg, resistance
Poly- agent hydroquinone 400g, polymerization inhibitor copper naphthenate 500g, crosslinking styrene 450Kg, wherein bisphenol A type epoxy resin with
The molar ratio of HET acid is 1:0.5, and trichloroethyl phosphate accounts for 4% that raw material always puts into quality.
A kind of synthetic method of improved high-efficiency flame retardant type epoxy vinyl ester resin of the present invention, synthetic method include such as
Lower step:
(1) by weight ratio successively, accurately weigh each synthesis material component, review and validate equipment, electric appliance, instrument, valve
Whether door and raw material are normal；
(2) by first throw liq material, the rear sequence for throwing solid material successively puts into bisphenol A type epoxy resin into reaction kettle, and four
Chloro-o-phthalic acid, polymerization inhibitor, catalyst and antioxidant, reaction temperature are to slowly warm up to 85 DEG C, keep the temperature 2h, and reaction acid value is down to
1.75mgKOH/g；
(3) unsaturated monoacid is added dropwise into reaction kettle, rate of addition is controlled in 50ml/h, and pays attention to observing response temperature
Situation of change should not heat up too fast, lead to gelatin phenomenon；It is to slowly warm up to 110 DEG C after being added dropwise, 4.5h is kept the temperature, to acid value
It is down to 13.9mgKOH/g.
(4) it is diluted, is sufficiently stirred with crosslinking agent, flame retardant is then added, material temperature is down to 45 DEG C hereinafter, stopping stirring
It mixes, close cooling water, pack.
Embodiment 3
A kind of synthetic method of improved high-efficiency flame retardant type epoxy vinyl ester resin of the present invention, synthesis material include such as
Lower component: bisphenol A type epoxy resin 370Kg, HET acid 157Kg, unsaturated unitary acid acrylic acid 75Kg, flame retardant tricresyl phosphate
Ethyl ester 46.5Kg, catalyst tetraethylammonium bromide 5Kg, triphenyl phosphite 2.5Kg, hydroquinone of polymerization retarder 350g, polymerization inhibitor
Copper naphthenate 400g and crosslinking styrene 500Kg, wherein the molar ratio of bisphenol A type epoxy resin and HET acid is 1:
0.55, triethyl phosphate ester accounts for 4% that raw material always puts into quality.
A kind of synthetic method of improved high-efficiency flame retardant type epoxy vinyl ester resin of the present invention, synthetic method include such as
Lower step:
(1) by weight ratio successively, accurately weigh each synthesis material component, review and validate equipment, electric appliance, instrument, valve
Whether door and raw material are normal；
(2) by first throw liq material, the rear sequence for throwing solid material successively puts into double bisphenol A type epoxy resin resins into reaction kettle,
HET acid, polymerization inhibitor (i.e. hydroquinone and copper naphthenate), catalyst (i.e. tetraethylammonium bromide) and antioxidant, reaction temperature liter
Temperature keeps the temperature 2h to 75 DEG C, and reaction acid value is down to 1.8mgKOH/g；
(3) unsaturated monoacid (i.e. acrylic acid) is added dropwise into reaction kettle, rate of addition is controlled in 50ml/h, and pays attention to seeing
Reaction temperature situation of change is examined, should not heat up too fast, lead to gelatin phenomenon；110 DEG C are to slowly warm up to after being added dropwise, heat preservation
4.5h is down to 13.2mgKOH/g to acid value.
(4) it is diluted, is sufficiently stirred with crosslinking agent (i.e. styrene), flame retardant is then added, material temperature is down to 45 DEG C
Hereinafter, stop stirring, close cooling water, packaging.
It should be noted that chain extender binary acid is the binary acid containing ignition-proof element halogen in the present invention, in addition to
Individually using outside above-mentioned HET acid, also can be used in HET acid, tetrachlorophthalic acid and tetrabromophthalate wherein one
Kind or a variety of mixtures.
