CN109438921A - A method of glass fiber reinforced plastics product material is prepared with modified benzoxazine-polyvinyl butyral - Google Patents
A method of glass fiber reinforced plastics product material is prepared with modified benzoxazine-polyvinyl butyral Download PDFInfo
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- CN109438921A CN109438921A CN201811256247.4A CN201811256247A CN109438921A CN 109438921 A CN109438921 A CN 109438921A CN 201811256247 A CN201811256247 A CN 201811256247A CN 109438921 A CN109438921 A CN 109438921A
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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
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Chemical Kinetics & Catalysis (AREA)
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- Reinforced Plastic Materials (AREA)
Abstract
The invention discloses a kind of methods for preparing glass fiber reinforced plastics product material with modified benzoxazine-polyvinyl butyral, benzoxazine resin matrix, curing agent phenolic resin, modifying agent, solvent butanone is added in the short glass fiber handled to concentrated nitric acid oxidation, it is sealed with preservative film, it heats in oil bath, modified benzoxazine glue is made；Polyvinyl butyral is added in epoxy resin, heating stirring sufficiently dissolves, and chlorinated paraffin is added and is sufficiently stirred, and promotor stirring is added, and curing agent stirring is added and obtains toughening-fire-retardant modified epoxy resin after vacuum defoamation processing；Gained toughening-fire-retardant modified epoxy resin and polyimides are heated in a water bath, it is down to room temperature after mixing, diluent dehydrated alcohol, gained modified benzoxazine glue is added, after stirring, curing agent diethylenetriamine is added to be uniformly mixed, in ice bath after vacuum defoamation, pours into mold and solidifies, it is down to room temperature demoulding, the glass fiber reinforced plastics product material is made.
Description
Technical field
The invention belongs to glass fiber reinforced plastics product fields, and in particular to a kind of to use modified benzoxazine-polyvinyl butyral system
The method of standby glass fiber reinforced plastics product material.
Background technique
Fiberglass-epoxy composite material has the characteristics that intensity is high, easy processing, be widely used in space flight and aviation,
The fields such as automobile, building.In recent years, defect present in high-performance composite materials is solved using polyimides and has become research heat
Point.But the big defect of epoxy resin cured product brittleness limits it in the application in high-performance composite materials field, is based on this defect,
The present invention carries out tough-increased and reinforced modification to epoxy resin-base using polyimides, polyvinyl butyral, chlorinated paraffin.
Summary of the invention
The purpose of the present invention is being directed to existing problem, a kind of modified benzoxazine-polyvinyl butyral is provided
The method for preparing glass fiber reinforced plastics product material, the glass fiber reinforced plastics product material according to this method production have excellent mechanical property, resistance to
Acid corrosion performance and flame retardant property.
The present invention is achieved by the following technical solutions:
A method of glass fiber reinforced plastics product material is prepared with modified benzoxazine-polyvinyl butyral, which is characterized in that including
Following steps:
(1) preparation of modified benzoxazine glue:
5-7 parts of benzoxazine resin matrixes, 0.5-0.7 are added in the short glass fiber handled to 10-13 parts of concentrated nitric acid oxidations
Part curing agent phenolic resin, 1-1.4 parts of modifying agent, 10-15 parts of solvent butanone, are sealed with preservative film, are added in 80-85 DEG C of oil bath
Modified benzoxazine glue is made in hot 20-30min；
(2) polyvinyl butyral toughening-chlorinated paraffin fire retarding epoxide resin preparation:
3-4 parts of polyvinyl butyrals are added in 90-110 parts of epoxy resin, heating stirring sufficiently dissolves, and 10-15 is added
Part chlorinated paraffin is sufficiently stirred, and 1-1.5 parts of promotors stirrings are added, and 80-85 parts of curing agent stirrings are added, and vacuum defoamation is handled
Afterwards, toughening-fire-retardant modified epoxy resin is obtained；
(3) casting molding process:
Gained toughening-fire-retardant modified epoxy resin in (2) and 0.4-0.5 parts of polyimides 200 are added in 50-55 DEG C of water-bath
Heat is down to room temperature after mixing, and 15-20 parts of diluent dehydrated alcohols, (1) middle gained modified benzoxazine glue are added, stir
After mixing 1-2h, 6-8 parts of curing agent diethylenetriamines are added and are uniformly mixed, in ice bath after vacuum defoamation 30-35min, pour into mould
Solidify in tool, is down to room temperature demoulding, the glass fiber reinforced plastics product material is made.
