CN111718561A - Halogen-free flame-retardant epoxy resin composition - Google Patents

Halogen-free flame-retardant epoxy resin composition Download PDF

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Publication number
CN111718561A
CN111718561A CN202010245354.8A CN202010245354A CN111718561A CN 111718561 A CN111718561 A CN 111718561A CN 202010245354 A CN202010245354 A CN 202010245354A CN 111718561 A CN111718561 A CN 111718561A
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Prior art keywords
epoxy resin
retardant
flame
halogen
resin composition
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Chinese (zh)
Inventor
康红伟
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Shenzhen Langbowan Advanced Materials Co ltd
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Shenzhen Langbowan Advanced Materials Co ltd
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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/2224—Magnesium hydroxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Reinforced Plastic Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a halogen-free flame-retardant epoxy resin composition, which consists of high-phosphorus-content epoxy resin, multi-benzene ring structure epoxy resin, superfine aluminum hydroxide, superfine magnesium hydroxide, a synergistic flame retardant, a smoke suppressant, a toughening agent, a curing agent and an accelerator, wherein the resin composition has the advantages of no halogen, environmental protection, high-efficiency flame retardance, low smoke generation, low smoke toxicity and low heat release, and a flame-retardant laminated board prepreg prepared from the resin meets the flame-retardant standard of UL94-V0, meets the requirement of the highest flame-retardant grade of European standard EN45545-2/R1/HL3 in the rail transit industry, and simultaneously meets the requirement of a FAR25.853 flame-retardant fire test for an interior material of an aircraft cabin.

