CN108424513A - A kind of N-B synergistics high-fire-resistance curing agent and its synthetic method - Google Patents
A kind of N-B synergistics high-fire-resistance curing agent and its synthetic method Download PDFInfo
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/698—Polyesters containing atoms other than carbon, hydrogen and oxygen containing boron
- C08G63/6984—Polyesters containing atoms other than carbon, hydrogen and oxygen containing boron derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6986—Dicarboxylic acids and dihydroxy compounds
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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
- C08G59/4246—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof polymers with carboxylic terminal groups
- C08G59/4269—Macromolecular compounds obtained by reactions other than those involving unsaturated carbon-to-carbon bindings
- C08G59/4276—Polyesters
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- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
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Abstract
The present invention relates to a kind of N B synergistic high-fire-resistance curing agent and its synthetic methods, the present invention, by polyalcohol, response type nitrogenous compound, response type boron-containing compound, polyacid, catalyst and end-capping reagent, is made using segmented synthetic method by adjusting each group distribution ratio, reaction temperature and reaction time.80~180mgKOH/g of acid value of the curing agent, 800~6000mPas/180 DEG C of melt viscosity range, 75~125 DEG C of softening point range, N content 1.9~4.8wt% of range, 0.35~1.05wt% of B content range.There are the curing agent two kinds of ignition-proof elements of nitrogen (N) and boron (B) not migrate and hyper-branched structure, so that curing agent has different anti-flammability and durability of fire-retardant, and easily crystallization, low viscosity, easy to be compatible, for electronic package material, it can be achieved that the halogen-free phosphorus-free inflaming retarding of electronic package material and excellent durability of fire-retardant.
Description
Technical field
The invention belongs to electronic package material field, especially a kind of N-B synergistics high-fire-resistance curing agent and its synthesis side
Method.
Background technology
Epoxy resin refers to being organised with aliphatic, alicyclic or aromatic series etc. containing two or more epoxy groups
Object is closed for skeleton and by the polymer of epoxy reaction formation；Epoxy group can be located at the end of molecule segment, centre or be in
Cyclic structure；It is one of most widely used matrix resin in polymer matrix composite.Due to the special molecule of epoxy resin
Structure determines that epoxy resin has excellent caking property, heat resistance, chemical resistance and excellent electric insulating quality
Can, at the same it is easy to process, shrinking percentage is low, linear expansion coefficient is small and it is of low cost the advantages that.It is widely used in varistor, pottery
The encapsulation of the electronic components such as porcelain condenser, diode, triode.
But epoxy resin belongs to combustible material, and limit oxygen index (LOI) is relatively low, and only 19.5, and epoxy resin quilt
It is widely used and with the frequent generation of safe fire in recent years, therefore is highly desirable to carry out flame retardant treatment to it.It is presently used for
The halogen and antimony oxide class fire proofing of ethoxyline resin antiflaming have been found to generate harm to human body and animal, such fire-retardant
Agent will produce the toxic smokes such as bioxin (Dioxin) and corrosive gas (such as hydrogen bromide) again in burning, seriously affect human health
And environment；The based flame retardant is disabled by European Union simultaneously.For this purpose, exploitation be halogen-free and antimony oxide and have simultaneously excellent
The epoxy resin of flame retardancy become the project sought of encapsulating material field.
In halogen-free flame retardants, organophosphorus compound belongs to a kind of important fire retardant, by extensive concern and
It uses.Its fire retardant mechanism mainly include gas phase it is fire-retardant/free radical is fire-retardant, condensed phase is fire-retardant, blanketing effect.Organic phosphorus flame retardant
It is divided into addition type and response type two major classes：Additive flame retardant is not involved in reaction, is scattered in material in a manner of physical mixed,
It is easy to migrate, flame retarding efficiency is low, fire-retardant stability and persistence are poor；Reactive flame retardant then on the contrary, P element not
Move, flame retarding efficiency, fire-retardant stability and persistence it is secure, and heat resistance is preferable, therefore, in organic phosphorus flame retardant,
The concerned degree of reactive flame retardant and dosage incrementally increase.Therefore, in general, organic phosphorus flame retardant belongs to an analogy
More promising and more environmentally friendly fire retardant, while also can guarantee current material to fire-retardant requirement.But from stricti jurise,
There are still certain environmental issue, phosphorus flame retardants may will produce toxic gas in combustion for organic phosphorus flame retardant
(for example first is seen).In consideration of it, the more environmentally-friendly and clean fire retardant of exploitation is forward-looking and change significance of times as one
Project.For this purpose, one of the bright spot of the present invention is：Used fire retardant belongs to non-halogen non-phosphate material.