Flame retardant in addition to individually use trichloroethyl phosphate other than, also can be used triethyl phosphate, tricresyl phosphate isopropyl ester,
One or more of them mixture in trichloroethyl phosphate.
Hydroquinone, aphthenic acids also can be used other than the combination using above-mentioned hydroquinone and copper naphthenate in polymerization inhibitor
Copper, methylnaphthohydroquinone, 1,4-benzoquinone 2- tert-butyl hydroquinone, p-hydroxyanisole and one of which in tert-butyl catechol or
A variety of mixtures.
Tetraethylammonium bromide, tetrabutyl phosphonium bromide also can be used other than individually using above-mentioned tetraethylammonium bromide in catalyst
Ammonium and N, the one or more of them mixture in N- dimethyl benzyl ammonium chloride.
Crosslinking agent in addition to individually use above-mentioned styrene other than, also can be used styrene, methyl styrene, methyl acrylate,
One or more of them mixture in methyl methacrylate.
Other than individually using acrylic acid acrylic acid, methacrylic acid also can be used, in butenoic acid in unsaturated monoacid
One or more of them mixture.
Triphenyl phosphite can be used in antioxidant, one or more of them in 2,5- di-tert-butyl hydroquinone and hypophosphorous acid
Mixture.
Embodiment 4
A kind of synthetic method of improved high-efficiency flame retardant type epoxy vinyl ester resin of the present invention, synthesis material include such as
Lower component: bisphenol A type epoxy resin 370Kg, HET acid 171Kg, unsaturated unitary acid acrylic acid 68Kg, flame retardant tricresyl phosphate
Ethyl ester 47.3Kg, catalyst tetraethylammonium bromide 4.5Kg, triphenyl phosphite 2.5Kg, hydroquinone of polymerization retarder 380g, polymerization inhibitor
Agent copper naphthenate 450g and crosslinking styrene 520Kg, wherein the molar ratio of bisphenol A type epoxy resin and HET acid is 1:
0.60, tricresyl phosphate ethyl ester accounts for 4% that raw material always puts into quality.
A kind of synthetic method of improved high-efficiency flame retardant type epoxy vinyl ester resin of the present invention, synthetic method include such as
Lower step:
(1) by weight ratio successively, accurately weigh each synthesis material component, review and validate equipment, electric appliance, instrument, valve
Whether door and raw material are normal；
(2) by first throw liq material, the rear sequence for throwing solid material successively puts into double bisphenol A type epoxy resin resins into reaction kettle,
HET acid, polymerization inhibitor (i.e. hydroquinone and copper naphthenate), catalyst (i.e. tetraethylammonium bromide) and antioxidant, reaction temperature liter
Temperature keeps the temperature 2h to 75 DEG C, and reaction acid value is down to 1.75mgKOH/g；
(3) unsaturated monoacid (i.e. acrylic acid) is added dropwise into reaction kettle, rate of addition is controlled in 50ml/h, and pays attention to seeing
Reaction temperature situation of change is examined, should not heat up too fast, lead to gelatin phenomenon；110 DEG C are to slowly warm up to after being added dropwise, heat preservation
4.5h is down to 14.3mgKOH/g to acid value.
(4) it is diluted, is sufficiently stirred with crosslinking agent (i.e. styrene), flame retardant is then added, material temperature is down to 45 DEG C
Hereinafter, stop stirring, close cooling water, packaging.
It should be noted that chain extender binary acid is the binary acid containing ignition-proof element halogen in the present invention, in addition to
Individually using outside above-mentioned HET acid, also can be used in HET acid, tetrachlorophthalic acid and tetrabromophthalate wherein one
Kind or a variety of mixtures.
Flame retardant in addition to individually use trichloroethyl phosphate other than, also can be used triethyl phosphate, tricresyl phosphate isopropyl ester,
One or more of them mixture in trichloroethyl phosphate.
