JP2615176B2 - Amorphous copolymer of perfluoro-2,2-dimethyl-1,3-dioxole - Google Patents

Description

BACKGROUND OF THE INVENTION The present invention relates to cladding materials in optical fiber structures as well as certain electronic applications, molded articles,
And certain amorphous perfluoropolymers that are particularly suitable in films.

Although tetrafluoroethylene homopolymers and copolymers have many excellent properties, they usually have low modulus, especially at elevated temperatures; poor creep resistance; insolubility; Difficult to handle. Various fluoropolymers have occasionally been proposed for clad optical fibers mainly because of their low refractive index. A good polymer cladding material for optical fibers must be completely amorphous. This is because the presence of microcrystals in the polymer will cause light scattering. Furthermore, it must have a high glass transition temperature, Tg, especially if use at high temperatures is intended. Because above its Tg, it will lose some of its desirable physical properties and especially it will not be able to maintain good adhesion to the fiber core.
Desirable Tg is 140 ° C. or higher, preferably 180 ° C. or higher, especially
It will be above 220 ° C. Suitable fully amorphous fluoropolymers having a rather high Tg have not been reported so far.

Resnick US Pat. No. 3,978,030 has the following formula: Certain polymers of perfluoro-2,2-dimethyl-1,3-dioxole (PDD) having the formula: The above patent describes both a less well characterized homopolymer of PDD and a crystalline copolymer with tetrafluoroethylene (TFE) having a melting point of about 265 ° C.

Since the discovery of Resnick's PDD homopolymer, it has been determined that this material is amorphous and has a very high Tg of about 330 ° C. However, this homopolymer is not easily melt-processable due to poor flow and some degradation.

Crystalline copolymers of PDD and TFE cannot be used in many applications, for example, where optical clarity, dimensional stability, solubility, or high Tg are required.

Thus, the polymer of US Pat. No. 3,978,030 was not produced commercially, despite the fact that a perfluoropolymer having the desired properties would have many possible uses in various high-tech applications.

Dioxol PDD has now been found to produce amorphous copolymers with unique properties, and these properties make these copolymers particularly suitable for a number of special applications requiring high performance.

Summary of the Invention According to the present invention, 65-99 mol% of perfluoro-2,2
-Dimethyl-1,3-dioxole and the following compounds: b) chlorotrifluoroethylene, c) vinylidene fluoride, d) hexafluoropropylene, e) trifluoroethylene, f) Formula CF ₂ = CFOR _F , R _F is a normal perfluoroalkyl group having 1 to 3 carbon atoms] of the formula perfluoro (alkyl vinyl ether, g) CF ₂ CCFOQZ wherein Q is a perfluorinated alkylene containing 0 to 5 ether oxygen atoms Group, where Q
The sum of C and O atoms in the Yes 2-10; and Z is -COOR, a -SO ₂ F, -CN, a group selected from the group consisting of -COF and -OCH _3, where R is C ₁ -C ₄ alkyl] fluorovinyl ether, h) vinyl fluoride, and i) R _f CHCHCH _{2 wherein} R _f is a C ₁ -C ₈ normal perfluoroalkyl group An amorphous copolymer with at least one supplemental amount of a comonomer selected from the group consisting of (perfluoroalkyl) ethylene, wherein the copolymer has a glass transition temperature of at least 140 ° C .; Maximum mole percent,
M _b ... M _i is as follows: b) for chlorotrifluoroethylene, M _b = 30, c) for vinylidene fluoride, M _c = 20, d) for hexafluoropropylene, M _d = 15. , with respect to e) trifluoroethylene, with respect to _{M e = 30, f) CF} 2 = CFOR F, with respect to _{M f = 30, g) CF} 2 = CFOQZ, with respect to M _g = 20, h) vinyl fluoride, M _h = 25, and i) for R _f CH = CH ₂ , M _i = 10; and, in the case of copolymers having more than one comonomer, the amount of each comonomer is the corresponding maximum percentage, M _b ... mol% for the M _i,
The sum of the ratios of m _b ... m _i , S is not greater than 1 as shown below: S = m _b / M _b + ... + m _i / M _i ≦ 1 It appears that the copolymer is here Provided.

As used herein, the term "supplementary" refers to the mole percent of perfluoro-2,2-dimethyl-1,3-dioxole and any of the above copolymers (b)-(i) present in the copolymer. Means that when added together the mole percent of

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a plot of the mole fraction of TFE in a dipolymer with PDD versus the Tg of the dipolymer.

FIG. 2 is a plot of the mole fraction of PDD in a dipolymer with TFE versus the Tg of the dipolymer.

FIG. 3 is a plot of the dynamic modulus of a PDD copolymer with TFE and a comparative resin.

DETAILED DESCRIPTION OF THE INVENTION The copolymers of the present invention preferably have a Tg of at least 180 ° C.
Having. When such a copolymer comprises a comonomer copolymerized with more than one PDD, the value of S is less than one. Particularly preferred copolymers of the present invention are at least
It has a Tg of 220 ° C. When these copolymers contain comonomers copolymerized with more than one PDD, the value of S is much less than 1, for example, 0.8 or less.

