CN106883337A - Can be by expanded HMW tetrafluoroethene copolymerization dispersion resin - Google Patents
Can be by expanded HMW tetrafluoroethene copolymerization dispersion resin Download PDFInfo
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- CN106883337A CN106883337A CN201510933000.1A CN201510933000A CN106883337A CN 106883337 A CN106883337 A CN 106883337A CN 201510933000 A CN201510933000 A CN 201510933000A CN 106883337 A CN106883337 A CN 106883337A
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- tetrafluoroethene
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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
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/26—Tetrafluoroethene
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Abstract
The present invention relates to it is a kind of can be by expanded HMW tetrafluoroethene copolymerization dispersion resin, the resin is with ultra-high purity tetrafluoroethylene monomer and extraordinary comonomer, copolymerization forms dispersion emulsion in autoclave, the size of primary particle is at 60 ~ 300 nanometers, the standard specific gravity SSG of resin is between 2.13 ~ 2.18 after drying, comonomer used by the copolymer tetrafluoroethylene resin is a kind of not fluorine-containing, hydrogeneous monomer, there are 5 10 carbon and there is the unsaturated bond energy to carry out free machine copolymerization, comonomer consumption used account for the gross dry weight amount of polytetrafluoroethyldispersion dispersion resin than 0.1% ~ 5.0%, the super high molecular weight tetrafluoroethene copolymerization dispersion resin can be made material of the varicosity containing microcellular structure by expanding processing, and can be degraded by microorganisms, solve environmental issue.
Description
Technical field
Be able to can be degraded by microorganisms by expanded HMW tetrafluoroethene copolymerization dispersion resin and its varicosity poromerics the present invention relates to a kind of, environmental issue is alleviated.
Background technology
Fluorine resin especially polyflon be earliest by du pont company in
1938
Year, invented during World War II.Because having excellent physical and mechanical properties and chemical stability, extensive use is obtained in each fields such as chemical, mechano-electronic, space flight military project, new material and new energy.Polytetrafluoroethylene (PTFE) homopolymers dispersion resin is extruded and extrusion and de-oiling using paste, again by uniaxial or biaxial stretching, can obtain according to the expanded polytetrafluoroethylsealing material for having microcellular structure, due to its property, the material has turned into a kind of high-end functional fluoropolymer material, is used for example as filter membrane, garment film, man-made organ, wire-insulating material and encapsulant etc..But proplast is entirely free of hydrogen, cannot be degraded by microorganisms in the Nature, cause environmental issue.
Expanded polytetrafluoroethylsealing poromerics is because with excellent mechanical performance, water-proof breathable properties, and chemical stability, late nineteen seventies just be used to do wire cable insulating material, artificial blood vessel, band, filter membrane, and garment film upon coming out.It is industrial generally to use high-purity tetrafluoroethylene monomer, carry out dispersion polymerization processes and prepare dispersion resin.Because polytetrafluoroethyldispersion dispersion resin can not carry out molten thermoplastic processing, but can be by paste extruding, extrusion, de-oiling, then uniaxial or biaxial stretching, as with micro- porous excellent material.Problem is that varicosity proplast is entirely free of hydrogen, cannot be degraded by microorganisms in the Nature, causes environmental issue.
Modified polytetrafluoroethyldispersion dispersion resin is in U.S. Patent number
3819594
And
5756620
In have teaching
,
Modified polytetrafluoroethyldispersion dispersion resin refers to that its weight ratio is added in proplast
< 0.1%
Modified monomer, du pont company's modified monomer used herein is perfluor
(
Alkyl vinyl ether
),
Such as perfluor
(
Propyl vinyl ether
),
And hexafluoropropene
,
But the resin obtained by preparing cannot be processed makes expanded PTFE.Japan Patent
26242/1981
Teaching CTFE does modified polytetrafluoroethyldispersion dispersion resin
,
But its heat endurance can not show a candle to the resin polytetrafluoroethyldispersion dispersion resin not being modified.Japanese great Jing companies are in U.S. Patent number
4840998
And
5176958
In also instruct the preparation method of modified polytetrafluoroethyldispersion dispersion resin
,
Modified monomer wherein used has following structure
: X-(CF2)nOCF=CF2
And
C3F7
（
OCF2CF2CF2
）
m
(OCF(CF3)CF2)lOCF=CF2;
But these modified monomers used are too expensive, and cannot be also degraded by microorganisms because not hydrogeneous.
Expanded polytetrafluoroethylsealing generally uses Patent No.
US 3953566
With
US 4187390
United States Patent (USP) disclosed in preparation method prepare, the preparation method of the expanded polytetrafluoroethylsealing mainly includes the following steps that：After polytetrafluoroethyldispersion dispersion resin and lubricating oil blending, paste extruding extrusion, de-oiling, then uniaxial or biaxial stretching is carried out under polytetrafluoroethylene (PTFE) fusing point, and expanded PTFE microporous barrier is obtained final product, such membrane material is because being that perfluorinated material cannot also be degraded by microorganisms.
The Patent No. of great Jing companies
US 5234739
United States Patent (USP) disclose the preparation method of another expanded PTFE microporous barrier, it is by after polytetrafluoroethyldispersion dispersion resin and kerosene blending, paste extruding extrusion, de-oiling, sizing is first sintered more than polytetrafluoroethylene (PTFE) fusing point again, then uniaxial or biaxial stretching is carried out below polytetrafluoroethylene (PTFE) fusing point, the microporous teflon membran of micropore multifilament is obtained.The aperture of the microporous barrier obtained by the method is more than
100
Nanometer, exists more
200~500
Between nanometer, such membrane material cannot also be degraded by microorganisms.
Patent No.
