CN109553789A - A kind of prepreg, composite material and preparation method and application - Google Patents
A kind of prepreg, composite material and preparation method and application Download PDFInfo
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- CN109553789A CN109553789A CN201710890230.3A CN201710890230A CN109553789A CN 109553789 A CN109553789 A CN 109553789A CN 201710890230 A CN201710890230 A CN 201710890230A CN 109553789 A CN109553789 A CN 109553789A
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
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- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
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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
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- 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
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- 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
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
-
- 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
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- 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
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
-
- 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
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
Abstract
The present invention provides a kind of preparation methods of prepreg, comprising: is handled using coupling agent ammonium polyphosphate, to form the ammonium polyphosphate of coupling agent treatment；The ammonium polyphosphate of coupling agent treatment and expansible graphite are added in resin to obtain hybrid resin；And prepreg is prepared by hybrid resin and reinforcing fiber.The present invention also provides a kind of preparation methods of composite material, including prepreg obtained above is laid with 3-7 layers according to 0 ° of direction, using vacuum-bag process technique, obtain composite material after solidification.In the present invention by adjusting the ratio of ammonium polyphosphate modifying and expansible graphite in composite flame-retardant agent, the two can be made to have the function that cooperative flame retardant, flame retardant property reaches best.So as to improve the flame retardant rating of composite material, expand application field, so that prepreg and composite material that the method provided through the invention is prepared can be applied in the fields such as automobile, sports equipment, fitness equipment, aerospace.
Description
Technical field
The present invention relates to a kind of prepreg, more particularly, to a kind of halogen-free flame-retardant prepreg, composite material and it
Preparation method and application.
Background technique
With the development of science and technology, prepreg and composite material gradually increase in various industries application, to prepreg and compound
The flame retardant property of material is also gradually increased.Currently, the majority that fire retardant uses be it is halogen planned, have in combustion
Malicious, harmful gas pollutes environment.
LOI (limit oxygen index) is the flammable bench scale flame assay for assessment material.It is that assessment is various
The relatively flammable process useful of material and also help obtain how may be adapted to require answering for high flame resistance about material
Some instructions.Flame retardant composite material will have higher LOI value 28.3% at present, it is necessary to a large amount of fire retardant be added, if resistance
The addition of combustion agent necessarily will affect whole mechanical property, to influence use scope.In addition, if adding a large amount of halogen primitive elements
Element, combustion process generate pernicious gas, life threatening.Therefore, it is necessary to develop a kind of halogen-free type prepreg and halogen-free type composite woods
Material.
Summary of the invention
In order to solve the problems in the existing technology, according to an aspect of the invention, there is provided a kind of prepreg
Preparation method, comprising: ammonium polyphosphate is handled using coupling agent, to form the ammonium polyphosphate of coupling agent treatment；It will be described
The ammonium polyphosphate and expansible graphite of coupling agent treatment are added in resin to obtain hybrid resin；And by the hybrid resin and
Prepreg is prepared in reinforcing fiber.
In the above preparation method, the coupling agent is compound esters coupling agent, and the compound esters coupling agent is selected from
One of TLZJ-901 type coupling agent, TLZJ-902 type coupling agent or TLZJ-903 type coupling agent or a variety of combinations.
In the above preparation method, described that ammonium polyphosphate is handled using coupling agent, to form coupling agent treatment
The step of ammonium polyphosphate, further comprises: by ammonium polyphosphate and the compound esters coupling agent with the mass ratio of 40:1-60:1
After mixing, rapid dispersion 10-20 minutes under high speed disperser effect, 30-50 DEG C of taking-up obtains described for vacuum drying 3-5 hours
The ammonium polyphosphate of coupling agent treatment.
In the above preparation method, described that ammonium polyphosphate is handled using coupling agent, to form coupling agent treatment
The step of ammonium polyphosphate, further comprises: ammonium polyphosphate is mixed with the compound esters coupling agent with the mass ratio of 50:1
Afterwards, rapid dispersion 15 minutes under high speed disperser effect, 40 DEG C of vacuum drying is taken out and obtain the coupling agent treatment within 4 hours
Ammonium polyphosphate.
