CN104448074B - Special modified graphene for polymerization of vinyl chloride - Google Patents
Special modified graphene for polymerization of vinyl chloride Download PDFInfo
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- CN104448074B CN104448074B CN201410745546.XA CN201410745546A CN104448074B CN 104448074 B CN104448074 B CN 104448074B CN 201410745546 A CN201410745546 A CN 201410745546A CN 104448074 B CN104448074 B CN 104448074B
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Abstract
The invention belongs to the technical field of graphene materials and particularly relates to special modified graphene for polymerization of vinyl chloride. The special modified graphene for polymerization of vinyl chloride comprises graphene powder and multiple surface modifiers, wherein the weight ratio of the surface modifiers is 0.5-5wt% and the surface and edges of graphene are uniformly coated with the surface modifiers. The preparation method is simple, efficient and environment-friendly, industrialized mass production can be achieved, the obtained product is particularly suitable for a vinyl chloride suspension polymerization system, the properties including thermal property, mechanical property and electrical property of polyvinyl chloride (PVC) can be significantly improved and thus the market application range of PVC is expanded.
Description
Technical field
The invention belongs to grapheme material technical field, particularly to a kind of special modified graphene of chloroethylene polymerization.
Background technology
Graphene is with the mechanical strength of its superelevation, the specific surface area of super large and excellent electricity, calorifics and optical property, quilt
It is considered to strengthen the ideal filler of polymer performance.Research shows, adding a small amount of Graphene series material can be obviously improved
Some performances of traditional material, such as electric conductivity, thermal conductivity, photocatalysis characteristic, heat endurance, hardness, modulus etc..Graphene-based
Polymer composites be the focus of domestic and international expert research it is considered to be the important directions of Graphene industrialization, have wide
Application prospect.However, the research that Graphene strengthens composite property faces huge challenge, the maximum bottleneck of its industrialization
Restriction is the reunion-scattering problem of Graphene and its is combined problem with polymer interface.The preparation method of composite at present
Mainly there are solution mixing, melting mixing and in-situ polymerization.Solution blending technique needs a large amount of solvents, brings the environmental protection of sternness to ask
Topic, and its high energy consumption, process length, yield low it is virtually impossible to industrialization.The subject matter of melt-blending process is that Graphene is difficult to reach
To nanoscale dispersion.Situ aggregation method had both enabled the dispersed of nano particle, can make filler and matrix In-situ reaction, work again
The feasibility that industry metaplasia is produced is higher.
At home and abroad under economic overall situation, polyvinyl chloride (PVC) industry face the energy rise steadily, downstream dull sale
Situation, is especially affected by national regulation and control policy of real estate, and real estate causes for the slump in demand of PVC and door and window
PVC industry continues and declines tendency, and PVC industry is in heavy losses state, and PVC price is all around under below cost average line
The narrow oscillatory operation of rail, defines the management mode of " mending chlorine with alkali ".The one of long-standing problem PVC industry survival and development makes greatly
About, the three big pressure that two large impacts of raw material route, enterprise operation face and the four major contradictions of the industrial structure more manifest and dash forward
Go out.Chinese PVC production capacity is expanded a road and is sung heartily at present, but single varieties, production capacity surplus, cost up, dog-eat-dog become its row
The potential problems that industry development faces.Solve the breach of these problems, be foreign company mode, with user for guiding, make
Polyvinyl chloride resin specialized and differentiation on specification, product species and applicating category, seeks new growth in high-end product
Point.
Using in-situ suspension polymerization, Graphene is added in polyvinyl chloride resin, prepares PVC- Graphene Special Resin, can obtain
Composite to excellent performance.However, at present Graphene on the market is mostly general, mass product, for a certain field, certain
The special graphite alkene of one product development is also fewer, only has certain progress at aspects such as battery, coating.It is directed to composite wood
Material, the general-purpose plastics such as particularly PVC, the exploitation of special graphite alkene product have not been reported.The present invention suspends poly- according to vinyl chloride
The feature closed, takes into full account safety factor and the products obtained therefroms such as polymerization system compatibility, kinetics of polymerization reaction, diabatic process
Combination property it is intended to exploitation a kind of is suitable for the special modified graphene of suspension polymerization of VC.