Nitrogenated flame retardant is another representational fire retardant in halogen-free flame retardants.Nitrogenous flame ratardant has corrosivity
Small, low, malicious flame retarding efficiency height and thermosets compatibility is good, decomposition temperature is high, becomes and is popular the advantages that being suitble to processing
A based flame retardant.Its fire retardant mechanism is：One, dilution effect is heated and releases CO2、NH3、N2Gas and H2O is reduced in air
The combustable gas concentration that oxygen and epoxy-resin systems generate when being thermally decomposed；Two, endothermic effect, the non-flammable gases of generation, band
A part of heat has been walked, the temperature of polymer surfaces is reduced；Three, free radical is fire-retardant, the N of generation2, free radical can be captured, is pressed down
The chain reaction of high polymer processed, to prevent to burn；Four, synergistic is fire-retardant, when a kind of fire retardant and another fire retardant are deposited simultaneously
When, fire retardation is typically larger than the sum of fire retardation of one-component.Nitrogenated flame retardant is also classified into addition type and response type
Two major classes.Additive flame retardant also has delustring, obviously increases system in addition to having the shortcomings that addition type organic phosphorus flame retardant
The shortcomings that viscosity；The characteristic of response type nitrogenous flame ratardant is then substantially identical as organic phosphorus reactive flame retardant, is not repeated.Mirror
In this, bright spot of the invention second is that：Response type nitrogenous flame ratardant is introduced into macromolecular curing agent, to assign epoxy resin
Higher flame retarding efficiency and more preferably fire-retardant persistence.
Another representational fire retardant is boron flame retardant in halogen-free flame retardants.Its fire retardant mechanism is：In combustion process
It is middle to generate sticky glassy matter object and be covered on material, play the role of heat-insulated and oxygen-impermeable, is dehydrated in decomposable process, heat absorption,
Combustibles temperature is reduced, and promotes incarbonization in condensed phase.Boron flame retardant is also classified into addition type and response type two major classes,
Zinc borate is the representative of additive flame retardant, is widely used, but equally exists the defect of additive flame retardant.In consideration of it, this
The three of the bright spot of invention are, by synthetic reaction, boron element to be introduced on macromolecular chain, to assign material preferably fire-retardant effect
With.
About the fire-retardant of material, in order to reach more preferable effect, often take special measure, by two kinds or two kinds with
On fire proofing organic combination, to realize the fire-retardant optimization of material.In consideration of it, the four of the bright spot of the present invention are：By nitrogen
(N) a kind of novel flame redundant material is prepared, finally realizes Electronic Packaging by chemosynthesis reaction with two kinds of fire proofings of boron (B)
The halogen-free phosphorus-free inflaming retarding of material.Hyper-branched structure can often be such that many performances of material are taken into account well, can make
Material has the characteristics that easy crystallization, low viscosity, without chain entanglement, multiple functionalized and easy processing, is used for electronic package material, can make electricity
Craftsmanship, Halogen performance, chemical resistance and being optimal of electrical property of sub- encapsulating material.In consideration of it, the present invention
The five of bright spot are：The fire retardant with polyfunctional structure is selected, realizes the hyper-branched of material.
Invention content
The purpose of the present invention is to overcome the deficiencies of the prior art, provide a kind of N-B synergistics high-fire-resistance curing agent and
Its synthetic method, synthesis technology is simple, and production is stablized；The color and luster of synthesized flame retardant curing agent is shallower, flame retarding efficiency is high and fire-retardant
Stablize.