US 5814405
United States Patent (USP) disclose the preparation method of another expanded PTFE microporous barrier：After polytetrafluoroethyldispersion dispersion resin and kerosene blending, paste extruding extrusion, de-oiling, longitudinal stretching is carried out below polytetrafluoroethylene (PTFE) fusing point again, sizing is first sintered more than polytetrafluoroethylene (PTFE) fusing point again, then cross directional stretch is carried out below polytetrafluoroethylene (PTFE) fusing point, the microporous teflon membran of micropore multifilament has been obtained, the aperture of the microporous barrier obtained by the method is more than
200
Nanometer, exists more
1000
Ran, such membrane material cannot also be degraded by microorganisms.
The patent No.
201110191315.5
China's patent of invention disclose a kind of ultrahigh-molecular-weight modified polytetrafluoroethyldispersion dispersion resin, though varicosity micropore membrane material can be fabricated to by expanded, this resinoid cannot also be degraded by microorganisms, or do not solve environmental issue.
A kind of tetrafluoro ethylene polymer being degraded by microorganisms is needed on the market, and can be processed to material of the varicosity containing microcellular structure.
The content of the invention
To be solved by this invention is environmental issue, it is the difficulty for overcoming prior art products to be degraded by microorganisms, offer is a kind of can be by expanded HMW tetrafluoroethene copolymerization dispersion resin, comprising its preparation method, the high molecular weight polytetrafluoroethyldispersions copolymerization dispersion resin for obtaining in this approach, it was found that its purposes may be alternatively used for preparing high intensity expanded PTFE poromerics unexpectedly, disclosure satisfy that tensile strength application higher, fortunately because containing enough hydrogen on its main chain, can progressively be degraded from hydrogeneous by microorganism, environmental issue is releived, it is satisfactory to both parties neat U.S..
To solve above technical problem, the present invention is adopted the following technical scheme that：
A kind of preparation method of HMW tetrafluoroethene copolymerization dispersion resin, the preparation method comprises the following steps：
（
1
）, autoclave vacuumize deoxygenation：In autoclave, pure water is added, a small amount of paraffin of preferably adding some points again after reactor good seal, vacuumizes deoxygenation, until oxygen content is less than
50ppm
；
（
2
）, high pressure polymerisation reaction：Purity is passed through in reactor to be at least up to
99.995%
Tetrafluoroethene（
CF2=CF2
）Monomer and add it is not fluorine-containing, it is hydrogeneous, contain
5-10
The comonomer of individual carbon, adds a small amount of radical initiator and emulsion dispersion agent, reaction temperature control to exist
25
℃
~150
Between DEG C, reaction pressure control exists
1~3MPa
, the reaction time
1~9
Hour.
Table Cheng and post processing：Gained dispersion emulsion solid content exists
15~45%
, primary particle particle mean size exists
60~300
Nanometer between, cohesion drying after resin, its standard specific gravity be
2.13~2.18
Between, represent that the molecular weight of this resin at least exists
107
More than.
Preferably, described polytetrafluoroethyldispersion dispersion resin：Primary particle particle mean size exists
100~290
Nanometer between, cohesion drying after resin, its standard specific gravity be
2.13~2.169
Between
,
And can be degraded by microorganisms, use
DSC
Thermal analyzer surveys this melting point resin has heat absorption peak to exist
320-350
Between degree.
Step（
1
）In, described autoclave is preferably horizontal high-pressure kettle, and described paraffin is preferably low molecular weight polyethylene homopolymers, and fusing point exists
60~90
Between degree.
Step（
2
）In, described comonomer is free from fluorine, hydrogeneous monomer, contains
5-10
Individual carbon, and free machine copolymerization is carried out containing a unsaturated bond energy and tetrafluoroethene, and have following structure：
R1-CH=C
（
R2
）
R3
, wherein
R1
It is
H
Or
R
（Not fluorine-containing, hydrogeneous alkyl, has
3-8
Individual carbon）Or
-O-R
（Not fluorine-containing, hydrogeneous ether alkyl, has
3-8
Individual carbon）；
R2
It is
H
Or methyl；
R3
It is
H
Or methyl.Described comonomer can be a mixture.The consumption of comonomer used accounts for the gross weight of tetrafluoroethene copolymerization dispersion resin
0.1%~5.0%
, preferably exist
0.1%~3.0%
Between.
Described radical initiator is persulfate, the redox system of permanganate, or its mixture
,
Consumption accounts for total resin weight
0.0001%~0.01%
.The fluorine-containing dispersant is that fluorine-containing have
6~12
The carboxylic acid or sulfonate or its mixture of individual carbon
,
Consumption accounts for total resin weight
0.05%~1.0%
。
Described super high molecular weight tetrafluoroethene copolymerization dispersion resin is through experiment, it was found that can be extruded by paste unexpectedly, calendering, uniaxial or biaxial stretching turns into material of the varicosity TFE copolymer containing nanofiber microcellular structure, its tensile strength can be degraded by microorganisms better than the material containing micropore that general tetrafluoroethene homopolymerization dispersion resin is made.The proportion of this porous structural material exists
0.1
~
1.5
, preferably exist
0.2
~
1.2
Between.
Described comonomer, comprising
CH2=CH-R4,
（
R4
It is
3-8
The alkyl of individual carbon）；Also include
CH2=CH-O-R5,
（
R5
It is
3-8
The alkyl of individual carbon）.
The present invention has advantages below compared with prior art：Produced super high molecular weight tetrafluoroethene copolymerization dispersion resin can be degraded by microorganisms, environmental issue is releived, and cost is relatively low, and can be extruded by paste, calendering, uniaxial or biaxial stretching turns into material of the varicosity TFE copolymer containing microcellular structure, and its physical mechanical strength such as tension stress etc. is higher, can be fabricated to high strength microporous film for clothes and filter, fiber, sealing material, pad, tubing etc..
Specific embodiment
With reference to specific embodiment, the present invention is further detailed explanation, but the invention is not restricted to these embodiments.
