GB2055874A - Process for the fabrication of coagulated dispersion polytetrafluoroethylene resins - Google Patents
Process for the fabrication of coagulated dispersion polytetrafluoroethylene resins Download PDFInfo
- Publication number
- GB2055874A GB2055874A GB8017115A GB8017115A GB2055874A GB 2055874 A GB2055874 A GB 2055874A GB 8017115 A GB8017115 A GB 8017115A GB 8017115 A GB8017115 A GB 8017115A GB 2055874 A GB2055874 A GB 2055874A
- Authority
- GB
- United Kingdom
- Prior art keywords
- surface active
- active agent
- lubricant
- fabrication
- coagulated dispersion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D21/00—Nestable, stackable or joinable containers; Containers of variable capacity
- B65D21/02—Containers specially shaped, or provided with fittings or attachments, to facilitate nesting, stacking, or joining together
- B65D21/06—Containers specially shaped, or provided with fittings or attachments, to facilitate nesting, stacking, or joining together with movable parts adapted to be placed in alternative positions for nesting the containers when empty and for stacking them when full
- B65D21/062—Containers specially shaped, or provided with fittings or attachments, to facilitate nesting, stacking, or joining together with movable parts adapted to be placed in alternative positions for nesting the containers when empty and for stacking them when full the movable parts being attached or integral and displaceable into a position overlying the top of the container, e.g. bails, corner plates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or 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; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/18—Homopolymers or copolymers or tetrafluoroethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
Abstract
The process comprises the step of mixing a powder of the coagulated dispersion polytetrafluoroethylene resin with a lubricant (e.g. a hydrocarbon, alcohol, ether, ketone or halogenated solvent) and a surface active agent which is a derivative of an oligomer of tetrafluoroethylene, prior to fabrication, e.g. into tubing, rod or unsintered tape.
Description
SPECIFICATION
Process for the fabrication of coagulated dispersion polytetrafluoroethylene resins
The present invention relates to a process for the fabrication of coagulated dispersion polytetrafluoroethylene resins, and, in particular, to a process in which a derivative of a fluoro-oligomer is used as a wetting agent.
Polytetrafluoroethylene is used in the plastics industry in three forms, namely as a granular polymer, a coagulated dispersion polymer or a liquid dispersion having a solids content of approximately 60%.
At the present time, coagulated dispersion polymers are used in an annual amount of up to about 5,000 tons. A large proportion of this is used in the manufacture of tubing and unsintered tape.
Coagulated dispersion polymers are extremely pressure-sensitive and special techniques are needed for their extrusion. Conventionally a hydrocarbon lubricant such as petroleum ether or solvent naphtha has been added to the polytetrafluoroethylene resin to assist the extrusion. However, since the surface tension of the lubricant is above the critical surface tension of wetting of the polytetrafluoroethylene, the polymer is not wetted uniformly by the lubricant. A small quantity of pigment grade carbon black is sometimes added to the polytetrafluoroethylene powder, before the addition of the lubricant, in order to assist the wetting. The addition of carbon black does not, however, prevent some agglomeration of the polytetrafluoroethylene occurring and this is an indication that the distribution of lubricant is far from uniform.The agglomerates are normally removed by passing the material through a 3.35 mm sieve (BS 410), on which from 1 to 3% of the polytetrafluoroethylene is generally retained.
A particular disadvantage associated with the incorporation of carbon black in these polymers is that polytetrafluoroethylene does not become truly fluid during fabrication and the inclusion of carbon black weakens the structure and can render the structure more permeable to gases by virtue of the carbon black remaining at the particle boundaries.
We have now developed a process for the fabrication of polytetrafluoroethylene which overcomes these disadvantages.
Accordingly, the present invention provides a process for the fabrication of a coagulated dispersion polytetrafluoroethylene resin, which process comprises the step of mixing a powder of the coagulated dispersion polytetrafluoroethylene resin with a lubricant and a surface active agent which is a derivative of a fluoro-oligomer of tetrafluoroethylene, prior to fabrication.
The coagulated dispersion polytetrafluoroethylene resin may be any commercially available resin such as those sold under the Registered Trade marks "FLUON" and "TEFLON".
