CN106065088A - A kind of preparation method of the modified expanded graphite being grafted silicon P elements - Google Patents
A kind of preparation method of the modified expanded graphite being grafted silicon P elements Download PDFInfo
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- CN106065088A CN106065088A CN201610387873.1A CN201610387873A CN106065088A CN 106065088 A CN106065088 A CN 106065088A CN 201610387873 A CN201610387873 A CN 201610387873A CN 106065088 A CN106065088 A CN 106065088A
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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
- C08K9/06—Ingredients treated with organic substances with silicon-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
- 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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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/44—Carbon
- C09C1/46—Graphite
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/06—Treatment with inorganic compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/12—Treatment with organosilicon compounds
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Abstract
The invention belongs to field of material technology, be specifically related to the preparation method of a kind of modified expanded graphite being grafted silicon P elements.Concretely comprise the following steps: utilize silane coupler to hydrolyze generation silicone hydroxyl in water-containing organic solvent, C O Si key is generated with hydroxyl or the carboxyl functional group generation dehydration condensation on EG surface, it is subsequently adding phosphoric acid, it is made to react generation Si O P key with the silicone hydroxyl on EG surface, wash by ethanol or water, filter, dry, obtain the EG of modification.The heat resistance of products obtained therefrom is improved significantly；And due to EG surface grafting Organic substance, improve the interface compatibility of itself and polymeric matrix so that it is in polymeric matrix, have good dispersibility, therefore can give full play to the fire resistance of EG.The modified EG that the present invention prepares can be applicable in many polymeric matrixs, it is achieved that the expansion of high molecular fire retardant modification application.
Description
Technical field
The invention belongs to field of material technology, be specifically related to the preparation side of a kind of modified expanded graphite being grafted silicon P elements
Method.
Background technology
Along with the extensive application of polymeric material, people are more and more higher to the requirement of its anti-flammability, and fire retardant is as it
Maximally efficient flame-retardant modified additive, has developed in order to of a great variety, the system that performance is various.According to fire retardant poly-
Existence form in compound matrix, can be classified as addition type and response type two kinds.Wherein additive flame retardant is the simplest
Be scattered in matrix, fire-retardant during not with matrix and other component generation chemical reactions；And reactive flame retardant is often with list
The form of body or cross-linking agent participates in chemical reaction, and final presented in construction unit in polymeric system.
Expanded graphite (EG), as inorganic expansion type fire retardant, has that speed of expansion is fast, expansion multiplying power is high, flame retardant effect
Good, LSZH, advantages of environment protection, and be widely used.Its fire retardant mechanism is in pyroprocess, rapid at matrix surface
Expand the layer of charcoal forming one layer of " anthelmintic " shape, isolation flame and the propagation of fuel gas, thus reach fire-retardant purpose.
But, EG is as inorganic combustion inhibitor, and it is poor with the interface compatibility of polymeric matrix, can destroy foam structure
Integrity, causes the deterioration of polymeric material mechanical property；It addition, expand " anthelmintic " the shape layer of charcoal formed, disturb at flame impingement
Easily come off under Dong, had a strong impact on the flame retardant effect of EG.Accordingly, it would be desirable to EG is modified process to improve it at polymer
The performance of matrix, modified approach currently mainly has:
(1) surface processes.Utilize surface conditioning agent that EG surface is processed, reach to increase EG and the polymeric matrix compatibility or
Improve the purpose of EG expansion multiplying power.
(2) surface grafting.Utilize the oxygen-containing functional group on EG surface, such as hydroxyl, carboxyl and ketone etc., participate in chemical reaction, make
The chemical substance on surface increases, and reaches modified purpose.
(3) emulsion cladding.Utilize the method that emulsion is polymerized, make one layer of other chemical substance of EG Surface coating, promote EG and exist
Dispersibility in matrix and anti-flammability.
Summary of the invention
It is an object of the invention to provide the preparation method of a kind of modified expanded graphite being grafted silicon P elements.
For reaching above-mentioned purpose, the solution of the present invention is:
First prepare aqueous organic solvent, in organic solvent, add silane coupler class material, make silane coupler occur
Hydrolysis produces silicone hydroxyl.
Utilizing the functional group such as hydroxyl or carboxyl on EG surface, there is dehydration contracting in the silicone hydroxyl produced with silane coupler hydrolysis
Close reaction, generate C-O-Si and be good for.