Contrast example
A
（Modified polytetrafluoroethyldispersion dispersion resin）
It is essentially repeated the patent of du pont company
5756620
In example one：
In a horizontal garden column type（Draw ratio
1.7
：
1
）Jacketed can lead to cold water
/
In the autoclave of steam, kettle inner volume is about
36
Rise, there are four blades, add
21
Kilogram deionized water,
600
Gram paraffin（Fusing point is about
56-58
Degree）,
1
Gram succinic acid,
0.5
Gram oxalic acid,
25
Milliliter concentration
20%
Perfluoro caprylic acid ammonia spirit.Reactor is sealed, rotating speed is raised to
65 rpm,
Temperature rise is arrived in kettle
65
After degree, deoxygenation is vacuumized, reactor is boosted to normal pressure by logical tetrafluoroethylene monomer, then vacuumizes deoxygenation, leads to tetrafluoroethene, then vacuumizes deoxygenation, until oxygen content in kettle
<
25ppm
, under micro-vacuum state, suction in kettle
30
The perfluor of milliliter（Propyl vinyl ether）Modified monomer, then arrives temperature rise in kettle
80
Degree, rotating speed is transferred to
70 rpm,
Purity is passed through in toward kettle at least
99.999%
Tetrafluoroethylene monomer about
1.7
Kilogram, pressure is up to about in kettle
2.72
MPa
, the octarius that then starts to use tricks is toward squeezing into initiator in kettle：
0.1
Gram
/
The potassium permanganate solution of water is risen, with per minute
25
The speed of milliliter is squeezed into, equivalent to per minute
2.5
The amount of milligram potassium permanganate is squeezed into.After reaction starts, tetrafluoroethylene monomer has consumption in kettle, and kettle is interior to be passed through tetrafluoroethylene monomer again, pressure in kettle is maintained about
2.6-2.7
MPa.
Reaction is about
10
After minute,
1.4
Kilogram tetrafluoroethylene monomer be also passed through in kettle again, octarius of at this moment using tricks is toward squeezing into concentration in kettle
27.5
Gram perfluoro caprylic acid ammonia
/
Aqueous solution, with
50
Milliliter
/
The speed of minute is squeezed into,
20
Minute squeezes into altogether
1000
Milliliter, waits altogether
11.8
Kilogram tetrafluoroethylene monomer be passed through in kettle, the amount of initiator is changed to
1
Milliliter
/
Minute, wait altogether
15.4
Kilogram tetrafluoroethylene monomer be passed through in kettle after, cooling stop stirring, stop reaction, the reaction time is about
108
Minute.The emulsion solid content for obtaining is about
41%
, primary particle particle mean size is about
0.18
Micron, modified monomer accounts for the total amount of dried resin
0.097%
, the standard specific gravity of dried resin
SSG=2.165,
With
DSC
Melting point resin peak is surveyed to exist
323-343
Between degree.
Expanded PTFE stretching experiment：The dried polytetrafluoroethyldispersion dispersion resin and boiling point obtained by this example
180-200
DEG C the U.S.
Exxon Mobile
Senior lubricant（The trade mark
Isopar
K
）With
100:18
Weight mixed than mutually, it is gentle stir after be first pressed into cylinder in advance, then
30
High pressure is extruded into paste rod at DEG C, and compression ratio is about
200
：
1
.The wet rod is existed
220
DEG C baking oven in de-oiling obtain dry rod.The dry rod is existed
250
DEG C hot conditions under carry out longitudinal stretching：Draw speed exists
10%/
In the case of second, rod is once just pulled off, it is impossible to obtain the micropore bar of expanded PTFE；Draw speed exists
100%/
In the case of second, rod is moved to about
50%
Just it is pulled off during elongation, cannot also obtains the micropore bar of preferable expanded PTFE.So this modified polytetrafluoroethylresin resin cannot bring the materials application for doing expanded PTFE.
Contrast example
B
（Super high molecular weight polytetrafluoroethylene (PTFE) homopolymers dispersion resin, does not have comonomer）
In a horizontal garden column type（Draw ratio
1.7
：
1
）Jacketed can lead to cold water
/
In the autoclave of steam, kettle inner volume is about
36
Rise, there are four blades, add
21
Kilogram deionized water,
600
Gram paraffin（Fusing point
56-58
Degree）,
1
Gram succinic acid,
0.5
Gram oxalic acid,
25
Milliliter concentration
20%
Perfluoro caprylic acid ammonia spirit.Reactor is sealed, rotating speed is raised to
65 rpm,
Temperature rise is arrived in kettle
65
After degree, deoxygenation is vacuumized, reactor is boosted to normal pressure by logical tetrafluoroethylene monomer, then vacuumizes deoxygenation, leads to tetrafluoroethene, then vacuumizes deoxygenation, until oxygen content in kettle
<
25ppm
, then temperature rise in kettle is arrived
80
Degree, rotating speed is transferred to
70 rpm,
Purity is passed through in toward kettle at least
99.999%
Tetrafluoroethylene monomer about
1.7
Kilogram, pressure is up to about in kettle
2.72
MPa
, the octarius that then starts to use tricks is toward squeezing into initiator in kettle：
0.1
Gram
/
The potassium permanganate solution of water is risen, with per minute
20
The speed of milliliter is squeezed into, equivalent to per minute
2
The amount of milligram potassium permanganate is squeezed into.After reaction starts, tetrafluoroethylene monomer has consumption in kettle, and kettle is interior to be passed through tetrafluoroethylene monomer again, pressure in kettle is maintained about
2.6-2.7
MPa.
Reaction is about
15
After minute,
1.5
Kilogram tetrafluoroethylene monomer be also passed through in kettle again, octarius of at this moment using tricks is toward squeezing into concentration in kettle
27.5
Gram perfluoro caprylic acid ammonia
/
Aqueous solution, with
50
Milliliter
/
The speed of minute is squeezed into,
20
Minute squeezes into altogether
1000
Milliliter, waits altogether about
10
Kilogram tetrafluoroethylene monomer be passed through in kettle, initiator stop squeeze into kettle, wait altogether
12.5
Kilogram tetrafluoroethylene monomer be passed through in kettle after, cooling stop stirring, stop reaction, the reaction time is about
128
Minute.The emulsion solid content for obtaining is about
35%
, primary particle particle mean size is about
0.3
Micron, the standard specific gravity of dried resin
SSG=2.168,
With
DSC
Melting point resin peak is surveyed to exist
327-345
Between degree.