Such resins comprise agglomerate particles of average5Iiameter in the range 400 to 500 m. The surface of the agglomerate particles have a microcrazed structure which can be clearly seen under low magnification on a scanning electron microscope. The interior of the agglomerate particle is made up of riumerous primary particles whose size ranges from 0.05 to 0.5 ym. The primary particles are not tightly packed hence the interior of the agglomerate particle is spongy or porous. It is believed that using this invention not only does the exterior of the agglomerate particle beccome more effectively wetted by the lubricant but also the interior so that entrained air becomes more rapidly displaced.
Perfluoro-olefin oligomers of tetrafluoroethylene are prepared by the ionic polymerization of tetrafluoroethylene in the presence of fluoride ions. Low molecular weight perfluoro-olefin oligomers are produced which, in contrast to polytetrafluoroethylene in which the C2F4 groups are linked in long unbranched chains, are highly branched structures. For example, the structure of the pentamer C10F20, perfluoro-4-ethyl-3,4-dimethyl hex-cis-2-ene is
The tertiary allyjic fluorine in all oligomers of this type is very reactive and reaction with nucleophiles is capable of yielding a range of derivatives which are surface-active agents that are either anionic, cationic or non-ionic.
Examples of surface active agents, in which the fluoro-oligomer radical is designated Rf, are given below: (a) Anionic RfOC6H4COOH RfOC6H4SO3H (b) Cationic
+ RfOCsH4NCH3 CH3SO4 (c) Non-ionic RfOQH5SO2N(C2H5)(CH2CH2O)nH
RfO(CH2CH2O)nCH3
RfO(CH2CH20)nRf Examples of commerically available surface active agents which are derivatives of perfluoro-olefin oligomers of tetrafluoroethylene are products sold by.lmperial Chemical Industries Limited under the
Registered Trade Mark "MONFLOR". Examples of anionic surfactants are MONFLOR 31 and
MONFLOR 32; an example of a non-ionic surfactant is MONFLOR 53 and an example of a cationic surfactant is MONFLOR 71.
Surfactants containing perfluorinated chains are marketed by 3M United Kingdom Limited under the designations FC430, FC431 and FC128.
The surface active agent is preferably used in an amount of from 0.01 to 2% w/v more preferably from 0.05 to 0.5% w/v, in a simple hydrocarbon solvent or a mixture of hydrocarbon or mainly hydrocarbon solvents.
The derivatives of oligomers of tetrafluoroethylene used in the process of the invention are surface active agents and have the ability to lower liquid surface tensions at extremely low concentrations. It is preferred in carrying out the process of the invention to use as the surface active agent a derivative of an oligomer of tetrafluoroethylene, as hereinbefore described, which is either a liquid or semi-solid at normal ambient temperatures and which is freely soluble in the hydrocarbon lubricant. It will be understood therefore that the lubricant should be chosen to be compatible with the particular surface active agent which it is intended to use.
When the surface active agent is non-ionic the preferred lubricants are solvent naptha, deodorised kerosene and petroleum ether. Cationic and anionic surface active agents may be used with more polar solvents such as alcohols, ethers, ketones or halogen-containing solvents.
The lubricant containing the surface active agent is generally used in an amount of from 11 to 18% w/w and preferably from 1 3 to 1 6% w/w, based on the coagulated dispersion polytetrafluoroethylene resin to be fabricated.
The process of the present invention eliminates sieve waste in the fabrication of coagulated dispersion polytetrafluoroethylene resins. The enhanced wetting of the polytetrafluoroethylene also results in certain other advantages, such asL (i) the ability to use lower lubricant levels
(ii) faster extrusion speeds at a given lubricant level
(iii) improved dimensional consistency
(iv) higher given strength
(v) ability to extrude thicker sections
(vi) elimination of carbon black with attendant improved in product mechanical properties,
reduced gaseous permeability, and lower void contents
(vii) re-cycling of cull scrap.
The present invention will be further described with reference to the following Examples, In these
Examples the abbreviation SSG represents standard specific gravity and the abbreviation EAB represents elongation at break.
EXAMPLE 1 1 g. of polytetrafluoroethylene powder was added to 50cc of a solution containing a derivative of a fluoro-oligomer, namely MONFLOR 53, in petroleum ether contained in a 75 cc beaker. The mixture was stirred for 20 seconds, using a constant, low-speed laboratory stirrer equipped with an impeller.
After stirring, the time for the PTFE powder to settle out completely was noted. With no MONFLOW 53 addition the PTFE was incompletely wetted and powder particles remained in suspension. The following results were obtained with increasing concentration of MONFLOR 53 in petroleum ether.