In the above preparation method, the ammonium polyphosphate of the coupling agent treatment and the mass ratio of the expansible graphite are
The quality sum of 2.5:1-0.67:1, the ammonium polyphosphate of the coupling agent treatment and the expansible graphite and the matter of the resin
Amount the ratio between be 5-15:100, and the resin be the resin comprising curing agent, and the ammonium polyphosphate of the coupling agent treatment,
The incorporation time of expansible graphite and the resin is 20-40 minutes.
In the above preparation method, the ammonium polyphosphate of the coupling agent treatment and the mass ratio of the expansible graphite are
The quality sum of 1.5:1, the ammonium polyphosphate of the coupling agent treatment and the expansible graphite and the mass ratio of the resin
For 1:10, the resin is selected from one of epoxy resin, bismaleimide resin, cyanic acid resin or a variety of combinations, and the idol
The incorporation time for joining ammonium polyphosphate, the expansible graphite and the resin that agent is handled is 30 minutes.
In the above preparation method, the step of prepreg being prepared by the hybrid resin and reinforcing fiber is further wrapped
It includes: first using film applicator that glue film is prepared the hybrid resin, then use and contain dipping machine for the glue film and reinforcing fiber
Prepreg is prepared.
In the above preparation method, the reinforcing fiber is in glass fibre, carbon fiber, quartz fibre or aramid fiber
One or more combinations.
In the above preparation method, the surface density of the glue film is 65g/m2± 3, the density of the prepreg is 210g/m2
±10。
According to the second aspect of the invention, a kind of prepreg being prepared by above-mentioned preparation method is provided.
According to the third aspect of the present invention, a kind of preparation method of composite material is additionally provided, comprising: will be according to above-mentioned
The prepreg that method is prepared is laid with 3-7 layers according to 0 ° of direction, using vacuum-bag process technique, obtains composite wood after solidification
Material.
According to the fourth aspect of the present invention, a kind of composite material being prepared according to above-mentioned preparation method is provided.
According to the fifth aspect of the present invention, above-mentioned prepreg and above-mentioned composite material are additionally provided in automobile, sport device
Material, fitness equipment, the application in aerospace field.
In the present invention, by the ammonium polyphosphate in the addition coupling agent treatment in hybrid resin, as main resistance
Agent is fired, the compatibility of ammonium polyphosphate and resin can be improved.Meanwhile the expansible graphite in resin due to its own at charcoal
Can, the neat coal amout of material at high temperature is improved, so that phosphorus content is improved in combustion, to play fire-retardant effect.
Therefore, pass through in the present invention while adding ammonium polyphosphate as main fire retardant and expansible graphite as association
Same fire retardant avoids use largely containing halogens, so as to avoid the generation of evil gas in combustion process.And pass through
Experiment discovery, additive amount of the composite flame-retardant agent being made of ammonium polyphosphate with expansible graphite in resin change in 5-15%
When, as the amount of fire retardant increases, flame retardant effect is obviously improved, and when additive amount is 10%, effect is best, and LOI value reaches
29.5%, there is excellent flame retardant property.
In addition, in the present invention by adjusting the ratio of ammonium polyphosphate modifying and expansible graphite in composite flame-retardant agent, it can
So that the two has the function that cooperative flame retardant, flame retardant property reaches best.So as to improve the flame retardant rating of composite material,
Expand application field, so that prepreg and composite material that the method provided through the invention is prepared can be applied to vapour
In the fields such as vehicle, sports equipment, fitness equipment, aerospace.
Detailed description of the invention
It in order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, below will be to institute in embodiment
Attached drawing to be used is needed to be briefly described, it should be apparent that, the accompanying drawings in the following description is only some implementations of the invention
Example, for those of ordinary skill in the art, without creative efforts, can also obtain according to these attached drawings
Obtain other attached drawings.
Fig. 1 shows the process flow of the preparation method of prepreg and composite material according to some embodiments of the present invention
Figure.
Specific embodiment
It in order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, below will be to institute in embodiment
Attached drawing to be used is needed to be briefly described, it should be apparent that, the accompanying drawings in the following description is only some implementations of the invention
Example, for those of ordinary skill in the art, without creative efforts, can also obtain according to these attached drawings
Obtain other attached drawings.In addition, in the present invention, identical reference label indicates identical component.