Content of the invention
The technical problem to be solved in the present invention is aiming at above-mentioned the deficiencies in the prior art and provides a kind of chloroethylene polymerization
Special modified graphene.
This modified graphene is particularly suitable for suspension polymerization of VC system, to kinetics of polymerization reaction and diabatic process no
Impact, can comprehensively improve polyvinyl chloride performance, be the new product aiming at chloroethylene polymerization offer.
The present invention also provides a kind of preparation method of the special modified graphene of chloroethylene polymerization, and its technical process is simple,
Can industrial volume production, high-efficiency environment friendly.
In order to solve above technical problem, the solution of the present invention is：
A kind of special modified graphene of chloroethylene polymerization, described modified graphene is changed by graphene powder and kinds of surface
Property agent composition, the wherein ratio of weight shared by surface modifier is for 0.5-5wt%, and is uniformly wrapped on graphenic surface and edge.
A size of 0.01-2 μm of described Graphene, thickness is less than 5nm.
The a large amount of defect of marginal existence of described Graphene, has greater activity, is easily modified processing.
Described kinds of surface modifying agent is the specific auxiliary agent of chloroethylene polymerization or the water solubility fully compliant with polymerization system
Surface modifier.
Described kinds of surface modifying agent be hydroxymethyl cellulose, hydroxypropyl methyl cellulose, neopelex, ten
Sodium dialkyl sulfate, polyvinyl alcohol, the binary of odium stearate or multiplexed combination.
Described modifying agent be uniformly wrapped on graphenic surface and edge be by physical absorption, chemisorbed, Electrostatic Absorption,
The active forces such as covalent bond complete.
A kind of preparation method of the special modified graphene of chloroethylene polymerization, preparation process is as follows：
(1) graphite raw material is added in strong base solution, 150 DEG C of water-baths 2 hours, takes out, washing suction filtration, to neutral, obtains stone
The proportion that in black slurry, wherein solution, highly basic accounts for is 2-10wt%, and the proportion that graphite accounts for is 1-5%；
(2) surface modifier is substantially dissolved in water, wiring solution-forming, the proportion that wherein in solution, surface modifier accounts for is
0.005-0.25wt%；
(3) graphite slurry in step (1) is added in the solution in step (2), is sufficiently mixed, obtain uniform stone
In black dispersion liquid, wherein dispersion liquid, the proportion shared by graphite is 1-5wt%；
(4) graphite dispersing solution in step (3) is added in nanometer sand mill, is fully ground, rotating speed is 2000-
2500rpm, the time is 5-15 hour, obtains modified graphene slurries；
(5) modified graphene slurries, dry modified graphene powder are taken out.
Described graphite raw material is crystalline flake graphite, expanded graphite, Delanium, amorphous graphite.
Described strong base solution is potassium hydroxide, NaOH, calcium hydroxide, barium hydroxide, sodium carbonate, sodium acid carbonate, carbon
The aqueous solution of sour potassium, saleratus etc..
Described drying process is freeze-drying, microwave drying, critical point drying, spray drying.
The feature of the present invention and beneficial effect：
The special modified graphene of a kind of chloroethylene polymerization that the present invention provides, is particularly suitable for suspension polymerization of VC body
System, no affects on kinetics of polymerization reaction and diabatic process；This modified graphene possesses the general performance of Graphene, such as high connductivity
Property, high-termal conductivity, high intensity, high-modulus, high-fire resistance etc., can comprehensively improve polyvinyl chloride performance, simultaneously it in particle diameter, change
Property the aspect such as agent, dispersiveness, local edge done specially modify and design, be aim at chloroethylene polymerization offer new product.
It possesses following advantage：(1) modifying agent is the dispersant of chloroethylene polymerization or the material similar with dispersant, favorably
Dispersed in Graphene；(2) particle diameter is less than the primary particle diameter of Corvic, can be coated completely by resin particle,
Beneficial to reinforced resin performance；(3) edge defect is many, and activity is high, the agent that is modified under dry powder cladding, passivation, is made into dispersion
After liquid, active site exposes, and can interact with polyvinyl chloride strand, the performance of reinforced resin；(4) preparation method is simple, can
Industrial volume production, high-efficiency environment friendly.
