CN104629261A - Filler-free halogen-free flame-retardant epoxy resin composition - Google Patents

Filler-free halogen-free flame-retardant epoxy resin composition Download PDF

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Publication number
CN104629261A
CN104629261A CN201510017485.XA CN201510017485A CN104629261A CN 104629261 A CN104629261 A CN 104629261A CN 201510017485 A CN201510017485 A CN 201510017485A CN 104629261 A CN104629261 A CN 104629261A
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CN
China
Prior art keywords
epoxy resin
component
halogen
flame retardant
bisphenol
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Pending
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CN201510017485.XA
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Chinese (zh)
Inventor
金威
林燕建
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Cypress New Material Technology (shanghai) Co Ltd
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Cypress New Material Technology (shanghai) Co Ltd
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Priority to CN201510017485.XA priority Critical patent/CN104629261A/en
Publication of CN104629261A publication Critical patent/CN104629261A/en
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Abstract

The invention relates to a flame-retardant composite material formed by multiple techniques, particularly a filler-free halogen-free flame-retardant epoxy resin composition. The filler-free halogen-free flame-retardant epoxy resin composition comprises a component A and a component B. The component A comprises the following components in percentage by weight: 55-75% of low-halogen bisphenol A epoxy resin 128, 5-15% of bisphenol F epoxy resin 170, 10-30% of phosphorus-nitrogen flame retardant and 10-20% of phosphate flame retardant. The component B comprises the following components in percentage by weight: 10-20% of polyetheramine curing agent D230, 50-70% of isophorone diamine (IPDA) and 20-30% of N-aminoethyl piperazidine. The component A and component B are mixed according to the weight ratio of 100:(19-21) to obtain the composition. On the premise of ensuring various physiochemical properties of the cured resin and especially the mechanical properties and halogen-free flame retardancy, the composition does not use any filler-type flame retardant, and satisfies the operating requirements for multiple techniques.