Further, the concentrated nitric acid oxidation of short glass fiber is handled in step (1): body being added into short glass fiber
The acetone soln that fraction is 50% after impregnating 20-25h in 40-50 DEG C of water-bath, is cleaned, in 60-65 DEG C of baking oven with distilled water
After middle dry 10-12h, it is placed in oxidation processes 50-70min in concentrated nitric acid, wash with distilled water to neutrality, in 60-65 DEG C of baking oven
Middle dry 10-12h obtains the short glass fiber of concentrated nitric acid oxidation processing.
Further, modifying agent is propylene oxide copolymer glycols or polyether sulfone in step (1).
Further, epoxy resin is bisphenol A type epoxy resin E-51 in step (2), and promotor is 2-methylimidazole, Gu
Agent is methyl tetrahydro phthalic anhydride.
Further, in step (3) curing process be at room temperature solidify 1-2h, at 65-75 DEG C solidify 50-70min,
In 115-125 DEG C of solidification 55-65min, at 135-155 DEG C solidifies 50-70min, at 165-175 DEG C solidifies 25-35min.
The present invention has the advantage that compared with prior art
(1) short glass fiber handled using concentrated nitric acid oxidation using modifying agent propylene oxide copolymer glycols or gathers as reinforcement
Ether sulfone modified benzoxazine resin can introduce flexible polyether key in benzoxazine resin rigidity network structure, and modifying agent is added
So that resin matrix and fiberglass surfacing binding ability enhance, resin matrix toughness increases.
(2) by the way that polyvinyl butyral, chlorinated paraffin is added in epoxy resin-base, polyvinyl butyral is to ring
The toughening effect of oxygen resin is good, and material surface is more coarse, has more micro-cracks and occurs, polyvinyl butyral is as one
Kind thermoplastic resin, can be absorbed part energy by the effect of power in material, to improve material mechanical performance；
Adding chlorinated paraffin is mainly the flame retardant property for improving resin matrix；When fire retardant being added in epoxy, the poly- second of toughener
Enol butyral and fire retardant chlorinated paraffin can play the effect of small molecule toughening, in composite material stress, Ke Yi simultaneously
The generation and propagation for hindering micro-crack to a certain extent, to play the role of coordination plasticizing.
(3) tough-increased and reinforced modification is carried out to epoxy resin-base using polyimides, in toughening-fire-retardant modified epoxy resin
The short glass fiber that concentrated nitric acid oxidation processing is mixed in matrix, improves the mechanical property and acid-resistant corrosion of composite material
Energy.
Specific embodiment
Embodiment 1
A method of glass fiber reinforced plastics product material is prepared with modified benzoxazine-polyvinyl butyral, which is characterized in that including
Following steps:
(1) preparation of modified benzoxazine glue:
5 parts of benzoxazine resin matrixes, 0.5 part of curing agent phenol are added in the short glass fiber handled to 10 parts of concentrated nitric acid oxidations
Urea formaldehyde, 1 part of modifying agent, 10 parts of solvent butanone, are sealed with preservative film, heat 20min in 80-85 DEG C of oil bath, are made and are modified
Benzoxazine glue；
(2) polyvinyl butyral toughening-chlorinated paraffin fire retarding epoxide resin preparation:
3 parts of polyvinyl butyrals are added in 90 parts of epoxy resin, heating stirring sufficiently dissolves, and 10 parts of chlorinated paraffins are added
It is sufficiently stirred, the stirring of 1 part of promotor is added, 80 parts of curing agent stirrings are added, after vacuum defoamation processing, obtain that toughening-is fire-retardant to be changed
Property epoxy resin；
(3) casting molding process:
Gained toughening-fire-retardant modified epoxy resin and 0.4 part of polyimides 200 in (2) are heated in 50-55 DEG C of water-bath, mixed
It is down to room temperature after closing uniformly, 15 parts of diluent dehydrated alcohols are added, (1) middle gained modified benzoxazine glue adds after stirring 1h
Enter 6 parts of curing agent diethylenetriamines to be uniformly mixed, in ice bath after vacuum defoamation 30min, pours into mold and solidify, be down to room temperature
Demoulding, is made the glass fiber reinforced plastics product material.
Further, the concentrated nitric acid oxidation of short glass fiber is handled in step (1): body being added into short glass fiber
The acetone soln that fraction is 50% after impregnating 20h in 40-50 DEG C of water-bath, is cleaned with distilled water, is done in 60-65 DEG C of baking oven
After dry 10h, it is placed in oxidation processes 50min in concentrated nitric acid, wash with distilled water to neutrality, the dry 10h in 60-65 DEG C of baking oven,
Obtain the short glass fiber of concentrated nitric acid oxidation processing.
Further, modifying agent is propylene oxide copolymer glycols or polyether sulfone in step (1).
