NL8201697A - STABILIZED ETHENE / TETRAFLUOROETHEENE COPOLYMERS. - Google Patents

Description

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Stabilized ethylene / tetrafluoroethylene copolymers.

The present invention relates to an ethylene-tetrafluoroethylene copolymer, which is stabilized against thermal degradation, and more particularly, to an ethylene-tetrafluoroethylene copolymer, which is stabilized against thermal degradation, by adding CuJ or CuCl.

Ethylene-tetrafluoroethylene copolymers have good thermal, chemical, electrical and mechanical properties and are melt processable. These copolymers are known to be thermoplastic resins with heat resistance having a melting point of 260 ° to 300 ° C.

However, these copolymers thermally deteriorate and become colored, brittle and foamed when heated to a temperature higher than the melting point for a long period of time. As a result, it is desirable to use the thermal backbone of ethylene-tetrafluoroethylene copolymers during the conventional application of injection molding and extrusion molding processes. to prevent.

U.S. Pat. No. 4,110,308 discloses that a copper compound such as metallic copper, copper (II) oxide, copper (I) oxide, copper (II) nitrate, copper; per (II) chloride or copper alloys stabilizes the copolymers against degradation at different temperatures.

It has now been found that copper (II) chloride or copper (I) iodide provides better protection of ethylene-tetrafluoroethylene copolymers (hereinafter E / TEE copolymers) against thermal degradation, than the metallic copper or copper (II) oxide, disclosed in U.S. Pat. No. 4,110,308 and therefore can be used at lower concentrations thereby avoiding harmful pigmentation and the like.

Addition of copper (I) chloride or iodide to an E / TEE copolymer allows the copolymer to be exposed to very high temperatures in air without rapid loss of weight, loss of molecular weight, color or bubble development. Such protection greatly enhances the usefulness of E / TEE copolymers for applications such as rotary molding, surface coating, molding and wire insulation involving high temperature manufacturing and / or use at high temperatures.

For example, the E / TEE powder is exposed to rotational molding at temperatures that are above the melting point for more than an hour, with oxygen generally present. Under such conditions, untreated E / TEE powders turn brown, foam and become extremely brittle due to molecular weight reduction. The addition of small amounts of copper (I) chloride or iodide prevents such degradation.

The ethylene-tetrafluoroethylene copolymers used in the invention can be achieved by various known polymerization methods, such as emulsion polymerization in an aqueous medium or suspension polymerization.

The ratio of ethylene to tetrafluoroethylene units can be varied in a conventional manner and it is possible to have a small amount (eg, up to 20 mole percent) of a copolymerizable ethylenically unsaturated comonomer having 3 to 12 carbon atoms, such as propylene, isobutylene, vinyl fluoride. , hexafluoropropene, chlorotrifluoroethylene, acrylic acid, alkyl esters thereof, chloroethyl vinyl ether, perfluoroalkyl perfluorovinyl ethers, hexafluoroacetone, perfluorobutyl ethylene and the like. The ratio of ethylene to tetrafluoroethylene units in the copolymer can vary within wide limits. For example, the mole ratio of tetrafluoroethylene to ethylene can be units of 4-0 / 60-70 / 30 and preferably about 4-5 / 55-60 / 4-0.

The copper (I) chloride of iodide provides excellent oxidation inhibition for E / TEE resins within the concentration range of 0.05 to 500 ppm, preferably 5-50 ppm, as copper. The protection is the same over this range at both 5ppm and 50ppm. Copper in other forms is not as powerful at lower concentrations; e.g. copper powder, C 2 O and CuO all give protection, but become effective only at concentrations higher than 50 ppm or more. There are important advantages achieved at the lower concentrations: (I) the pigmentation by the additive is minimized, (2) conversion of the halide to black copper (II) oxide at high temperatures is 4-0 not so noticeable, (3) problems such as roughening of the surface, cloudiness and electrical weaknesses are avoided.

CuJ or CuCl stabilized © E / TEE resins can be heated in air above their melting point and held for two hours and longer without significant losses in molecular weight (strength) or color.

Another advantage of using the halides, and especially CuJ, is their ability to significantly stabilize E / TEE melts during processing; this allows longer residence times without loss in molecular weight of the final product.

Inclusion of the copper (I) halides in E / TEE resin also improves stress cracking resistance in high temperature applications. Color degradation is also noticeably delayed. For example, with 5 ppm CuJ, 90% of the original elongation is kept at room temperature after 215 hours of aging at 230 ° C, while a control (no copper) lasts only 27 hours and a sample containing 50 ppm copper metal powder lasts exactly 70 hours. . Use of copper (I) chloride or iodide in finished products of E / TEE provides good protection against heat induced color formation during 400 hours of aging at 23 ° C. Better protection can be expected at lower temperatures.

It is preferable to optimize the particle size, specific surface area and distribution of the particles of the copper (I) halides in accordance with the desired properties of the copolymer composition. It deserves e.g. it is preferred to use a copper (I) halide with a relatively small average particle diameter, usually less than 100 micrometers and preferably 1-50 micrometers. It is also preferable to have a narrow particle distribution.