The present invention realizes that the technical solution of purpose is as follows：
A kind of N-B synergistics high-fire-resistance curing agent and its synthetic method, steps are as follows：
(1) polyalcohol and response type nitrogenous compound are added in a reservoir, is warming up to 110~130 DEG C, stirring fusing；
(2), response type boron-containing compound and catalyst are added；150 DEG C are to slowly warm up under logical nitrogen, and has by-product water
It distillates, control distillation column temperature is not higher than 100 DEG C in reaction process, then carries out segmented esterification, and 150~160 DEG C anti-
Answer 1~3h, 160~170 DEG C of 1~2h of reaction；
(3) 150 DEG C are cooled to, polyacid and catalyst is added, is to slowly warm up to 150 DEG C under logical nitrogen, carries out segmented ester
Change reaction, 150~170 DEG C reaction 1~3h, 170~190 DEG C reaction 1~2h, 190~210 DEG C reaction 0.5~1.5h, 210~
225 DEG C of 0.5~1.5h of reaction；When the acid value of reaction system is less than 10mgKOH/g, carry out vacuumizing polycondensation reaction, vacuum degree-
0.04~0MPa, the 10~20min of time vacuumized；
(4) after reaction, it is cooled to 190 DEG C, end-capping reagent is added, continues to stir, react 1 between 170~180 DEG C~
It after 2h, vacuumizes, vacuum degree -0.04~0MPa, 10~15min of time；
(5) discharge, through cooling tabletting, obtain N-B synergistic high-fire-resistance curing agent.
Wherein, the mass fraction of each component is：
Moreover, 80~180mgKOH/g of acid value of the N-B synergistics high-fire-resistance curing agent, melt viscosity range
800~6000mPas/180 DEG C, 75~125 DEG C of softening point range, N content 1.9~4.8wt% of range, B content range 0.35
~1.05wt%.
Moreover, the polyalcohol be neopentyl glycol, ethylene glycol, diethylene glycol, propylene glycol, 1,3 propylene glycol of 2- methyl its
At least one of.
Moreover, the response type nitrogenous compound is 1,3- dihydroxymethyl -5,5- Dimethyl Hydan, hindered for organic nitrogen system
Fire agent.
Moreover, the response type boron-containing compound, is multifunctional material, is 2- Carboxybenzeneboronic acids, 3- Carboxybenzeneboronic acids
One of which.
Moreover, the polyacid is M-phthalic acid, terephthalic acid (TPA), adipic acid wherein at least one.
Moreover, the catalyst is dibutyl tin laurate, Mono-n-butyltin, Dibutyltin oxide, metatitanic acid four
The one of which of butyl ester.
Moreover, the end-capping reagent is trimellitic anhydride.
The advantages and positive effects of the present invention are:
(1) N-B synergistics high-fire-resistance curing agent provided by the invention, belongs to non-halogen non-phosphate type, the feature of environmental protection is more preferable.
(2) N-B synergistics high-fire-resistance curing agent provided by the invention passes through association using two kinds of fire proofings of nitrogen system and boron system
It imitates fire-retardant, realizes the fire-retardant optimization of material.
(3) N-B synergistics high-fire-resistance curing agent provided by the invention has hyper-branched structure, to make the curing agent have
Have the advantages that easily crystallize, low viscosity and easily it is compatible, make the curing agent have excellent machinability, craftsmanship and physical chemistry
Energy.
(4) N-B synergistics high-fire-resistance curing agent provided by the invention, using two kinds of reaction-type flame-retarding materials of nitrogen system and boron system,
By segmented synthesis technology, two kinds of ignition-proof elements of N and B are firmly embedded on macromolecular chain, to realize two kinds of resistances of N and B
Combustion element does not migrate, and the curing agent is made to have excellent anti-flammability and preferable durability of fire-retardant.
(5) N-B synergistics high-fire-resistance curing agent provided by the invention, halogen-free flameproof, phosphorus-free flame-retarding, nitrogen-boron synergistic is fire-retardant
Organic unity, and make the curing agent that there is hyper-branched molecular structure, it is used for electronic package material, not only solves Electronic Packaging
The anti-flammability and durability of fire-retardant problem of material, and can realize the fire-retardant non-halogen non-phosphate of electronic package material；Meanwhile it can make
Electronic package material have excellent machinability, dispersion homogeneity, craftsmanship and excellent physical and chemical performance.
Specific implementation mode
With reference to specific embodiment, the invention will be further described, and following embodiment is descriptive, is not limit
Qualitatively, protection scope of the present invention cannot be limited with this.
The synthetic method of N-B synergistics high-fire-resistance curing agent of the present invention provides 2 embodiments altogether, synthesized curing agent at
Product mark A, B respectively.