The preparation method of prepreg and composite material provided by the invention, comprising the following steps:
Step S101: as shown in Figure 1, in this step, being handled using coupling agent ammonium polyphosphate, to form coupling
The ammonium polyphosphate of agent processing, wherein coupling agent is compound esters coupling agent, and compound esters coupling agent is coupled selected from TLZJ-901 type
One of agent, TLZJ-902 type coupling agent or TLZJ-903 type coupling agent or a variety of combinations.Specifically, which includes:
By ammonium polyphosphate and compound esters coupling agent with the mass ratio of 40:1-60:1, it is preferable that mixed with the mass ratio of 50:1
Afterwards, rapid dispersion 10-20 minutes, preferably 15 minutes under high speed disperser effect, take out at 30-50 DEG C, preferably 40 DEG C
Under, it is dried in vacuo 3-5 hours, is preferably dried in vacuo 4 hours and obtains the ammonium polyphosphate of coupling agent treatment.
Step S103: as shown in Figure 1, in this step, the ammonium polyphosphate of coupling agent treatment and expansible graphite are added
To obtain hybrid resin in resin, wherein the ammonium polyphosphate of coupling agent treatment and the mass ratio of expansible graphite are 2.5:1-
0.67:1, it is preferable that 1.5:1；The ammonium polyphosphate of coupling agent treatment and the quality sum of expansible graphite and the quality of resin it
Than for 5-15:100, it is preferable that 1:10；And resin be the resin comprising curing agent, and the ammonium polyphosphate of coupling agent treatment,
The incorporation time of expansible graphite and resin is 20-40 minutes, and preferably incorporation time is 30 minutes.Resin be selected from epoxy resin,
One of bismaleimide resin, cyanic acid resin or a variety of combinations.
Step S105: as shown in Figure 1, in this step, prepreg is prepared by the hybrid resin and reinforcing fiber.
Specifically, first use film applicator that surface density is prepared as 65g/m hybrid resin2± 3 glue film, then using will containing dipping machine
It is 210g/m that density, which is prepared, in glue film and reinforcing fiber2± 10 prepreg, reinforcing fiber be selected from glass fibre, carbon fiber,
One of quartz fibre or aramid fiber or a variety of combinations.
Step S107: as shown in Figure 1, in this step, being laid with 3-7 layers according to 0 ° of direction for above-mentioned prepreg, and preferably 5
Layer, using vacuum-bag process technique, obtains composite material after solidification.
It can be with as composite flame-retardant agent one side by adding ammonium polyphosphate and expansible graphite simultaneously in the present invention
Up to 29.5% LOI value is obtained, it on the other hand, can be to avoid largely containing the use of halogens, so as to avoid burned
The generation of evil gas in journey.So that the prepreg and composite material that are prepared by the above method can be applied to automobile, body
It educates in the fields such as equipment, fitness equipment, aerospace.
Embodiment 1
1, the processing of ammonium polyphosphate (APP): by ammonium polyphosphate and TLZJ-901 type coupling agent according to the mass ratio of 50:1,
It is added in beaker, is acted on rapid dispersion 15 minutes in high speed disperser, take out 40 DEG C of vacuum drying and obtain coupling agent treatment in 4 hours
Ammonium polyphosphate, as T-APP.
2, the preparation of hybrid resin: by the ammonium polyphosphate (T-APP) of coupling agent treatment and expansible graphite (EG) according to one
Determine mass ratio 0.67:1 to be added in epoxy resin, wherein the ammonium polyphosphate (T-APP) and expansible graphite (EG) of coupling agent treatment
Quality sum and epoxy resin mass ratio be 1:10, rapid dispersion uniform 30 minutes, obtain the hybrid resin of anti-flammability.
3, the preparation of prepreg: first use film applicator that surface density is prepared the above-mentioned hybrid resin with flame retarding function
For 65g/m2Then the glue film of ± 3g uses and density is prepared as 210g/m in the glue film and glass fibre containing dipping machine2±10
Prepreg.
4, the preparation of composite material: and then according to 0 ° of direction laying, 5 layers, using vacuum-bag process technique, solidification obtains sample
Product.