Expanded PTFE stretching experiment：The dried polytetrafluoroethyldispersion dispersion resin and boiling point obtained by this example
180-200
DEG C the U.S.
Exxon Mobile
Senior lubricant（The trade mark
Isopar
K
）With
100:18
Weight mixed than mutually, it is gentle stir after be first pressed into cylinder in advance, then
30
High pressure is extruded into paste rod at DEG C, and compression ratio is about
200
：
1
.The wet rod is existed
220
DEG C baking oven in de-oiling obtain dry rod.The dry rod is existed
250
DEG C hot conditions under carry out longitudinal stretching：Draw speed exists
10%/
It is stretchable in the case of second
500%
, obtain the micropore bar of expanded PTFE；Draw speed exists
100%/
It is also stretchable in the case of second
500%
Elongation, obtains the micropore bar of expanded PTFE, and the micropore bar of the expanded PTFE of gained exists
360
Shaped under degree high temperature
30
Second.It is about by the tensile strength of the micropore bar of the polytetrafluoroethylene (PTFE) after sizing
70
MPa
.So this super high molecular weight polytetrafluoroethyl-ne polyamino alkenyl resin can bring the application for doing expanded PTFE, but tensile strength is necessary to improve again.
Implement example
1
（Super high molecular weight tetrafluoroethene copolymerization dispersion resin）
In a horizontal garden column type（Draw ratio
1.7
：
1
）Jacketed can lead to cold water
/
The autoclave of steam, kettle inner volume is about
36
Rise, there are four blades, add
21
Kilogram deionized water,
600
Gram low molecular weight polyethylene（Fusing point
70-78
Degree）,
1
Gram succinic acid,
0.5
Gram oxalic acid,
25
Milliliter concentration
20%
Perfluoro caprylic acid ammonia spirit.Reactor is sealed, rotating speed is raised to
65 rpm,
Temperature rise is arrived in kettle
65
After degree, deoxygenation is vacuumized, reactor is boosted to normal pressure by logical tetrafluoroethylene monomer, then vacuumizes deoxygenation, leads to tetrafluoroethene, then vacuumizes deoxygenation, until oxygen content in kettle
<
25ppm
, under micro-vacuum state, suction in kettle
12.5
Gram, purity
>98%
,
1-
Hexene（
CH2=CH-C4H9
）It is comonomer, then temperature rise in kettle is arrived
60
Degree, rotating speed is transferred to
70 rpm,
Purity is passed through in toward kettle at least
99.999%
Tetrafluoroethene（
CF2=CF2
）Monomer is about
1.7
Kilogram, pressure is up to about in kettle
2.72
MPa
, the octarius that then starts to use tricks is toward squeezing into initiator in kettle：
0.1
Gram
/
The potassium permanganate solution of water is risen, with per minute
20
The speed of milliliter is squeezed into, equivalent to per minute
2
The amount of milligram potassium permanganate is squeezed into.After reaction starts, tetrafluoroethylene monomer has consumption in kettle, and kettle is interior to be passed through tetrafluoroethylene monomer again, pressure in kettle is maintained about
2.6-2.7
MPa.
Reaction is about
17
After minute, about
1.5
Kilogram tetrafluoroethylene monomer be passed through in kettle, octarius of at this moment using tricks is toward squeezing into concentration in kettle
27.5
Gram perfluoro caprylic acid ammonia
/
Aqueous solution, with
50
Milliliter
/
The speed of minute is squeezed into,
20
Minute squeezes into altogether
1000
Milliliter, waits altogether about
7
Kilogram tetrafluoroethylene monomer be passed through in kettle after, initiator stop squeeze into kettle, wait altogether
12.5
Kilogram tetrafluoroethylene monomer be passed through in kettle after, cooling stop stirring, stop reaction, the reaction time is about
139
Minute.The emulsion solid content for obtaining is about
33%
, primary particle particle mean size is about
0.29
Micron（
290
Nanometer）, comonomer consumption accounts for the total amount of dried resin
0.1%
, the standard specific gravity of dried resin
SSG=2.169,
With
DSC
Survey melting point resin and find there is heat absorption peak to exist
320-350
Between degree.
Expanded PTFE stretching experiment：The dried polytetrafluoroethyldispersion dispersion resin and boiling point obtained by this example
180-200
DEG C the U.S.
Exxon Mobile
Senior lubricant（The trade mark
Isopar
K
）With
100:18
Weight mixed than mutually, it is gentle stir after be first pressed into cylinder in advance, then
30
High pressure is extruded into paste rod at DEG C, and compression ratio is about
200
：
1
.The wet rod is existed
220
DEG C baking oven in de-oiling obtain dry rod.The dry rod is existed
250
DEG C hot conditions under carry out longitudinal stretching：Draw speed exists
10%/
It is stretchable in the case of second
1000%
, obtain the micropore bar of expanded PTFE；Draw speed exists
100%/
It is also stretchable in the case of second
1000%
Elongation, obtains the micropore bar of expanded PTFE, and the micropore bar of the expanded PTFE of gained exists
360
Shaped under degree high temperature
30
Second.It is about by the tensile strength of the micropore bar of the polytetrafluoroethylene (PTFE) after sizing
172
MPa
.So this ultrahigh-molecular-weight modified polytetrafluoroethyldispersion dispersion resin can be used to do the application of high intensity expanded PTFE, its tensile strength can meet many high-end applications, can also be degraded by microorganisms.
