CN104262622B - The preparation method of the in-situ inserted solution of carboxylated graphene oxide Benzoxazine nanocomposite - Google Patents
The preparation method of the in-situ inserted solution of carboxylated graphene oxide Benzoxazine nanocomposite Download PDFInfo
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Abstract
The preparation method of the in-situ inserted solution of a kind of carboxylated graphene oxide Benzoxazine nanocomposite, step is as follows: with natural flake graphite as raw material, prepares graphite oxide by the Hummers method improved；Graphite oxide is carried out chemical modification by chloroactic acid method to it, obtains carboxylated graphene oxide；Carboxylated graphene oxide ultrasonic disperse is obtained carboxylated graphene oxide solution in organic solvent；Again Benzoxazine performed polymer is dissolved in organic solvent and obtains Benzoxazine prepolymer solution；Use in-situ inserted solution polymerization process, carboxylated graphene oxide solution is blended with Benzoxazine prepolymer solution and prepares in-situ inserted solution.Present invention process is simple, raw material is easy to get and adds carboxylated graphene oxide and reduces the solidification temperature of compound resin, improve processability and glass transition temperature, resin heat resistance strengthens, and has great application prospect in fields such as copper-clad plate, laminate, spacecrafts.
Description
Technical field
The invention belongs to polymer material science and field of engineering technology, more particularly to a kind of carboxyl
Change the preparation method of the in-situ inserted solution of graphene oxide Benzoxazine nanocomposite.
Background technology
Benzoxazine is the class benzo six with phenols, aldehydes and primary amine compound as Material synthesis
The intermediate of unit's heterocycle structure, ring-opening polymerisation under heating or catalyst action, generate nitrogenous and class
Like the network structure of phenolic resin, referred to as polybenzoxazine or benzoxazine resins (BOZ) (Yagci
Y,et al.Journal of Polymer Science:Part A,2009,47,5565；Wu Y,Zeng M,
et al.Tribology International,2012,54,51).Benzoxazine resins has good heat-resisting
Property, moisture-proof, mechanical performance and electric property, it essential difference is in that with phenolic resin
Not having little molecule to discharge during forming and hardening, goods porosity is low, shrinks close to zero, and energy
Enough carry out Molecular Design according to performance requirement within the specific limits.Benzoxazine resins is as one
Kind has the great application prospect of excellent heat resistance, anti-flammability, insulating properties and physical and mechanical properties
Resin, its scientific research and engineering development all have the biggest development space.But benzoxazine resins
Also there are some shortcomings, the high further application limiting it of as big in fragility, heat curing temperature.
Natural flake graphite is a kind of raw material being easy to get, and graphite oxide is the oxidation product of graphite,
Heat, power, the effect such as ultrasonic is lower can peel off by genetic horizon-layer, obtains graphene oxide.Carboxylated aoxidizes
Graphene (GO-COOH) be carry out further on the basis of graphite oxide carboxylated (Park KW,
Jung JH.Journal of Power Sources,2012,199,379).Carboxylated graphene oxide table
Face, rich in carboxyl, on the one hand can occur chemistry and hydroxyl effect to strengthen and to be polymerized with Benzoxazine
The compatibility of thing, on the other hand carboxyl can also be catalyzed the solidification of benzoxazine resins, thus reduces
The solidification temperature of benzoxazine resins.It is additionally, since carboxylated graphene oxide and Benzoxazine tree
Interaction between fat and preferably compatibility are such that it is able to improve the calorifics of benzoxazine resins
Performance.
Reduction solidification temperature is one of important process of modified benzoxazine resins, mainly by dividing
Son design synthesizing new benzoxazine resins reduces heat curing temperature and interpolation catalyst reduces benzo
The solidification temperature of piperazine resin.
International monopoly 00/00535 discloses Benzoxazine cationic initiator PCl5、PCl3、POCl3、
TiCl5Etc. making Benzoxazine ring-opening polymerisation at 150 DEG C.International monopoly WO2008/034753
Disclose nitrogen heterocyclic ring and derivative (such as imidazoles) thereof and urging that organic sulfonic acid and derivative thereof form
Agent can solidify benzoxazine resins at 130～160 DEG C.