All major monomers used in the present invention are known in the art. Perfluoro (alkyl vinyl ether) f) is perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether)
And perfluoro (n-propyl vinyl ether). Ether g) is, for example, of the formula (3,6-dioxa-4-methyl-8-nonenoate) (hereinafter referred to as EVE)
And the following equation Perfluoro (4-methyl-3,6-dioxa-7-octenyl) sulfonyl fluoride represented by
PSEPVE). TFE is made in large quantities by EI DuPont de Nimoasu and Company; Other suitable representative monomers are available from the following sources: SCM Specialty Chemicals, Geinsubiru (Gainesville), VF ₂ from FL, Kurorotori Fluoroethylene (CTFE), Hexafluoropropylene (HF
P), vinyl fluoride and trifluoroethylene; perfluoro (methyl vinyl ether) (PMVE) and perfluoro (propyl vinyl ether) (PPVE) are US 3,180,
Made as described in 895; (EVE) is
Made as described in US 4,138,740; and PSEPVE made as described in US 3,282,875. PDD is based on U.S. Pat.
It is stated in 30.

It has now been found that PDD can be copolymerized with any one or more of the above named monomers into an amorphous copolymer.

The amorphous copolymer of the present invention is soluble at room temperature in perfluoro (2-butyltetrahydrofuran), a commercially available solvent available under the trademark FC-75 from 3M. In addition, they have a combination of the following excellent properties: 1. High glass transition temperature; 2. High modulus, especially at elevated temperatures; 3. High strength, especially at elevated temperatures; 4. Compression 5. Low creep under load; 5. Melt processability at mild temperatures; 6. Processability to films and coatings by solvent casting; 7. Low temperature sprayability; 8. Extraordinarily low refractive index; Dielectric properties; 10. Excellent chemical resistance.

The first four property properties of the copolymers of the present invention are particularly advantageous in applications where the polymer must be loaded at elevated temperatures. Due to their chemical inertness and excellent insulating properties, they are also suitable for a number of specialized electrical applications. Also, due to their chemical inertness, good optical properties and good physical properties,
They are suitable for the manufacture of optical lenses. The polymers of the present invention can also be filled or reinforced with a solid material to form a composite. These additives are, for example,
Including graphite, graphite fiber, aramid fiber, mica, wollastonite, glass fiber and the like. The fibrous material is
It may be in the form of loose fibers, fabrics or mats.
Such composites exhibit desirable properties, such as enhanced modulus.

The amorphous copolymer films of the present invention are useful when thermally laminated to other polymer films or metal foils. Laminates of the amorphous copolymers and copper foils of the present invention are excellent substrates for flexible circuit manufacturing because the copolymers adhere directly to copper without the need for intervening adhesives. Conventional copper / adhesive / polyimide / adhesive / copper structures for electronic circuit substrates have high dielectric constant material defects next to copper. This limits the ultimate speed of the electronic circuit. The copper / amorphous copolymer / copper laminate allows for very high circuit speeds because the amorphous copolymer film has a low dielectric constant (2.1) and can be directly thermally bonded to the copper of the circuit.

Thermal laminates of the amorphous copolymer / polyimide / amorphous copolymer are useful as electronic circuit substrates. Compared to the polyimide film itself, this laminate is
(A) it can be thermally bonded to copper foil without an adhesive; (b) the low water absorption of the amorphous copolymer gives the substrate greater dimensional stability in a humid environment; and (c) the amorphous copolymer It is an excellent circuit substrate because its low dielectric constant allows the production of high speed circuits.

The amorphous copolymer / polyimide thermal laminate is useful as a vacuum bag for the curing of components, for example, helicopter wings made from a thermoset resin reinforced with carbon fiber. The high glass transition temperature, thermal stability and low surface energy of the amorphous copolymer
When this side is placed against the thermoset part to be cured, it gives the laminate excellent release properties. The polyimide layer of the laminate provides strength to prevent pinhole formation when the bag enclosing the thermoset resin component is evacuated and raised to cure temperature. After curing and cooling, the laminate is easily separated from the part.

A thermal laminate having an amorphous copolymer film as its outer surface and an oriented polypropylene film as the core has a low chemical and stain resistance combined with excellent mechanical properties. Useful as a cost film structure. Such a laminate can be used to protect sensitive equipment from environmental damage.

Pipes, tubes and fittings (fittin) made from or lined with the amorphous copolymers of the present invention
gs) prevents contamination of the process liquid by metal ions, plasticizers, or degradation products from the fluid handling system. Such fluid handling components are of very high purity, are inert to most common chemicals, and are easily manufactured from raw materials by injection molding, extrusion, and machining. Alternatively, the fluid handling system components are made of metal, glass or other plastic, and subsequently lined with the amorphous copolymer of the present invention by solution coating, dispersion coating or electrostatic powder coating. In addition to pipes, tubes and fittings, other useful fluid handling articles made from the amorphous copolymers of the present invention include pump housings, pump impellers, valve bodies, valve stems, valve seals, diaphragms, tank,
Tray, pipette, laboratory container. Such articles are particularly useful in semiconductor processing fluid handling systems where process water and chemicals require ppb purity. Also, in molecular biology research laboratories where extreme purity is required and microgram quantities must be completely removed from the containers in which they are handled, the amorphous copolymers of the present invention are made. Particularly useful are fluid handling articles.