Hydroquinone, aphthenic acids also can be used other than the combination using above-mentioned hydroquinone and copper naphthenate in polymerization inhibitor
Copper, methylnaphthohydroquinone, 1,4-benzoquinone 2- tert-butyl hydroquinone, p-hydroxyanisole and one of which in tert-butyl catechol or
A variety of mixtures.
Tetraethylammonium bromide, tetrabutyl phosphonium bromide also can be used other than individually using above-mentioned tetraethylammonium bromide in catalyst
Ammonium and N, the one or more of them mixture in N- dimethyl benzyl ammonium chloride.
Crosslinking agent in addition to individually use above-mentioned styrene other than, also can be used styrene, methyl styrene, methyl acrylate,
One or more of them mixture in methyl methacrylate.
Other than individually using acrylic acid acrylic acid, methacrylic acid also can be used, in butenoic acid in unsaturated monoacid
One or more of them mixture.
Triphenyl phosphite can be used in antioxidant, one or more of them in 2,5- di-tert-butyl hydroquinone and hypophosphorous acid
Mixture.
Embodiment 5
A kind of synthetic method of improved high-efficiency flame retardant type epoxy vinyl ester resin of the present invention, synthesis material include such as
Lower component: bisphenol A type epoxy resin 370Kg, HET acid 210Kg, unsaturated unitary acid acrylic acid 52Kg, flame retardant tricresyl phosphate
Ethyl ester 49.1Kg, catalyst tetraethylammonium bromide 4.5Kg, triphenyl phosphite 3.0Kg, hydroquinone of polymerization retarder 420g, polymerization inhibitor
Agent copper naphthenate 430g and crosslinking styrene 530Kg, wherein the molar ratio of bisphenol A type epoxy resin and HET acid is 1:
0.69, tricresyl phosphate ethyl ester accounts for 4% that raw material always puts into quality.
A kind of synthetic method of improved high-efficiency flame retardant type epoxy vinyl ester resin of the present invention, synthetic method include such as
Lower step:
(1) by weight ratio successively, accurately weigh each synthesis material component, review and validate equipment, electric appliance, instrument, valve
Whether door and raw material are normal；
(2) by first throw liq material, the rear sequence for throwing solid material successively puts into double bisphenol A type epoxy resin resins into reaction kettle,
HET acid, polymerization inhibitor (i.e. hydroquinone and copper naphthenate), catalyst (i.e. tetraethylammonium bromide) and antioxidant, reaction temperature liter
Temperature keeps the temperature 2h to 75 DEG C, and reaction acid value is down to 1.80mgKOH/g；
(3) unsaturated monoacid (i.e. acrylic acid) is added dropwise into reaction kettle, rate of addition is controlled in 50ml/h, and pays attention to seeing
Reaction temperature situation of change is examined, should not heat up too fast, lead to gelatin phenomenon；110 DEG C are to slowly warm up to after being added dropwise, heat preservation
4.5h is down to 14.6mgKOH/g to acid value.
(4) it is diluted, is sufficiently stirred with crosslinking agent (i.e. styrene), flame retardant is then added, material temperature is down to 45 DEG C
Hereinafter, stop stirring, close cooling water, packaging.
It should be noted that chain extender binary acid is the binary acid containing ignition-proof element halogen in the present invention, in addition to
Individually using outside above-mentioned HET acid, also can be used in HET acid, tetrachlorophthalic acid and tetrabromophthalate wherein one
Kind or a variety of mixtures.
Flame retardant in addition to individually use trichloroethyl phosphate other than, also can be used triethyl phosphate, tricresyl phosphate isopropyl ester,
One or more of them mixture in trichloroethyl phosphate.
Hydroquinone, aphthenic acids also can be used other than the combination using above-mentioned hydroquinone and copper naphthenate in polymerization inhibitor
Copper, methylnaphthohydroquinone, 1,4-benzoquinone 2- tert-butyl hydroquinone, p-hydroxyanisole and one of which in tert-butyl catechol or
A variety of mixtures.