Implement example
2
（Super high molecular weight tetrafluoroethene copolymerization dispersion resin）
In a horizontal garden column type（Draw ratio
1.7
：
1
）Jacketed can lead to cold water
/
The autoclave of steam, kettle inner volume is about
36
Rise, there are four blades, add
21
Kilogram deionized water,
600
Gram low molecular weight polyethylene（Fusing point
70-78
Degree）,
1
Gram succinic acid,
0.5
Gram oxalic acid,
25
Milliliter concentration
20%
Perfluoro caprylic acid ammonia spirit.Reactor is sealed, rotating speed is raised to
65 rpm,
Temperature rise is arrived in kettle
65
After degree, deoxygenation is vacuumized, reactor is boosted to normal pressure by logical tetrafluoroethylene monomer, then vacuumizes deoxygenation, leads to tetrafluoroethene, then vacuumizes deoxygenation, until oxygen content in kettle
<
25ppm
, under micro-vacuum state, suction in kettle
130
Gram, purity
>98%
,
1-
Octene（
CH2=CH-C6H13
）It is comonomer, then temperature rise in kettle is arrived
65
Degree, rotating speed is transferred to
80 rpm,
Purity is passed through in toward kettle at least
99.999%
Tetrafluoroethene（
CF2=CF2
）Monomer is about
1.7
Kilogram, pressure is up to about in kettle
2.7
MPa
, the octarius that then starts to use tricks is toward squeezing into initiator in kettle：
0.1
Gram
/
The potassium permanganate solution of water is risen, with per minute
20
The speed of milliliter is squeezed into, equivalent to per minute
2
The amount of milligram potassium permanganate is squeezed into.After reaction starts, tetrafluoroethylene monomer has consumption in kettle, and kettle is interior to be passed through tetrafluoroethylene monomer again, pressure in kettle is maintained about
2.6-2.7
MPa.
Reaction is about
23
After minute, about
1.5
Kilogram tetrafluoroethylene monomer be passed through in kettle, octarius of at this moment using tricks is toward squeezing into concentration in kettle
27.5
Gram perfluoro caprylic acid ammonia
/
Aqueous solution, with
50
Milliliter
/
The speed of minute is squeezed into,
20
Minute squeezes into altogether
1000
Milliliter, waits altogether about
7
Kilogram tetrafluoroethylene monomer be passed through in kettle after, initiator stop squeeze into kettle, wait altogether about
13
Kilogram tetrafluoroethylene monomer be passed through in kettle after, cooling stop stirring, stop reaction, the reaction time is about
158
Minute.The emulsion solid content for obtaining is about
35%
, primary particle particle mean size is about
0.19
Micron（
190
Nanometer）, comonomer consumption accounts for the total amount of dried resin
1.0%
, the standard specific gravity of dried resin
SSG=2.15,
With
DSC
Survey melting point resin and find there is heat absorption peak to exist
320-350
Between degree.
Expanded PTFE stretching experiment：The dried polytetrafluoroethyldispersion dispersion resin and boiling point obtained by this example
180-200
DEG C the U.S.
Exxon Mobile
Senior lubricant（The trade mark
Isopar
K
）With
100:18
Weight mixed than mutually, it is gentle stir after be first pressed into cylinder in advance, then
30
High pressure is extruded into paste rod at DEG C, and compression ratio is about
200
：
1
.The wet rod is existed
220
DEG C baking oven in de-oiling obtain dry rod.The dry rod is existed
250
DEG C hot conditions under carry out longitudinal stretching：Draw speed exists
10%/
It is stretchable in the case of second
1000%
, obtain the micropore bar of expanded PTFE；Draw speed exists
100%/
It is also stretchable in the case of second
1000%
Elongation, obtains the micropore bar of expanded PTFE, and the micropore bar of the expanded PTFE of gained exists
360
Shaped under degree high temperature
30
Second.It is about by the tensile strength of the micropore bar of the polytetrafluoroethylene (PTFE) after sizing
189
MPa
.So this ultrahigh-molecular-weight modified polytetrafluoroethyldispersion dispersion resin can be used to do the application of high intensity expanded PTFE, its tensile strength can meet many high-end applications, can also be degraded by microorganisms.
Implement example
3
（Super high molecular weight tetrafluoroethene copolymerization dispersion resin）
In a horizontal garden column type（Draw ratio
1.7
：
1
）Jacketed can lead to cold water
/
The autoclave of steam, kettle inner volume is about
36
Rise, there are four blades, add
21
Kilogram deionized water,
600
Gram low molecular weight polyethylene（Fusing point
70-78
Degree）,
1
Gram succinic acid,
0.5
Gram oxalic acid,
25
Milliliter concentration
20%
Perfluoro caprylic acid ammonia spirit.Reactor is sealed, rotating speed is raised to
65 rpm,
Temperature rise is arrived in kettle
65
After degree, deoxygenation is vacuumized, reactor is boosted to normal pressure by logical tetrafluoroethylene monomer, then vacuumizes deoxygenation, leads to tetrafluoroethene, then vacuumizes deoxygenation, until oxygen content in kettle
<
25ppm
, under micro-vacuum state, suction in kettle
25
Gram, purity
>98%
, IVE（
CH2=CH-OC4H9
）It is comonomer, then temperature rise in kettle is arrived
68
Degree, rotating speed is transferred to
75
rpm,
Purity is passed through in toward kettle at least
99.999%
Tetrafluoroethene（
CF2=CF2
）Monomer is about
1.7
Kilogram, pressure is up to about in kettle
2.7
MPa
, the octarius that then starts to use tricks is toward squeezing into initiator in kettle：
0.1
Gram
/
The potassium permanganate solution of water is risen, with per minute
20
The speed of milliliter is squeezed into, equivalent to per minute
2
The amount of milligram potassium permanganate is squeezed into.After reaction starts, tetrafluoroethylene monomer has consumption in kettle, and kettle is interior to be passed through tetrafluoroethylene monomer again, pressure in kettle is maintained about
2.6-2.7
MPa.