5, performance test: the composite material being prepared by the above method is tested for the property, wherein material it is curved
Qu Qiangdu is tested according to GB/T 9341-2008, tensile strength is tested according to GB/T1447-2005 and limit oxygen index (LOI) is pressed
It is tested according to GB/T 2406-1993.
Embodiment 2
1, the processing of ammonium polyphosphate (APP): by ammonium polyphosphate and TLZJ-903 type coupling agent according to the mass ratio of 60:1,
It is added in beaker, is acted on rapid dispersion 15 minutes in high speed disperser, take out 50 DEG C of vacuum drying and obtain coupling agent treatment in 5 hours
Ammonium polyphosphate, as T-APP.
2, the preparation of hybrid resin: by the ammonium polyphosphate (T-APP) of coupling agent treatment and expansible graphite (EG) according to one
Determine mass ratio 1:1 to be added in bismaleimide resin, the quality of the ammonium polyphosphate (T-APP) of coupling agent treatment and expansible graphite (EG) it
With with the mass ratio of bismaleimide resin be 1:10, rapid dispersion uniform 40 minutes, obtain the hybrid resin of anti-flammability.
3, the preparation of prepreg: first use film applicator that surface density is prepared the above-mentioned hybrid resin with flame retarding function
For 65g/m2Then the glue film of ± 3g uses and density is prepared as 210g/m in the glue film and carbon fiber containing dipping machine2± 10
Prepreg.
4, the preparation of composite material: and then according to 0 ° of direction laying, 6 layers, using vacuum-bag process technique, solidification obtains sample
Product.
5, performance test: the composite material being prepared by the above method is tested for the property, wherein material it is curved
Qu Qiangdu is tested according to GB/T 9341-2008, tensile strength is tested according to GB/T1447-2005 and limit oxygen index (LOI) is pressed
It is tested according to GB/T 2406-1993.
Embodiment 3
1, the processing of ammonium polyphosphate (APP): by ammonium polyphosphate and TLZJ-902 type coupling agent according to the mass ratio of 40:1,
It is added in beaker, is acted on rapid dispersion 10 minutes in high speed disperser, take out 30 DEG C of vacuum drying and obtain coupling agent treatment in 3 hours
Ammonium polyphosphate, as T-APP.
2, the preparation of hybrid resin: by the ammonium polyphosphate (T-APP) of coupling agent treatment and expansible graphite (EG) according to one
Determine mass ratio 1.5:1 to be added in cyanic acid resin, wherein the ammonium polyphosphate (T-APP) and expansible graphite (EG) of coupling agent treatment
Quality sum and cyanic acid resin mass ratio be 1:20, rapid dispersion uniform 20 minutes, obtain the hybrid resin of anti-flammability.
3, the preparation of prepreg: first use film applicator that surface density is prepared the above-mentioned hybrid resin with flame retarding function
For 65g/m2Then the glue film of ± 3g uses and density is prepared as 210g/m in the glue film and glass fibre containing dipping machine2±10
Prepreg.
4, the preparation of composite material: and then according to 0 ° of direction laying, 4 layers, using vacuum-bag process technique, solidification obtains sample
Product.
5, performance test: the composite material being prepared by the above method is tested for the property, wherein material it is curved
Qu Qiangdu is tested according to GB/T 9341-2008, tensile strength is tested according to GB/T1447-2005 and limit oxygen index (LOI) is pressed
It is tested according to GB/T 2406-1993.
Embodiment 4
1, the processing of ammonium polyphosphate (APP): by ammonium polyphosphate and TLZJ-901 type coupling agent according to the mass ratio of 50:1,
It is added in beaker, is acted on rapid dispersion 20 minutes in high speed disperser, take out 45 DEG C of vacuum drying and obtain at coupling agent for 3.5 hours
The ammonium polyphosphate of reason, as T-APP.
2, the preparation of hybrid resin: by the ammonium polyphosphate (T-APP) of coupling agent treatment and expansible graphite (EG) according to one
Determine mass ratio 1.5:1 to be added in epoxy resin, wherein the ammonium polyphosphate (T-APP) and expansible graphite (EG) of coupling agent treatment
Quality sum and epoxy resin mass ratio be 7:100, rapid dispersion uniform 30 minutes, obtain the hydridization tree of anti-flammability
Rouge.