Tetraethylammonium bromide, tetrabutyl phosphonium bromide also can be used other than individually using above-mentioned tetraethylammonium bromide in catalyst
Ammonium and N, the one or more of them mixture in N- dimethyl benzyl ammonium chloride.
Crosslinking agent in addition to individually use above-mentioned styrene other than, also can be used styrene, methyl styrene, methyl acrylate,
One or more of them mixture in methyl methacrylate.
Other than individually using acrylic acid acrylic acid, methacrylic acid also can be used, in butenoic acid in unsaturated monoacid
One or more of them mixture.
Triphenyl phosphite can be used in antioxidant, one or more of them in 2,5- di-tert-butyl hydroquinone and hypophosphorous acid
Mixture.
Embodiment 6
A kind of synthetic method of improved high-efficiency flame retardant type epoxy vinyl ester resin of the present invention, synthesis material include such as
Lower component: bisphenol A type epoxy resin 370Kg, HET acid 221Kg, unsaturated unitary acid acrylic acid 48Kg, flame retardant tricresyl phosphate
Ethyl ester 50.1Kg, catalyst tetraethylammonium bromide 4.0Kg, triphenyl phosphite 3.0Kg, hydroquinone of polymerization retarder 420g, polymerization inhibitor
Agent copper naphthenate 430g and crosslinking styrene 535Kg, wherein the molar ratio of bisphenol A type epoxy resin and HET acid is 1:
0.73, tricresyl phosphate ethyl ester accounts for 4% that raw material always puts into quality.
A kind of synthetic method of improved high-efficiency flame retardant type epoxy vinyl ester resin of the present invention, synthetic method include such as
Lower step:
(1) by weight ratio successively, accurately weigh each synthesis material component, review and validate equipment, electric appliance, instrument, valve
Whether door and raw material are normal；
(2) by first throw liq material, the rear sequence for throwing solid material successively puts into double bisphenol A type epoxy resin resins into reaction kettle,
HET acid, polymerization inhibitor (i.e. hydroquinone and copper naphthenate), catalyst (i.e. tetraethylammonium bromide) and antioxidant, reaction temperature liter
Temperature keeps the temperature 2h to 75 DEG C, and reaction acid value is down to 1.80mgKOH/g；
(3) unsaturated monoacid (i.e. acrylic acid) is added dropwise into reaction kettle, rate of addition is controlled in 50ml/h, and pays attention to seeing
Reaction temperature situation of change is examined, should not heat up too fast, lead to gelatin phenomenon；110 DEG C are to slowly warm up to after being added dropwise, heat preservation
4.5h is down to 14.6mgKOH/g to acid value.
(4) it is diluted, is sufficiently stirred with crosslinking agent (i.e. styrene), flame retardant is then added, material temperature is down to 45 DEG C
Hereinafter, stop stirring, close cooling water, packaging.
It should be noted that chain extender binary acid is the binary acid containing ignition-proof element halogen in the present invention, in addition to
Individually using outside above-mentioned HET acid, also can be used in HET acid, tetrachlorophthalic acid and tetrabromophthalate wherein one
Kind or a variety of mixtures.
Flame retardant in addition to individually use trichloroethyl phosphate other than, also can be used triethyl phosphate, tricresyl phosphate isopropyl ester,
One or more of them mixture in trichloroethyl phosphate.
Hydroquinone, aphthenic acids also can be used other than the combination using above-mentioned hydroquinone and copper naphthenate in polymerization inhibitor
Copper, methylnaphthohydroquinone, 1,4-benzoquinone 2- tert-butyl hydroquinone, p-hydroxyanisole and one of which in tert-butyl catechol or
A variety of mixtures.
Tetraethylammonium bromide, tetrabutyl phosphonium bromide also can be used other than individually using above-mentioned tetraethylammonium bromide in catalyst
Ammonium and N, the one or more of them mixture in N- dimethyl benzyl ammonium chloride.