Reaction is about
19
After minute, about
1.5
Kilogram tetrafluoroethylene monomer be passed through in kettle, octarius of at this moment using tricks is toward squeezing into concentration in kettle
27.5
Gram perfluoro caprylic acid ammonia
/
Aqueous solution, with
50
Milliliter
/
The speed of minute is squeezed into,
20
Minute squeezes into altogether
1000
Milliliter, waits altogether about
7
Kilogram tetrafluoroethylene monomer be passed through in kettle after, initiator stop squeeze into kettle, wait altogether
12.5
Kilogram tetrafluoroethylene monomer be passed through in kettle after, cooling stop stirring, stop reaction, the reaction time is about
148
Minute.The emulsion solid content for obtaining is about
33%
, primary particle particle mean size is about
0.26
Micron（
260
Nanometer）, comonomer consumption accounts for the total amount of dried resin
0.2%
, the standard specific gravity of dried resin
SSG=2.16,
With
DSC
Survey melting point resin and find there is heat absorption peak to exist
320-350
Between degree.
Expanded PTFE stretching experiment：The dried polytetrafluoroethyldispersion dispersion resin and boiling point obtained by this example
180-200
DEG C the U.S.
Exxon Mobile
Senior lubricant（The trade mark
Isopar
K
）With
100:18
Weight mixed than mutually, it is gentle stir after be first pressed into cylinder in advance, then
30
High pressure is extruded into paste rod at DEG C, and compression ratio is about
200
：
1
.The wet rod is existed
220
DEG C baking oven in de-oiling obtain dry rod.The dry rod is existed
250
DEG C hot conditions under carry out longitudinal stretching：Draw speed exists
10%/
It is stretchable in the case of second
1000%
, obtain the micropore bar of expanded PTFE；Draw speed exists
100%/
It is also stretchable in the case of second
1000%
Elongation, obtains the micropore bar of expanded PTFE, and the micropore bar of the expanded PTFE of gained exists
360
Shaped under degree high temperature
30
Second.It is about by the tensile strength of the micropore bar of the polytetrafluoroethylene (PTFE) after sizing
178
MPa
.So this ultrahigh-molecular-weight modified polytetrafluoroethyldispersion dispersion resin can be used to do the application of high intensity expanded PTFE, its tensile strength can meet many high-end applications, can also be degraded by microorganisms.
Implement example
4
（Super high molecular weight tetrafluoroethene copolymerization dispersion resin）
In a horizontal garden column type（Draw ratio
1.7
：
1
）Jacketed can lead to cold water
/
The autoclave of steam, kettle inner volume is about
36
Rise, there are four blades, add
21
Kilogram deionized water,
600
Gram low molecular weight polyethylene（Fusing point
70-78
Degree）,
1
Gram succinic acid,
0.5
Gram oxalic acid,
25
Milliliter concentration
20%
Perfluoro caprylic acid ammonia spirit.Reactor is sealed, rotating speed is raised to
65 rpm,
Temperature rise is arrived in kettle
65
After degree, deoxygenation is vacuumized, reactor is boosted to normal pressure by logical tetrafluoroethylene monomer, then vacuumizes deoxygenation, leads to tetrafluoroethene, then vacuumizes deoxygenation, until oxygen content in kettle
<
25ppm
, under micro-vacuum state, suction in kettle
195
Gram, purity
>98%
, butyl vinyl ether（
CH2=CH-OC4H9
）It is comonomer, then temperature rise in kettle is arrived
70
Degree, rotating speed is transferred to
80
rpm,
Purity is passed through in toward kettle at least
99.999%
Tetrafluoroethene（
CF2=CF2
）Monomer is about
1.7
Kilogram, pressure is up to about in kettle
2.7
MPa
, the octarius that then starts to use tricks is toward squeezing into initiator in kettle：
0.1
Gram
/
The potassium permanganate solution of water is risen, with per minute
20
The speed of milliliter is squeezed into, equivalent to per minute
2
The amount of milligram potassium permanganate is squeezed into.After reaction starts, tetrafluoroethylene monomer has consumption in kettle, and kettle is interior to be passed through tetrafluoroethylene monomer again, pressure in kettle is maintained about
2.6-2.7
MPa.
Reaction is about
25
After minute, about
1.5
Kilogram tetrafluoroethylene monomer be passed through in kettle, octarius of at this moment using tricks is toward squeezing into concentration in kettle
27.5
Gram perfluoro caprylic acid ammonia
/
Aqueous solution, with
50
Milliliter
/
The speed of minute is squeezed into,
20
Minute squeezes into altogether
1000
Milliliter, waits altogether about
7
Kilogram tetrafluoroethylene monomer be passed through in kettle after, initiator stop squeeze into kettle, wait altogether about
13
Kilogram tetrafluoroethylene monomer be passed through in kettle after, cooling stop stirring, stop reaction, the reaction time is about
169
Minute.The emulsion solid content for obtaining is about
35%
, primary particle particle mean size is about
0.13
Micron（
130
Nanometer）, comonomer consumption accounts for the total amount of dried resin
1.5%
, the standard specific gravity of dried resin
SSG=2.141,
With
DSC
Survey melting point resin and find there is heat absorption peak to exist
320-350
Between degree.
Expanded PTFE stretching experiment：The dried polytetrafluoroethyldispersion dispersion resin and boiling point obtained by this example
180-200
DEG C the U.S.
Exxon Mobile
Senior lubricant（The trade mark
Isopar
K
）With
100:18
Weight mixed than mutually, it is gentle stir after be first pressed into cylinder in advance, then
30
High pressure is extruded into paste rod at DEG C, and compression ratio is about
200
：
1
.The wet rod is existed
220
DEG C baking oven in de-oiling obtain dry rod.The dry rod is existed
250
DEG C hot conditions under carry out longitudinal stretching：Draw speed exists
10%/
It is stretchable in the case of second
1000%
, obtain the micropore bar of expanded PTFE；Draw speed exists
100%/
It is also stretchable in the case of second
1000%
Elongation, obtains the micropore bar of expanded PTFE, and the micropore bar of the expanded PTFE of gained exists
360
Shaped under degree high temperature
30
Second.It is about by the tensile strength of the micropore bar of the polytetrafluoroethylene (PTFE) after sizing
207
MPa
.So this ultrahigh-molecular-weight modified polytetrafluoroethyldispersion dispersion resin can be used to do the application of high intensity expanded PTFE, its tensile strength can meet many high-end applications, can also be degraded by microorganisms.