Brief description
Accompanying drawing 1：The scanning electron microscope diagram of the special modified graphene of chloroethylene polymerization（SEM)
Specific embodiment
In order to be better understood from the present invention, it is further elucidated with present disclosure with reference to embodiment, but in the present invention
Hold and be not limited solely to following specific embodiment.
Embodiment 1
(1) weigh 30g NaOH and be made into sodium hydroxide solution with 300g water, add 5g amorphous graphite, water at 150 DEG C
Bath 2 hours；Mixed liquor is taken out and filters, washing suction filtration, to neutral, obtains graphite slurry.
(2) by 0.15g neopelex, 0.1g hydroxypropyl methyl cellulose is substantially dissolved in 600g water, joins
Become composite modified agent solution.
(3) graphite slurry in step (1) is added in the composite modified agent solution in step (2), is sufficiently mixed, obtains
Obtain uniform graphite dispersing solution.
(4) graphite dispersing solution in step (3) is added in nanometer sand mill, is fully ground, rotating speed is 2500rpm,
Time is 5 hours, obtains modified graphene slurries.
(5) take out modified graphene slurries, be spray-dried to obtain modified graphene powder.
Embodiment 2
(1) weigh 30g NaOH and be made into sodium hydroxide solution with 300g water, add 5g amorphous graphite, water at 150 DEG C
Bath 2 hours；Mixed liquor is taken out and filters, washing suction filtration, to neutral, obtains graphite slurry.
(2) by 0.1g neopelex, 0.1g hydroxypropyl methyl cellulose, 0.05g odium stearate fully dissolves
In 600g water, it is made into composite modified agent solution.
(3) graphite slurry in step (1) is added in the composite modified agent solution in step (2), is sufficiently mixed, obtains
Obtain uniform graphite dispersing solution.
(4) graphite dispersing solution in step (3) is added in nanometer sand mill, is fully ground, rotating speed is 2500rpm,
Time is 5 hours, obtains modified graphene slurries.
(5) take out modified graphene slurries, be spray-dried to obtain modified graphene powder.
Embodiment 3
(1) weigh 10g potassium hydroxide and be made into potassium hydroxide solution with 200g water, add 4g amorphous graphite, water at 150 DEG C
Bath 2 hours；Mixed liquor is taken out and filters, washing suction filtration, to neutral, obtains graphite slurry.
(2) by 0.1g neopelex, 0.1g hydroxypropyl methyl cellulose, it is substantially dissolved in 400g water, join
Become composite modified agent solution.
(3) graphite slurry in step (1) is added in the composite modified agent solution in step (2), is sufficiently mixed, obtains
Obtain uniform graphite dispersing solution.
(4) graphite dispersing solution in step (3) is added in nanometer sand mill, is fully ground, rotating speed is 2000rpm,
Time is 8 hours, obtains modified graphene slurries.
(5) take out modified graphene slurries, be spray-dried to obtain modified graphene powder.
Embodiment 4
(1) weigh 10g potassium hydroxide and be made into potassium hydroxide solution with 200g water, add 4g crystalline flake graphite, water at 150 DEG C
Bath 2 hours；Mixed liquor is taken out and filters, washing suction filtration, to neutral, obtains graphite slurry.
(2) by 0.1g lauryl sodium sulfate, 0.1g polyvinyl alcohol, it is substantially dissolved in 400g water, be made into composite modified
Agent solution.
(3) graphite slurry in step (1) is added in the composite modified agent solution in step (2), is sufficiently mixed, obtains
Obtain uniform graphite dispersing solution.
(4) graphite dispersing solution in step (3) is added in nanometer sand mill, is fully ground, rotating speed is 2000rpm,
Time is 8 hours, obtains modified graphene slurries.
(5) take out modified graphene slurries, be spray-dried to obtain modified graphene powder.
Embodiment 5
(1) weigh 10g potassium hydroxide and be made into potassium hydroxide solution with 200g water, add 9.5g amorphous graphite, at 150 DEG C
Water-bath 2 hours；Mixed liquor is taken out and filters, washing suction filtration, to neutral, obtains graphite slurry.
(2) by 0.2g lauryl sodium sulfate, 0.25g polyvinyl alcohol, it is substantially dissolved in 200g water, be made into composite modified
Agent solution.
(3) graphite slurry in step (1) is added in the composite modified agent solution in step (2), is sufficiently mixed, obtains
Obtain uniform graphite dispersing solution.
(4) graphite dispersing solution in step (3) is added in nanometer sand mill, is fully ground, rotating speed is 2500rpm,
Time is 7 hours, obtains modified graphene slurries.
(5) take out modified graphene slurries, be spray-dried to obtain modified graphene powder.
Embodiment 6
(1) weigh 10g potassium hydroxide and be made into potassium hydroxide solution with 200g water, add 9.5g amorphous graphite, at 150 DEG C
Water-bath 2 hours；Mixed liquor is taken out and filters, washing suction filtration, to neutral, obtains graphite slurry.
(2) 0.2g lauryl sodium sulfate, 0.25g polyvinyl alcohol, 0.05 hydroxymethyl cellulose are substantially dissolved in 200g
In water, it is made into composite modified agent solution.
(3) graphite slurry in step (1) is added in the composite modified agent solution in step (2), is sufficiently mixed, obtains
Obtain uniform graphite dispersing solution.
(4) graphite dispersing solution in step (3) is added in nanometer sand mill, is fully ground, rotating speed is 2500rpm,
Time is 7 hours, obtains modified graphene slurries.
(5) take out modified graphene slurries, be spray-dried to obtain modified graphene powder.
Embodiment 7
(1) weigh 10g potassium hydroxide and be made into potassium hydroxide solution with 200g water, add 9.5g Delanium, at 150 DEG C
Water-bath 2 hours；Mixed liquor is taken out and filters, washing suction filtration, to neutral, obtains graphite slurry.
(2) 0.2g lauryl sodium sulfate, 0.25g polyvinyl alcohol, 0.05 hydroxymethyl cellulose are substantially dissolved in 200g
In water, it is made into composite modified agent solution.
(3) graphite slurry in step (1) is added in the composite modified agent solution in step (2), is sufficiently mixed, obtains
Obtain uniform graphite dispersing solution.
(4) graphite dispersing solution in step (3) is added in nanometer sand mill, is fully ground, rotating speed is 2500rpm,
Time is 7 hours, obtains modified graphene slurries.
(5) take out modified graphene slurries, be spray-dried to obtain modified graphene powder.
Embodiment 8
(1) weigh 10g potassium hydroxide and be made into potassium hydroxide solution with 200g water, add 9.5g expanded graphite, at 150 DEG C
Water-bath 2 hours；Mixed liquor is taken out and filters, washing suction filtration, to neutral, obtains graphite slurry.
(2) by 0.2g lauryl sodium sulfate, 0.25g polyvinyl alcohol, it is substantially dissolved in 200g water, be made into composite modified
Agent solution.
(3) graphite slurry in step (1) is added in the composite modified agent solution in step (2), is sufficiently mixed, obtains
Obtain uniform graphite dispersing solution.
(4) graphite dispersing solution in step (3) is added in nanometer sand mill, is fully ground, rotating speed is 2500rpm,
Time is 7 hours, obtains modified graphene slurries.
(5) take out modified graphene slurries, be spray-dried to obtain modified graphene powder.
Embodiment 9
(1) weigh 10g potassium hydroxide and be made into potassium hydroxide solution with 200g water, add 9.5g crystalline flake graphite, at 150 DEG C
Water-bath 2 hours；Mixed liquor is taken out and filters, washing suction filtration, to neutral, obtains graphite slurry.
(2) by 0.2g lauryl sodium sulfate, 0.25g polyvinyl alcohol, it is substantially dissolved in 200g water, be made into composite modified
Agent solution.
(3) graphite slurry in step (1) is added in the composite modified agent solution in step (2), is sufficiently mixed, obtains
Obtain uniform graphite dispersing solution.
(4) graphite dispersing solution in step (3) is added in nanometer sand mill, is fully ground, rotating speed is 2500rpm,
Time is 7 hours, obtains modified graphene slurries.
(5) take out modified graphene slurries, be spray-dried to obtain modified graphene powder.