Embodiment 1：
A kind of synthetic method of N-B synergistics high-fire-resistance curing agent (A), steps are as follows：
(1) after arranging four-hole boiling flask, blender, distillation column, condenser pipe and temperature-controlled heating mantle, 120g new penta is added
Glycol and 168.21g1,3- dihydroxymethyl -5,5- Dimethyl Hydan are warming up to 110~130 DEG C, stirring fusing；
(2), 85.48g 3- carboxy phenyls boric acid and 0.37g ethyltriphenylphosphonium bromides are added；It is to slowly warm up under logical nitrogen
150 DEG C, and there is by-product water to distillate, control distillation column temperature is not higher than 100 DEG C in reaction process, then carries out segmented esterification
Reaction, 150~160 DEG C of 1~3h of reaction, 160~170 DEG C of 1~2h of reaction；
(3) 150 DEG C are cooled to, 248.83g M-phthalic acids, 84.18g adipic acids and 0.33g ethyltriphenyl phosphonium bromides is added
Phosphine is to slowly warm up to 150 DEG C under logical nitrogen, carries out segmented esterification, 150~170 DEG C of 1~3h of reaction, 170~190 DEG C
React 1~2h, 190~210 DEG C of 0.5~1.5h of reaction, 210~225 DEG C of 0.5~1.5h of reaction；When the acid value of reaction system is small
When 10mgKOH/g, carry out vacuumizing polycondensation reaction, vacuum degree -0.04~0MPa, the 10~20min of time vacuumized；
(4) 190 DEG C after reaction, are cooled to, 143.87g trimellitic anhydrides are added, continue to stir, in 170~180 DEG C
Between reaction 1~2h after, vacuumize, vacuum degree -0.04~0MPa, 10~15min of time；
(5) discharge, through cooling tabletting, can get the N-B synergistic high-fire-resistance curing agent (A) of light yellow clear shape.
The acid value of curing agent (A) manufactured in the present embodiment is 110mgKOH/g, and melt viscosity is 2900mPas/180 DEG C,
Softening point is 96 DEG C, N content 3.35wt%, B content 0.78wt%.
Embodiment 2：
A kind of synthetic method of the fire-retardant flexible curing agent (B) of hyper-branched N-P synergistics, steps are as follows：
(1) after arranging four-hole boiling flask, blender, distillation column, condenser pipe and temperature-controlled heating mantle, 105g new penta is added
Glycol and 184.33g1,3- dihydroxymethyl -5,5- Dimethyl Hydan are warming up to 110~130 DEG C, stirring fusing；
(2), 76.32g 3- carboxy phenyls boric acid and 0.36g ethyltriphenylphosphonium bromides are added；It is to slowly warm up under logical nitrogen
150 DEG C, and there is by-product water to distillate, control distillation column temperature is not higher than 100 DEG C in reaction process, then carries out segmented esterification
Reaction, 150~160 DEG C of 1~3h of reaction, 160~170 DEG C of 1~2h of reaction；
(3) 150 DEG C are cooled to, 239.26g M-phthalic acids, 105.23g adipic acids and 0.34g ethyl triphenyl bromines is added
Change phosphine, 150 DEG C are to slowly warm up under logical nitrogen, carries out segmented esterification, 150~170 DEG C of 1~3h of reaction, 170~190
DEG C reaction 1~2h, 190~210 DEG C reaction 0.5~1.5h, 210~225 DEG C reaction 0.5~1.5h；When the acid value of reaction system
When less than 10mgKOH/g, carry out vacuumizing polycondensation reaction, vacuum degree -0.04~0MPa, the 10~20min of time vacuumized；
(4) 190 DEG C after reaction, are cooled to, 166g trimellitic anhydrides are added, continue to stir, between 170~180 DEG C
After reacting 1~2h, vacuumize, vacuum degree -0.04~0MPa, 10~15min of time；
(5) discharge, through cooling tabletting, can get the N-B synergistic high-fire-resistance curing agent (B) of light yellow clear shape.
The acid value of curing agent (B) manufactured in the present embodiment is 125mgKOH/g, and melt viscosity is 2700mPas/180 DEG C,
Softening point is 94 DEG C, N content 3.55wt%, B content 0.67wt%.
The each component referred in above-mentioned two embodiment further includes following ingredient, and same function or the following institute of effect can be used
Component replacement is stated, obtained curing agent has equivalent effect, no longer combination citing one by one.