Implement example
5
（Super high molecular weight tetrafluoroethene copolymerization dispersion resin）
In a horizontal garden column type（Draw ratio
1.7
：
1
）Jacketed can lead to cold water
/
The autoclave of steam, kettle inner volume is about
36
Rise, there are four blades, add
21
Kilogram deionized water,
600
Gram low molecular weight polyethylene（Fusing point
70-78
Degree）,
1
Gram succinic acid,
0.5
Gram oxalic acid,
25
Milliliter concentration
20%
Perfluoro caprylic acid ammonia spirit.Reactor is sealed, rotating speed is raised to
65 rpm,
Temperature rise is arrived in kettle
65
After degree, deoxygenation is vacuumized, reactor is boosted to normal pressure by logical tetrafluoroethylene monomer, then vacuumizes deoxygenation, leads to tetrafluoroethene, then vacuumizes deoxygenation, until oxygen content in kettle
<
25ppm
, under micro-vacuum state, suction in kettle
390
Gram, purity
>98%
,
1-
Hexene（
CH2=CH-C4H9
）It is comonomer, then temperature rise in kettle is arrived
60
Degree, rotating speed is transferred to
90 rpm,
Purity is passed through in toward kettle at least
99.999%
Tetrafluoroethene（
CF2=CF2
）Monomer is about
1.7
Kilogram, pressure is up to about in kettle
2.7MPa
, the octarius that then starts to use tricks is toward squeezing into initiator in kettle：
0.1
Gram
/
The potassium permanganate solution of water is risen, with per minute
20
The speed of milliliter is squeezed into, equivalent to per minute
2
The amount of milligram potassium permanganate is squeezed into.After reaction starts, tetrafluoroethylene monomer has consumption in kettle, and kettle is interior to be passed through tetrafluoroethylene monomer again, pressure in kettle is maintained about
2.6-2.7
MPa.
Reaction is about
29
After minute, about
1.5
Kilogram tetrafluoroethylene monomer be passed through in kettle, octarius of at this moment using tricks is toward squeezing into concentration in kettle
27.5
Gram perfluoro caprylic acid ammonia
/
Aqueous solution, with
50
Milliliter
/
The speed of minute is squeezed into,
20
Minute squeezes into altogether
1000
Milliliter, waits altogether about
7
Kilogram tetrafluoroethylene monomer be passed through in kettle after, initiator stop squeeze into kettle, wait altogether
13
Kilogram tetrafluoroethylene monomer be passed through in kettle after, cooling stop stirring, stop reaction, the reaction time is about
199
Minute.The emulsion solid content for obtaining is about
35%
, primary particle particle mean size is about
0.10
Micron（
100
Nanometer）, comonomer consumption accounts for the total amount of dried resin
3.0%
, the standard specific gravity of dried resin
SSG=2.13,
With
DSC
Survey melting point resin and find there is heat absorption peak to exist
320-350
Between degree.
Expanded PTFE stretching experiment：The dried polytetrafluoroethyldispersion dispersion resin and boiling point obtained by this example
180-200
DEG C the U.S.
Exxon Mobile
Senior lubricant（The trade mark
Isopar
K
）With
100:18
Weight mixed than mutually, it is gentle stir after be first pressed into cylinder in advance, then
30
High pressure is extruded into paste rod at DEG C, and compression ratio is about
200
：
1
.The wet rod is existed
220
DEG C baking oven in de-oiling obtain dry rod.The dry rod is existed
250
DEG C hot conditions under carry out longitudinal stretching：Draw speed exists
10%/
It is stretchable in the case of second
1000%
, obtain the micropore bar of expanded PTFE；Draw speed exists
100%/
It is also stretchable in the case of second
1000%
Elongation, obtains the micropore bar of expanded PTFE, and the micropore bar of the expanded PTFE of gained exists
360
Shaped under degree high temperature
30
Second.It is about by the tensile strength of the micropore bar of the polytetrafluoroethylene (PTFE) after sizing
232
MPa
.So this ultrahigh-molecular-weight modified polytetrafluoroethyldispersion dispersion resin can be used to do the application of high intensity expanded PTFE, its tensile strength can meet many high-end applications, can also be degraded by microorganisms.
By implementation example
1-5
And contrast example
A-B
Can be seen that, using the super high molecular weight tetrafluoroethene copolymerization dispersion resin made by the comonomer that this patent is recommended out, cost is relatively low, and can bring making high intensity expanded PTFE material, its tensile strength can meet many high-end applications, and can be degraded by microorganisms.
The lubricating oil that above example is used can use the U.S.
Exxon Mobile
The similar products of company.
The method of testing of the data foundation in above example or the instrument for being used are respectively：Emulsion primary particle granular size is to use electron microscope（
SEM
）After shooting calculating Average Particle Diameters are removed with computer.The solid content of emulsion is to calculate dry weight and weight in wet base ratio with weight method.Dried resin standard specific gravity
SSG
Measure be basis
ASTM D-4895
Method.Tensile strength is to use tension intensity machine（
Instron
）Surveyed.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allowing person skilled in the art to will appreciate that present disclosure and implementing according to this, it is not intended to limit the scope of the present invention.Any equivalent change or modification in accordance with the spirit of the invention, should all be included within the scope of the present invention.
Claims (12)
1. a kind of can be by expanded high molecular weight polytetrafluoroethyldispersions copolymerization dispersion resin, Qi Te Disorder are that the resin is by ultra-high purity tetrafluoroethene and extraordinary comonomer, copolymerization forms dispersion emulsion in autoclave, the size of primary particle is at 60 ~ 300 nanometers, the standard specific gravity SSG of dry powder resin is between 2.13 ~ 2.18, comonomer used by the tetrafluoroethene copolymerization dispersion resin is free from fluorine, hydrogeneous monomer, contain 5-10 carbon, and there is a unsaturated bond energy and the tetrafluoroethene to carry out free machine copolymerization, the consumption of comonomer used accounts for the 0.1% ~ 5.0% of the gross dry weight amount of polytetrafluoroethyldispersion dispersion resin.