TABLE 1
Concentration of MONFLOR 53% wt/v Sedimentation Time
O Sedimentation incomplete
0.001
0.01
0.05 15 seconds
0.1 5-10 seconds
0.2 5-10 seconds
0.5 5-10 seconds
1.0 5-10 seconds.
It was concluded from these data that 0.1% w/v of MONFLOR 53 was required to provide a sufficient
concentration to achieve efficient wetting of the PTFE coagulated dispersion resin.
EXAMPLE 2
A comparative evaluation was carried out in which certain polytetrafluoroethylene polymers were
made into tubing using a lubricant selected from petroleum ether, solvent naphtha and de-odorized
kerosene with or without the addition of 0.1% wt/v MONFLOR 53. The mixes with MQNFLOR 53 did not
contain carbon black whereas those without MONFLOR 53 did.
The batch mix comprised
Polytetrafluoroethylene resin 4086 g
Lubricant 1100 cc
MONFLOR 53 + 0.1%
Carbon black 9 g (where appropriate)
It was observed that the mixes containing MONFLOR 53 gave no sieve waste.
Extrusion speeds in the presence of MONFLOR 53 were significantly faster (about 50% increase), whereas die swell was less.
No major differences were found in the physical properties of the resulting tubing as shown in
Table II below.
TABLE II
PTFE Tubing made using Standard 17% w/w Solvent Naphtha Lubricant (STD) Compared with Tubing made using 17% w/w
Solvent Naphtha:Containing 0.1% MONFLOR 53 (M53)
Wall (mm) STD Wall (mm) M53 S.G. S.S.G. Weep Pressure % POLYMER TYPE Min Max Min Max STD M53 STD M53 STD M53 FLUON CD1 1.4 1.55 1.3 1.5 2.155 2.150 2.236 2.218 67.1 64.8 FLUON 123 1.3 1.6 1.4 1.5 2.144 2.148 2.182 2.180 71.3 70.0 TEFLON 669 1.3 1.6 1.3 1.55 2.143 2.146 2.190 2.186 69.8 71.7 TEFLON 62N 1.25 1.6 1.3 1.6 2.132 2.132 2.159 2.158 72.2 76.2 TEFLON 636 1.4 1.5 1.4 1.5 2.144 2.146 2.209 2.213 68.6 71.7 EXAMPLE Ill
Experimental work was carried to determine the optimum level of lubricant required when 0.1%
MONFLOR 53 was used on the manufacture of tubing for either hose or pipe liner. The lubricant levels were progressively decreased from the approximately 17% w/w level normally used down to 1 1% and various physical properties were determined.
The mixes used were as follows: (A) Polymer: FLUON CD1
Lubricant: Solvent Naphtha
This mix was used for the extrusion of tubing having an outer diameter of 0.82 inches and a wall thickness of 0.048 inches. No carbon black was included in the mix. The preforming pressure was nominally constant at 100 psi and the extrusion reduction ratio was in the range 10:1 to 500:1. The results are given in Table Ill.
(B) Polymer: TEFLON 636
Lubricant: Solvent Naphtha
This mix was used for the extrusion of tubing having an outer diameter of 0.82 inches and a wall thickness of 0.048 inches. No carbon black was included in the mix. The preforming pressure was nominally constant at 100 psi and the extrusion reduction ratio was in the range 10:1 to 500:1. The results are given in Table IV.
In these experiments the sieve waste after mixing was totally eliminated on all of the mixes.
Perform density as reflected by the length of the preform, decreased as the lubricant level was reduced.
Extrusion speeds decreased as the level of lubricant was reduced. Extrudate quality and dimensional consistency passed through a peak at 15% lubricant content.
TABLE III
FLUON CDI with solvent naphtha lubricant containing 0.1% w/v MONFLOR 53
Tensile Str.