80~180mgKOH/g of acid value of the N-B synergistics high-fire-resistance curing agent, melt viscosity range 800~
6000mPas/180 DEG C, 75~125 DEG C of softening point range, N content 1.9~4.8wt% of range, B content range 0.35~
1.05wt%.
The polyalcohol be neopentyl glycol, ethylene glycol, diethylene glycol, propylene glycol, 1,3 propylene glycol of 2- methyl wherein at least
It is a kind of.
The response type nitrogenous compound is 1,3- dihydroxymethyl -5,5- Dimethyl Hydan, is organic nitrogenated flame retardant.
The response type boron-containing compound, be multifunctional material, be 2- Carboxybenzeneboronic acids, 3- Carboxybenzeneboronic acids wherein
It is a kind of.
The polyacid is M-phthalic acid, terephthalic acid (TPA), adipic acid wherein at least one.
The catalyst is dibutyl tin laurate, Mono-n-butyltin, Dibutyltin oxide, butyl titanate
One of which.
The end-capping reagent is trimellitic anhydride.
Testing performance index method according to the present invention is as follows：
(1) softening point：According to GB12007.6-89《Epoxy resin softening point measurement method ring and ball method》Method measures.
(2) melt viscosity：Viscosity under different melting temperatures is measured using Brookfield cone and plate viscometers.
(3) the measurement of acid value：According to GB6743-86《The measuring method of paint and varnish paint base acid value》Method measures.
(4) anti-flammability measures：According to UL94《The flammable performance test of equipment and device component material》In vertical combustion examination
Proved recipe method measures.
Verification test：Three verification tests below, for the excellent of the N-B synergistic high-fire-resistance curing agent of the invention prepared
Effect.
Anti-flammability and the cold-resistant thermal impact of 1 epoxy composite component proportion of table and curing of coatings object
| Component | Unit | Comparative example | Embodiment 1 | Embodiment 2 |
| Epoxy resin (E-12) | g | 50 | 38 | 39 |
| N-B synergistic high-fire-resistance curing agent (A) | g | — | 12 | — |
| N-B synergistic high-fire-resistance curing agent (B) | g | — | — | 11 |
| Other curing agent：Trimellitic anhydride | g | 3.9 | 1.8 | 1.8 |
| Curing accelerator；2- phenylimidazoles | g | 0.08 | 0.08 | 0.08 |
| Inorganic filler：Silica | g | 30 | 30 | 30 |
| Fire retarding synergist：Aluminium hydroxide | g | 20 | 20 | 20 |
| Anti-flammability | Grade | V-2 | V-0 | V-0 |
Claims (8)
1. a kind of N-B synergistics high-fire-resistance curing agent and its synthetic method, it is characterised in that：Steps are as follows：
(1) polyalcohol and response type nitrogenous compound are added in a reservoir, is warming up to 110~130 DEG C, stirring fusing；
(2), response type boron-containing compound and catalyst are added；150 DEG C are to slowly warm up under logical nitrogen, and has by-product water to distillate,
Control distillation column temperature is not higher than 100 DEG C in reaction process, then progress segmented esterification, and 150~160 DEG C of reactions 1~
3h, 160~170 DEG C of 1~2h of reaction；
(3) 150 DEG C are cooled to, polyacid and catalyst is added, 150 DEG C are to slowly warm up under logical nitrogen, it is anti-to carry out segmented esterification
Answer, 150~170 DEG C reaction 1~3h, 170~190 DEG C reaction 1~2h, 190~210 DEG C reaction 0.5~1.5h, 210~225 DEG C
React 0.5~1.5h；When the acid value of reaction system is less than 10mgKOH/g, carry out vacuumizing polycondensation reaction, vacuum degree -0.04
~0MPa, the 10~20min of time vacuumized；
(4) 190 DEG C after reaction, are cooled to, end-capping reagent is added, continues to stir, after reacting 1~2h between 170~180 DEG C,
It vacuumizes, vacuum degree -0.04~0MPa, 10~15min of time；
(5) discharge, through cooling tabletting, obtain N-B synergistic high-fire-resistance curing agent；
Wherein, the mass fraction of each component is：
2. N-B synergistics high-fire-resistance curing agent according to claim 1 and its synthetic method, it is characterised in that：The N-B
80~180mgKOH/g of acid value of synergistic high-fire-resistance curing agent, 800~6000mPas/180 DEG C of melt viscosity range,
75~125 DEG C of softening point range, N content 1.9~4.8wt% of range, 0.35~1.05wt% of B content range.