2. the preparation method of the HMW tetrafluoroethene copolymerization dispersion resin described in comprises the following steps：
1., autoclave vacuumizes deoxygenation：In autoclave, pure water, a small amount of paraffin of preferably adding some points again is added after reactor good seal, to vacuumize deoxygenation, until oxygen content is less than 50 ppm；
2., high pressure polymerisation reaction：Purity is passed through in reactor to be at least up to 99.995% tetrafluoroethylene monomer and add above-mentioned comonomer, add a small amount of radical initiator and fluorine-containing dispersant, reaction temperature is controlled between 25 ~ 150 DEG C, and reaction pressure is controlled in 1.0 ~ 3.0 MPa, 1 ~ 9 hour reaction time；
3., table Cheng and post processing：15 ~ 45%, primary particle particle mean size condenses the resin after drying to gained dispersion emulsion solid content between 60 ~ 300 nanometers, and its standard specific gravity is between 2.13 ~ 2.18.
3. it is according to claim 1 can be by expanded HMW tetrafluoroethene copolymerization dispersion resin, its special Cheng：Step 1. in, described paraffin is low molecular weight polyethylene, and fusing point is between 60 ~ 90 degree.
4. it is according to claim 1 can be by expanded HMW tetrafluoroethene copolymerization dispersion resin, its special Cheng：Step 2. in, described comonomer is free from fluorine, hydrogeneous monomer, containing 5-10 carbon, and carries out free machine copolymerization containing a unsaturated bond energy and tetrafluoroethene, and have following structure： R1-CH=C（R2）R3, wherein R1It is H or R（Not fluorine-containing, hydrogeneous alkyl, there is 3-8 carbon）Or-O-R（Not fluorine-containing, hydrogeneous ether alkyl, there is 3-8 carbon）；R2It is H or methyl；R3It is H or methyl.
5. it is according to claim 1 can be by expanded HMW tetrafluoroethene copolymerization dispersion resin, its special Cheng：Step 2. in, described radical initiator is persulfate, the redox system of permanganate, or its mixture, and consumption is account for total resin weight 0.0001 ~ 0.01%.
6. fluorine-containing dispersant described in be it is fluorine-containing have 6 ~ 12 carboxylic acids or sulfonate or its mixture of carbon, consumption is account for total resin weight 0.05% ~ 1.0%.
7. according to claim 1 can be its dispersion emulsion by expanded HMW tetrafluoroethene copolymerization dispersion resin, its special Cheng, and the size of primary particle is at 100 ~ 290 nanometers.
8. according to claim 1 can be by expanded HMW tetrafluoroethene copolymerization dispersion resin, its special Cheng is that the fusing point of its dry powder resin has heat absorption peak between 320-350 degree, between 2.13 ~ 2.169, resin can be degraded by microorganisms the standard specific gravity SSG of resin.
9. it is according to claim 1 can by expanded HMW tetrafluoroethene copolymerization dispersion resin, its special Cheng be its comonomer consumption account for polytetrafluoroethyldispersion dispersion resin gross weight 0.1% ~ 3.0%.
10. according to claim 1 can be by expanded HMW tetrafluoroethene copolymerization dispersion resin, its special Cheng is that described super high molecular weight tetrafluoroethene copolymerization dispersion resin can be extruded by paste, calendering, uniaxial or biaxial stretching turns into the material that varicosity TFE copolymer contains microcellular structure.
11. comonomers according to claim 3, comprising CH2=CH-R4,（R4 is the 3-8 alkyl of carbon）.
12. comonomers according to claim 3, comprising CH2=CH-O-R5,（R5 is the 3-8 alkyl of carbon）.
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|---|---|---|---|
| CN201510933000.1A CN106883337B (en) | 2015-12-15 | 2015-12-15 | Dispersion resin can be copolymerized by the high molecular weight tetrafluoroethene of extruding |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1262496A1 (en) * | 1999-11-16 | 2002-12-04 | Daikin Industries, Ltd. | Fluorocopolymer |
| US20030069343A1 (en) * | 1998-08-06 | 2003-04-10 | Paul Smith | Melt-processible poly(tetrafluoroethylene) |
| CN102336858A (en) * | 2011-07-08 | 2012-02-01 | 吴慧生 | Ultrahigh-molecular-weight modified polytetrafluoroethylene dispersion resin |
| CN102395611A (en) * | 2009-03-20 | 2012-03-28 | 戈尔企业控股股份有限公司 | Expandable tfe copolymers, method of making, and porous, expanded articles thereof |
-
2015
- 2015-12-15 CN CN201510933000.1A patent/CN106883337B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030069343A1 (en) * | 1998-08-06 | 2003-04-10 | Paul Smith | Melt-processible poly(tetrafluoroethylene) |
| EP1262496A1 (en) * | 1999-11-16 | 2002-12-04 | Daikin Industries, Ltd. | Fluorocopolymer |
| CN102395611A (en) * | 2009-03-20 | 2012-03-28 | 戈尔企业控股股份有限公司 | Expandable tfe copolymers, method of making, and porous, expanded articles thereof |
| CN102336858A (en) * | 2011-07-08 | 2012-02-01 | 吴慧生 | Ultrahigh-molecular-weight modified polytetrafluoroethylene dispersion resin |
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Address after: 201499, No. 5, Lane 1515, Yuandong Road, Fengxian District, Shanghai Patentee after: Shanghai Hanpu New Material Technology Co.,Ltd. Patentee after: Shanghai Hancheng Industrial Co.,Ltd. Address before: 201499, No. 5, Lane 1515, Yuandong Road, Fengxian District, Shanghai Patentee before: Shanghai Hanpu New Material Technology Co.,Ltd. Patentee before: ZHEJIANG HANCHENG TECHNOLOGY Co.,Ltd. |
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