Description

A kind of no-arbitrary pricing halogen-free flame retardant epoxy resin composition
Technical field
The present invention relates to the flame-proof composite material that kinds of processes is shaping, particularly relate to a kind of composition epoxy resin of track traffic.
Background technology
Track traffic, as a kind of public transport, the safety of material is paid attention in China and even the whole world.Matrix material uses extensively in track traffic, all adopted unsaturated polyester in the past, there is halogen fire retardant, but along with people are to the deep understanding of material, unsaturated polyester, there is halogen fire retardant to burn when track traffic presence of fire and send dense smoke and harmful gas, very unfavorable to the rescue after presence of fire.
In order to solve the problem, epoxy resin, as a kind of engineering materials of high strength, has the excellent weathering resistance thus selected making track traffic parts that are used for.Wherein bisphenol A type epoxy resin (as epoxy resin 128) adopts amine curing agent to solidify the non-volatile smell of matrix material obtained.But halogen fire retardant discharges a large amount of hydrogen halide obnoxious flavour after combustion, packing type fire retardant cannot meet the techniques such as RTM (Resin Transfer Molding), vacuum diversion.
In addition, the choice relation of the performance of product and epoxy type and curing system thereof is close, and therefore, this is a problem that needs consider from mechanical property and the fire retardancy of processing characteristics, product.
Summary of the invention
The present invention is intended to solve the problem, and provides a kind of no-arbitrary pricing halogen-free flame retardant epoxy resin composition.The present invention, under the prerequisite of various physicochemical properties, particularly mechanical property ensureing cured resin, ensure that flame retardant properties, improves its processing characteristics.
For solving the problem, a kind of no-arbitrary pricing halogen-free flame retardant epoxy resin composition of the present invention, it comprises the first and second two components, and described first component comprises:
Low halogen bisphenol A type epoxy resin 128 55-75%
Bisphenol f type epoxy resin 170 5-15%
Phosphorus nitrogen fire-retardant 10-30%
Phosphate flame retardant 10-20%
Described second component comprises:
Polyetheramine solidifying agent D230 10-20%
Isophorone diamine IPDA 50-70%
N-aminoethyl piperazine N-AEP 20-30%;
Described each component percentages is weight percentage;
Namely described first and second components obtain described composition according to after the ratio mixing of weight part 100:19-21.
Described a kind of no-arbitrary pricing Halogenless fire retarded epoxy resin group, the appearance colorless of described first component or micro-yellow viscous body, its viscosity is 1300-1800cps, density 1.1-1.3/cm 3, epoxy equivalent (weight) is 245-265 g/eq.
Described a kind of no-arbitrary pricing halogen-free flame retardant epoxy resin composition, the mixed composition viscosity of described first and second component is 400-600cps, and operable time is 30-900min.
The preparation method of described a kind of no-arbitrary pricing halogen-free flame retardant epoxy resin composition, it comprises each component and the following step of described ratio:
Step one, preparation first component
A, by bisphenol A type epoxy resin 128, is preheating to 60 DEG C-65 DEG C;
B, by the bisphenol A type epoxy resin 128 through step one preheating, bisphenol f type epoxy resin 170 adds reactor successively;
C, adds reactor by phosphorus nitrogen fire-retardant, is warming up to 130-150 DEG C;
D, turn on agitator, stops after stirring 90-120min with the speed of 24-28rpm;
E, after being cooled to 70-80 DEG C, adds phosphate flame retardant,
F, under the environment vacuumized, starts whipping procedure, controls high speed 28rpm, low speed 24rpm, Keep agitation 30-60min, close whipping procedure;
G, stops vacuumizing, and namely obtains described first component by recovering normal pressure in reactor;
Step 2, preparation second component;
H, by each auxiliary agent precise, and adds in another reactor;
I, stirs, at a high speed 28 rpm, low speed 24rmp, and Keep agitation 50-60min closes and stirs;
J, adds solidifying agent polyetheramine solidifying agent D230 and isophorone diamine IPDA; And mix; Obtain described second component;
K, by nominal tank bucket, rushes nitrogen protection gas during barrel filling.
The present invention select phosphorus-nitrogen containing flame retardant can with epoxy resin melting at a certain temperature, then by adding phosphate flame retardant and auxiliary phosphorus-nitrogen containing flame retardant, promote flame retardant effect.Composition of the present invention, does not use filler, is particularly suitable for RTM, small size vacuum water conservancy diversion technique; Good wetting property is revealed to glass and carbon fiber surface, ensures product property.
Embodiment
Below, in conjunction with specific embodiments, the present invention is further illustrated:
A kind of no-arbitrary pricing halogen-free flame retardant epoxy resin composition, it comprises the first and second two components, and described first component comprises:
Low halogen bisphenol A type epoxy resin 128 55-75%
Bisphenol f type epoxy resin 170 5-15%
Phosphorus nitrogen fire-retardant 10-30%
Phosphate flame retardant 10-20%
Described second component comprises:
Polyetheramine solidifying agent D230 10-20%
Isophorone diamine IPDA 50-70%
N-aminoethyl piperazine N-AEP 20-30%;
Described each component percentages is weight percentage; Code name GT-910B.
Namely described first and second components obtain described composition according to after the ratio mixing of weight part 100:19-21.
Described a kind of no-arbitrary pricing Halogenless fire retarded epoxy resin group, the appearance colorless of described first component or micro-yellow viscous body, its viscosity is 1300-1800cps, density 1.1-1.3/cm 3, epoxy equivalent (weight) is 245-265 g/eq.That in embodiment, code name is GT-901A.
Described a kind of no-arbitrary pricing halogen-free flame retardant epoxy resin composition, the mixed composition viscosity of described first and second component is 400-600cps, and operable time is 30-900min.
The preparation method of a kind of no-arbitrary pricing halogen-free flame retardant epoxy resin composition stated, it comprises each component and the following step of described ratio:
Step one, preparation first component
A, by bisphenol A type epoxy resin 128, is preheating to 60 DEG C-65 DEG C;
B, by the bisphenol A type epoxy resin 128 through step one preheating, bisphenol f type epoxy resin 170 adds reactor successively;
C, adds reactor by phosphorus nitrogen fire-retardant, is warming up to 130-150 DEG C;
D, turn on agitator, stops after stirring 90-120min with the speed of 24-28rpm;
E, after being cooled to 70-80 DEG C, adds phosphate flame retardant,
F, under the environment vacuumized, starts whipping procedure, controls high speed 28rpm, low speed 24rpm, Keep agitation 30-60min, close whipping procedure;
G, stops vacuumizing, and namely obtains described first component by recovering normal pressure in reactor;
Step 2, preparation second component;
H, by each auxiliary agent precise, and adds in another reactor;
I, stirs, at a high speed 28 rpm, low speed 24rmp, and Keep agitation 50-60min closes and stirs;
J, adds solidifying agent polyetheramine solidifying agent D230 and isophorone diamine IPDA; And mix; Obtain described second component;
K, by nominal tank bucket, rushes nitrogen protection gas during barrel filling.
The performance of the flame retardant properties of inventing, basic parameter and casting matrix is as following each table
Table 1
Table 2
Table 3

Claims (4)

