CN106496427A - A kind of method for preparing surface modification ptfe micropowder - Google Patents
A kind of method for preparing surface modification ptfe micropowder Download PDFInfo
- Publication number
- CN106496427A CN106496427A CN201610959444.7A CN201610959444A CN106496427A CN 106496427 A CN106496427 A CN 106496427A CN 201610959444 A CN201610959444 A CN 201610959444A CN 106496427 A CN106496427 A CN 106496427A
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- Prior art keywords
- ptfe
- emulsion
- surface modification
- preparation
- micropowder
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F259/00—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00
- C08F259/08—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing fluorine
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
Abstract
The invention discloses a kind of surface modification ptfe micropowder and preparation method thereof, politef dispersion emulsion is placed in reaction vessel, deionized water is added, under agitation, makes PTFE emulsion be dispersed into homogeneous latex emulsion；Disposable addition vinyl monomer, under room temperature after 15～30min of stirring, is heated to 75 DEG C or so；Initiator is added, after 6～10h of isothermal reaction, terminates reaction, maintain to stir and lead to nitrogen in whole process；After reaction terminates；Emulsion is transferred out from reaction vessel, add water breakdown of emulsion, is filtered, through distilled water and washing with alcohol, be filtrated to get solid product, after drying, smash into powder to pieces.The present invention causes in commodity PTFE emulsion particle surface and is polymerized using vinyl monomer as modifying agent, and on the granule of PTFE emulsion, obvious gap disappears substantially, smoothened, granule increases, and the shape of granule is changed into spherical, and the spherical powder for obtaining is beneficial to disperse in other materials.
Description
Technical field
A kind of the invention belongs to field of new material preparation, more particularly to side for preparing surface modification ptfe micropowder
Method.
Background technology
Politef (PTFE) additive can be used in oils and fatss, coating, plastic or other material system, for increasing other
The greasy property of material, wear resistance, other flame retardant of plastics, anti-dripping melt performance of easy firing polymer etc..For
The performance of original material kept as far as possible, and the addition of PTFE needs sufficiently low, thus requires that the particle diameter of PTFE is little, i.e., will
Seek PTFE micropowders.Further, since the surface energy of PTFE is low, poor with the compatibility of other materials, it is more difficult to be evenly distributed on other
The stable material of dispersive property is formed in material so that the effect as additive is deteriorated, and performance can not be not fully exerted, because
And require that PTFE micropowders have moderate surface energy.In order to prepare PTFE micropowders, people take number of ways, such as：Using spoke
Prepare the PTFE micropowders of surface modification, directly prepare the methods such as PTFE micropowders from PTFE emulsion sedimentation according to cracking.Though non-lazy
Property gas in irradiation to crack can prepare the PTFE micropowders of surface modification, the molecular weight of the PTFE micropowders prepared due to cracking process compared with
Low, the fields such as oils and fatss are only used for, when for purposes such as anti-dripping melts, effect is poor does not even possess anti-dripping melt performance, therefore,
PTFE micropowders are prepared from emulsion sedimentation will be with wider purposes.PTFE micropowders due to directly settling preparation are easily reunited, and obtain
, typically more than 100 μm, particle diameter is larger for the particle diameter of the PTFE micropowders for obtaining, and the addition when additive is used as is big, it is possible to shadow
Ring the performance of matrix material.The method for preparing PTFE micropowders in existing PTFE emulsion, the particle diameter of the micropowder of preparation is typically at 100 μm
Hereinafter, mean diameter is at 25 μm or so；As, during this micropowder application, the bad dispersibility in other polymeric materials is difficult
Dispersed, thus the PTFE micropowders for being necessary to prepare good dispersion.The PTFE micropowders of favorable dispersibility to be prepared, most convenient
Method is in one layer of other polymeric material of PTFE micropowders surface-coated, by PTFE emulsion or micropowder and Merlon (PC) or third
The solution of alkene nitrile-BS (ABS) is mixed, and is evaporated volatile component afterwards and is obtained polymer bag
The PTFE resin for covering, easily drips the fire-retardant and anti-dripping agent of material when can serve as easy firing and burning, but these methods are related to
And solvent is arrived, the feature of environmental protection is poor, and there is potential safety hazard.Side in high molecular PTFE resin external sheath low-molecular-weight PTFE
Method, the micropowder of preparation as the anti-dripping agent of exotic material, but can be affected due to preparation method and raw material, the valency of micropowder
Lattice are expensive.The preparation method of modified Teflon, i.e., by emulsion polymerisation process PTFE particle surfaces be polymerized one layer its
Its polymer, the product for obtaining are 0.05～20 μm of powder, can be used as the anti-dripping agent of other materials.But use more
Silicone oil, chelating agen etc., raw material are complicated, the PTFE contents in the anti-dripping agent of preparation relatively low (less than 50%), and granule is big, as
When anti-dripping agent is used, usage amount is relatively large, is unfavorable for that this is material modified as other purposes such as self-lubricating modifying agent.