Agag T utilizes sol-gel process to prepare the hybrid inorganic-organic material of benzoxazine resins and titanium
Material.With pure Benzoxazine resin-phase ratio, curing initiation temperature declines 30～70 DEG C, heat endurance and residual
Carbon rate is all improved (Agag T, et al.Polymer, 2004,45:7903).Zeng M uses height
Graphite oxide and benzoxazine resins are carried out being blended by speed planetary ball mill method, intercalation, then hot setting
Obtaining graphite oxide Benzoxazine nanocomposite, graphite oxide contains carboxyl functional group, has
The ability of catalytic curing Benzoxazine, reduces the solidification temperature of benzoxazine resins, also carries simultaneously
High the heat endurance of benzoxazine resins (Zeng M, et al.Polymer, 2013,54,3107).
Carboxyl functional group can promote the solidification of benzoxazine resins, reduces solidification temperature, but so far
Till the most do not utilize carboxylated graphene oxide and benzoxazine resins that preparation nano combined is blended
Resin reduces the report of the solidification temperature of benzoxazine resins.
Summary of the invention
For above-mentioned problems of the prior art, it is an object of the invention to provide a kind of carboxylated
The preparation method of the in-situ inserted solution of graphene oxide Benzoxazine nanocomposite.
In order to realize the purpose of foregoing invention, the present invention adopts the following technical scheme that
A kind of system of the in-situ inserted solution of carboxylated graphene oxide Benzoxazine nanocomposite
Preparation Method, comprises the following steps:
(1) with natural flake graphite as raw material, oxidation is prepared by the Hummers method improved
Graphite；
(2) gained graphite oxide is carried out chemical modification by chloroactic acid method to it, obtain carboxylated
Graphene oxide；
(3) gained carboxylated graphene oxide is scattered in organic solvent, ultrasonically treated after obtain
Carboxylated graphene oxide solution；
(4) Benzoxazine performed polymer is dissolved in organic solvent, and is sufficiently stirred for dissolving, prepare matter
Amount concentration is 10%～25% Benzoxazine prepolymer solution；
(5) in-situ inserted solution polymerization process is used, in mass ratio, by 0.5%～5% carboxylated oxidation
Graphene solution and 95%～99.5% Benzoxazine prepolymer solution are blended, and prepare in-situ inserted solution.
In-situ inserted for gained solution is vacuumized at 80～100 DEG C degassing 1～2h, then at
150～190 DEG C of curing reactions 4～20h, make the carboxylated nano combined tree of graphene oxide Benzoxazine
Fat.
Further, the particle diameter of the natural flake graphite raw material described in step (1) is 20～50 μm.
Further, the Hummers method of the improvement described in step (1) prepares graphite oxide,
It is in sulfuric acid/phosphoric acid mixed liquor that natural flake graphite is joined 9:1, stirs, add permanganic acid
Potassium；Being specially in mass ratio, natural flake graphite accounts for 1%～3%, and sulfuric acid/phosphoric acid mixed liquor accounts for
79%～93%, potassium permanganate accounts for 6%～18%；Control concentrated sulfuric acid temperature 0～10 DEG C, react 30～60
min；It is warming up to 45～55 DEG C, reacts 12～24h；Product passes through centrifuge washing to without sulfuric acid
After radical ion, in 40～80 DEG C of drying, prepare graphite oxide.
Further, described in step (2), by chloroactic acid method, graphite oxide is carried out chemical modification,
It is specially and gained graphite oxide in step (1) is configured to the solution of 2mg/mL, the most ultrasonic
1～2h, add NaOH and monoxone ultrasonic 2～3h, be washed to neutral being dried and prepare carboxylated
Graphene oxide, the most in mass ratio, graphite oxide accounts for 0.45%～0.5%, NaOH
53.55%～48.5%, monoxone accounts for 46%～51%.
Further, the carboxylated graphene oxide solution ultrasonication described in step (3) is:
Carboxylated graphene oxide solution is carried out in ice-water bath 10～30min ultrasonically treated, ultrasonic power
It is 400～800W.