3. N-B synergistics high-fire-resistance curing agent according to claim 1 and its synthetic method, it is characterised in that：Described
Polyalcohol is neopentyl glycol, ethylene glycol, diethylene glycol, propylene glycol, 1,3 propylene glycol wherein at least one of 2- methyl.
4. N-B synergistics high-fire-resistance curing agent according to claim 1 and its synthetic method, it is characterised in that：Described
Response type nitrogenous compound is 1,3- dihydroxymethyl -5,5- Dimethyl Hydan, is organic nitrogenated flame retardant.
5. N-B synergistics high-fire-resistance curing agent according to claim 1 and its synthetic method, it is characterised in that：Described
Response type boron-containing compound is multifunctional material, is the one of which of 2- Carboxybenzeneboronic acids, 3- Carboxybenzeneboronic acids.
6. N-B synergistics high-fire-resistance curing agent according to claim 1 and its synthetic method, it is characterised in that：Described
Polyacid is M-phthalic acid, terephthalic acid (TPA), adipic acid wherein at least one.
7. N-B synergistics high-fire-resistance curing agent according to claim 1 and its synthetic method, it is characterised in that：Described
Catalyst is the one of which of dibutyl tin laurate, Mono-n-butyltin, Dibutyltin oxide, butyl titanate.
8. N-B synergistics high-fire-resistance curing agent according to claim 1 and its synthetic method, it is characterised in that：Described
End-capping reagent is trimellitic anhydride.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109467688A (en) * | 2018-09-17 | 2019-03-15 | 天津慧瑞科技有限公司 | A kind of phosphorus-nitrogen-flexible curing agent of boron synergistic high fire-retardance and its synthetic method |
| CN111808252A (en) * | 2020-07-31 | 2020-10-23 | 浙江万盛股份有限公司 | Preparation method of N-P synergistic cardanol-based flame-retardant curing agent |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735601A (en) * | 2009-12-23 | 2010-06-16 | 东莞市信诺橡塑工业有限公司 | Heat and flame resistant nylon composite |
| 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 |
| CN103304797A (en) * | 2013-06-20 | 2013-09-18 | 天津市凯华绝缘材料有限公司 | Flexible flame-retardant polyester curing agent with star-like branched structure, and synthesis method thereof |
| CN103333461A (en) * | 2013-06-20 | 2013-10-02 | 天津市凯华绝缘材料有限公司 | Epoxy resin composition with high flame-retardant property and preparation method thereof |
| CN105086139A (en) * | 2015-08-06 | 2015-11-25 | 丁德凤 | High-temperature-resistant flame-retardant plastic formula |
-
2018
- 2018-03-30 CN CN201810295268.0A patent/CN108424513B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735601A (en) * | 2009-12-23 | 2010-06-16 | 东莞市信诺橡塑工业有限公司 | Heat and flame resistant nylon composite |
| 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 |
| CN103304797A (en) * | 2013-06-20 | 2013-09-18 | 天津市凯华绝缘材料有限公司 | Flexible flame-retardant polyester curing agent with star-like branched structure, and synthesis method thereof |
| CN103333461A (en) * | 2013-06-20 | 2013-10-02 | 天津市凯华绝缘材料有限公司 | Epoxy resin composition with high flame-retardant property and preparation method thereof |
| CN105086139A (en) * | 2015-08-06 | 2015-11-25 | 丁德凤 | High-temperature-resistant flame-retardant plastic formula |
Non-Patent Citations (1)
| Title |
|---|
| 陈荣圻: "有机硼系阻燃剂的研发", 《印染》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109467688A (en) * | 2018-09-17 | 2019-03-15 | 天津慧瑞科技有限公司 | A kind of phosphorus-nitrogen-flexible curing agent of boron synergistic high fire-retardance and its synthetic method |
| CN109467688B (en) * | 2018-09-17 | 2021-01-15 | 天津慧瑞科技有限公司 | Phosphorus-nitrogen-boron synergistic high-flame-retardant flexible curing agent and synthesis method thereof |
| CN111808252A (en) * | 2020-07-31 | 2020-10-23 | 浙江万盛股份有限公司 | Preparation method of N-P synergistic cardanol-based flame-retardant curing agent |
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| CN108424513B (en) | 2020-04-17 |
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