CA2131757A1

CA2131757A1 - Preparation of a modified polytetrafluorethylene and use thereof

Info

Publication number: CA2131757A1
Application number: CA002131757A
Authority: CA
Inventors: Bernd Felix; Klaus Hintzer; Gernot Lohr
Original assignee: Hoechst AG
Current assignee: Dyneon GmbH
Priority date: 1993-10-20
Filing date: 1994-09-09
Publication date: 1995-04-21
Also published as: RU2141488C1; EP0649863A1; EP0649863B1; JPH07233223A; ZA948194B; RU94038263A; US5530078A; JP3941971B2; DE4335705A1; CN1106414C; KR100350558B1; DE59400234D1; KR950011486A; CN1103870A

Abstract

Abstract Process for preparing a modified polytetrafluoroethylene and use thereof Polymerizing tetrafluoroethylene with modifying amounts of a perfluoro(alkyl vinyl ether) at temperatures below 60°C using permanganate or similar initiators by the suspension process and milling the raw polymer to an average particle size of from 10 to 50 µm gives molding powders which are suitable for the preform free-sintering technique.

Description

21~17S7 - `

HOECHST AKTIENGESELLSCHAFT HOE 93/F 926 Dr.KL-nu Werk Gendorf Preparation of a modified polytetrafluoroethylene and use thereof Description The invention relates to a process for preparing a polytetrafluoroethylene (PTFE) modified with perfluoro-(alkyl vinyl ether) (PAVE) units and the use thereof for the preform free-sintering technique. "Modified" PTFE
means that the tetrafluoroethylene (TFE) polymer contains relatively small proportions of ether units, namely usually below 0.1 mol%, and that the copolymer, like the homopolymeric PTFE, is not processible from the melt. On the other hand, the content of ether units in the polymer must be su~ficiently high for the tendency to crystalli7ation from the melt to be inhibited and for the amorphous content to be increased within certain limits.
In this way, the good mechanical properties such as tensile strength and elongation at broak of the unmodified PTFE are achieved even at significantly lower molecular weights.

The lower molecular weights of the modi~ied products are evident in a melt viscosity by the Ajroldi method (US-A 3 855 191, column 8) of from about 1 to 100 GPas, while the melt viscosity of the unmodified polymers for comparably good mechanical properties is more than 300 GPas.

This drastic lowering of the melt viscosity improves the properties of the shaped parts produced from these modified molding powders. Since the particles of the molding powder melt together more easily, the shaped parts contain fewer pores and consequently have an improved electrical breakdown resistance; in addition, the creep resistance is almost doubled. In particular, . ;,." ~

' ~ ;, ?i, : . .

21317~
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however, the weldability of the shaped parts is considerably improved.

As already mentioned above, the invention also provides for the use of the modified PTFE for the pre~orm free-sintering technique. For this purpose, good millabilityof the raw polymer is imperative. In contrast thereto, ram extrusion requires a hard, i.e. poorly millable, grain and good flowability.

The invention provides a process for preparing polymers of TFE containing from 0.02 to 0.25% by weight of PAVE
units having from 1 to 4 carbon atoms in the perfluoro-alkyl chain, which comprises polymerizing the monomers by the suspension process in aqueous medium using an initiator containing manganese in a higher oxidation state at a temperature below 60C. For use according to the invention, the raw polymer thus obtained is milled to an average particle size of from 10 to 50 ~m.
:
The preferred PAVE is perfluoro(n-propyl vinyl ether), hereinafter referred to as PPVE.

20 The polymerization temperature is preferably in a range `-from 10 to 50C, the polymerization pressure is in the range from 4 to 25 bar, in particular from 5 to 15 bar.

Suitable initiators are salts of permanganic, manganic and manganous acid. Preference is given to the permanga-nates, in particular the alkali metal permanganates. Theyare advantageously used in combination with a soluble oxalate such as ammonium oxalate or an alkali metal oxalate.

Further preferred embodiments of the invention are illustrated below in more detail.

The preparation of copolymers comprising TFE and PAVE
units using permanganate and similar initiators is 21317~7 already known. Thus, US-A 4 262 101 discloses the preparation of a terpolymer by copolymerization of TFE
with from 1 to 6 mol% of PAVE and from 5 to 25 mol% of hexafluoropropene in the presence of a chain transfer agent. The polymerization temperature can be from 10 to 150-C, preferably from 10 to 50-C. The terpolymer thus obtained is processible from the melt.

US-A 4 078 134 discloses the polymerization of TFE with only very small amounts of PAVE, namely from 0.0004 to 0.0029 mol%. The preferred polymerization temperature is from 10 to 35-C, in the examples using potassium permanganate as initiator it is 15 or 25-C. The products thus obtained are distinguished both from unmodified PTFE
and from the products having higher proportions of modifier, namely above 0.0029 mol% (column 4, lines 18 to 68). They are suitable for the production of shaped bodies by forming, sintering and, in particular, ram extrusion. As a result, they cannot meet the specific demands which are nowadays made of a molding powder for the preform free-sintering technique.