Further, described Benzoxazine performed polymer includes the monoamine of single functionality and single phenolic benzene
And piperazine, the bisphenol-A of bifunctionality, Bisphenol F and two amine type Benzoxazine, polyfunctionality benzo
Piperazine, bis-phenol main chain and two amine type main chain Benzoxazine and naphthalene system Benzoxazine, described benzo
Piperazine performed polymer need not purify before use.
Further, the organic solvent described in step (3) and step (4) be ethanol, acetone,
Toluene.
Owing to using above technical scheme, the beneficial effect comprise that
The original position of a kind of carboxylated graphene oxide Benzoxazine nanocomposite that the present invention provides
In the preparation method of intercalation solution, prepared carboxylated surface of graphene oxide contains substantial amounts of carboxylic
Base, improves the compatibility of itself and macromolecule resin, can realize it well at Benzoxazine high score
Uniformly and stably dispersion in subbase body.
The original position of a kind of carboxylated graphene oxide Benzoxazine nanocomposite that the present invention provides
In the preparation method of intercalation solution, use in-situ inserted solution polymerization process, utilize carboxylated to aoxidize stone
Active oxy radical and macromolecule resin network that ink alkene surface is abundant form certain physics and chemistry
Interact, construct novel high polymer compound resin network structure, prepare carboxylated graphite oxide
Alkene Benzoxazine nanocomposite.This modified heat convertible resin, maintain or improves benzo
Piperazine resin solidification ungauged regions, good heat resistance, moisture-proof, mechanical performance and electric property, and
There is the solidification temperature of reduction, faster solidification rate, the processing characteristics of improvement and higher glass
Change the performances such as transition temperature.
The original position of a kind of carboxylated graphene oxide Benzoxazine nanocomposite that the present invention provides
In the preparation method of intercalation solution, single factor test organon is used to regulate carboxylated oxygen by series of studies
Graphite and the mass ratio of benzoxazine resins performed polymer, prepared the nanometer of excellent performance again
Resin.
Present invention process is simple, raw material is easy to get, prepared compound resin copper-clad plate, laminate,
The fields such as spacecraft, friction material, resin transfer moulding (RTM) are with a wide range of applications.
Accompanying drawing explanation
Consolidating of the carboxylated graphene oxide Benzoxazine nanocomposite that Fig. 1 provides for the present invention
Change batten figure, wherein:
A represents that carboxylated graphene oxide mass ratio accounts for carboxylated graphene oxide after the solidification of 0%
Benzoxazine nanocomposite, i.e. pure after solidification benzoxazine resins；
B represents that carboxylated graphene oxide mass ratio accounts for carboxylated graphene oxide after the solidification of 1%
Benzoxazine nanocomposite；
C represents that carboxylated graphene oxide mass ratio accounts for carboxylated graphene oxide after the solidification of 3%
Benzoxazine nanocomposite.
Detailed description of the invention
In order to make the purpose of the present invention, technical scheme and advantage clearer, below in conjunction with attached
The present invention is described in further detail by figure and embodiment.Should be appreciated that described herein specifically
Embodiment only in order to explain the present invention, is not intended to limit the present invention.
Embodiment 1
A kind of system of the in-situ inserted solution of carboxylated graphene oxide Benzoxazine nanocomposite
Preparation Method, specifically comprises the following steps that
With particle diameter 20 μm natural flake graphite as raw material, prepared by the Hummers method improved
Graphite oxide, is specially in sulfuric acid/phosphoric acid mixed liquor that natural flake graphite joins 9:1, stirs
Mixing, add potassium permanganate, in mass ratio, natural flake graphite accounts for 2%, and sulfuric acid/phosphoric acid mixed liquor accounts for
86%, potassium permanganate accounts for 12%, controls concentrated sulfuric acid temperature 4 DEG C, reacts 45min, is warming up to 50
DEG C, react 14h, after product is by centrifuge washing to sulfate radical-free ion, in 55 DEG C of drying,
Prepare graphite oxide；Gained graphite oxide is carried out chemical modification to it, specifically by chloroactic acid method
For gained graphite oxide being configured to the solution of 2mg/mL, the most ultrasonic 1h, add hydroxide
Sodium and the ultrasonic 2h of monoxone, be washed to neutral being dried and prepare carboxylated graphene oxide, wherein by matter
Amount ratio, graphite oxide accounts for 0.45%, and NaOH 53.55%, monoxone accounts for 46%；Further will
The carboxylated graphene oxide of gained is scattered in alcohol solvent, and solution is through the ultrasonic place of power 500W
Reason 20min, obtains the carboxylated graphene oxide solution being effectively peeled off；Again by phenol type benzo
Piperazine performed polymer is dissolved in alcohol solvent, and is sufficiently stirred for dissolving, and obtaining mass concentration is 15% phenol
Type Benzoxazine prepolymer solution.Use in-situ inserted solution polymerization process, in mass ratio, by 3% institute
Obtain carboxylated graphene oxide solution and system is blended with 97% gained phenol type Benzoxazine prepolymer solution
For obtaining in-situ inserted solution.