Various methods can be used to mix the copper (I) halide with the E / TEE. For example, commercially available CuJ or CuCl powder can be mixed with the copolymer in a mixer. An aqueous suspension or a suspension of ethylene-tetrafluoroethylene copolymer in organic solvent and CuJ or CuCl 40 can also be prepared.

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Examples.

In the examples, the E / IEE copolymer designated E / IEE-I was a copolymer of ethylene / tetrafluoroethylene / hexafluoroacetone (21.3 / 72.9 / 5.8 wt%) with a melt viscosity of 18 x 10 poise and a melting point of 262 C. The co-5 polymer was in the form of partially compressed brittle powder.

The E / TEE copolymer designated E / TEE-II was a copolymer of ethylene / tetrafluoroethylene / perfluorobutyl ether (18.9 / 29.35 / 1.75) with a melt viscosity of 5.85 x 10 ^ 10 poise in powder form.

Example I and Comparative Examples.

The following powdered joints were used:

(I) copper (I) iodide, CuJ

(II) copper metal

(III) copper (II) oxide, CuO

15 (IV) oc-A1203

(V) ZnO

(VI) CuJ / KJ mixture absorbed on α-AlgO ^ (VII) copper (II) nitrate absorbed on ce-A ^ O ^ (VIII) CuJ / KJ mixture.

The various powdered additives were added to Ε / ΦΕΕ-Ι powder in a mixer along with sufficient trifluoro-1,1,2-trichloroethane (F-113) solvent to prepare a flowable suspension and poured into a pan. bet F-113 evaporates. The resulting powdery cake was then dried under vacuum at 120 ° C for one hour.

Ratings. Two grams of each mixture was weighed out on a bob glass and all the mixtures prepared were annealed in an oven at 300 ° C for two hours using constantly circulating air. At 300 ° C, the E / TFE-I powder is clearly above its melting point of 262 °. The cooled mixtures were examined for signs of degradation, such as color development, foaming and cracks.

Results The results are tabulated below in order of 35 good to bad behavior.

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The results show that copper (I) iodide (Example I) provides exceptional protection against oxidation. Its behavior is much better than that of any of the other additives examined (equations A / K). Based on 5 of the visual observations, (CuJ ^ uJ / KJotA ^ O ^ Cu (50 ^ 2 absorbed on o-AlgOj in unwashed form and copper powder) gave some protection, but in fact accelerated (Gu0, Cu (N0 ^) 2 absorbed on cc-AlgO ^ in washed form, α-Α ^ Ο ^, ΖηΟ and CuJ / KJ degradation of E / TPE-I.

Example II.

10 Tasting. Powdered E / TPE-I samples were prepared in the same manner as described in Example I. Samples containing (CuJ, Cul, CuBr, Cu, Cu20, Cu0, at 5.50 * 500 and 1000 ppm) were copper investigated. Other additives tested were CuCl2. 2H20 and CuBr2 with 5.50 and 500 ppm 15 as copper plus CuPg-2¾0 as ^ pm copper mixed with 749 ppm KJ, 1000 and 500 ppm -AlgOj, 100 ppm CuilO ^^ / aA ^ O ^) mixtures, both washed if not washed and 1000 ppm CuJ / KJ / a-Al2 O ^ mixtures, both washed and unwashed.

The particle size distributions of the additive were measured using the Sedigraph and Coulter Counter techniques. The average particle size in micrometers for each additive type is as follows: (Cu metal powder, 42; 0 ^ 0.13; Cu0.7; CuJ, 19.7; CuC ^ 2 ^ 0.14.6; -Al2 O3, 11 , 4).

Each sample was placed on a watch glass plate in a weighed amount of two grams and then exposed for two hours to aging under heating at 300 ° C in circulating air. After being cooled, each sample was photographed and then weighed to determine the amount of e-30 weight loss. The samples were then exposed as a group to the oven for an additional two hours at 300 ° C, cooled, photographed and reweighed. This method was repeated six times, thus exposing the samples in the oven at 300 ° C for 12 hours.

Results. Large differences in stability were evident after the first two hours of exposure. The control resin without additives turned dark brown and foamed excessively. Of the samples containing 5 ppm copper, the samples with CuJ and CuCl showed no color change or foaming. The CuC ^. The sample showed no foaming, but underwent slight yellowing and some weight loss. Of the remaining samples, CuBr op-5 foaming, but slightly yellowed, while copper metal 0 ^ 0, CuO and CuBr 2 showed some foaming and significant color development.

At 50 ppm copper, all additives except Gu20, CuO, Cu2 · 2¾0 and copper metal prevented both coloration and bubble formation. At 500 and 1000 ppm, all additives gave good protection.

The CuJ samples containing 500 and 1000 ppm copper were resp. gray and black after the first two hours of aging. The dark staining is not a result of degradation of the polymer, but is instead the result of copper (II) oxide (black) formation. These samples did not darken further with continued oven exposures. Evidence of CuO formation was also seen in the CuCl, CuBr and C ^ O samples. Of these, the CuJ was the most reactive with respect to oxygen.

The weight loss over time for the different samples is summarized in Table A.

At 5 ppm copper, Table A shows a wide range of additive effectiveness, with CuJ being the potent inhibitor in order of decreasing activity by 0 uCl, CuCl 2. 2 ^ 0, CuBr, Cu20, CuBr2 and CuO.

The CuJ and CuCl compounds are by far the most effective additives: (1) they protect against color formation for the longest time (4-6 hours), (2) prevent foaming up to 50 hours for CuJ and 4 hours for CuCl, (3 ) maintain the dependent low weight loss the longest and (4) give the lowest final weight loss (12 hours).

At 50 ppm, the order of efficiency remains essentially the same. Here, the sample containing copper metal 35 provides the least protection. The overall order of efficiency from good to bad is: CuJ, CuCl, CuBr, CuCl2 «2H20, Cu20, CuBr2, CuO and Cu metal.

At 500 ppm, all additives showed the same efficiency. However, at this concentration many additives pigment the resin. This pigmentation is for many applications 8201697 9 w. - 5 '' fits desired. The CuO makes the resin gray, the CuJ tan colored and the C-rose. From the pigmentation point of view, CuCl gives the least color with the maximum protection and does not color as much as the CuJ black to CuO.

Copper metal has the least pigmentation of all additives, but does not provide adequate protection for the E / TFE-I. 1 8201697 10

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Example III.

Test The E / TFE-I samples were the same as used in Example II. Stabilized E / TPE-II samples were prepared in the same manner as the Ε / ΤΪΈ-Ι samples (see Example I), however several changes from the method of Example I were made: (1) the powder samples were weighed directly in heat-cleaned (300 ° C for 2 hours) aluminum scales instead of on watch glasses to allow easy removal of the polymer discs after aging by heating; (2) a larger sample (5 5 grams) was used to provide sufficient polymer for MV measurements and (3) the samples were photographed against a white background to better compare color changes and differences.

Each sample is weighed in its aluminum dish using a gravimetric balance. All samples were put together in a circulating air oven; set at 300 ° C, aged with heating. After aging, the samples were reweighed to determine the weight loss rate. Each sample was then separated from the aluminum dish and the other samples were photographed.

Results. .The weight loss results are included in Tables B and C- | The weight loss results for both E / TPE-I and E / TPE-II are largely parallel. A concentration dependence is clear for the Gu, Cu20 and CuO additives, while CuJ and CuCl show no concentration dependence over the wide range of 5 to 500 ppm copper. More importantly, CuJ and GuCl are much more potent stabilizers than copper or its oxides at low concentrations.

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18

Example 17.

Tests, CuJ or CuCl was mixed with E / TEE-I or II powder by mixing in a tumbler mixer. The blends were then passed through a twin screw extruder. Extruded 28 mm.

The extruded samples were molded under pressure at 500 ° C into 10 cm x 10 cm x 0.025 cm films. These films were cut into halves of 5 d x 5 cm sn and one half subjected to thermal aging in air at 200 ° C for a specified time. The other half was not aged and served as a contrdle. A new foil sample was formed for each aging cycle. The unaged and aged samples were measured for color, degree of oxidation by absorption in the range of 1755 cm @ 1 (carbonyl region) and percent elongation at both room temperature and 200 ° C. The E / TEE-I samples were samples which had a control (no additive), 5 ppm Cu as CuJ, 50 ppm Cu as CuJ, 500 ppm as CuJ, 5 ppm Cu as CuCl, 50 ppm Cu as CuCl, 50 ppm copper metal powder, 50 ppm Cu as C 2 O. Extruded Ε / ΤΙΈ-ΙΙ 20 samples were samples containing 0.25 ppm Cu as CuJ, 5 ppm Cu as CuJ, 5 ppm Cu as C ^ O and 50 ppm Cu as C ^ O. The E / TEE-II powder served as a control.

Results are shown in Table D.

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Claims (7)

1. Ethylene / tetrafluoroethylene copolymer composition with good thermal stability, characterized in that. that the composition a) is an ethylene / tetrafluoroethylene copolymer. containing 40 to 70 mole percent tetrafluoro-5 thene units and complementary 60-30 mole percent ethylene units and optionally up to 20 mole units of at least one copolymerizable ethylenically unsaturated comonomer having 3 to 12 carbon atoms and b) 0.05 to 500 ppm, based on parts a) and b) contains copper (I) iodide or 10 (I) chloride (as copper) free from other inorganic halide salts. 2. A composition according to claim 1, characterized in that the copolymer contains units of ethylene, tetrafluoroethylene and hexafluoroacetone. 15 3. A composition according to claim 1, characterized in that the copolymer comprises units of. ethylene, tetrafluoroethylene and perfluorobutyl ether. 4. A composition according to claim 1 or 2, characterized in that the copper (I) compound is copper (I) 20 iodide. Composition according to claim 2 or 3i, characterized in that the copper (I) compound is copper (I) chloride. 6. A composition according to claim 4, characterized in that the copper (I) iodide is present in an amount of 5 to 50 ppm. 7. A composition according to claim 5, characterized in that the copper (I) chloride is present in an amount of 5 to 50 ppm. 82.0 1 6 9 7 ____________ *