Further, epoxy resin is bisphenol A type epoxy resin E-51 in step (2), and promotor is 2-methylimidazole, Gu
Agent is methyl tetrahydro phthalic anhydride.
Further, in step (3) curing process be at room temperature solidify 1h, at 65-75 DEG C solidify 50min,
115-125 DEG C of solidification 55min, solidify 50min at 135-155 DEG C, solidify 25min at 165-175 DEG C.
Embodiment 2
A method of glass fiber reinforced plastics product material is prepared with modified benzoxazine-polyvinyl butyral, which is characterized in that including
Following steps:
(1) preparation of modified benzoxazine glue:
7 parts of benzoxazine resin matrixes, 0.7 part of curing agent phenol are added in the short glass fiber handled to 13 parts of concentrated nitric acid oxidations
Urea formaldehyde, 1.4 parts of modifying agent, 15 parts of solvent butanone, are sealed with preservative film, heat 30min in 80-85 DEG C of oil bath, are made and are changed
Property benzoxazine glue；
(2) polyvinyl butyral toughening-chlorinated paraffin fire retarding epoxide resin preparation:
4 parts of polyvinyl butyrals are added in 110 parts of epoxy resin, heating stirring sufficiently dissolves, and 15 parts of chlorination stones are added
Wax is sufficiently stirred, and 1.5 parts of promotor stirrings are added, and 85 parts of curing agent stirrings are added and obtain toughening-resistance after vacuum defoamation processing
Fire modified epoxy；
(3) casting molding process:
Gained toughening-fire-retardant modified epoxy resin and 0.5 part of polyimides 200 in (2) are heated in 50-55 DEG C of water-bath, mixed
It is down to room temperature after closing uniformly, 20 parts of diluent dehydrated alcohols are added, (1) middle gained modified benzoxazine glue adds after stirring 2h
Enter 8 parts of curing agent diethylenetriamines to be uniformly mixed, in ice bath after vacuum defoamation 35min, pours into mold and solidify, be down to room temperature
Demoulding, is made the glass fiber reinforced plastics product material.
Further, the concentrated nitric acid oxidation of short glass fiber is handled in step (1): body being added into short glass fiber
The acetone soln that fraction is 50% after impregnating 25h in 40-50 DEG C of water-bath, is cleaned with distilled water, is done in 60-65 DEG C of baking oven
After dry 12h, it is placed in oxidation processes 70min in concentrated nitric acid, wash with distilled water to neutrality, the dry 12h in 60-65 DEG C of baking oven,
Obtain the short glass fiber of concentrated nitric acid oxidation processing.
Further, modifying agent is propylene oxide copolymer glycols or polyether sulfone in step (1).
Further, epoxy resin is bisphenol A type epoxy resin E-51 in step (2), and promotor is 2-methylimidazole, Gu
Agent is methyl tetrahydro phthalic anhydride.
Further, in step (3) curing process be at room temperature solidify 2h, at 65-75 DEG C solidify 70min,
115-125 DEG C of solidification 65min, solidify 70min at 135-155 DEG C, solidify 35min at 165-175 DEG C.
Comparative example 1
This comparative example 1 compared with Example 1, is not in step (1) modified benzoxazine resin using modifying agent,
Method and step in addition to this is all the same.
Comparative example 2
This comparative example 2 compared with Example 2, is not added with chlorinated paraffin in step (2), method and step in addition to this is homogeneous
Together.
Control group pure epoxy resin
In order to compare the mechanical property, acid corrosion-resistant performance and flame retardant property of glass fiber reinforced plastics product material produced by the present invention, to upper
State the corresponding obtained glass fiber reinforced plastics product material of embodiment 1, embodiment 2, comparative example 1,2 method of comparative example and right
Performance detection is carried out according to professional standard according to corresponding pure epoxy resin is organized, specific correlation data is as shown in table 1 below:
Table 1
There is excellent mechanical property, acid corrosion-resistant and flame retardant property according to the glass fiber reinforced plastics product material of the method for the present invention production,
Benzoxazine resin is not modified using modifying agent in comparative example 1, leads to resin matrix and fiberglass surfacing
Binding ability reduces, and resin matrix toughness reduces；It is not added with chlorinated paraffin in comparative example 2, leads to glass fiber reinforced plastics product material
The limit oxygen index of material declines, and flame retardant property reduces.