Lube Long Trans Orietn E @ B Volds % (psi) (psi) Index % SG SSG % 17.3 3531 3295 0.067 L 320 2.125 2.186- L.0.24 T 310 2.197 T 0.47 17.3 3841 3050 0.206 L 330 2.132 Beyond L 0.42 T 300 Column T 0.70 17.3 3728 3804 -0.02 L 300 2.128 Beyond L 0.70 T 335 Column T 0.84 15 4812 3574 0.225 L 320 2.129 2.202 L 0.47 T 340 T 1.41 15 4.98 3585 0.125 L 320 2.130 Beyond L 0.38 T 340 Column T 0.99 15 4293 3050 0.289 L 285 2.130 Beyond L 0.24 T 320 Column T 0.70 13 - - - - - - 13 - - - - - - 13 - - - - - - 11 - - - - - - TABLE III (Continued)
Preform Ext Extrusion Dimensions Lube Length Pressure Rate Relect % (Ins) Extruslon (psi) Ft/Min O.D. Wall % 17.3 15.7 1000 27.7 .800 .047 0 .835 .052 17.3 15.6 Over 1000 26.6 .820 .420 9.7 Lubricated .840 .053 17.3 15.7 1000 28.9 .820 .047 0 .850 .052 15 16.4 1000 8.4 .850 .042 0 .870 .048 Preform and Extrusion 15 16.2 1200 17.1 .850 .040 0 V. Good .860 .055 15 16.2 1200 17.45 .840 .046 0 .860 .054 13 17.1 Preform 1100 1.45 - - & Extr.
13 16.9 Good 1200 2.8 .870 .047 100 .890 .053 13 16.9 1500 4.3 .870 .050 100 .890 .055 11 17.9 Preform 1500 1.225 Not 100 Uneven Measurable Exten. Poor TABLE IV
TEFLON 636 with solvent naphtha:lubricant containing 0.1% w/v MONFLOR 53
Preform Ext Extrusion Dimensions Lube Length pressure Rate Relect % (Ins) Extrusion (psi) Ft/Mln O/D Wall % 17.3 15.3 1000 32.5 0.81- .042 0 0.83 .052 Over Lubricated 17.3 15.3 Cracked & 1000 37.2 0.81- .043- 0 Bowed 0.85 .057 Preform 17.3 15.3 1000 46.7 0.81- .043- 0 0.84 .053 15. 15.9 1000 11.1 0.83 .045 0 0.87 .053 15 15.9 1200 23.3 0.82 .046 0 Preform 0.87 .055 and 15 15.8 Extrusion 1500 30.0 0.84 .048 38 V.Good 0.85 .053 13 - 1000 21.28 0.850 .048 62.7 0.895 .059 Preform 13 16.4 and 1500 7.1 0.85 .047 4 Extrusion 0.89 .056 Good 13 16.4 1800 6.6 0.86 .046 0.89 .054 11 - Preform 1800 - - - 100 Uneven Extruslon Proof TABLE IV (Continued)
Tenslle Str.
Lube Long Trans Orletn E @ B Volds % (psi) (psl) lndex % SG SSG % 17.3 4076 3276 0.196 L 340 2.125 2.198 L 0.19 T 320 2.192 T 0.71 17.3 4019 3259 0.189 L 320 2.125 2.201 L 0.42 T 330 2,190 T 0.47 17.3 4019 3150 0.216 L 320 2.132 2.200 L 0.33 T 340 2.191 T 0.61 15 4098 3766 0.081 L 280 2.125 2.183 L 0.24 T 320 2.182 T 0.61 15 4050 3259 0.195 L 340 2.125 2.188 L 0.28 T 320 2.192 T 0.47 15 4087 2880 0.291 L 320 2.125 2.187 L 0.28 T 340 2.184 T 0.52 13 4874 3954 0.188 L 300 2.129 2.185 L 0.38 T 350 2.190 T 0.56 13 4313 3197 0.259 L 300 2.129 2.185 L 0.28 T 300 2.182 T 0.70 13 4563 4180 0.084 L 300 2.129 2.190 L 0.24 T 400 2.190 L 0.70 11 - - - - - -
Claims (9)
1. A process for the fabrication of a coagulated dispersion polytetrafluoroethylene resin, which process comprises the step of mixing a powder of the coagulated dispersion polytetrafluoroethylene resin with a lubricant and a surface active agent which is a derivative of an oligomer of tetrafluoroethylene, prior to fabrication.
2. A process as claimed in claim 1 wherein the polytetrafluoroethylene resin comprises agglomerate particles of average diameter in the range of from 400 to 500 Mm.
3. A process as claimed in claim 2 wherein the agglomerate particles are made up of a plurality of primary particles having a diameter of from 0.05 to 0.5 ,um.
4. A process as claimed in any one of the preceding claims wherein the surface active agent is an anionic surface active agent of the formula:
RfOC6H4COOH or RfOC6H4SO3H in which the fluoro-oligomer radical is designated Rf.
5. A process as claimed in any one of claims 1 to 3 wherein the surface active agent is a cationic surface active agent of the formula: RfOCsH4N OCH30CH,SO, in which the fluoro-oligomer radical is designated Rf.