Then in solvent, a certain amount of phosphoric acid,diluted is added so that it is with silicone hydroxyl generation dehydration condensation, generate Si-O-
P key, last filtration drying, obtain the modified expanded graphite of surface grafting silicon P elements.
The preparation method of a kind of modified expanded graphite being grafted silicon phosphorus ignition-proof element that the present invention proposes, concrete steps are such as
Under:
(1) hydrolysis of silane coupler class material
Preparation water content is the organic solvent 50 ~ 500mL of 5% ~ 10%, adds a small amount of dilute hydrochloric acid or acetic acid regulation oH value
It is 4 ~ 5, adds 1 ~ 4g silane coupler, at 20 ~ 40 DEG C, stir 10 ~ 30min, promote that silane coupler hydrolysis produces silicon hydroxyl
Base；
(2) silane coupler and expanded graphite react and generate C-O-Si key
According to the ratio of silane coupler Yu the mass ratio 1:5 ~ 1:50 of EG, in step (1) products therefrom, add EG, be warming up to
50 ~ 90 DEG C, stir 1 ~ 8h, make silicone hydroxyl and the hydroxyl on EG surface or carboxyl generation dehydration condensation, generate C-O-Si key；
(3) silane coupler generates Si-O-P key with phosphatase reaction
According to the ratio of silane coupler Yu the mol ratio 100:10 ~ 1:10 of phosphoric acid, in step (2) products therefrom, add dilute phosphorus
Acid, at a temperature of 50 ~ 90 DEG C, stirs 1 ~ 8h, makes the silicone hydroxyl generation dehydration condensation of phosphoric acid and EG surface, generate Si-O-P
Key；After reaction terminates, with ethanol and distilled water, it is carried out filtration washing respectively, even to remove the silane not reacted with EG surface
Connection agent and unnecessary phosphoric acid, the modified expanded graphite after filtration dries 8 ~ 24h at 50 ~ 120 DEG C；Obtain modified expansion stone
Ink.
In the present invention, the mixing speed in step (1), (2), (3) is 200 ~ 1000r/min.
In the present invention, the organic solvent in step (1) is methanol, ethanol, ethylene glycol, propanol, isopropanol, propylene glycol, fourth
Alcohol or acetone etc. can make silane coupler that one or more organic solvents of hydrolysis occur.
In the present invention, the silane coupler in step (1) is γ-aminopropyl triethoxysilane, γ-(2,3-epoxies
Third oxygen) propyl trimethoxy silicane, γ-(methacryloxypropyl) propyl trimethoxy silicane, vinyl triacetoxy silicon
Alkane, vinyltrimethoxy silane, VTES, propyl-triethoxysilicane, MTES, two
Phenyidimethoxysilane, phenyl triethoxysilane, 17 decyl trimethoxy silanes or 3-NCO propyl group three oxygen
Base silane etc. one or more.
In the present invention, the size of the expanded graphite in step (2) is 40 ~ 200 mesh.
In the present invention, the phosphoric acid percentage concentration in step (3) is 3% ~ 45%.
The beneficial effects of the present invention is: the present invention utilizes high-molecular organic material that inorganic expansion type fire retardant is expanded stone
Ink carries out surface graft modification, obtains the modified expanded graphite of siliceous phosphorus ignition-proof element.This method of modifying is simple, it is simple to
Controlling, the heat resistance of products obtained therefrom is improved significantly；And due to expanded graphite surface grafting Organic substance, improve its with
The interface compatibility of polymeric matrix so that it is have good dispersibility in polymeric matrix, therefore can give full play to expand
The fire resistance of graphite.The modified expanded graphite that the present invention prepares can be applicable in many polymeric matrixs, it is achieved that macromolecule
The expansion of flame-retardant modified application.
Accompanying drawing explanation
Fig. 1 is modified expanded graphite (CEG) and the infrared spectrogram of unmodified EG of embodiment 1 synthesis.
Fig. 2 is the partial enlarged drawing of Fig. 1, wherein at 1042cm-1、1038cm-1Place occurs in that the spy of Si-O-P, C-Si-O
Levy absworption peak.
Fig. 3 is modified expanded graphite (CEG) and the thermogravimetric curve of unmodified EG of embodiment 1 synthesis.
Fig. 4 is the modified expanded graphite (CEG of embodiment 3 synthesis1) and the x-ray photoelectron spectroscopy of unmodified EG
Si2p scanning curve.
Detailed description of the invention
The present invention is further illustrated below by embodiment.
Embodiment 1
Step 1: the silane coupling agent vinyl triethoxysilane (A-151) process to expanded graphite
The ethanol water 60mL of preparation 90%, adds dilute hydrochloric acid regulation pH to 5, adds 2gA-151,300r/ at 30 DEG C
After min mechanical agitation 20min, the expanded graphite that 20g size is 80 mesh is added thereto, is warming up to 80 DEG C, 400r/min machinery
Stirring 2h, makes the hydroxyl reaction of silicone hydroxyl and expanded graphite surface, generates C-O-Si key, and reaction equation is as follows:
Step 2: process the expanded graphite of A-151 modification with phosphoric acid,diluted
In solution, add the phosphoric acid,diluted of 4g mass fraction 42.5%, keep 80 DEG C, 400r/min mechanical agitation 2h so that it is with silicon
Hydroxyl reaction generates Si-O-P key, and reaction equation is as follows:
Then with absolute ethanol washing filter 5 times, in 80 DEG C of drying bakers be dried 12h, obtain containing Si, P element modified expanded
Graphite C EG.
The infrared spectrogram of this modified expanded graphite such as Fig. 1, thermogravimetric curve such as Fig. 3.As can be seen from the figure modified
Expanded graphite has successfully been grafted Si, P element, and heat resistance is improved significantly.
Embodiment 2
Step 1: the γ-aminopropyl triethoxysilane (KH-550) process to expanded graphite
The ethanol water 50mL of preparation 90%, adds acetic acid regulation PH to 5, adds 2gKH-550,300r/min at 30 DEG C
After mechanical agitation 20min, being added thereto by the expanded graphite that 20g size is 100 mesh, be warming up to 60 DEG C, 400r/min machinery stirs
Mix 4h, make the hydroxyl reaction of silicone hydroxyl and expanded graphite surface, generate C-O-Si key；
Step 2: process the expanded graphite of KH-550 modification with phosphoric acid,diluted
Adding the phosphoric acid,diluted of 4g mass fraction 25% in solution, keep 80 DEG C, 400r/min mechanical agitation 4 hours, is itself and silicon
Hydroxyl reaction generates Si-O-P key, then filters 5 times with absolute ethanol washing, is dried 12h, is grafted in 80 DEG C of drying bakers
Si, the modified expanded graphite of P element.
Table 1 is the Partial Elements percentage composition before and after this embodiment modified expanded graphite.
Table 1
| Sample | C(%) | O(%) | Si(%) | P(%) |
| EG | 92.16 | 5.74 | 0.84 | 0 |
| Modified EG | 81.73 | 12.82 | 1.51 | 0.92 |
Embodiment 3
Same as in Example 1, but silane coupler is changed into the mixed of 2g VTES (A-151) and KH560
Closing liquid, both mole dosage ratio is for 1:1, and other conditions are constant.
Embodiment 4
Same as in Example 1, step 1,80 DEG C of reaction temperatures in 2 are adjusted to 60 DEG C, when the 2h in step 1 is stirred reaction
Between be adjusted to 4h, other conditions are constant.
Table 2 is the Partial Elements percentage composition before and after this embodiment modified expanded graphite.
Table 2
| Sample | C(%) | O(%) | Si(%) | P(%) |
| EG | 92.16 | 5.74 | 0.84 | 0 |
| Modified EG | 81.70 | 12.79 | 1.55 | 0.94 |
Claims (6)
1. the preparation method of a modified expanded graphite, it is characterised in that specifically comprise the following steps that
(1) hydrolysis of silane coupler class material
Preparation water content is the organic solvent 50 ~ 500mL of 5% ~ 10%, adds dilute hydrochloric acid or vinegar acid for adjusting pH value is 4 ~ 5,
Add 1 ~ 4g silane coupler, at 20 ~ 40 DEG C, stir 10 ~ 30min promote that silane coupler hydrolysis produces silicone hydroxyl；
(2) silane coupler and expanded graphite react and generate C-O-Si key
According to the ratio of silane coupler Yu the mass ratio 1:5 ~ 1:50 of EG, in step (1) products therefrom, add EG, be warming up to
50 ~ 90 DEG C, stir 1 ~ 8h, make silicone hydroxyl and the hydroxyl on EG surface or carboxyl generation dehydration condensation, generate C-O-Si key；
(3) silane coupler generates Si-O-P key with phosphatase reaction
According to the ratio of silane coupler Yu the mol ratio 100:10 ~ 1:10 of phosphoric acid, in step (2) products therefrom, add dilute phosphorus
Acid, at a temperature of 50 ~ 90 DEG C, stirs 1 ~ 8h, makes the silicone hydroxyl generation dehydration condensation of phosphoric acid and EG surface, generate Si-O-P
Key；After reaction terminates, with ethanol and distilled water, it is carried out filtration washing respectively, even to remove the silane not reacted with EG surface
Connection agent and unnecessary phosphoric acid, the modified expanded graphite after filtration dries 8 ~ 24h at 50 ~ 120 DEG C；Obtain modified expansion stone
Ink.
The preparation method of modified expanded graphite the most according to claim 1, it is characterised in that in step (1), (2) and (3)
Mixing speed be 200 ~ 1000r/min.
The preparation method of modified expanded graphite the most according to claim 1, it is characterised in that the organic solvent in step (1)
For in methanol, ethanol, ethylene glycol, propanol, isopropanol, propylene glycol, butanol or acetone one or more.
The preparation method of modified expanded graphite the most according to claim 1, it is characterised in that silane coupled in step (1)
Agent is γ-aminopropyl triethoxysilane, γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane, γ-(metering system
Acyl-oxygen) propyl trimethoxy silicane, vinyltriacetoxy silane, vinyltrimethoxy silane, vinyl triethoxyl
Silane, propyl-triethoxysilicane, MTES, dimethoxydiphenylsilane, phenyl triethoxysilane, ten
In seven decyl trimethoxy silanes or 3-NCO propyl group three TMOS one or more.
The preparation method of modified expanded graphite the most according to claim 1, it is characterised in that the expanded graphite in step (2)
Size be 40 ~ 200 mesh.
The preparation method of modified expanded graphite the most according to claim 1, it is characterised in that the phosphoric acid percentage in step (3)
Concentration is 3% ~ 45%.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109081899A (en) * | 2018-07-23 | 2018-12-25 | 德清顾舒家华高分子材料有限公司 | A kind of fire-retardant heat insulation polyurethane foam |
| CN109810512A (en) * | 2019-01-16 | 2019-05-28 | 西安科技大学 | A kind of preparation method of Bio-sil fire retardant |
| CN112778754A (en) * | 2021-01-28 | 2021-05-11 | 浙江工业大学 | Preparation method of antistatic flame-retardant nylon 6 composite material |
| CN112841219A (en) * | 2020-12-31 | 2021-05-28 | 广东金发科技有限公司 | Efficient antibacterial agent and preparation method and application thereof |
| CN116589777A (en) * | 2023-06-16 | 2023-08-15 | 高尚蓉 | Halogen-free flame-retardant crosslinked polyethylene cable material and preparation method thereof |
| CN116589779A (en) * | 2023-07-19 | 2023-08-15 | 山东艾科高分子材料有限公司 | Polyolefin halogen-free flame-retardant master batch |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109081899A (en) * | 2018-07-23 | 2018-12-25 | 德清顾舒家华高分子材料有限公司 | A kind of fire-retardant heat insulation polyurethane foam |
| CN109810512A (en) * | 2019-01-16 | 2019-05-28 | 西安科技大学 | A kind of preparation method of Bio-sil fire retardant |
| CN109810512B (en) * | 2019-01-16 | 2021-03-30 | 西安科技大学 | Preparation method of porous silica gel flame retardant |
| CN112841219A (en) * | 2020-12-31 | 2021-05-28 | 广东金发科技有限公司 | Efficient antibacterial agent and preparation method and application thereof |
| CN112778754A (en) * | 2021-01-28 | 2021-05-11 | 浙江工业大学 | Preparation method of antistatic flame-retardant nylon 6 composite material |
| CN116589777A (en) * | 2023-06-16 | 2023-08-15 | 高尚蓉 | Halogen-free flame-retardant crosslinked polyethylene cable material and preparation method thereof |
| CN116589779A (en) * | 2023-07-19 | 2023-08-15 | 山东艾科高分子材料有限公司 | Polyolefin halogen-free flame-retardant master batch |
| CN116589779B (en) * | 2023-07-19 | 2023-09-12 | 山东艾科高分子材料有限公司 | Polyolefin halogen-free flame-retardant master batch |
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Application publication date: 20161102 |