In sum, the method for the existing PTFE micropowders for preparing favorable dispersibility, the feature of environmental protection are poor, there is safety hidden
Suffer from, expensive, granule is big, and usage amount is relatively large when using as anti-dripping agent, be unfavorable for that this is material modified as from profit
Other purposes such as sliding modifying agent.
Content of the invention
It is an object of the invention to provide a kind of method for preparing surface modification ptfe micropowder, it is intended to solve existing
In technology, Technology is complicated, the production process feature of environmental protection is poor, there is potential safety hazard, and effectively reduces surface modification PTFE micropowder
Production cost, improves the compatibility of itself and other materials and reduces addition, beneficial to such micropowder as fire-retardant for plastic, anti-drop
Fall agent, the popularization and application of self-lubricating abrasion-proof material additive.
The present invention is achieved in that a kind of surface modification ptfe micropowder, the surface modification politef
Micropowder, is directly appended to enter in PTFE emulsion with 1～2 times of amount of politef quality as modifying agent using vinyl monomer
Row polyreaction；
The vinyl monomer is any one of methyl methacrylate, styrene, acrylonitrile or theirs is mixed
Compound.
Another object of the present invention is to a kind of preparation method of the surface modification ptfe micropowder is provided, described
Preparation method includes：
Step one, in the reaction vessel equipped with reflux condenser, agitator, thermometer and nitrogen inlet, adds one
Quantitative deionized water, quantitative PTFE emulsion under agitation, is added the quality hundred of PTFE after diluting in reaction vessel
Fraction is 2%～6%, makes PTFE emulsion be dispersed into homogeneous latex emulsion；
Step 2, the disposable vinyl monomer for adding 1～2 times of PTFE mass, under room temperature after 15～30min of stirring, plus
Heat is warming up to 75 DEG C；
Step 3, adds the initiator of vinyl monomer quality 0.2%～2%, terminates reaction after 6～10h of isothermal reaction,
Maintain to stir and lead to nitrogen in whole process；
Step 4, after reaction terminates, emulsion is transferred out from reaction vessel, and add water breakdown of emulsion, then filters, through distillation
Water and ethanol cyclic washing are multiple；Solid product is filtrated to get, solid product obtains solid product after drying, the solid is produced
Product smash into powder to pieces.
Further, the vinyl monomer is any one of MMA, St, An or mixture；
Further, the vinyl monomer is using front carrying out vacuum distillation purification.
Further, initiator is water soluble starter.
Further, solid product adopts drying under reduced pressure, baking temperature to be not more than 60 DEG C.
Further, nitrogen is 99.6% High Purity Nitrogen.
Another object of the present invention is to providing a kind of preparation using the surface modification ptfe micropowder
PTFE micropowders.
The present invention using vinyl monomers such as methyl methacrylate, styrene as modifying agent, at a certain temperature in business
The surface of product PTFE emulsion particle is caused and is polymerized, and is prepared for the modified ptfe micropowder of high PTFE contents, after cladding,
On the granule of PTFE emulsion, obvious gap disappears substantially, becomes more to smooth；Particle size slightly increases, and from mean diameter is
168nm increases to 230nm or so；The shape of granule is also changed into spherical；Spherical after drying be substantially achieved reservation, obtained is spherical
Powder is beneficial to disperse in other materials.
Description of the drawings
Fig. 1 is the method flow diagram for preparing surface modification ptfe micropowder provided in an embodiment of the present invention.
Fig. 2 is the SEM that employing JSM-7500F scanning electron microscopies provided in an embodiment of the present invention obtain surface modification PTFE micropowder
Figure；
In figure：Particle in (a) PTFE emulsion；(b) surface modification PTFE micropowder (S1 emulsions)；(c) surface modification PTFE (S5
Emulsion)；(d) surface modification PTFE micropowder (S1-50).
Specific embodiment
In order that the objects, technical solutions and advantages of the present invention become more apparent, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that specific embodiment described herein is not used to only in order to explain the present invention
Limit the present invention.
Below in conjunction with the accompanying drawings the application principle of the present invention is explained in detail.
Refer to Fig. 1 to Fig. 2：
Surface modification ptfe micropowder provided in an embodiment of the present invention adopts vinyl monomer (methyl methacrylate
Ester, styrene, acrylonitrile) as modifying agent, it is directly appended to enter in PTFE emulsion with 1～2 times of amount of politef quality
Row polyreaction；Prepare modified ptfe micropowder.
As shown in figure 1, the preparation method of surface modification ptfe micropowder provided in an embodiment of the present invention is specially：
S101, in the reaction vessel equipped with reflux condenser, agitator, thermometer and nitrogen inlet, add certain
The deionized water of amount, the PTFE emulsion of ormal weight under agitation, is added in reaction vessel (the quality hundred of PTFE after dilution
Fraction be 2%～6%), make PTFE emulsion be dispersed into homogeneous latex emulsion；
S102, the disposable vinyl monomer for adding 1～2 times of PTFE mass, under room temperature after 15～30min of stirring, heating
It is warming up to 75 DEG C or so；
S103, the initiator for adding vinyl monomer quality 0.2%～2%, terminate reaction after 6～10h of isothermal reaction, whole
Maintain to stir and lead to nitrogen during individual；
After S104, reaction terminate, emulsion is transferred out from reaction vessel, add water breakdown of emulsion, then filters, through distilled water
And ethanol cyclic washing is repeatedly, is finally filtrated to get solid product, solid product obtains solid product after drying, by the solid
Product smashs into powder to pieces.
Further, the vinyl monomer is any one of MMA, St, An or their mixture；
Further, the vinyl monomer is using front carrying out vacuum distillation purification.
Further, initiator is water soluble starter.
Further, solid product adopts drying under reduced pressure, baking temperature to be not more than 60 DEG C.
Further, nitrogen is 99.6% High Purity Nitrogen.
For prove the embodiment of the present invention obtain beneficial effect, the embodiment of the present invention by taking MMA as an example, the numbering of four samples
And preparation condition is：
S1 samples are finally designated as S1-50 in 50 DEG C of drying, are designated as S1-100 in 100 DEG C of drying.
The embodiment of the present invention carries out the measure of size and distribution using following methods：
Using JL-6000 laser particle analyzers, the test of initial particle is determined using wet method, will unseasoned products in water point
Directly determine after dissipating；The test of final powder diameter adopts dry method, i.e., test under pressure 30bar gases.D50Data display, bag
PTFE after covering belongs to micropowder.
| Sample | D50(μm) | D90(μm) |
| S1 | 1.05 | 4.42 |
| S5 | 0.93 | 4.04 |
| S1-50 | 14.82 | 53.75 |
| S1-100 | 23.74 | 58.67 |
Fig. 2 is the SEM figures that the embodiment of the present invention obtains surface modification PTFE micropowder using JSM-7500F scanning electron microscopies, with
When determine emulsion and powder, as a result show, after cladding, on the granule of PTFE emulsion, obvious gap disappears substantially, become
Obtain and more smooth；Particle size slightly increases, and increases to 230nm or so from mean diameter for 168nm；The shape of granule is also changed into
Spherical；Spherical after drying be substantially achieved reservation, the spherical powder for obtaining be beneficial in other materials disperse.
The present invention using vinyl monomers such as methyl methacrylate, styrene as modifying agent, at a certain temperature with business
The surface of product PTFE emulsion particle is caused and is polymerized, and is prepared for the modified ptfe micropowder of high PTFE contents, after cladding,
On the granule of PTFE emulsion, obvious gap disappears substantially, becomes more to smooth；Particle size slightly increases, and from mean diameter is
168nm increases to 230nm or so；The shape of granule is also changed into spherical；Spherical after drying be substantially achieved reservation, obtained is spherical
Powder is beneficial to disperse in other materials.
Presently preferred embodiments of the present invention is the foregoing is only, not in order to limit the present invention, all in essence of the invention
Any modification, equivalent and improvement that is made within god and principle etc., should be included within the scope of the present invention.
Claims (7)
1. a kind of surface modification ptfe micropowder, it is characterised in that the surface modification ptfe micropowder adopts second
Alkenyl monomer is directly appended to carry out being polymerized instead in PTFE emulsion with 1～2 times of amount of politef quality as modifying agent
Should；
The vinyl monomer is methyl methacrylate, styrene, any one in acrylonitrile.
2. a kind of preparation method of surface modification ptfe micropowder as claimed in claim 1, it is characterised in that the preparation
Method includes：
Step one, in the reaction vessel equipped with reflux condenser, agitator, thermometer and nitrogen inlet, adds deionization
Water, under agitation, quantitative PTFE emulsion is added in reaction vessel, after dilution the mass percent of PTFE be 2%～
6%, make PTFE emulsion be dispersed into homogeneous latex emulsion；
Step 2, the disposable vinyl monomer for adding 1～2 times of PTFE mass, under room temperature after 15～30min of stirring, heating rises
Temperature is to 75 DEG C；
Step 3, adds the initiator of vinyl monomer quality 0.2%～2%, terminates reaction, entirely after 6～10h of isothermal reaction
During maintain stir and lead to nitrogen；
Step 4, after reaction terminates, emulsion is transferred out from reaction vessel, and add water breakdown of emulsion；Then filter, through distilled water and
Ethanol cyclic washing is multiple；Solid product is filtrated to get, solid product obtains solid product after drying, and the solid product is smash
It is broken into powder.
3. the preparation method of surface modification ptfe micropowder as claimed in claim 2, it is characterised in that the vinyl
Monomer is using front carrying out vacuum distillation purification.
4. the preparation method of surface modification ptfe micropowder as claimed in claim 2, it is characterised in that initiator is water
Soluble initiator.
5. the preparation method of surface modification ptfe micropowder as claimed in claim 2, it is characterised in that solid product is adopted
With drying under reduced pressure, no more than 60 DEG C of baking temperature.
6. the preparation method of surface modification ptfe micropowder as claimed in claim 2, it is characterised in that nitrogen is
99.6% High Purity Nitrogen.
7. PTFE micropowders of the preparation of surface modification ptfe micropowder described in a kind of utilization claim 1.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108878172A (en) * | 2017-05-10 | 2018-11-23 | 东莞东阳光科研发有限公司 | A kind of preparation method of electrode for super capacitor |
| CN109280135A (en) * | 2018-08-30 | 2019-01-29 | 铨盛聚碳科技股份有限公司 | A kind of anti-dripping agent and preparation method thereof with superior compatibility |
| CN111675799A (en) * | 2020-06-29 | 2020-09-18 | 徐州市久隆密封件科技有限公司 | Modified polyurethane elastomer and preparation method and application thereof |
| CN113136129A (en) * | 2021-03-18 | 2021-07-20 | 广东至诚紫光新材料有限公司 | Water-based high-weather-resistance fluorocarbon coating composition and preparation method thereof |
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| CN101597412A (en) * | 2009-07-07 | 2009-12-09 | 上海安特洛普化学有限公司 | A kind of modified Teflon and its production and application |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108878172A (en) * | 2017-05-10 | 2018-11-23 | 东莞东阳光科研发有限公司 | A kind of preparation method of electrode for super capacitor |
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| CN111675799A (en) * | 2020-06-29 | 2020-09-18 | 徐州市久隆密封件科技有限公司 | Modified polyurethane elastomer and preparation method and application thereof |
| CN113136129A (en) * | 2021-03-18 | 2021-07-20 | 广东至诚紫光新材料有限公司 | Water-based high-weather-resistance fluorocarbon coating composition and preparation method thereof |
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Application publication date: 20170315 |