1. a no-arbitrary pricing halogen-free flame retardant epoxy resin composition, it comprises the first and second two components, it is characterized in that,
Described first component comprises:
Low halogen bisphenol A type epoxy resin 128 55-75%
Bisphenol f type epoxy resin 170 5-15%
Phosphorus nitrogen fire-retardant 10-30%
Phosphate flame retardant 10-20%
Described second component comprises:
Polyetheramine solidifying agent D230 10-20%
Isophorone diamine IPDA 50-70%
N-aminoethyl piperazine N-AEP 20-30%;
Described each component percentages is weight percentage;
Namely described first and second components obtain described composition according to after the ratio mixing of weight part 100:19-21.
2. a kind of no-arbitrary pricing halogen-free flame retardant epoxy resin composition according to claim 1, is characterized in that, the appearance colorless of described first component or micro-yellow viscous body, its viscosity is 1300-1800cps, density 1.1-1.3/cm 3, epoxy equivalent (weight) is 245-265 g/eq.
3. a kind of no-arbitrary pricing halogen-free flame retardant epoxy resin composition according to claim 1, is characterized in that, the mixed composition viscosity of described first and second component is 300-700cps, and operable time is 30-90min.
4. the preparation method of a kind of no-arbitrary pricing halogen-free flame retardant epoxy resin composition according to claim 1, is characterized in that, it comprises each component and the following step of described ratio:
Step one, preparation first component
A, by bisphenol A type epoxy resin 128, is preheating to 60 DEG C-65 DEG C;
B, by the bisphenol A type epoxy resin 128 through step one preheating, bisphenol f type epoxy resin 170 adds reactor successively;
C, adds reactor by phosphorus nitrogen fire-retardant, is warming up to 130-150 DEG C;
D, turn on agitator, stops after stirring 90-120min with the speed of 24-28rpm;
E, after being cooled to 70-80 DEG C, adds phosphate flame retardant,
F, under the environment vacuumized, starts whipping procedure, controls high speed 28rpm, low speed 24rpm, Keep agitation 30-60min, close whipping procedure;
G, stops vacuumizing, and namely obtains described first component by recovering normal pressure in reactor;
Step 2, preparation second component;
H, by each auxiliary agent precise, and adds in another reactor;
I, stirs, at a high speed 28 rpm, low speed 24rmp, and Keep agitation 50-60min closes and stirs;
J, adds solidifying agent polyetheramine solidifying agent D230 and isophorone diamine IPDA; And mix; Obtain described second component;
K, by nominal tank bucket, rushes nitrogen protection gas during barrel filling.
CN201510017485.XA 2015-01-14 2015-01-14 Filler-free halogen-free flame-retardant epoxy resin composition Pending CN104629261A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106496950A (en) * 2016-11-11 2017-03-15 惠柏新材料科技(上海)股份有限公司 A kind of low smoke combustion-proof epoxide resin composition
CN108299624A (en) * 2018-03-12 2018-07-20 雅安市弘利展化工有限公司 A kind of epoxy curing agent, composition epoxy resin and preparation method thereof
CN111057220A (en) * 2019-12-31 2020-04-24 道生天合材料科技(上海)有限公司 Vacuum infusion flame-retardant epoxy resin and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101186744A (en) * 2007-08-29 2008-05-28 上纬企业股份有限公司 Epoxy resin and use thereof
CN102061064A (en) * 2010-12-23 2011-05-18 东方电气集团东方汽轮机有限公司 Fast curing epoxy resin system for blades of wind driven generator and preparation method thereof
US20110166259A1 (en) * 2008-06-13 2011-07-07 Sika Technology Ag Water soluble amine and uses thereof
CN102516914A (en) * 2011-11-21 2012-06-27 烟台德邦电子材料有限公司 Halogen-free flame-retardant epoxy resin electronic pouring sealant
CN104151780A (en) * 2014-01-22 2014-11-19 惠柏新材料科技(上海)有限公司 Vacuum flow guide epoxy resin composition for wind turbine blade

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101186744A (en) * 2007-08-29 2008-05-28 上纬企业股份有限公司 Epoxy resin and use thereof
US20110166259A1 (en) * 2008-06-13 2011-07-07 Sika Technology Ag Water soluble amine and uses thereof
CN102061064A (en) * 2010-12-23 2011-05-18 东方电气集团东方汽轮机有限公司 Fast curing epoxy resin system for blades of wind driven generator and preparation method thereof
CN102516914A (en) * 2011-11-21 2012-06-27 烟台德邦电子材料有限公司 Halogen-free flame-retardant epoxy resin electronic pouring sealant
CN104151780A (en) * 2014-01-22 2014-11-19 惠柏新材料科技(上海)有限公司 Vacuum flow guide epoxy resin composition for wind turbine blade

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
刘正英,杨鸣波: "《工程塑料改性技术》", 31 October 2007 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106496950A (en) * 2016-11-11 2017-03-15 惠柏新材料科技(上海)股份有限公司 A kind of low smoke combustion-proof epoxide resin composition
CN108299624A (en) * 2018-03-12 2018-07-20 雅安市弘利展化工有限公司 A kind of epoxy curing agent, composition epoxy resin and preparation method thereof
CN111057220A (en) * 2019-12-31 2020-04-24 道生天合材料科技(上海)有限公司 Vacuum infusion flame-retardant epoxy resin and preparation method thereof
CN111057220B (en) * 2019-12-31 2021-11-12 道生天合材料科技(上海)股份有限公司 Vacuum infusion flame-retardant epoxy resin and preparation method thereof

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Address after: Jiading District Jiangqiao Town Garden Road 201821 Shanghai City No. 558 Building 2

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