The amorphous copolymers of the present invention are particularly useful when processed into articles for transporting materials and components through chemical processing processes. For example, in a manufacturing process for semiconductor chips, silicon wafers must be transported through a series of chemical processing steps; the containers in which the silicon wafers are transported are chemically inert to prevent chip contamination. And they must be rigid and dimensionally stable to allow accurate automatic positioning at each stage of the process. Compared to conventional fluoroplastics used for such wafer carriers, such as copolymers of tetrafluoroethylene and perfluoro (propyl vinyl ether), the amorphous copolymers of the present invention have greater stiffness and greater dimensional stability Has the property. This advantage allows the manufacture of larger wafer carriers, for example baskets for holding silicon wafers with a diameter of 30 cm; wafer carriers made from conventional fluoroplastics can be used for wafers larger than about 15 cm in diameter. Too low in flexural modulus to be useful.

Other transportation system components for which articles made from the amorphous copolymers of the present invention are particularly well suited include guide rails, conveyor belt links, bearings and rollers,
Clamps, racks, hooks, locating pins, robot arm jaws and fingers, gears, cams, and precisely machined, have good high temperature mechanical properties, retain dimensions, are chemically pure and chemically inert Similar mechanical parts that must be. Transport system components made from the amorphous copolymers of the present invention, which are exposed to corrosive chemicals or ultrapure water, require all conventional fluoropolymers due to the superior high temperature mechanical properties and dimensional stability of the polymers of the present invention. Better than plastic.

The low dielectric constant (2.1) and low coefficient of thermal expansion of the amorphous copolymers of the present invention make them particularly useful as insulators in electrical and electronic applications. For example, insulators used between separate circuit layers in a high-speed digital multilayer circuit board have very low dielectric constants and can range from -20 ° C to about 225 ° C.
It must be dimensionally very stable (comparable to ceramic and copper) up to the soldering temperature of. Polyimide is dimensionally stable but has a high dielectric constant (>3); in addition, it is sensitive to atmospheric humidity; the amorphous copolymers of the invention do not have these defects and Multilayer circuits having this polymer as an insulator between them can be of higher speed and higher circuit density.

The low water absorption, outstanding chemical resistance, purity, thermal stability and dimensional stability of the amorphous copolymers of the present invention make them particularly suitable for protecting sensitive electronic circuits and components. Unlike conventional fluoroplastics, the polymers of the present invention can be dissolved to form a coating and encapsulation solution. For example, the so-called “smart connector”. Example 1
Can be encapsulated by pinning and immersing it in a solution of the amorphous copolymer of E.C. and leaving the protective film of the polymer to evaporate the FC-75 solvent and eliminate environmental water and corrosive chemicals. it can. In another embodiment, the polymer of the present invention is a thin layer of gold, a so-called "gold flash", to protect electronic connectors from corrosion from atmospheric chemicals.
Can be used instead of The entire electronic or electro-optical circuit can be encapsulated by the solution coating method with the amorphous copolymers of the present invention, but this is not possible with conventional fluoropolymers because they do not dissolve in practical solvents . It is well known that conventional aqueous dispersions of fluoropolymers can be used for impregnating and encapsulating articles such as glass fibers and metal parts; however, the application of such dispersions is known as fluoroplastics. Are limited to substrates that can withstand the high baking temperatures (> 200 ° C.) required to melt into a pinhole-free coating. In contrast to conventional aqueous dispersions of fluoroplastics, the solutions of the amorphous copolymers of the invention can be applied to temperature-sensitive substrates, such as electronic circuits or components made from thermoplastics, and The solvent can be evaporated at a mild temperature (100 ° C. or less), leaving a protective polymer film without the need for high temperature baking to melt the polymer.

As the amount of PDD in the copolymer of the present invention increases, the Tg also increases, although not necessarily in a linear fashion. The relationship between the molar fraction of TFE in the dipolymer with PDD and Tg is shown in FIG. For example, a copolymer containing about 30 mole percent TFE has a Tg of 153 ° C., while about
It can be seen that the copolymer containing 23 mole% TFE has a Tg of 176 ° C.

FIG. 2 shows the molar fraction of PDD in the dipolymer with TFE and Tg.
Shows the relationship between In this case, the mole fractions of these monomers were measured by a technique different from the technique used to obtain the plot of FIG.

Tg is measured by Differential Scanning Calorimetry (DSC) according to ASTM method D-3418. Examination of the DSC curve shows that there is only a second order transition and no first order transition, which indicates no crystallinity. The relative proportions of the comonomers in the copolymer can be determined by nuclear magnetic resonance spectroscopy of fluorine -19 ⁽¹⁹ F NMR). This was the technique used to obtain the plot of FIG. The percentage of hydrogen-containing monomers can be measured by proton NMR along with ¹⁹ F NMR.

The proportion of comonomer in the copolymer can also be measured by X-ray fluorescence (XRF). This is the second
The technique used to draw the plot of the figure. The measurements were performed on a Philips Electronic instrument 1404XRF spectrometer. The sample was in the form of a 50 mm disk approximately 1 mm thick. Calibration of X-ray fluorescence intensity as a function of weight percentage of oxygen and fluorine was performed using three polymer samples of known composition containing the expected fluorine and oxygen content of the unknown PDD-TFE copolymer. . These standards are PDD homopolymer, copolymer of 40% by weight of perfluoro (methyl vinyl ether) and 60% by weight of tetrafluoroethylene, and 96.1% by weight of tetrafluoroethylene and 3.9% by weight of perfluoro (propyl vinyl ether) And a copolymer of The composition of the latter two polymers was determined by infrared spectroscopy calibrated by accurate measurements of off-gas during the polymerization.

The analytical crystals used had an effective d-spacing of about 5.0 nm. The fluorescence intensity maximum of fluorine was 43.5 ° 2θ, and the oxygen intensity maximum was 57.1 ° 2θ. About 20
Five Ps of unknown composition spanning the composition range of ~ 90 mol% PDD
DD-TFE copolymer was analyzed by XRF. 63.7% by weight
Of fluorine and 11.2% by weight of oxygen (71.9% by mole of PDD, 28.
Ten replicate measurements of a sample containing 1 mol% of TFE yielded a root mean square variance of 0.34% for fluorine and 1.9% for oxygen.
ance).

Because the PDD and perfluoromonomer copolymers of the present invention can be easily melt processed, they can be processed into articles by techniques such as, for example, injection molding and extrusion. Furthermore, they have a low refractive index, which is a particularly desirable property for optical fiber cladding. Since they are soluble in FC-75, they are:
A substrate such as an optical fiber or a flexible or rigid circuit board can be conveniently applied from a solution to provide a thin polymer layer. Furthermore, films of these copolymers are clear and transparent as compared to cloudy or translucent films of crystalline polymers. For this reason, the amorphous copolymers according to the invention are suitable for applications such as, for example, windows in chemical reactors, especially for processes using or producing hydrogen fluoride.

It should be noted that although PDD homopolymers are also amorphous and have good chemistry, they cannot be easily melt processed due to some degradation that occurs at the high processing temperatures required. .

The copolymerization is carried out in the presence of a free radical generator at a temperature suitable for the chosen initiator. A well-stirred pressure device and a nontelogenic solvent or diluent should be used, preferably those with sufficient volatility to allow easy removal from the polymer.

The invention will now be illustrated by the following examples of certain preferred embodiments, unless otherwise specified.
Percentages and percentages are by weight. Most Tg's were measured using a DuPont Differential Thermal Analyzer model 1090 and 910 or 912 DSC module. All units have been converted to SI units.

Reference Example 1 In a 330 ml cold stainless steel shaker tube, 51 g (0.21 mol) of PDD and 330 g of cold 1,1,2-
Trichloro-1,2,2-trifluoroethane and 0.2 g of 4,
4'-bis (t-butylcyclohexyl) peroxydicarbonate was charged. The tube was sealed, cooled further between −50 ° C. and −80 ° C. in a dry ice-acetone mixture, alternately evacuated and flushed with nitrogen three times,
Then, 1 g (0.01 mol) of TFE was charged. The tube was shaken horizontally while heating at 55 ° C, 65 ° C and 70 ° C for 1 hour respectively. After cooling to room temperature, the solvent was distilled off, leaving behind a solid white polymer, which was dried at 130 ° C. in a vacuum oven. The monomer composition was 98 mol% PDD by NMR.
And 2 mol% TFE.

Reference Example 2 In a cold 400 ml stainless steel shaker tube, place 270 g of cold 1,1,2-trichloro-1,2,2-trifluoroethane and 42.2 g (0.17 mol) of cold PDD (this is the last step). (Purified by passing through silica gel) and 0.2 g of 4,4'-bis (t-butylcyclohexyl) peroxydicarbonate.
The tube was sealed and further cooled between -50 ° C and -80 ° C. At this point, the tube was placed on a horizontal shaker and connected to the required tubing and temperature sensing device. The tube was then alternately evacuated and purged with nitrogen at least three times. Next, 2 g (0.02 mol) of tetrafluoroethylene (TFE) was charged into the evacuated tube. 180 per minute
Rocking at the speed of the stroke was started and the tube contents were heated to 55 ° C; after 1 hour at 55 ° C, the temperature was increased to 6 ° C.
The temperature was raised to 0 ° C, 65 ° C, 70 ° C and 75 ° C and held at each of these sequential temperatures for 1 hour. Tube pressure is initially 5
C. was 124.1 kPa and gradually increased to 172 kPa at 75.degree. The tubes and contents were cooled to room temperature and the contents, a dark white slurry, were poured into a still. The solvent was distilled off at room temperature and reduced pressure; the solid polymer was then removed in a vacuum oven at 60 ° C and finally in a circulating air oven.
Dried at 5 ° C. The weight of the dried polymer was 39.4 g; the Tg was 250 ° C and the polymer was amorphous as evidenced by the absence of a melting endotherm; the intrinsic viscosity at 25 ° C was perfluoro (2-butyl). 0.0719 m ³ / kg measured on a 0.36% w / v solution in tetrahydrofuran)
Met.

Portions of the polymer were molded at 300 ° C. into 0.32 cm thick bars having a width of 1.3 cm, and these were treated as shown in Table I,
Used for the measurement of modulus versus temperature: the analysis showed that
89 mol% PDD / 11 mol% TFE polymer.

Another part of the polymer is 280-300 ° C. with a thickness of 1 cm and 1.3
It was compression molded into a cm wide bar. These pieces were used in a deformation test under a compressive load of 6.895 MPa shown in Table II.

Another portion of the polymer was compression molded at 280 ° C. into a 0.027 cm thick film. These were tested for tensile properties and reported as polymer C in Table III.

Comparative Example A A polymer was prepared from 2 parts of PDD and 10 parts of TFE following the intact procedure of Example 3 of Lesnick US Pat. No. 3,978,030. The polymeric product was extracted with 1,1,2-trichloro-1,2,2-trifluoroethane for 25 hours. About 0.2 percent of the product weight was thus removed; the extracted portion was grease and appeared to consist of shaker tube lubricant and a small amount of unknown fluorocarbon. This was clearly a low molecular weight material.
The extracted product had no Tg between 25 and 200 ° C. It was different from the amorphous copolymer described above. The solid extraction residue was a crystalline rather than an amorphous polymer as shown by wide angle X-ray powder diffraction spectroscopy. This comparative experiment is based on U.S. Pat.
It shows that the monomer ratios used in Example 3 of 978,030 do not yield amorphous PDD / TFE copolymers.

Comparative Example B 5.0 g PDD, 0.100 g 4,4'-bis (t-butylcyclohexyl) peroxydicarbonate and 40.0 g 1,1,2
The mixture of trichloro-1,2,2-trifluoroethane was placed in a pressure tube. The mixture was completely degassed, sealed, and placed in a constant temperature bath at 30 ° C. for 20 hours. The polymerization mixture appeared as a thick, translucent slurry of polymer particles dispersed in 1,1,2-trichloro-1,2,2-trifluoroethane. Volatile substances are removed by distillation,
And 4.7 g when polymer residue is dried at 150 ° C for 20 hours
Of PDD homopolymer was obtained. The products of four identical experiments were combined. This polymer had two glass transition temperatures at 333 and 350 ° C.

Some physical properties of typical PDD homopolymers are compared with those of the 89PDD / 11TFE dipolymer of Reference Example 2 and those of the prior art polymers, as shown below in Tables I and II.

It must be mentioned that PDD homopolymers could not be melt processed by compression molding without some degradation (as evidenced by outgassing). 355 moldings
It could be obtained in the temperature range of 370370 ° C. Above 370 ° C., the degradation was very pronounced; below 350 ° C., the fluidity of the polymer was insufficient to produce molded parts and a coalescense to a homogeneous test slab was achieved Was not done.

PDD homopolymer could be cast from perfluoro (2-butyltetrahydrofuran) solution. Although the material had good physical properties (eg, high modulus), this technique was not practical due to the thick sections.

The polymer samples were also tested for deformation under a compressive load of 1000 psi (6.895 MPa). The results measured by ASTM D-621 are shown in Table II.

The above amorphous soluble copolymers are well known
It can be seen that it has lower deformation under compressive loading than either the TFE homopolymer or the crystalline PDD / TFE copolymer reported by Lesnick in US 3,977,030. This difference is particularly significant at 100 ° C.

Due to its lower creep under compressive load compared to commercial fluoropolymers, this copolymer, like the other copolymers of the invention, is particularly suitable for corrosive atmospheres.
For example, it is suitable for manufacturing gaskets for use in chemical reactors, oil rigs, automotive engines, and the like.

Evaluation of film A film having a thickness of 0.025 to 0.05 cm
Compression molding was performed at 700 to 7000 kPa at ~ 300 ° C. One of these polymers is the amorphous 89PDD / 11TFE copolymer described above, while the prior art crystalline copolymer is
It was made as described in Comparative Example A herein following the teachings of US 3,978,030. The physical properties of these films are reported in Table III below, where both the modulus and tensile strength of the amorphous copolymer are
It can be seen from this table that there is a significant improvement over those of the crystalline copolymers. The amorphous copolymer is thus stiffer and stronger.

Example 1 In a 2 liter vertical reactor equipped with a four-blade impeller type stirrer, 1500 ml of deoxygenated, deionized water,
3.75 g of ammonium perfluorononanoate surfactant and 4.70 g of ammonium sulfite were charged. The reactor was pressurized with chlorotrifluoroethylene (CTFE) and then vented.

While running the stirrer at 600 rpm, 25 ml of a 7% aqueous ammonium persulfate (APS) solution was introduced into the reactor heated to 60 ° C .; then an initial charge of 2.63 g of CTFE and 16 g of PDD was added. After stirring the mixture for 30 minutes, 5.
25g / hr CTFE, 32g / hr PDD (CTFE / PDD molar ratio of 0.344)
And a continuous feed of 10 ml / hr APS solution was started and continued for 4.5 hours. The reactor was cooled to 30 ° C. and a dispersion containing 9.4% solids was collected.

To this dispersion in the blender was added concentrated nitric acid (15 ml) and stirred. The dispersion separated into an aqueous phase and a copolymer phase. The copolymer was filtered off, dried in an oven at 110 ° C. for 24 hours, and further dried in a vacuum oven at 100 ° C. to remove traces of water. The copolymer was then placed in a reactor evacuated and purged with nitrogen at 25: 7
Fluorinated with 5 fluorine / nitrogen mixture at 100 ° C for 6 hours. All gas streams reached 0.132 parts fluorine per part copolymer. The reactor was then purged with nitrogen and cooled. 174 ° C recovered granulated amorphous copolymer
Had a single glass transition temperature. Its composition is 19.7
Mole% CTFE and 80.3 mol% PDD.

Example 2 A PDFE / CTFE copolymer was prepared using an initial charge of 2.66 g of CTFE.
And 16 g of PDD (CTFE / PDD molar ratio of 0.348), except that it was prepared in the same manner as described in Example 1. The dispersion recovered from the polymerization reactor contained 9.03% solids. The resulting copolymer was fluorinated as described in Example 1. It is amorphous, has a single Tg of 184 ° C., and 23:77 mol%
Had a monomer composition of CTFE / PDD.

REFERENCE EXAMPLE 3 A. Coated Article Typical Polymer Consisting of 72 mol% PDD / 28 mol% TFE
According to the procedure of Reference Example 2 using the appropriate monomer ratio
Manufactured. This PDD / TFE copolymer was converted to perfluoro (2
-Butyl tetrahydrofuran) (FC-75 Melted in)
To form a 5% solution. Two aluminum coupons (10
1.6mm × 12.7mm × 0.127mm) is 1,1,2-trichloro-1,2,2
-Washing with trifluoroethane removes residual processing oil
Removed. An aluminum coupon is immersed in this solution.
And then allow the solvent to evaporate in air at room temperature for at least 10 minutes.
And coated with PDD / TFE polymer. This dipping
4 dipping / drying processes on aluminum coupons
This was repeated twice to form a PDD / TFE polymer layer. Last
After room temperature drying cycle, coated aluminum coupon
Bake at 200 ° C for 3 hours in a nitrogen purged oven
After being completely dried and cooling to room temperature, the coated
Partially immerse one of the specimens in 6N hydrochloric acid at 25 ° C
And another at 25 ° C in 5M aqueous potassium hydroxide
Was partially immersed. After immersion in these reagents and
During the subsequent 30 minute period, no gas was released and
No discoloration of the minium sample and no obvious chemical reaction
Nothing happened.

Aluminum coupons coated with PDD / TFE were removed from the acid / base reagent. As a comparison, two similar aluminum coupons not coated with PDD / TFE were then subjected to 6N at 25 ° C.
It was immersed in hydrochloric acid and a 5M aqueous solution of potassium hydroxide. For both acids and bases, the chemical reaction started immediately with outgassing and discoloration of the sample. Uncoated aluminum coupons in potassium hydroxide solution reacted vigorously for 15 minutes. After 15 minutes it was removed from the reagent. The uncoated aluminum coupon in hydrochloric acid reacted violently and completely dissolved within 2 minutes after immersion in the reagent.

This reference example shows that metal articles can be coated with the polymers of the reference examples and that such coatings provide excellent resistance to corrosion of metal substrates by aggressive reagents such as concentrated acids and bases.

B. Preparation of Film and Lamination on Copper Foil A typical polymer consisting of 72 mol% PDD / 28 mol% TFE was prepared according to the procedure of Reference Example 2. 5.5 g of resin to 88.9
Process this polymer into a film by heating to 250 ° C for 10 minutes between platens of a hydraulic lamination press under an applied force of kN for 10 minutes and then rapidly cooling to 25 ° C while maintaining the applied pressure did. When the round film thus manufactured is measured, the diameter is 140 mm and the thickness is 0.14.
It varied between mm and 0.19 mm. This polymer film is
The multilayer structure is contacted between two sheets of rolled and annealed copper foil of 5.4 mm thickness and under a pressure of 2.07 MPa between the platens of a hydraulic lamination press at 250 ° C. for 5 minutes. The polymer film was laminated to the copper foil on both sides by heating to 25 ° C and then rapidly cooling to 25 ° C while maintaining the applied pressure. When inspecting the object after removing from the hydraulic press, the copper foil is PDD / TF
A copper clad laminate was firmly attached to the E-polymer film. Various properties of the laminate were measured to evaluate its suitability for electrical and electronic applications. The results of these tests are given in Table IV.

This reference example shows that metal foils can be laminated to films made from the polymers of the reference examples, and that these laminates have unique properties that are highly desirable for electrical and electronic applications.

Table IV Test method) result Dimensional stability: -0.72% (IPC-FC-241A method 2.2.4) 90 ° C peel strength: 158 Newton / m (IPC-FC-241A method 2.4.9) Dielectric constant: less than 2.3 (ASTM-D at 1mhz) −1531) Insulation strength: 2000 volts / mil thickness (ASTM D−149) (7.9 × 10⁷Bolt / m thickness) Volume resistivity: 3.0 × 10¹⁷Ohm-cm (ASTM D-257) (3.0 × 10^FifteenOhm-m) C. Preparation of Composite Structures Typical Polymer Consisting of 72 mol% PDD / 28 mol% TFE
Was produced according to the procedure of Reference Example 2. This PDD / TFE Copo
The rimer is converted to perfluoro (2-butyltetrahydrofura)
To yield a 5% solution. Enter commercially
Kevlar that you can handle 101.6mm of aramid fabric
Bake a × 101.6mm sheet at 125 ° C for 24 hours in a nitrogen atmosphere
To remove all absorbed water vapor. Cool to room temperature
Afterwards to eliminate trapped air pockets
Carefully remove the Kevlar fabric from the PDD / TFE polymer solution
The fabric by PDD / TF
Impregnated with E-polymer. Then FC-75 Dissolution
When the medium is evaporated at room temperature, the PDD / TFE polymer
It was deposited in the fabric in good contact with the various fibers. Next
Baked fabric at 200 ° C for 4 hours
Therefore, it was completely dried.

 The resulting composite structure contains 45% PDD / TFE resin by weight
And flexible unimpregnated Kevlar Flatter than woven
It was a tight sheet. This reference example is a textile material
Is impregnated with the polymer of Reference Example by appropriate application in solution
To produce a composite structure.

Reference Example 4 Copolymer containing 97.2 mol% of PDD and 2.8 mol% of TFE
Was prepared according to the general technique of the Reference Example. This kori
Ma is FC-75 Measured at 30 ℃ in 0.0333Kg / L solution
0.128m^ThreeIt had an intrinsic viscosity of / Kg and a Tg of 311 ° C.

Reference Example 5 A PDD copolymer with TFE was prepared as follows: In a 400 ml stainless steel shaker tube, 0.15 g of 4,4'-bis (t-butylcyclohexyl)
Peroxydicarbonate, 50.0 g (0.205 mol) PD
D, 450 g of 1,1,2-trichloro-1,2,2-trifluoroethane and 1.5 g (0.015 mol) of TFE were charged and heated at 60 ° C. for 6 hours. Evaporate volatiles and remove residue
Drying at 150 ° C. for 24 hours yielded 45.3 g of dipolymer. This dipolymer has an intrinsic viscosity of 0.0927 m ³ / Kg and 261.4
C. of Tg.

FIG. 3 is a plot of dynamic flex modulus versus temperature for the same type of polymer from a different experiment (Tg = 250 ° C.). This curve was obtained using a DuPont DMA-981 dynamic mechanical analysis module temperature controlled by a DuPont Series 99 thermal analyzer. The heating rate was controlled at 10 ° C./min. Polymer samples were in the form of small compression molded bars. In this instrument, the sample is vibrated at its resonant frequency, typically between 2 and 70 Hz. An amount of energy equivalent to that lost by the sample is applied during each cycle to keep the sample oscillating at a constant amplitude. As the temperature is changed, the resonance frequency also changes and is monitored by the instrument. The Young's modulus at any temperature is proportional to the square of the resonance frequency, so the resonance frequency data as a function of temperature is described in the "Instruction Manual, 981 Dynamic Mechanical Analyzer" PN 980010-00.
0, EI Dupont de Nimores and Company, Wilmington, Delaware, 1979, can be converted to Young's modulus as a function of temperature using the formula found in the B revision.

A control plot for a commercial fluoropolymer named "PFA" was also obtained.

Explanation of the curve: The vertical axis of the plot is the dynamic modulus in GPa. This curve encounters the Tg of the resin (upper
Until the temperature of use) is characterized by a modulus that gradually decreases with increasing temperature. At the Tg of the resin, the decrease in modulus is very steep. The curves clearly show the superior modulus of the PDD dipolymer compared to the commercial fluoropolymer. At all temperatures (below Tg) within the working limits of the PDD dipolymer, its dynamic modulus is significantly higher than that of commercial resins. Horizontal lines at 5.5 GPa are visual aids. It emphasizes that at 200 ° C. the polymer has a modulus equal to that of PFA at room temperature.

Reference Example 6 A dipolymer of PDD and TFE was prepared according to the general techniques described herein. It contained about 90 mol% PDD. The coefficient of thermal expansion of this sample was measured using a Dupont 943 thermomechanical analyzer controlled by a Dupont 990 thermal analyzer. This method is based on ASTM Method E-8318-
Similar to the method described in 81, but modified to test polymer samples that have been pulled in the form of a thin film. The coefficient of thermal expansion of the clamp used to hold the sample was determined by measuring the apparent change in length of a standard quartz rod clamped in the instrument over the temperature range of interest. Next, a standard copper sample was measured over the same temperature range. The true corrected change in copper sample length was obtained as the difference between the quartz and copper data. Since the coefficient of thermal expansion of copper as a function of temperature is precisely known, a constant for the change in length with respect to the coefficient of thermal expansion can be calculated for this instrument as a function of temperature.