Crosslinking agent in addition to individually use above-mentioned styrene other than, also can be used styrene, methyl styrene, methyl acrylate,
One or more of them mixture in methyl methacrylate.
Other than individually using acrylic acid acrylic acid, methacrylic acid also can be used, in butenoic acid in unsaturated monoacid
One or more of them mixture.
Triphenyl phosphite can be used in antioxidant, one or more of them in 2,5- di-tert-butyl hydroquinone and hypophosphorous acid
Mixture.
Embodiment 7
A kind of synthetic method of improved high-efficiency flame retardant type epoxy vinyl ester resin of the present invention, synthesis material include such as
Lower component: bisphenol A type epoxy resin 370Kg, chain extender binary acid tetrabromophthalate 385Kg, unsaturated unitary acid propylene
Sour 60Kg, flame retardant trichloroethyl phosphate 59.6Kg, catalyst tetraethylammonium bromide 5.0Kg, 2,5- di-t-butyls are to benzene
Diphenol 300g, polymerization inhibitor methylnaphthohydroquinone 400g, polymerization inhibitor copper naphthenate 700g, crosslinking styrene 600Kg, wherein bisphenol A-type
Epoxy resin and the molar ratio of tetrabromophthalate are 1:0.8, and trichloroethyl phosphate accounts for raw material and always puts into quality
4%.
A kind of synthetic method of improved high-efficiency flame retardant type epoxy vinyl ester resin of the present invention, synthetic method include such as
Lower step:
(1) by weight ratio successively, accurately weigh each synthesis material component, review and validate equipment, electric appliance, instrument, valve
Whether door and raw material are normal；
(2) by first throw liq material, the rear sequence for throwing solid material successively puts into bisphenol A type epoxy resin into reaction kettle, and four
Bromine leads phthalic acid, polymerization inhibitor, catalyst and antioxidant, and reaction temperature is to slowly warm up to 85 DEG C, keeps the temperature 2.5h, reaction acid value drop
To 1.65mgKOH/g or less；
(3) unsaturated monoacid is added dropwise into reaction kettle, rate of addition is controlled in 50ml/h, and pays attention to observing response temperature
Situation of change should not heat up too fast, lead to gelatin phenomenon；It is to slowly warm up to 115 DEG C after being added dropwise, 5.0h is kept the temperature, to acid value
It is down to 15mgKOH/g.
(4) it is diluted, is sufficiently stirred with crosslinking agent, flame retardant is then added, material temperature is down to 45 DEG C hereinafter, stopping stirring
It mixes, close cooling water, pack.
Embodiment 8
A kind of synthetic method of improved high-efficiency flame retardant type epoxy vinyl ester resin of the present invention, synthesis material include such as
Lower component: bisphenol A type epoxy resin 370Kg, chain extender binary acid tetrabromophthalate 430Kg, unsaturated unitary acid propylene
Sour 50Kg, flame retardant trichloroethyl phosphate 64.1Kg, catalyst tetraethylammonium bromide 6.0Kg, triphenyl phosphite
2.0Kg, polymerization inhibitor methylnaphthohydroquinone 600g, polymerization inhibitor copper naphthenate 750g, crosslinking styrene 680Kg, wherein bisphenol type epoxy
Resin and the molar ratio of tetrabromophthalate are 1:0.9, and trichloroethyl phosphate accounts for 4% that raw material always puts into quality.
A kind of synthetic method of improved high-efficiency flame retardant type epoxy vinyl ester resin of the present invention, synthetic method include such as
Lower step:
(1) by weight ratio successively, accurately weigh each synthesis material component, review and validate equipment, electric appliance, instrument, valve
Whether door and raw material are normal；
(2) by first throw liq material, the rear sequence for throwing solid material successively puts into bisphenol A type epoxy resin into reaction kettle, and four
Bromine leads phthalic acid, polymerization inhibitor, catalyst and antioxidant, and reaction temperature is to slowly warm up to 85 DEG C, keeps the temperature 2.5h, reaction acid value drop
To 1.85mgKOH/g or less；Since the molar ratio of bisphenol A type epoxy resin and tetrabromophthalate is excessive, cause to synthesize
Polymer molecular weight it is excessive, macro manifestations are that viscosity is excessive, and the heat dissipation of the system reacted during subsequent dropwise addition is very poor, heat
Amount, which is excessively concentrated, makes it finally gelatin phenomenon occur when the reaction of acrylic acid is added dropwise, and eventually leads to reaction failure.
Embodiment 9
A kind of synthetic method of improved high-efficiency flame retardant type epoxy vinyl ester resin of the present invention, synthesis material include such as
Lower component: bisphenol A type epoxy resin 370Kg, chain extender binary acid tetrachlorophthalic acid 151Kg, unsaturated unitary acid propylene
Sour 100Kg, flame retardant trichloroethyl phosphate 22Kg, catalyst tetraethylammonium bromide 6.0Kg, triphenyl phosphite 2Kg, resistance
Poly- agent hydroquinone 400g, polymerization inhibitor copper naphthenate 500g, crosslinking styrene 450Kg, wherein bisphenol A type epoxy resin with
The molar ratio of HET acid is 1:0.5, and trichloroethyl phosphate accounts for 2% that raw material always puts into quality.
A kind of synthetic method of improved high-efficiency flame retardant type epoxy vinyl ester resin of the present invention, synthetic method include such as
Lower step:
(1) by weight ratio successively, accurately weigh each synthesis material component, review and validate equipment, electric appliance, instrument, valve
Whether door and raw material are normal；
(2) by first throw liq material, the rear sequence for throwing solid material successively puts into bisphenol A type epoxy resin into reaction kettle, and four
Chloro-o-phthalic acid, polymerization inhibitor, catalyst and antioxidant, reaction temperature are to slowly warm up to 85 DEG C, keep the temperature 2h, and reaction acid value is down to
1.90mgKOH/g following；
(3) unsaturated monoacid is added dropwise into reaction kettle, rate of addition is controlled in 50ml/h, and pays attention to observing response temperature
Situation of change should not heat up too fast, lead to gelatin phenomenon；It is to slowly warm up to 110 DEG C after being added dropwise, 4.5h is kept the temperature, to acid value
It is down to 14.6mgKOH/g or less.
(4) it is diluted, is sufficiently stirred with crosslinking agent, flame retardant is then added, material temperature is down to 45 DEG C hereinafter, stopping stirring
It mixes, close cooling water, pack.
Embodiment 10
A kind of synthetic method of improved high-efficiency flame retardant type epoxy vinyl ester resin of the present invention, synthesis material include such as
Lower component: bisphenol A type epoxy resin 370Kg, chain extender binary acid tetrachlorophthalic acid 151Kg, unsaturated unitary acid propylene
Sour 100Kg, flame retardant trichloroethyl phosphate 68.9Kg, catalyst tetraethylammonium bromide 6.0Kg, triphenyl phosphite 2Kg,
Hydroquinone of polymerization retarder 400g, polymerization inhibitor copper naphthenate 500g, crosslinking styrene 450Kg, wherein bisphenol A type epoxy resin
Molar ratio with HET acid is 1:0.5, and trichloroethyl phosphate accounts for 6% that raw material always puts into quality.
A kind of synthetic method of improved high-efficiency flame retardant type epoxy vinyl ester resin of the present invention, synthetic method include such as
Lower step:
(1) by weight ratio successively, accurately weigh each synthesis material component, review and validate equipment, electric appliance, instrument, valve
Whether door and raw material are normal；
(2) by first throw liq material, the rear sequence for throwing solid material successively puts into bisphenol A type epoxy resin into reaction kettle, and four
Chloro-o-phthalic acid, polymerization inhibitor, catalyst and antioxidant, reaction temperature are to slowly warm up to 85 DEG C, keep the temperature 2h, and reaction acid value is down to
1.97mgKOH/g following；
(3) unsaturated monoacid is added dropwise into reaction kettle, rate of addition is controlled in 50ml/h, and pays attention to observing response temperature
Situation of change should not heat up too fast, lead to gelatin phenomenon；It is to slowly warm up to 110 DEG C after being added dropwise, 4.5h is kept the temperature, to acid value
It is down to 14.3mgKOH/g.
(4) it is diluted, is sufficiently stirred with crosslinking agent, flame retardant is then added, material temperature is down to 45 DEG C hereinafter, stopping stirring
It mixes, close cooling water, pack.
Two, performance test
It can be seen that the flame retardant property of (one) embodiment 2- embodiment 7 with bisphenol A-type from the performance test results of upper table
There is fluctuation in the reduction of the molar ratio of epoxy resin and chain extender binary acid, but better than the flame retardant property of embodiment 1.It is special
It is not that the performance characterizations such as mechanical property, the hardness Barcol of casting matrix of embodiment 2,4,5 and 7 show well, flame retardant effect is excellent
Different, therefore, fire-retardant numerical value of the invention is not the simple linear relationship of increase presentation with chain extender content of halogen, fire-retardant
Effect is unpredictable.Wherein the molar ratio of the bisphenol A type epoxy resin in embodiment 1 and chain extender binary acid is 1:0.3, halogen
The content of race's element is lower, and final limit oxygen index is lower than 30%, cannot reach flame-retardancy requirements.Bisphenol-A type ring in embodiment 8
The molar ratio of oxygen resin and chain extender binary acid is 1:0.9, although the ratio of ignition-proof element increases, the molar ratio
Under cause the viscosity of polymer excessive, finally during dropwise reaction reaction occur gelatin phenomenon and cause reaction fail, because
The molar ratio of this bisphenol A type epoxy resin and chain extender binary acid should control between 1:0.5-1:0.8, just be able to satisfy certain
Highly effective flame-retardant requirement under harsh environment, meets industry requirement.(2) by the experimental result of embodiment 9 as it can be seen that flame-retardant additive
When the adding proportion of phosphoric acid ester is 2%, flame retardant effect is unobvious, and analysis reason, which should be that phosphorus content is too low, not to be played with halogen
Synergistic effect well, by the experimental result of embodiment 10 as it can be seen that flame retardant effect is very when the adding proportion of phosphoric acid ester is 6%
It is good, but phosphoric acid ester belongs to outer addition type auxiliary agent, it is larger to the Effect on Mechanical Properties of product, therefore phosphate ester flame retardants
Adding proportion should be controlled to be advisable between 3-5%, and additive amount need to be in conjunction with the synergistic effect of phosphoric acid ester and ignition-proof element halogen
Careful consideration, and test and obtain, it is specific magnitude relation, can not arbitrarily adjusts.
Above-described embodiment and non-limiting method of the invention, any person of an ordinary skill in the technical field do it
Appropriate changes or modifications, all should be regarded as not departing from patent category of the invention.