6. A process as claimed in any one of claims 1 to 3 wherein the surface active agent is a non-ionic surface active agent of the formula: RfOC6H5SO2N(C2H5)(CH2CH20)nH, RfO(CH2CH20)nCH3 or RfO(CH2CH20)nRf in which the fluoro-oligomer radical is designated Rf.
7. A process as claimed in any one of the preceding claims wherein the surface active agent is used in an amount of from 0.01 to 2% w/v.
8. A process as claimed in claim 7 wherein the surface active agent is used in an amount of from 0.05 to 0.5% w/v.
9. A process as claimed in any one of claims 1 to 3 or claim 6, or claims 7 or 8 when appendant to any one of claims 1 to 3 or claim 6; wherein the surface active agent is non-ionic and the lubricant is solvent naphtha deodorised kerosene or petroleum ether.
9. A process as claimed in any one of claims 1 to 3 or claim 6, or claims 7 or 8 when appendant to any one of claims 1 to 3 or claim 6, wherein the surface active agent is non-ionic and the lubricant is solvent naphtha deodorised kerosene petroleum ether.
10. A process as claimed in any one of claims 1 to 5, or claim 7 or claim 8 when appendant to any one of claims 1 to 5, wherein the surface active agent is cationic or anionic and the lubricant is an alcohol, ether, ketone or halogen-containing solvent.
11. A process as claimed in claim 9 or claim 10 wherein the lubricant is used in an amount of from 11 to 18% w/v of lubricant containing the surface active agent.
12. A process as claimed in claim 11 wherein the lubricant is used in an amount of from 13 to 16% w/w of lubricant containing the surface active agent.
1 3. A process as claimed in claim 1 substantially as hereinbefore described with reference to any one of the Examples.
14. Caagulated dispersion polytetrafl uoroethylene whenever fabricated using a process as claimed in any one of the preceding claims.
1 5. Coagulated dispersion polytetrafluoroethylene as claimed in claim 14 which is in the form of tubing, rod or unsintered tape.
Amendments to claims filed on 22/9/80.
Amended claim:- Claim 9
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8017115A GB2055874A (en) | 1979-06-05 | 1980-05-23 | Process for the fabrication of coagulated dispersion polytetrafluoroethylene resins |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB7919569A GB2053851B (en) | 1979-06-05 | 1979-06-05 | Stack and nest containers |
| GB8017115A GB2055874A (en) | 1979-06-05 | 1980-05-23 | Process for the fabrication of coagulated dispersion polytetrafluoroethylene resins |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB2055874A true GB2055874A (en) | 1981-03-11 |
Family
ID=26271765
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8017115A Withdrawn GB2055874A (en) | 1979-06-05 | 1980-05-23 | Process for the fabrication of coagulated dispersion polytetrafluoroethylene resins |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2055874A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5041480A (en) * | 1984-07-09 | 1991-08-20 | Daikin Industries, Ltd. | Fluoroelastomer composition |
| US5420191A (en) * | 1992-07-21 | 1995-05-30 | E. I. Du Pont De Nemours And Company | Polytetrafluoroethylene with improved creep resistance, and preparation thereof |
| US5532310A (en) * | 1995-04-28 | 1996-07-02 | Minnesota Mining And Manufacturing Company | Surfactants to create fluoropolymer dispersions in fluorinated liquids |
-
1980
- 1980-05-23 GB GB8017115A patent/GB2055874A/en not_active Withdrawn
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5041480A (en) * | 1984-07-09 | 1991-08-20 | Daikin Industries, Ltd. | Fluoroelastomer composition |
| US5420191A (en) * | 1992-07-21 | 1995-05-30 | E. I. Du Pont De Nemours And Company | Polytetrafluoroethylene with improved creep resistance, and preparation thereof |
| US5532310A (en) * | 1995-04-28 | 1996-07-02 | Minnesota Mining And Manufacturing Company | Surfactants to create fluoropolymer dispersions in fluorinated liquids |
| US5660888A (en) * | 1995-04-28 | 1997-08-26 | Minnesota Mining & Manufacturing Company | Surfactants to create fluoropolymer dispersions in fluorinated liquids |
| US5844034A (en) * | 1995-04-28 | 1998-12-01 | Minnesota Mining And Manufacturing Company | Surfactants to create dispersions in fluorinated liquids |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |