JPH0115528B2 - - Google Patents

Description

Claim 1: A thermoplastic fluorinated carbon polymer containing an organic titanate as a filler.

2. The polymer according to claim 1, characterized in that the polymer is a copolymer.

3. The polymer according to claim 1, characterized in that the polymer is a block copolymer.

4. The polymer according to claim 1, wherein the polymer is a foamed polymer.

5 Claims 1 to 4, characterized in that they contain conventional fillers in addition to organic titanates.
Polymer according to any one of paragraphs.

Description The present invention relates to fluorocarbon polymers containing organic titanates as fillers.

Fluorinated carbon polymers are in growing demand as materials with desirable properties that make them suitable for specialized applications. Such fluorocarbon polymers include, for example, polymers of simple fluoroolefins or copolymers or terpolymers containing fluoroalkoxyethylene, fluoroethylene, fluoropropylene, etc., and also soft and hard segments of each fluorocarbon polymer that are chemically bonded to each other. These include block copolymers bonded to

These known fluorinated carbon polymers can also be used in the form of foams using suitable blowing agents.

These known fluorinated carbon polymers are often mixed with organic or inorganic fillers in order to modify their mechanical and/or electrical properties. However, the incorporation of these fillers has the disadvantage of compromising important properties of the polymer. For example, the melt viscosity of fluorocarbon polymers is typically increased significantly by the incorporation of these fillers, making extrusion difficult or impossible.

The main object of the present invention is to lower the melt viscosity of these fluorinated carbon polymers without impairing their mechanical and electrical properties. It has been found that this object of the invention can be achieved by using organic titanate compounds as fillers.

The blending of an organic titanate into a fluorocarbon polymer is disclosed in Japanese Patent Application Laid-Open No. 169572/1983, in which n-butyl titanate, 2-ethylhexyl titanate, or tripropoxytitanium stearate is mixed with a fluorocarbon polymer and applied to cloth. However, examples have been shown of improving the water repellency and antistatic properties of materials such as sportswear.

However, this known technique relates to a fluorinated carbon polymer that is soluble in a solvent, and its intended effect is to impart antistatic properties, which is completely different from the present invention. That is, the present invention anticipates that by blending a specific organic titanate described in detail below with a general fluorinated carbon polymer raw material for molding, the melt viscosity of the polymer can be lowered and the moldability can be significantly improved. It is based on the discovery of effects that have not been previously observed.

In the present invention, the fluorocarbon polymer mixed with the filler in the form of organic titanate can be exemplified as follows.

Polymers of fluorinated carbon polymers such as tetrafluoroethylene, hexafluoropropylene, perfluoroalkoxyolefin, chlorotrifluoroethylene, vinylidene fluoride: Can be copolymerized with each other or with the above fluorinated carbon polymers Copolymer or terpolymer with other monomers: Block copolymer consisting of the above polymer, copolymer or terpolymer, in which soft segments and hard segments with completely different properties are chemically bonded to each other: The above fluorocarbon polymer and Mechanical mixtures of block copolymers: Each of the above fluorocarbon polymers foamed using a blowing agent: etc.

More specific examples include tetrafluoroethylene-hexafluoropropylene copolymer (FEP); ethylene-chlorotrifluoroethylene copolymer (ECTFE); ethylene-tetrafluoroethylene copolymer (ETFE); tetrafluoroethylene-fluoroalkoxyethylene copolymer (PFA); Polyvinylidene fluoride (PVDF);
A block copolymer having a soft segment of vinylidene fluoride-hexafluoropropylene copolymer and a hard segment of polyvinylidene fluoride or ethylene-tetrafluoroethylene copolymer or ethylene-chlorotrifluoroethylene copolymer; a combination of the above block copolymer and ETFE or modified ETFE. mechanical mixture;
etc.

The organic titanate used in the present invention is selected from the following group of compounds.

1 Alkoxy compounds consisting of, for example, neoalkoxytriisostearoyl titanate, isopropyltriisostearyl titanate, methacryl diisostearoyl titanate, and dicumyl phenyloxyacetyl titanate.

2 Sulfonyl compounds such as dodecylbenzenesulfonyl titanate and tridodecylbenzenesulfonyl titanate.

3 Tri(dioctyl phosphate) titanate, tri(dioctyl pyrophosphate) titanate, tetraisopropyl di(dioctyl phosphite) titanate, tetraoctyloxytitanium-di-(tridecyl phosphite)
Tetra(2,2, diallyloxymethyl)-1,
1-Butoxytitanium di-(ditridetorphosphite), titanium-di(dioctyl phosphate)oxyacetate and di(dioctyl pyrophosphate) ethylene titanate, di(butylmethylpyrophosphate) ethylene titanate-di(di Phospho compounds such as (dioctyl hydrophosphite).

4 Chelate compounds such as tri(N-ethylaminoethylamino) titanate.

5 A quaternary titanate compound consisting of an acrylic group and an amine.

As already mentioned, the melt viscosity of fluorinated carbon polymers increases when combined with conventionally known fillers, but by adding organic titanates according to the present invention, extrusion molding becomes possible. Its melt viscosity can be reduced. For example, isopropyl-tri(dioctylpyrophosphate)
By adding titanate, the melt viscosity can be reduced to 1/6 of that without addition.

Inorganic fillers that combine with fluorocarbon polymers include, for example, mineral fibers. Such mineral fibers have a composition of calcium aluminum silicate, have a length of about 3 mm, and are usually used in a mixture of 25% by weight. In this case, for example, by adding neoalkoxy-tri(N-ethylaminoethylamino)) titanate, the melt viscosity can be reduced to 1/5 of that when the titanate is not added, which is considerably It is now possible to make even thin walled products using injection molding.

Another utility of the present invention is that the addition of such titanium compounds also increases the tensile strength and elongation of molded products.

As already mentioned, the addition of organotitanium compounds according to the invention can also be effectively applied to foamed fluorinated carbon polymers. For example, ethylene-tetrafluoroethylene copolymer (ETFE) can be made into foam molded articles using blowing agents such as magnesium carbonate, azodicarbamide, and p-toluenesulfonic acid. At this time, isopropyl-tri(N
- By adding ethylaminoethylamino) titanate, the melt density of the compound is lowered, making extrusion possible, as well as reducing the cell size and making the cell size distribution more uniform. effective. As a result, the resulting foam moldings exhibit better mechanical and electrical properties than those without the addition of titanates.

In order to more specifically explain the effects of the present invention,
Examples are shown below.

EXAMPLE 1 A mixture of fluoroethylene-fluoropropylene copolymer (FEP) and carbon black is used as a radio wave shield, a low noise coaxial cable, or a heating element with or without temperature control. However, in general, when carbon black is added to the fluorinated carbon polymer, the melt viscosity increases,
Melt molding becomes difficult or impossible.

By adding isopropyl tri(dioctylpyrophosphate) titanate to this composition, the melt viscosity was lowered and melt molding became possible.

Comparative Example 2 80 parts by weight of ETFE was mixed with 20 parts by weight of glass fiber in a drum, and this mixture was extruded into a continuous strand while being kneaded at 290°C. After extrusion, the strands were water cooled and shredded into fine pellets. Injection molding or extrusion molding was performed at 290°C using this pellet. Raw material ETFE
The melt flow rate (MFR) measured by the method of ASTM-3959 was 1.0 g/10 minutes, and injection molding was easy, and the surface of the molded product was smooth and no residual air bubbles were observed.

On the other hand, in the composition of this example in which 20% of glass fiber was mixed, the MFR decreased to 10.0 g/10 min.
The surface of the injection molded product was rough and had a poor appearance, and at the same time, the flow into the mold was poor and residual air bubbles were observed. In particular, the narrow and detailed parts of the mold were not filled with material.

Example 2 In Comparative Example 2, 0.5 part of neoalkoxytriisostearoyl titanate was added to a mixture of 80 parts of ETFE and 20 parts of glass fiber. After thorough mixing in a drum, the mixture was extruded into strands at 290°C, rapidly cooled in water, and shredded into pellets.

In bench tests, the MFR of this pellet with organic titanate addition was approximately 2.5 grams/10 minutes.

The results of an injection molding test of this composition at 290°C were satisfactory; due to its low viscosity, the surface of the molded product was smooth, the narrow and fine parts of the mold were completely filled, and there were no residual air bubbles.