The preparation of a TFE polymer which is modified with PAVE and is suitable for the preform free-sintering technique is known from US-A 3 855 191. Here, the polymerization is carried out at from 50 to lOO C, with inorganic persulfates being preferred as initiators.
Although redox initiator systems are specified, salts of manganese acids are not mentioned. The desired low amorphous content of below 8% by weight, preferably below 6.5% by weight, is achieved by the use of a fluorinated dispersant which has no telogenic action. However, it has been found that these dispersants lead to lump formation during the polymerization, particularly at lower temperatures, as they are used according to the invention. Thus, a controlled reaction up to a desired solids content of about 30% by weight is no longer ensured.

21317~7 ; - 4 -.:, It has furthermore been found that the specified lump formation occurs when using the fluorinated dispersants, particularly at a relatively low salt content in the polymerization liquid. However, the process of the invention allows low salt contents which not only simplify the disposal of waste water, but also have a positive influence on the product properties.

The polymerization carried out according to the invention gives a raw polymer which is very readily millable. ~he considerably improved millability is evident in a more than doubled throughput and/or a lower energy consumption of the mill.

It has furthermore been found that the ready millability of the raw polymers is coupled with advantageous mechanical and electrical properties. The molding powders thus obtained have a high pressability or deformability.
For the purposes of the present invention, this means the alteration of the gravimetrically determined densities of the moIding powder pressed under various high pressures without sintering, i.e. in the form of the so-called green body (US-A 3 245 972, column 2, lines 28 to 37).
Increasing pressability or deformability improves the technical properties of the sintered material, because the contact between the individual particles is thereby more readily ensured.

The shaped bodies produced from the products obtained according to the invention have a combination of valuable `l properties, namely, in particular, a high tensile strength with good elongation at break and a high electrical breakdown resistance.
:
The good millability and also the improved properties of the final products is probably caused by an improved grain structure of the polymer. This is evident in a drastic increase in the specific surface area. It has been found that this grain improvement is significantly ~ 5 ~
influenced in the desired direction by relatively high TFE pressures, for example in the range from 15 to 25 bar. However, for technical reasons, a pressure range from 5 to 15 bar is preferred, since a higher TFE
pressure leads to a higher loss of the expensive PAVE
and, in addition, the explosion risk inherent in the system is increased at high pressures.

The desired influence on the grain structure is, according to the invention, achieved principally by means of the low polymerization temperatures. As mentioned, a low salt content in the polymerization medium is also advantageous. With the initiator used according to the invention, the polymerization temperature can be reduced ; to about lO-C, without the space-time yield (at comparable molecular weight and the same degree of modification) being unjustifiably reduced. This is surprising since the polymerization is considerably slowed by PAYE.
. ..-, The initiators of the invention have a strongly temperature-dependent decomposition rate. Therefore, with falling polymerization temperature an increasing proportion of the total amount of initiator is initially charged at the beginning of the polymerization and the remainder is metered in, preferably continuously over the whole duration of the polymerization. The metered addition is advantageously controlled in such a way that the polymerization rate for a constant degree of incorporation of the PAVE over time does not decrease.

The polymerization can also be carried out by the process known from US-A 5 153 285, in which a mixture of TFE and inert gas is injected under pressure prior to the polymerization and the total pressure of the injected mixture is from 5 to 50 bar, with the concentration of the TFE in this mixture being from 30 to 70 mol% and being maintained in this range by appropriate further injection during the polymerization.

21317~7 -If a free-flowing product is desired, the millod product obtained according to the invention can be granulated ln a known manner. The agglomeration proces~ known from US-A 4 439 3a5 is suitable.

The invention is illu~trated by the following xamples.
Percentages are by weight.

Examples A 150 l reactor is charged with 100 l of deionized water and the amount of ammonium oxalate (AmOx) given in Table 1 is added. The contents of the roactor are freed of atmospheric oxygen by alternate evacuation and flushing with nitrogen. TFE is injected up to a pressure of 10 bar and the total pressure is increased to 15 bar by injection of nitrogen. This pressure is kept constant over the whole polymerization time by further injection of TFE. The amount of PPVE given in Table 1 is metered into the reactor and the contents of the reactor are brought to the temperature given in Table 1. This temperature is likewise kept constant over the whole duration of the polymerization. The polymerization is startod by rapid metered addition (within 5 minutes) of the amount of potassium permanganate given in Table 1 under "initiation~, dissolved in 300 ml of water. The reaction starts virtually instantaneously. After about 20 minutes, an aqueous solution of the amount of potassium permanganate given in Table 1 and also the further amount of PPVE are continuously metered in.

After the desired amount of TFE has been introduced, the reaction is ~topped by the metering-in of initiator, PPVE
and TFE being interrupted. After a further period of about 20 minutes, the pressure drops to about 6 bar. The contents of the reactor are then cooled to room temperature and are substantially freed of the residual monomers by repeated evacuation.

. :

21317~7 The product obtained i8 washed three times with deionized water, dried for 10 hours at 220C and mllled ln a spiral-~et mill. The averago particle slze d50 f the milled product is about 20 ~m. The further propertle~ of the milled powder are given in Table 1. These propertles were determlned as follows:

Ths amorphous content is determined by IR spectroscopy on 100 ~m films by measurement of the absorption at 778 and 2353 cm~l in accordance with the method givon in US-A 3 855 191, column 5.

The PPVE content is likewise determlned by IR
spectroscopy on 100 ~m fllms by measurement of the absorption at 995 and 2353 cm~l in accordance with the relatlonship % PPVE content = 0.95 Aggs/A2353~ -' The specific surface area is determined by measurement of the nitrogen adsorption in accordance with the method described by F. M. Nelson and F. T. Eggertson ~Anal.
Chem. 30, 1387 (1958)].

The millability of the raw polymer in the spiral-jet mill was measured by the throughput amount per hour at a milling-air pressure of 6 bar and with the same -~
~; proportion of particles larger than 33 ~m, measured by ~ieving.

25 The molecular weight given in Table 1 (number average) ~-was estimated, under thé plausible assumption that the initiator used is practically guantitatively reacted under the reaction conditions indicated, in accordance ~ -with the following relation~hip:

N~ = 2 100 mp/I0, where mp is the amount of TFE reacted in mole, Io i8 the amount of initiator used in mole, the factor 100 is the , ::

21 31 7~7 ,~ .

molecular weight of TFE and the factor 2 represents a combination termination.

The standard ~peclfic gravity is determined ln accordance with ASTM testlng ~tandard D-1457-69.

Table 1 also ~hows, under "final properties~, the tensile strength (TS), the elongation at break (EB) and the electrical breakdown resistance (EBR). These properties are determined on films which are produced as follows:
a) washing of the raw polymer with deionized water, b) predrying in a fluidized bed at temperature~ up to 130C, c) further drying for 4 hours at 220C, d) milling in an air-jet mill to a d50 f about 20 ~m, e) pressing at 350 bar into a cylindrical, 13 kg block about 208 mm in both height and diameter, f) sintering at 380C in accordance with a temperature program and g) shaving off a film having a thickness of 100 ~m in 200 ~m steps.

Samples of the 100 ~m thick films from the middle zone of the block are used for determining the tensile strength ; and elongation to break in accordance with DIN 53455 (strip method) and the electrical breakdown resistance in accordance with DIN 53481.

Table 2 shows comparative examples. Since the disintegration rate of the initiatoro uYed according to the invention becomes 60 high at temperatures above 60C
that a readily reproducible polymerization can be achieved only with difficulty, a~monium persulfate (APS) was used as initiator. Besides ammonlum oxalate, ammonium carbonate (AmCb) was al30 used as buffer substance. The ; molecular weight was estimated using the following relationshlp~
.~:
Mn = 100 mp/[I0(1 - e - kd t)] ~

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where mp is the molar amount of TFE reacted, Io is the amount of initiator used in mole, k~ is the decomposition constant of ammonium persulfate and t is the polymeriza-tion time. This relationship assumes that the persul~ate disintegrates into two initiator free radicals.

The value used for the disintegration constant k~ was 1.2 10-5 sec~1 at 70C and 0.5 10-5 sec~l at 63~C
[I. M. Kolthoff, I. H. Miller, J. Am. Chem. Soc. 37 (1951) 3055].

A comparison of the average values from the Tables 1 and 2 gives the following property profile:

The product of the process of the invention has, at comparable molecular weight and degree of modification, a significantly higher specific surface area, a drastically improved millability, an electrical breakdown resistance increased by 30% and a tensile strength increased by 10 NJmm2, with only slightly decreased elongation at break.

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Claims

1. A process for preparing a polymer of tetrafluoro-ethylene containing from 0.02 to 0.25% by weight of units of a perfluoro(alkyl vinyl ether) having from 1 to 4 carbon atoms in the perfluoroalkyl chain, which comprises polymerizing the monomers in aqueous medium by the suspension process at temperatures below 60°C using the salt of an acid containing manganese in a higher oxidation state as initiator.

2. The process as claimed in claim 1, wherein the salts of permanganic acid are used as initiator.

3. The process as claimed in claim 1 or 2, wherein perfluoro(n-propyl vinyl ether) is used as ether.

4. The process as claimed in one or more of the preceding claims, wherein the raw polymer is milled to an average particle size of from 10 to 50 µm.

5. The process as claimed in claim 4, wherein the milled product is granulated.

6. Use of products obtained by the process as claimed in claim 4 or 5 in the preform free-sintering technique.