Description

Halogen-free flame-retardant epoxy resin composition
Technical Field
The invention relates to a halogen-free flame-retardant epoxy resin composition.
Background
In the prior art, the prepreg resin is mostly prepared by adopting an additive phosphorus-nitrogen flame retardant, and the additive flame retardant does not participate in the reaction, so that the mechanical property of a composite material product is greatly reduced. The prepreg resin prepared by the existing flame retardant technology is generally not over-concerned in heat release, and can not meet the low heat release requirements in the flame retardant grades of EN45545/R1/HL3 in the rail transit industry and the flame retardant grades of FAR25.853 of the interior materials of the airplane cabins.
One of the prior art adopts a phosphorus-nitrogen system as a flame retardant, which affects the mechanical property and has overhigh combustion heat release.
The diphosphorus epoxy resin in the prior art is prepared by DOPO, the phosphorus content of the final epoxy resin is generally 1-5%, in order to ensure the flame retardant effect, a large amount of the epoxy resin with low phosphorus content needs to be added, so that other functional epoxy resins cannot be added, for example, the toughened epoxy resin improves the mechanical property, and the high-temperature resistant epoxy resin improves the high temperature resistance of the product.
The third flame-retardant epoxy resin composition in the prior art generally has no strict requirement on the content of chlorine in the used epoxy resin, so that a cured product is combusted to produce hydrogen chloride, and the smoke toxicity of a final composite material product is greatly influenced.
When aluminum hydroxide and magnesium hydroxide are added into the flame-retardant epoxy resin composition in the fourth prior art, the two flame-retardant fillers are not required to be treated by the epoxy silane coupling agent, and the mechanical property of the epoxy resin can be greatly improved after the epoxy silane coupling agent is treated; the particle size of the two fillers is not required to be less than or equal to 1 micron, and the flame-retardant filler in the resin cannot be soaked into each fiber in the tows when the particle size is too large, so that the flame-retardant property of the composite material product is greatly influenced.
Disclosure of Invention
In order to solve the above problems in the prior art, the present invention provides a halogen-free flame retardant epoxy resin composition.
The invention provides a halogen-free flame-retardant epoxy resin composition, which consists of high-phosphorus-content epoxy resin, multi-benzene ring structure epoxy resin, superfine aluminum hydroxide, superfine magnesium hydroxide, a synergistic flame retardant, a smoke suppressant, a toughening agent, a curing agent and an accelerator, and comprises the following components in percentage by mass:
10-30% of high-phosphorus-content epoxy resin
30-80% of multi-benzene ring structure epoxy resin
10 to 40 percent of superfine aluminum hydroxide
10 to 40 percent of superfine magnesium hydroxide
1-15% of synergistic flame retardant
1-15% of toughening agent
10-40% of curing agent
1 to 5 percent of accelerant
The rest is smoke suppressant.
In one preferred embodiment, the composition comprises the following components in percentage by mass:
10-25% of high-phosphorus-containing epoxy resin
40-80% of multi-benzene ring structure epoxy resin
10 to 35 percent of superfine aluminum hydroxide
10 to 38 percent of superfine magnesium hydroxide
2-13% of synergistic flame retardant
2-15% of toughening agent
10-30% of curing agent
1 to 5 percent of accelerant
The rest is smoke suppressant.
In one preferred embodiment, the composition comprises the following components in percentage by mass:
15-25% of high-phosphorus-containing epoxy resin
40-70% of multi-benzene ring structure epoxy resin
12 to 35 percent of superfine aluminum hydroxide
13 to 38 percent of superfine magnesium hydroxide
2-13% of synergistic flame retardant
2 to 11 percent of toughening agent
10-20% of curing agent
1 to 5 percent of accelerant
The rest is smoke suppressant.
Or the alloy comprises the following components in percentage by mass:
15 percent of high-phosphorus epoxy resin
40 percent of multi-benzene ring structure epoxy resin
12 percent of superfine aluminum hydroxide
13 percent of superfine magnesium hydroxide
4 percent of synergistic flame retardant
4 percent of toughening agent
10 percent of curing agent
1 percent of accelerator
1 percent of smoke suppressant.
In one preferred scheme, the halogen-free flame-retardant epoxy resin composition is synthesized from epoxy resin with high phosphorus content, and the phosphorus content is not less than 15%; a flame-retardant epoxy resin composition prepared from an epoxy resin with high phosphorus content; the halogen-free flame-retardant epoxy resin composition is used as a material for preparing a flame-retardant prepreg.
The invention has the beneficial effects that: the resin composition of the halogen-free flame-retardant epoxy resin composition prepared by the formula has the advantages of halogen-free environmental protection, high-efficiency flame retardance, low smoke generation, low smoke toxicity and low heat release, and the flame-retardant prepreg laminated board prepared by the resin meets the flame-retardant standard of UL94-V0, meets the requirement of the highest flame-retardant grade of European standard EN45545-2/R1/HL3 in the rail transit industry, and simultaneously meets the requirement of FAR25.853 flame-retardant fire-proof test of an interior material of an aircraft cabin.
Detailed Description
Example 1:
the composition comprises high-phosphorus-content epoxy resin, multi-benzene ring structure epoxy resin, superfine aluminum hydroxide, superfine magnesium hydroxide, a synergistic flame retardant, a smoke suppressant, a toughening agent, a curing agent and an accelerator, and is prepared from the following components in percentage by mass:
10-30% of high-phosphorus-content epoxy resin
30-80% of multi-benzene ring structure epoxy resin
10 to 40 percent of superfine aluminum hydroxide
10 to 40 percent of superfine magnesium hydroxide
1-15% of synergistic flame retardant
1-15% of toughening agent
10-40% of curing agent
1 to 5 percent of accelerant
The rest is smoke suppressant.
The halogen-free flame-retardant epoxy resin composition is synthesized by epoxy resin with high phosphorus content, and the phosphorus content is not less than 15 percent; a flame-retardant epoxy resin composition prepared from an epoxy resin with high phosphorus content; the halogen-free flame-retardant epoxy resin composition is used as a material for preparing a flame-retardant prepreg.
Example 2:
the halogen-free flame-retardant epoxy resin composition comprises the following components in parts by mass:
10-25% of high-phosphorus-containing epoxy resin
40-80% of multi-benzene ring structure epoxy resin
10 to 35 percent of superfine aluminum hydroxide
10 to 38 percent of superfine magnesium hydroxide
2-13% of synergistic flame retardant
2-15% of toughening agent
10-30% of curing agent
1 to 5 percent of accelerant
The rest is smoke suppressant.
The halogen-free flame-retardant epoxy resin composition is synthesized by epoxy resin with high phosphorus content, and the phosphorus content is not less than 15 percent; a flame-retardant epoxy resin composition prepared from an epoxy resin with high phosphorus content; the halogen-free flame-retardant epoxy resin composition is used as a material for preparing a flame-retardant prepreg.
Example 3:
the halogen-free flame-retardant epoxy resin composition comprises the following components in parts by mass:
15-25% of high-phosphorus-containing epoxy resin
40-70% of multi-benzene ring structure epoxy resin
12 to 35 percent of superfine aluminum hydroxide
13 to 38 percent of superfine magnesium hydroxide
2-13% of synergistic flame retardant
2 to 11 percent of toughening agent
10-20% of curing agent
1 to 5 percent of accelerant
The rest is smoke suppressant.
The halogen-free flame-retardant epoxy resin composition is synthesized by epoxy resin with high phosphorus content, and the phosphorus content is not less than 15 percent; a flame-retardant epoxy resin composition prepared from an epoxy resin with high phosphorus content; the halogen-free flame-retardant epoxy resin composition is used as a material for preparing a flame-retardant prepreg.
Example 4:
the halogen-free flame-retardant epoxy resin composition comprises the following components in parts by mass:
15 percent of high-phosphorus epoxy resin
40 percent of multi-benzene ring structure epoxy resin
12 percent of superfine aluminum hydroxide
13 percent of superfine magnesium hydroxide
4 percent of synergistic flame retardant
4 percent of toughening agent
10 percent of curing agent
1 percent of accelerator
1 percent of smoke suppressant.
The halogen-free flame-retardant epoxy resin composition is synthesized by epoxy resin with high phosphorus content, and the phosphorus content is not less than 15 percent; a flame-retardant epoxy resin composition prepared from an epoxy resin with high phosphorus content; the halogen-free flame-retardant epoxy resin composition is used as a material for preparing a flame-retardant prepreg.
The structure of the high phosphorous epoxy resin product used in the above example is as follows:
Figure 913555DEST_PATH_IMAGE001
C20H23O2P
Figure 784690DEST_PATH_IMAGE002
C18H19O4P
Figure 138662DEST_PATH_IMAGE003
C18H21O3P
Figure 735470DEST_PATH_IMAGE004
C15H15O3P
Figure 861427DEST_PATH_IMAGE005
C18H19O4P
Figure 47338DEST_PATH_IMAGE006
C7H15O4P
compared with the traditional processing technology, the invention has the following differences: the resin composition of the halogen-free flame-retardant epoxy resin composition disclosed by the invention has the advantages of halogen-free environmental protection, high-efficiency flame retardance, low smoke generation, low smoke toxicity and low heat release, and the flame-retardant prepreg laminated board made of the resin meets the flame-retardant standard of UL94-V0, meets the requirement of the highest flame-retardant grade of European standard EN45545-2/R1/HL3 in the rail transit industry, and simultaneously meets the requirement of FAR25.853 flame-retardant fire-proof test of an interior material of an aircraft cabin.
The present invention is not limited to the above embodiments, and various embodiments using the same principle and method to achieve the same technical effects are the same as the present patent.