3, the preparation of prepreg: first use film applicator that surface density is prepared the above-mentioned hybrid resin with flame retarding function
For 65g/m2Then the glue film of ± 3g uses and density is prepared as 210g/m in the glue film and quartz fibre containing dipping machine2±10
Prepreg.
4, the preparation of composite material: and then according to 0 ° of direction laying, 5 layers, using vacuum-bag process technique, solidification obtains sample
Product.
5, performance test: the composite material being prepared by the above method is tested for the property, wherein material it is curved
Qu Qiangdu is tested according to GB/T 9341-2008, tensile strength is tested according to GB/T1447-2005 and limit oxygen index (LOI) is pressed
It is tested according to GB/T 2406-1993.
Embodiment 5
1, the processing of ammonium polyphosphate (APP): by ammonium polyphosphate and TLZJ-901 type coupling agent according to the mass ratio of 55:1,
It is added in beaker, is acted on rapid dispersion 18 minutes in high speed disperser, take out 45 DEG C of vacuum drying and obtain at coupling agent for 4.5 hours
The ammonium polyphosphate of reason, as T-APP.
2, the preparation of hybrid resin: by the ammonium polyphosphate (T-APP) of coupling agent treatment and expansible graphite (EG) according to one
Determine mass ratio 1.5:1 to be added in bismaleimide resin, the ammonium polyphosphate (T-APP) of coupling agent treatment and the quality of expansible graphite (EG)
The sum of with the mass ratio of bismaleimide resin be 1:10, rapid dispersion uniform 40 minutes, obtain the hybrid resin of anti-flammability.
3, the preparation of prepreg: first use film applicator that surface density is prepared the above-mentioned hybrid resin with flame retarding function
For 65g/m2Then the glue film of ± 3g uses and density is prepared as 210g/m in the glue film and aramid fiber containing dipping machine2±10
Prepreg.
4, the preparation of composite material: and then according to 0 ° of direction laying, 5 layers, using vacuum-bag process technique, solidification obtains sample
Product.
5, performance test: the composite material being prepared by the above method is tested for the property, wherein material it is curved
Qu Qiangdu is tested according to GB/T 9341-2008, tensile strength is tested according to GB/T1447-2005 and limit oxygen index (LOI) is pressed
It is tested according to GB/T 2406-1993.
Embodiment 6
1, the processing of ammonium polyphosphate (APP): by ammonium polyphosphate and TLZJ-901 type coupling agent according to the mass ratio of 45:1,
It is added in beaker, is acted on rapid dispersion 12 minutes in high speed disperser, take out 30 DEG C of vacuum drying and obtain coupling agent treatment in 5 hours
Ammonium polyphosphate, as T-APP.
2, the preparation of hybrid resin: by the ammonium polyphosphate (T-APP) of coupling agent treatment and expansible graphite (EG) according to one
Determine mass ratio 1.5:1 to be added in cyanic acid resin, wherein the ammonium polyphosphate (T-APP) and expansible graphite (EG) of coupling agent treatment
Quality sum and cyanic acid resin mass ratio be 15:100, rapid dispersion uniform 30 minutes, obtain the hydridization tree of anti-flammability
Rouge.
3, the preparation of prepreg: first use film applicator that surface density is prepared the above-mentioned hybrid resin with flame retarding function
For 65g/m2Then the glue film of ± 3g uses and density is prepared as 210g/m in the glue film and quartz fibre containing dipping machine2±10
Prepreg.
4, the preparation of composite material: and then according to 0 ° of direction laying, 6 layers, using vacuum-bag process technique, solidification obtains sample
Product.
5, performance test: the composite material being prepared by the above method is tested for the property, wherein material it is curved
Qu Qiangdu is tested according to GB/T 9341-2008, tensile strength is tested according to GB/T1447-2005 and limit oxygen index (LOI) is pressed
It is tested according to GB/T 2406-1993.
Embodiment 7
1, the processing of ammonium polyphosphate (APP): by ammonium polyphosphate and TLZJ-902 type coupling agent according to the mass ratio of 60:1,
It is added in beaker, is acted on rapid dispersion 20 minutes in high speed disperser, take out 40 DEG C of vacuum drying and obtain coupling agent treatment in 4 hours
Ammonium polyphosphate, as T-APP.
2, the preparation of hybrid resin: by the ammonium polyphosphate (T-APP) of coupling agent treatment and expansible graphite (EG) according to one
Determine mass ratio 2:1 to be added in epoxy resin, wherein the ammonium polyphosphate (T-APP) of coupling agent treatment and expansible graphite (EG)
Quality sum and the mass ratio of epoxy resin are 1:10, rapid dispersion uniform 30 minutes, obtain the hybrid resin of anti-flammability.
3, the preparation of prepreg: first use film applicator that surface density is prepared the above-mentioned hybrid resin with flame retarding function
For 65g/m2Then the glue film of ± 3g uses and density is prepared as 210g/m in the glue film and glass fibre containing dipping machine2±10
Prepreg.
4, the preparation of composite material: and then according to 0 ° of direction laying, 5 layers, using vacuum-bag process technique, solidification obtains sample
Product.
5, performance test: the composite material being prepared by the above method is tested for the property, wherein material it is curved
Qu Qiangdu is tested according to GB/T 9341-2008, tensile strength is tested according to GB/T1447-2005 and limit oxygen index (LOI) is pressed
It is tested according to GB/T 2406-1993.
Embodiment 8
1, the processing of ammonium polyphosphate (APP): by ammonium polyphosphate and TLZJ-903 type coupling agent according to the mass ratio of 52:1,
It is added in beaker, is acted on rapid dispersion 18 minutes in high speed disperser, take out 35 DEG C of vacuum drying and obtain at coupling agent for 3.5 hours
The ammonium polyphosphate of reason, as T-APP.
2, the preparation of hybrid resin: by the ammonium polyphosphate (T-APP) of coupling agent treatment and expansible graphite (EG) according to one
Determine mass ratio 2.5:1 to be added in cyanic acid resin, wherein the ammonium polyphosphate (T-APP) and expansible graphite (EG) of coupling agent treatment
Quality sum and cyanic acid resin mass ratio be 1:10, rapid dispersion uniform 25 minutes, obtain the hybrid resin of anti-flammability.
3, the preparation of prepreg: first use film applicator that surface density is prepared the above-mentioned hybrid resin with flame retarding function
For 65g/m2Then the glue film of ± 3g uses and density is prepared as 210g/m in the glue film and glass fibre containing dipping machine2±10
Prepreg.
4, the preparation of composite material: and then according to 0 ° of direction laying, 7 layers, using vacuum-bag process technique, solidification obtains sample
Product.
5, performance test: the composite material being prepared by the above method is tested for the property, wherein material it is curved
Qu Qiangdu is tested according to GB/T 9341-2008, tensile strength is tested according to GB/T1447-2005 and limit oxygen index (LOI) is pressed
It is tested according to GB/T 2406-1993.
Comparative example
It is consistent with the preparation method of embodiment 1, unlike, in this embodiment, it is added without by the poly- of coupling agent treatment
The composite flame-retardant agent of ammonium phosphate (T-APP) and expansible graphite (EG) composition.Then, according to the test method of embodiment 1, respectively
Test its bending strength, tensile strength and limit oxygen index.
Ammonium polyphosphate (T-APP) and the inflatable stone of each embodiment described above and the coupling agent treatment in comparative example
The mass ratio of the mass ratio of black (EG) and the quality sum of T-APP and EG and resin and its about tensile strength,
Bending strength and the test result of LOI/% are shown in Table 1, and number 1-8, which is respectively corresponded, indicates embodiment 1-8, and number 9 indicates that comparison is real
Apply example.
The specific type and content of the used additive of formula are as shown in table 1.In table 1, the content of additive is
The mass percent being calculated based on formula gross mass.
Table 1
By above-mentioned experimental result it is found that when additive amount of the composite flame-retardant agent in resin changes in 5-15%, it is compound with
The increase of the additive amount of fire retardant, flame retardant effect be obviously improved, additive amount be 10% when effect it is best, LOI value reaches
29.5%, there is excellent flame retardant property.In the present invention by adjusting ammonium polyphosphate modifying in composite flame-retardant agent and may expand
The ratio of graphite can make the two have the function that cooperative flame retardant, and flame retardant property reaches best.So as to improve composite wood
The flame retardant rating of material expands application field, so that prepreg and composite material that the method provided through the invention is prepared
It can be applied in the fields such as automobile, sports equipment, fitness equipment, aerospace.
The above is merely preferred embodiments of the present invention, be not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (13)
1. a kind of preparation method of prepreg characterized by comprising
Ammonium polyphosphate is handled using coupling agent, to form the ammonium polyphosphate of coupling agent treatment；
The ammonium polyphosphate of the coupling agent treatment and expansible graphite are added in resin to obtain hybrid resin；And
Prepreg is prepared by the hybrid resin and reinforcing fiber.
2. preparation method according to claim 1, which is characterized in that the coupling agent is compound esters coupling agent, described
Compound esters coupling agent is selected from one of TLZJ-901 type coupling agent, TLZJ-902 type coupling agent or TLZJ-903 type coupling agent
Or a variety of combination.
3. preparation method according to claim 2, which is characterized in that it is described using coupling agent to ammonium polyphosphate at
The step of reason, ammonium polyphosphate to form coupling agent treatment includes:
After ammonium polyphosphate is mixed with the compound esters coupling agent with the mass ratio of 40:1-60:1, make in high speed disperser
With lower rapid dispersion 10-20 minutes, takes out 30-50 DEG C of vacuum drying and obtain the ammonium polyphosphate of the coupling agent treatment in 3-5 hours.
4. preparation method according to claim 3, which is characterized in that it is described using coupling agent to ammonium polyphosphate at
The step of reason, ammonium polyphosphate to form coupling agent treatment, further comprises:
It is fast under high speed disperser effect after ammonium polyphosphate is mixed with the compound esters coupling agent with the mass ratio of 50:1
Speed dispersion 15 minutes takes out 40 DEG C of vacuum drying and obtains the ammonium polyphosphate of the coupling agent treatment in 4 hours.
5. preparation method according to claim 1, which is characterized in that the ammonium polyphosphate of the coupling agent treatment and it is described can
The mass ratio of expanded graphite is 2.5:1-0.67:1, the matter of the ammonium polyphosphate of the coupling agent treatment and the expansible graphite
The sum of amount and the mass ratio of the resin are 5-15:100, and the resin is the resin comprising curing agent, and described
The incorporation time of the ammonium polyphosphate of coupling agent treatment, expansible graphite and the resin is 20-40 minutes.
6. preparation method according to claim 1, which is characterized in that the ammonium polyphosphate of the coupling agent treatment and it is described can
The mass ratio of expanded graphite is 1.5:1, the quality sum of the ammonium polyphosphate of the coupling agent treatment and the expansible graphite
Mass ratio with the resin is 1:10, and the resin is selected from one of epoxy resin, bismaleimide resin, cyanic acid resin or more
The combination of kind, and the incorporation time of the ammonium polyphosphate of the coupling agent treatment, the expansible graphite and the resin is 30
Minute.
7. preparation method according to claim 1, which is characterized in that described to be prepared by the hybrid resin and reinforcing fiber
The step of obtaining prepreg include:
It first uses film applicator that glue film is prepared the hybrid resin, then uses containing dipping machine by the glue film and reinforcing fiber
Prepreg is prepared.
8. preparation method according to claim 7, which is characterized in that the reinforcing fiber be selected from glass fibre, carbon fiber,
One of quartz fibre or aramid fiber or a variety of combinations.
9. preparation method according to claim 7, which is characterized in that the surface density of the glue film is 65g/m2± 3, it is described
The density of prepreg is 210g/m2±10。
10. a kind of prepreg as made from preparation method of any of claims 1-9.
11. a kind of preparation method of composite material, comprising: method of any of claims 1-9 to be prepared
Prepreg is laid with 3-7 layers according to 0 ° of direction, using vacuum-bag process technique, obtains composite material after solidification.
12. composite material made from a kind of preparation method as described in claim 11.
13. composite material described in prepreg according to claim 10 and claim 12 is in automobile, sports equipment, strong
Application in body equipment, aerospace field.
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