Selected embodiment is typical embodiments above, and described above is only intended to help and understands the method for the present invention
And its core concept.It should be pointed out that for those skilled in the art, before without departing from the principle of the invention
Put, the present invention can also be carried out with some improvement and modify, these improve and modify the guarantor also falling into the claims in the present invention
In the range of shield.
Claims (3)
1. a kind of special modified graphene of chloroethylene polymerization is it is characterised in that described modified graphene is by graphene powder and many
Kind of surface modifier composition, wherein weight shared by surface modifier ratio for 0.5-5wt%, and be uniformly wrapped on graphenic surface and
Edge, a size of 0.01-2 μm of described Graphene, thickness is less than 5nm, and described kinds of surface modifying agent is hydroxymethyl cellulose, hydroxyl
Propyl methocel, neopelex, lauryl sodium sulfate, polyvinyl alcohol, the multiplexed combination of odium stearate；Institute
The preparation process of the modified graphene stated is as follows：(1) graphite raw material is added in strong base solution, 150 DEG C of water-baths 2 hours, takes
Go out, washing suction filtration, to neutral, obtains graphite slurry, the proportion that wherein in solution, highly basic accounts for is 2-10wt%, the proportion that graphite accounts for is 1-
5%；(2) surface modifier is substantially dissolved in water, wiring solution-forming, the proportion that wherein in solution, surface modifier accounts for is
0.005-0.25wt%；(3) graphite slurry in step (1) is added in the solution in step (2), is sufficiently mixed, obtain all
In even graphite dispersing solution, wherein dispersion liquid, the proportion shared by graphite is 1-5wt%；(4) by the graphite dispersing solution in step (3)
It is added in nanometer sand mill, is fully ground, rotating speed is 2000-2500rpm, the time is 5-15 hour, obtain modified graphene slurry
Liquid；(5) modified graphene slurries, dry modified graphene powder are taken out.
2. a kind of special modified graphene of the chloroethylene polymerization according to claim 1 is it is characterised in that described graphite
Raw material is crystalline flake graphite, expanded graphite, Delanium, amorphous graphite.
3. a kind of special modified graphene of the chloroethylene polymerization according to claim 2 is it is characterised in that described drying
Technique is freeze-drying, microwave drying, critical point drying, spray drying.
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| CN105713422A (en) * | 2016-02-24 | 2016-06-29 | 青岛德通纳米技术有限公司 | Mixing process of graphene and other carbon materials |
| CN106589701A (en) * | 2016-12-19 | 2017-04-26 | 山东霞光实业有限公司 | Environmental-friendly and anti-aging outdoor wood plastic material and preparation method thereof |
| CN113462202A (en) * | 2021-06-24 | 2021-10-01 | 浙江工业大学 | Method for improving dispersion effect of graphene in acrylic emulsion |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102225759A (en) * | 2011-04-14 | 2011-10-26 | 温州医学院 | Low-temperature preparation method of hydroxy-functionalized graphene |
| CN103058176A (en) * | 2012-12-29 | 2013-04-24 | 华侨大学 | Method for preparing graphene efficiently |
| CN103466608A (en) * | 2013-09-11 | 2013-12-25 | 中南大学 | Ball milling preparation method of graphene |
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| US7824651B2 (en) * | 2007-05-08 | 2010-11-02 | Nanotek Instruments, Inc. | Method of producing exfoliated graphite, flexible graphite, and nano-scaled graphene platelets |
| CN104004294A (en) * | 2014-05-07 | 2014-08-27 | 武汉金牛经济发展有限公司 | Preparation method of graphene-modified hard polyvinyl chloride composite tubing |
| CN104177524B (en) * | 2014-08-14 | 2016-01-27 | 杭州华纳化工有限公司 | A kind of graphene/nanometer calcium carbonate/vinylchlorid terpolymer resin in-situ suspension polymerization method |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102225759A (en) * | 2011-04-14 | 2011-10-26 | 温州医学院 | Low-temperature preparation method of hydroxy-functionalized graphene |
| CN103058176A (en) * | 2012-12-29 | 2013-04-24 | 华侨大学 | Method for preparing graphene efficiently |
| CN103466608A (en) * | 2013-09-11 | 2013-12-25 | 中南大学 | Ball milling preparation method of graphene |
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