Claims (4)

1. The halogen-free flame-retardant epoxy resin composition is characterized by comprising high-phosphorus-content epoxy resin, multi-benzene ring structure epoxy resin, superfine aluminum hydroxide, superfine magnesium hydroxide, a synergistic flame retardant, a smoke suppressant, a toughening agent, a curing agent and an accelerator, and the components are arranged according to the following mass fractions:
Figure FDA0002433850130000011
2. the halogen-free flame retardant epoxy resin composition according to claim 1, wherein the composition comprises the following components in parts by mass:
Figure FDA0002433850130000012
3. the halogen-free flame retardant epoxy resin composition according to claims 1-2, wherein the composition comprises the following components in parts by mass:
Figure FDA0002433850130000021
or the alloy comprises the following components in percentage by mass:
Figure FDA0002433850130000022
4. the halogen-free flame retardant epoxy resin composition according to any of claims 1 to 3,
the halogen-free flame-retardant epoxy resin composition is synthesized by epoxy resin with high phosphorus content, and the phosphorus content is not less than 15 percent; a flame-retardant epoxy resin composition prepared from an epoxy resin with high phosphorus content; the halogen-free flame-retardant epoxy resin composition is used as a material for preparing a flame-retardant prepreg.
CN202010245354.8A 2020-03-31 2020-03-31 Halogen-free flame-retardant epoxy resin composition Pending CN111718561A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112778368A (en) * 2021-01-05 2021-05-11 江苏利思德新材料有限公司 Dialkyl phosphinate containing active epoxy group and preparation and application thereof
CN115181130A (en) * 2022-08-23 2022-10-14 江苏晶雪节能科技股份有限公司 Flame-retardant polyether polyol intermediate and preparation method and application thereof
CN115197537A (en) * 2022-04-27 2022-10-18 道生天合材料科技(上海)股份有限公司 Flame-retardant epoxy resin composition, prepreg, fiber-reinforced composite material and preparation

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016132709A (en) * 2015-01-19 2016-07-25 東レ株式会社 Epoxy resin composition, prepreg, and fiber-reinforced composite material
CN110894341A (en) * 2019-10-18 2020-03-20 成都鲁晨新材料科技有限公司 Halogen-free flame-retardant epoxy prepreg and composite material thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016132709A (en) * 2015-01-19 2016-07-25 東レ株式会社 Epoxy resin composition, prepreg, and fiber-reinforced composite material
CN110894341A (en) * 2019-10-18 2020-03-20 成都鲁晨新材料科技有限公司 Halogen-free flame-retardant epoxy prepreg and composite material thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112778368A (en) * 2021-01-05 2021-05-11 江苏利思德新材料有限公司 Dialkyl phosphinate containing active epoxy group and preparation and application thereof
WO2022147942A1 (en) * 2021-01-05 2022-07-14 江苏利思德新材料有限公司 Dialkyl phosphonate compound containing active epoxy group, preparation and application thereof
CN115197537A (en) * 2022-04-27 2022-10-18 道生天合材料科技(上海)股份有限公司 Flame-retardant epoxy resin composition, prepreg, fiber-reinforced composite material and preparation
CN115181130A (en) * 2022-08-23 2022-10-14 江苏晶雪节能科技股份有限公司 Flame-retardant polyether polyol intermediate and preparation method and application thereof

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