In-situ inserted for gained solution is vacuumized at 100 DEG C degassing 2h, anti-then at 190 DEG C of solidifications
Answer 4h, prepare carboxylated graphene oxide Benzoxazine nanocomposite.Gained compound resin
Index can be shown in Table 1.
Embodiment 2
A kind of system of the in-situ inserted solution of carboxylated graphene oxide Benzoxazine nanocomposite
Preparation Method, specifically comprises the following steps that
With particle diameter 24 μm natural flake graphite as raw material, prepared by the Hummers method improved
Graphite oxide, is specially in sulfuric acid/phosphoric acid mixed liquor that natural flake graphite joins 9:1, stirs
Mixing, add potassium permanganate, in mass ratio, natural flake graphite accounts for 1%, and sulfuric acid/phosphoric acid mixed liquor accounts for
93%, potassium permanganate accounts for 6%, controls concentrated sulfuric acid temperature 6 DEG C, reacts 50min, is warming up to 55 DEG C,
Reaction 24h, after product is by centrifuge washing to sulfate radical-free ion, in 50 DEG C of drying, system
Obtain graphite oxide；Gained graphite oxide is carried out chemical modification by chloroactic acid method to it, is specially
Graphite oxide is configured to the solution of 2mg/mL, the most ultrasonic 1.5h, add NaOH and
The ultrasonic 2h of monoxone, is washed to neutral being dried and prepares carboxylated graphene oxide, the most in mass ratio,
Graphite oxide accounts for 0.45%, and NaOH 53.55%, monoxone accounts for 46%；Further by gained
Carboxylated graphene oxide is scattered in alcohol solvent, and solution is through power 500W ultrasonically treated 20
Min, obtains the carboxylated graphene oxide solution being effectively peeled off；Again by phenol type Benzoxazine pre-polymerization
Body is dissolved in alcohol solvent, and is sufficiently stirred for dissolving, and obtaining mass concentration is 25% phenol type benzo
Piperazine prepolymer solution.Use in-situ inserted solution polymerization process, in mass ratio, by 1% gained carboxyl
Change graphene oxide solution is blended with 99% gained phenol type Benzoxazine prepolymer solution and prepares
In-situ inserted solution.
In-situ inserted for gained solution is vacuumized at 100 DEG C degassing 2h, anti-then at 170 DEG C of solidifications
Answer 10h, prepare carboxylated graphene oxide Benzoxazine nanocomposite.Gained compound resin
Performance indications are shown in Table 1.
Embodiment 3
A kind of system of the in-situ inserted solution of carboxylated graphene oxide Benzoxazine nanocomposite
Preparation Method, specifically comprises the following steps that
With particle diameter 30 μm natural flake graphite as raw material, prepared by the Hummers method improved
Graphite oxide, is specially in sulfuric acid/phosphoric acid mixed liquor that natural flake graphite joins 9:1, stirs
Mixing, add potassium permanganate, in mass ratio, natural flake graphite accounts for 3%, and sulfuric acid/phosphoric acid mixed liquor accounts for
79%, potassium permanganate accounts for 18%, controls concentrated sulfuric acid temperature 5 DEG C, reacts 60min, is warming up to 55
DEG C, react 24h, after product is by centrifuge washing to sulfate radical-free ion, in 60 DEG C of drying,
Prepare graphite oxide；Gained graphite oxide is carried out chemical modification to it, specifically by chloroactic acid method
For graphite oxide being configured to the solution of 2mg/mL, the most ultrasonic 1h, add NaOH and
The ultrasonic 2h of monoxone, is washed to neutral being dried and prepares carboxylated graphene oxide, the most in mass ratio,
Graphite oxide accounts for 0.5%, and NaOH 48.5%, monoxone accounts for 51%；Further by the carboxylic of gained
Base graphene oxide is scattered in alcohol solvent, solution through the ultrasonically treated 20min of power 500W,
Obtain the carboxylated graphene oxide solution being effectively peeled off；Again by molten for phenol type Benzoxazine performed polymer
In alcohol solvent, and being sufficiently stirred for dissolving, obtaining mass concentration is 20% phenol type Benzoxazine
Prepolymer solution.Use in-situ inserted solution polymerization process, in mass ratio, by 5% gained carboxylated oxygen
Functionalized graphene solution and 95% gained phenol type Benzoxazine prepolymer solution are blended and prepare in situ
Intercalation solution.
In-situ inserted for gained solution is vacuumized at 90 DEG C degassing 2h, then at 160 DEG C of curing reactions
20h, prepares carboxylated graphene oxide Benzoxazine nanocomposite.Gained compound resin performance
Index is shown in Table 1.
Embodiment 4
A kind of system of the in-situ inserted solution of carboxylated graphene oxide Benzoxazine nanocomposite
Preparation Method, specifically comprises the following steps that
With particle diameter 30 μm natural flake graphite as raw material, prepared by the Hummers method improved
Graphite oxide, is specially in sulfuric acid/phosphoric acid mixed liquor that natural flake graphite joins 9:1, stirs
Mixing, add potassium permanganate, in mass ratio, natural flake graphite accounts for 3%, and sulfuric acid/phosphoric acid mixed liquor accounts for
79%, potassium permanganate accounts for 18%, controls concentrated sulfuric acid temperature 3 DEG C, reacts 50min, is warming up to 55
DEG C, react 12h, after product is by centrifuge washing to sulfate radical-free ion, in 55 DEG C of drying,
Prepare graphite oxide；Gained graphite oxide is carried out chemical modification to it, specifically by chloroactic acid method
For graphite oxide being configured to the solution of 2mg/mL, the most ultrasonic 1h, add NaOH and
The ultrasonic 2h of monoxone, is washed to neutral being dried and prepares carboxylated graphene oxide, the most in mass ratio,
Graphite oxide accounts for 0.5%, and NaOH 48.5%, monoxone accounts for 51%；Further by the carboxylic of gained
Base graphene oxide is scattered in alcohol solvent, solution through the ultrasonically treated 20min of power 500W,
Obtain the carboxylated graphene oxide solution being effectively peeled off；Again by molten for phenol type Benzoxazine performed polymer
In alcohol solvent, and being sufficiently stirred for dissolving, obtaining mass concentration is 20% phenol type Benzoxazine
Prepolymer solution.Use in-situ inserted solution polymerization process, in mass ratio, by 3% gained carboxylated oxygen
Functionalized graphene solution and 97% gained phenol type Benzoxazine prepolymer solution are blended and prepare in situ
Intercalation solution.
In-situ inserted for gained solution is vacuumized at 100 DEG C degassing 2h, anti-then at 180 DEG C of solidifications
Answer 10h, prepare carboxylated graphene oxide Benzoxazine nanocomposite.Gained compound resin
Performance indications are shown in Table 1.
Embodiment 5
A kind of system of the in-situ inserted solution of carboxylated graphene oxide Benzoxazine nanocomposite
Preparation Method, specifically comprises the following steps that
With particle diameter 30 μm natural flake graphite as raw material, prepared by the Hummers method improved
Graphite oxide, is specially in sulfuric acid/phosphoric acid mixed liquor that natural flake graphite joins 9:1, stirs
Mixing, add potassium permanganate, in mass ratio, natural flake graphite accounts for 2%, and sulfuric acid/phosphoric acid mixed liquor accounts for
86%, potassium permanganate accounts for 12%, controls concentrated sulfuric acid temperature 3 DEG C, reacts 50min, is warming up to 55
DEG C, react 12h, after product is by centrifuge washing to sulfate radical-free ion, in 55 DEG C of drying,
Prepare graphite oxide；Gained graphite oxide is carried out chemical modification to it, specifically by chloroactic acid method
For graphite oxide being configured to the solution of 2mg/mL, the most ultrasonic 1h, add NaOH and
The ultrasonic 2h of monoxone, is washed to neutral being dried and prepares carboxylated graphene oxide, the most in mass ratio,
Graphite oxide accounts for 0.45%, and NaOH 53.55%, monoxone accounts for 46%；Further by gained
Carboxylated graphene oxide is scattered in alcohol solvent, and solution is through power 500W ultrasonically treated 20
Min, obtains the carboxylated graphene oxide solution being effectively peeled off；Again by phenol type Benzoxazine pre-polymerization
Body is dissolved in alcohol solvent, and is sufficiently stirred for dissolving, and obtaining mass concentration is 15% phenol type benzo
Piperazine prepolymer solution.Use in-situ inserted solution polymerization process, in mass ratio, by 3% gained carboxyl
Change graphene oxide solution is blended with 97% gained phenol type Benzoxazine prepolymer solution and prepares
In-situ inserted solution.
In-situ inserted for gained solution is vacuumized at 100 DEG C degassing 2h, anti-then at 190 DEG C of solidifications
Answer 4h, prepare carboxylated graphene oxide Benzoxazine nanocomposite.Gained compound resin
Index can be shown in Table 1.
Embodiment 6
A kind of system of the in-situ inserted solution of carboxylated graphene oxide Benzoxazine nanocomposite
Preparation Method, specifically comprises the following steps that
With particle diameter 45 μm natural flake graphite as raw material, prepared by the Hummers method improved
Graphite oxide, is specially in sulfuric acid/phosphoric acid mixed liquor that natural flake graphite joins 9:1, stirs
Mixing, add potassium permanganate, in mass ratio, natural flake graphite accounts for 1%, and sulfuric acid/phosphoric acid mixed liquor accounts for
93%, potassium permanganate accounts for 6%, controls concentrated sulfuric acid temperature 5 DEG C, reacts 30min, is warming up to 50 DEG C,
Reaction 12h, after product is by centrifuge washing to sulfate radical-free ion, in 50 DEG C of drying, system
Obtain graphite oxide；Gained graphite oxide is carried out chemical modification by chloroactic acid method to it, is specially
Graphite oxide is configured to the solution of 2mg/mL, the most ultrasonic 1h, adds NaOH and chlorine
The ultrasonic 2h of acetic acid, is washed to neutral being dried and prepares carboxylated graphene oxide, the most in mass ratio,
Graphite oxide accounts for 0.45%, and NaOH 53.55%, monoxone accounts for 46%；Further by gained
Carboxylated graphene oxide is scattered in alcohol solvent, and solution is through power 500W ultrasonically treated 20
Min, obtains the carboxylated graphene oxide solution being effectively peeled off；Again by phenol type Benzoxazine pre-polymerization
Body is dissolved in alcohol solvent, and is sufficiently stirred for dissolving, and obtaining mass concentration is 10% phenol type benzo
Piperazine prepolymer solution.Use in-situ inserted solution polymerization process, in mass ratio, by 1% gained carboxyl
Change graphene oxide solution is blended with 99% gained phenol type Benzoxazine prepolymer solution and prepares
In-situ inserted solution.
In-situ inserted for gained solution is vacuumized at 80 DEG C degassing 2h, then at 150 DEG C of curing reactions
20h, prepares carboxylated graphene oxide Benzoxazine nanocomposite.Gained compound resin performance
Index is shown in Table 1.
Embodiment 7
A kind of system of the in-situ inserted solution of carboxylated graphene oxide Benzoxazine nanocomposite
Preparation Method, specifically comprises the following steps that
With particle diameter 50 μm natural flake graphite as raw material, prepared by the Hummers method improved
Graphite oxide, is specially in sulfuric acid/phosphoric acid mixed liquor that natural flake graphite joins 9:1, stirs
Mixing, add potassium permanganate, in mass ratio, natural flake graphite accounts for 1%, and sulfuric acid/phosphoric acid mixed liquor accounts for
93%, potassium permanganate accounts for 6%, controls concentrated sulfuric acid temperature 10 DEG C, reacts 30min, is warming up to 50
DEG C, react 12h, after product is by centrifuge washing to sulfate radical-free ion, in 60 DEG C of drying,
Prepare graphite oxide；Gained graphite oxide is carried out chemical modification to it, specifically by chloroactic acid method
For graphite oxide being configured to the solution of 2mg/mL, the most ultrasonic 2h, add NaOH and
The ultrasonic 3h of monoxone, is washed to neutral being dried and prepares carboxylated graphene oxide, the most in mass ratio,
Graphite oxide accounts for 0.5%, and NaOH 48.5%, monoxone accounts for 51%；Further by the carboxylic of gained
Base graphene oxide is scattered in alcohol solvent, solution through the ultrasonically treated 20min of power 500W,
Obtain the carboxylated graphene oxide solution being effectively peeled off；Again by molten for phenol type Benzoxazine performed polymer
In alcohol solvent, and being sufficiently stirred for dissolving, obtaining mass concentration is 15% phenol type Benzoxazine
Prepolymer solution.Use in-situ inserted solution polymerization process, in mass ratio, by 1% gained carboxylated oxygen
Functionalized graphene solution and 99% gained phenol type Benzoxazine prepolymer solution are blended and prepare in situ
Intercalation solution.
In-situ inserted for gained solution is vacuumized at 90 DEG C degassing 1h, then at 180 DEG C of curing reactions
15h, prepares carboxylated graphene oxide Benzoxazine nanocomposite.Gained compound resin performance
Index is shown in Table 1.
Table 1
In table, BOZ represents that carboxylated graphene oxide mass ratio accounts for carboxylated oxygen after the solidification of 0%
Functionalized graphene Benzoxazine nanocomposite, i.e. pure after solidification benzoxazine resins.
As it can be seen from table 1 compared to pure benzoxazine resins, add carboxylated graphite oxide
Alkene makes the solidification temperature of compound resin reduce, this explanation carboxylated oxidation stone containing carboxyl functional group
Ink alkene has catalytic action as organic monoacid to the curing action of Benzoxazine.
The foregoing is only presently preferred embodiments of the present invention, be not used for limiting the enforcement model of the present invention
Enclose；If without departing from the spirit and scope of the present invention, the present invention is modified or equivalent,
All should contain in the middle of the protection domain of the claims in the present invention.
Claims (6)
1. the in-situ inserted solution of a carboxylated graphene oxide Benzoxazine nanocomposite
Preparation method, it is characterised in that comprise the following steps:
(1) with natural flake graphite as raw material, oxidation is prepared by the Hummers method improved
Graphite；
(2) gained graphite oxide is carried out chemical modification by chloroactic acid method to it, obtain carboxylated
Graphene oxide；
(3) gained carboxylated graphene oxide is scattered in organic solvent, ultrasonically treated after obtain
Carboxylated graphene oxide solution；
(4) Benzoxazine performed polymer is dissolved in organic solvent, and is sufficiently stirred for dissolving, prepare matter
Amount concentration is 10%～25% Benzoxazine prepolymer solution；
(5) in-situ inserted solution polymerization process is used, in mass ratio, by 0.5%～5% carboxylated oxidation
Graphene solution and 95%～99.5% Benzoxazine prepolymer solution are blended, and prepare in-situ inserted solution；
By chloroactic acid method, graphite oxide being carried out chemical modification described in step (2), being specially will
In step (1), gained graphite oxide is configured to the solution of 2mg/mL, the most ultrasonic 1～2h, then
Add NaOH and monoxone ultrasonic 2～3h, be washed to neutral being dried and prepare carboxylated graphite oxide
Alkene, the most in mass ratio, graphite oxide accounts for 0.45%～0.5%, NaOH 53.55%～48.5%,
Monoxone accounts for 46%～51%.
Carboxylated graphene oxide Benzoxazine nanocomposite the most according to claim 1
The preparation method of in-situ inserted solution, it is characterised in that the natural scale described in step (1)
The particle diameter of graphite raw material is 20～50 μm.
Carboxylated graphene oxide Benzoxazine nanocomposite the most according to claim 1
The preparation method of in-situ inserted solution, it is characterised in that the improvement described in step (1)
Hummers method prepares graphite oxide, is sulfuric acid/phosphoric acid that natural flake graphite joins 9:1
In mixed liquor, stir, add potassium permanganate；Being specially in mass ratio, natural flake graphite accounts for
1%～3%, sulfuric acid/phosphoric acid mixed liquor accounts for 79%～93%, and potassium permanganate accounts for 6%～18%；Control sulphur
Acid temperature 0～10 DEG C, reacts 30～60min；It is warming up to 45～55 DEG C, reacts 12～24h；Reaction
After product is by centrifuge washing to sulfate radical-free ion, in 40～80 DEG C of drying, prepare graphite oxide.
Carboxylated graphene oxide Benzoxazine nanocomposite the most according to claim 1
The preparation method of in-situ inserted solution, it is characterised in that the carboxylated oxidation described in step (3)
Graphene solution ultrasonication is: carboxylated graphene oxide solution carried out in ice-water bath
10～30min is ultrasonically treated, and ultrasonic power is 400～800W.
Carboxylated graphene oxide Benzoxazine nanocomposite the most according to claim 1
The preparation method of in-situ inserted solution, it is characterised in that described Benzoxazine performed polymer includes
The monoamine of single functionality and single phenolic Benzoxazine, the bisphenol-A of bifunctionality, Bisphenol F and diamines
Type Benzoxazine, polyfunctionality Benzoxazine, bis-phenol main chain and two amine type main chain Benzoxazine and
Naphthalene system Benzoxazine, described Benzoxazine performed polymer need not purify before use.
Carboxylated graphene oxide Benzoxazine nanocomposite the most according to claim 1
The preparation method of in-situ inserted solution, it is characterised in that institute in step (3) and step (4)
The organic solvent stated is ethanol, acetone, toluene.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410393264.8A CN104262622B (en) | 2014-08-12 | 2014-08-12 | The preparation method of the in-situ inserted solution of carboxylated graphene oxide Benzoxazine nanocomposite |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410393264.8A CN104262622B (en) | 2014-08-12 | 2014-08-12 | The preparation method of the in-situ inserted solution of carboxylated graphene oxide Benzoxazine nanocomposite |
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| Publication Number | Publication Date |
|---|---|
| CN104262622A CN104262622A (en) | 2015-01-07 |
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| CN105219078A (en) * | 2015-09-28 | 2016-01-06 | 中国地质大学（武汉） | Functional graphene oxide prepared by in-situ inserted solution method strengthens benzoxazinyl compound resin |
| CN105111437A (en) * | 2015-09-28 | 2015-12-02 | 中国地质大学（武汉） | Functionalized graphene oxide enhanced benzoxazine-based composite resin and preparation method thereof |
| CN105400195A (en) * | 2015-10-10 | 2016-03-16 | 苏州太湖电工新材料股份有限公司 | Benzoxazine/epoxy resin/oxidized graphene composite material and preparation method thereof |
| CN105219025B (en) * | 2015-10-30 | 2018-02-13 | 苏州太湖电工新材料股份有限公司 | A kind of benzoxazine/epoxy resin/graphene oxide composite material and preparation method thereof |
| CN107732255A (en) * | 2017-09-06 | 2018-02-23 | 福建农林大学 | A kind of combination electrode of graphene-containing and metal organic frame and preparation method thereof |
| CN108383227B (en) * | 2018-03-15 | 2021-06-04 | 长兴科创科技咨询有限公司 | Preparation method of coagulant for pretreatment of dyeing wastewater |
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| CN109942785B (en) * | 2019-02-26 | 2021-03-12 | 昆山嘉力普制版胶粘剂油墨有限公司 | Preparation method of carboxylated graphene oxide modified carboxylic acid type waterborne polyurethane |
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