Claims (5)
1. a kind of method for preparing glass fiber reinforced plastics product material with modified benzoxazine-polyvinyl butyral, which is characterized in that packet
Include following steps:
(1) preparation of modified benzoxazine glue:
5-7 parts of benzoxazine resin matrixes, 0.5-0.7 are added in the short glass fiber handled to 10-13 parts of concentrated nitric acid oxidations
Part curing agent phenolic resin, 1-1.4 parts of modifying agent, 10-15 parts of solvent butanone, are sealed with preservative film, are added in 80-85 DEG C of oil bath
Modified benzoxazine glue is made in hot 20-30min；
(2) polyvinyl butyral toughening-chlorinated paraffin fire retarding epoxide resin preparation:
3-4 parts of polyvinyl butyrals are added in 90-110 parts of epoxy resin, heating stirring sufficiently dissolves, and 10-15 is added
Part chlorinated paraffin is sufficiently stirred, and 1-1.5 parts of promotors stirrings are added, and 80-85 parts of curing agent stirrings are added, and vacuum defoamation is handled
Afterwards, toughening-fire-retardant modified epoxy resin is obtained；
(3) casting molding process:
Gained toughening-fire-retardant modified epoxy resin in (2) and 0.4-0.5 parts of polyimides 200 are added in 50-55 DEG C of water-bath
Heat is down to room temperature after mixing, and 15-20 parts of diluent dehydrated alcohols, (1) middle gained modified benzoxazine glue are added, stir
After mixing 1-2h, 6-8 parts of curing agent diethylenetriamines are added and are uniformly mixed, in ice bath after vacuum defoamation 30-35min, pour into mould
Solidify in tool, is down to room temperature demoulding, the glass fiber reinforced plastics product material is made.
2. according to claim 1 a kind of glass fiber reinforced plastics product material is prepared with modified benzoxazine-polyvinyl butyral
Method, which is characterized in that in step (1) short glass fiber concentrated nitric acid oxidation processing:
The acetone soln that volume fraction is 50% is added into short glass fiber, after impregnating 20-25h in 40-50 DEG C of water-bath,
It is cleaned with distilled water, in 60-65 DEG C of baking oven after dry 10-12h, oxidation processes 50-70min in concentrated nitric acid is placed in, with distillation
Water is cleaned to neutrality, and dry 10-12h, obtains the short glass fiber of concentrated nitric acid oxidation processing in 60-65 DEG C of baking oven.
3. according to claim 1 a kind of glass fiber reinforced plastics product material is prepared with modified benzoxazine-polyvinyl butyral
Method, which is characterized in that in step (1) modifying agent be propylene oxide copolymer glycols or polyether sulfone.
4. according to claim 1 a kind of glass fiber reinforced plastics product material is prepared with modified benzoxazine-polyvinyl butyral
Method, which is characterized in that in step (2) epoxy resin be bisphenol A type epoxy resin E-51, promotor is 2-methylimidazole,
Curing agent is methyl tetrahydro phthalic anhydride.
5. according to claim 1 a kind of glass fiber reinforced plastics product material is prepared with modified benzoxazine-polyvinyl butyral
Method, which is characterized in that curing process is to solidify 1-2h at room temperature, at 65-75 DEG C solidify 50- in step (3)
70min, in 115-125 DEG C of solidification 55-65min, at 135-155 DEG C solidify 50-70min, at 165-175 DEG C solidify 25-
35min。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811256247.4A CN109438921A (en) | 2018-10-26 | 2018-10-26 | A method of glass fiber reinforced plastics product material is prepared with modified benzoxazine-polyvinyl butyral |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811256247.4A CN109438921A (en) | 2018-10-26 | 2018-10-26 | A method of glass fiber reinforced plastics product material is prepared with modified benzoxazine-polyvinyl butyral |
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| CN109438921A true CN109438921A (en) | 2019-03-08 |
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| CN201811256247.4A Withdrawn CN109438921A (en) | 2018-10-26 | 2018-10-26 | A method of glass fiber reinforced plastics product material is prepared with modified benzoxazine-polyvinyl butyral |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112480441A (en) * | 2020-11-28 | 2021-03-12 | 安徽实力环保科技有限公司 | Method for improving wear resistance of epoxy glass fiber reinforced plastic |
| CN115895182A (en) * | 2022-08-30 | 2023-04-04 | 山东非金属材料研究所 | Flame-retardant toughened modified phenolic resin film and preparation method thereof |
-
2018
- 2018-10-26 CN CN201811256247.4A patent/CN109438921A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112480441A (en) * | 2020-11-28 | 2021-03-12 | 安徽实力环保科技有限公司 | Method for improving wear resistance of epoxy glass fiber reinforced plastic |
| CN115895182A (en) * | 2022-08-30 | 2023-04-04 | 山东非金属材料研究所 | Flame-retardant toughened modified phenolic resin film and preparation method thereof |
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Application publication date: 20190308 |
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