Claims (8)
1. a kind of synthetic method of improved high-efficiency flame retardant type epoxy vinyl ester resin, which comprises the following steps:
(1) included bisphenol A type epoxy resin, the chain extender binary acid containing halogen, polymerization inhibitor, urged by formula design preparation
Agent, antioxidant, unsaturated monoacid, crosslinking agent and flame retardant synthesis material, according to the ratio successively, accurately weigh each synthesis
Raw material, wherein the molar ratio of bisphenol A type epoxy resin and chain extender binary acid is 1:0.5~1:0.8, reviews and validate and sets
Whether standby, electric appliance, instrument, valve and raw material are normal；
(2) by first throw liq material, the rear sequence for throwing solid material successively puts into bisphenol A type epoxy resin, chain extender into reaction kettle
Binary acid, polymerization inhibitor, catalyst and antioxidant, reaction temperature are to slowly warm up to 75-85 DEG C, keep the temperature 2h, and reaction acid value is down to
2mgKOH/g or less；
(3) unsaturated monoacid is added dropwise into reaction kettle, rate of addition is controlled in 50ml/h, is to slowly warm up to after being added dropwise
110-115 DEG C, 4-5h is kept the temperature, is down to 15mgKOH/g or less to acid value；
(4) be diluted, be sufficiently stirred with crosslinking agent, be then added flame retardant, material temperature be down to 45 DEG C hereinafter, stop stirring,
Close cooling water, packaging.
2. a kind of synthetic method of improved high-efficiency flame retardant type epoxy vinyl ester resin as described in claim 1, feature
Be: the chain extender binary acid be include one of which in HET acid, tetrachlorophthalic acid and tetrabromophthalate
Or a variety of mixtures.
3. a kind of synthetic method of improved high-efficiency flame retardant type epoxy vinyl ester resin as described in claim 1, feature
Be: the polymerization inhibitor in step (1) is hydroquinone, methylnaphthohydroquinone, 1,4-benzoquinone 2- tert-butyl hydroquinone, para hydroxybenzene first
One or more of them mixture in ether, tert-butyl catechol and copper naphthenate.
4. a kind of synthetic method of improved high-efficiency flame retardant type epoxy vinyl ester resin as described in claim 1, feature
Be: catalyst in step (1) is tetraethylammonium bromide, tetrabutylammonium bromide and N, its in N- dimethyl benzyl ammonium chloride
In one or more mixtures.
5. a kind of synthetic method of improved high-efficiency flame retardant type epoxy vinyl ester resin as described in claim 1, feature
Be: antioxidant is one of or more in triphenyl phosphite, 2,5- di-tert-butyl hydroquinone and hypophosphorous acid in step (1)
Kind mixture.
6. a kind of synthetic method of improved high-efficiency flame retardant type epoxy vinyl ester resin as described in claim 1, feature
Be: unsaturated monoacid is acrylic acid, methacrylic acid, the one or more of them mixture in butenoic acid in step (1).
7. a kind of synthetic method of improved high-efficiency flame retardant type epoxy vinyl ester resin as described in claim 1, feature
Be: crosslinking agent is styrene, methyl styrene, methyl acrylate, the one of which in methyl methacrylate in step (1)
Or a variety of mixtures.
8. a kind of synthetic method of improved high-efficiency flame retardant type epoxy vinyl ester resin as described in claim 1, feature
Be: in step (1) flame retardant be triethyl phosphate, tricresyl phosphate isopropyl ester, the one of which in trichloroethyl phosphate or
A variety of mixtures, adding proportion account for the 3-5% that raw material always puts into quality.
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| CN111995755A (en) * | 2020-08-24 | 2020-11-27 | 浙江晨诺高分子材料有限公司 | Vinyl ester flame-retardant resin containing polyester structure and preparation method thereof |
| CN113024790A (en) * | 2021-02-04 | 2021-06-25 | 东莞市德聚胶接技术有限公司 | Intrinsic flame-retardant acrylate oligomer and acrylate structural adhesive |
| CN113201116A (en) * | 2021-04-30 | 2021-08-03 | 华南农业大学 | Vinyl ester resin and preparation method thereof, vinyl ester resin modified castor oil-based polyurethane resin and preparation method and application thereof |
| CN114249879A (en) * | 2022-01-12 | 2022-03-29 | 广东美亨新材料科技有限公司 | Environment-friendly vinyl ester resin |
| CN115160571A (en) * | 2022-07-27 | 2022-10-11 | 宁夏清研高分子新材料有限公司 | Flame-retardant polysulfone polymer and preparation method thereof |
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