 To measure the coefficient of thermal expansion of a polymer sample
The thickness of the sample, typically between 0.127 and 0.381 mm
A new film into this equipment and as a function of temperature
Change in length at a controlled rate of 10 ° C / min.
Measured over the entire temperature range. Indicate each sample
Heating twice through the given temperature range, from the second heating
Data is used to calculate the coefficient of thermal expansion versus temperature
Was. For comparison, DuPont tetrafluoroethylene
And hexafluoropropylene copolymer (Teflon
FEP fluorocarbon resin) and perfluoro (Pro
(Teflon) PFA
Fluorocarbon resin), and commercially available tetrafluoro
Ethylene homopolymer (Teflon TFE fluorocarbo
Similar measurements on commercially available samples of
Was. The results are shown in Table V below.

The above data indicates that the present PDD / TFE copolymer has a very low coefficient of thermal expansion compared to commercially available polymers of tetrafluoroethylene, and thus applications where such properties are important, such as flexible circuits Or it is particularly suitable in metal / plastic or plastic / plastic laminates for use in high-speed computer interconnects.

Example 3 200 ml cold Hastelloy (TM) C shaker tu
30 g of 1,1,2-trichloro-1,2,2-trifluoro
Roethane, 6 g (0.0246 mol) PDD, 0.02 g 4,4'-bi
(T-butylcyclohexyl) peroxydicarbonate
And 1 g (0.00237 mol) of EVE. This tu
Exhaust the tube while cold and flush with nitrogen several times
And then rocked at 40 ° C. for 12 hours. Dipolymer to be generated
And at 100 ° C. in a vacuum oven at a pressure of 20.3 kPa
For 24 hours. 4.5g dipolymer yield (64% conversion)
Conversion). The dipolymer is amorphous, 186.
Has a Tg of 7 ° C, and¹⁹Measured by F NMR spectroscopy
Contained 90.8 mol% PDD. Its intrinsic viscosity is FC
−75 3.33kg / m in^Three0.0735m measured at 27 ° C in solution^Three/
kg.

Example 4 240ml cold Hastelloy (TM) C shaker tu
Add 50 g of 1,1,2-trichloro-1,2,2-trifluoro
Loethane and 10 g (0.041 mol) of PDD, 0.1 g of 4,4'-bi
(T-butylcyclohexyl) peroxydicarbonate
Was charged. Evacuate this tube while it is cold
2 g (0.0133 mol) of hexafluoropropene
It is. Rock tube at 60 ° C for 2 hours and at 70 ° C for 2 hours
I did it. Collect the resulting dipolymer and vacuum oven
And dried at 130 ° C. for 10 hours. White dipolymer powder,
7.4 g (62% conversion) were obtained. This dipolymer is indefinite
In the form, having a Tg of 265-270 ° C., and 94.6 mol%
PDD included. The intrinsic viscosity of the dipolymer is FC-75
3.33kg / m in^Three0.0293m measured at 23 ° C in solution^Three/ kg
Was.

Example 5 Equipped with mechanical stirrer, nitrogen sparger and syringe inlet
200ml into a 500ml pleated jacketed flask
Water and 1.02 g ammonium perfluorononanoate
Was charged. Warm flask and add ammonium perfluo
The rononanoate was dissolved and then cooled to room temperature.
Strong ammonium hydroxide (3ml), sodium sulfite
(0.85 g, 0.0067 mol), PDD (25 g, 0.1025 mol) and
Perfluoro (n-propyl vinyl ether) (11.7
g, 0.044 mol) were charged into the flask in this order. H
The contents of Lasco were stirred at 500 rpm. Potassium persulfate
(0.90 g, 0.0033 mol) was injected into the flask. reaction
The mixture was stirred overnight (total reaction time 21.5 hours). Generate
The coagulum that forms is filtered off and the remaining latex is methanol
And then with 20 g of magnesium sulfate in 100 ml of water
Coagulated. Collect the resulting dipolymer and add methanol /
Washed three times with a water mixture and dried overnight. Dry
The weight of the dipolymer was 12.6 g. This amorphous copoly
The intrinsic viscosity of the mer is FC-75 3.33kg / m in^Three30 in solution
0.0904m measured at ℃^Three/ kg, and its Tg is 228 ° C
Met.

Reference Example 7 240ml cold Hastelloy (TM) C shaker tu
Add 80 g of 1,1,2-trichloro-1,2,2-trifluoro
Roethane, 15 g (0.0615 mol) PDD, 2 g (0.00474 mol)
EVE) and 0.05 g of 4,4'-bis (t-butylcyclo).
Hexyl) peroxycarbonate was charged. This switch
The tube was sealed, evacuated while cold, and 0.8 g (± 0.
2 g) (0.008 mol) of TFE was charged. Tube at 40 ° C
Rocked for 12 hours. Collect the terpolymer produced
And dried in a vacuum oven at 120 ° C. for 20 hours. White tree
10.5 g of fat (59% conversion) were obtained. This terpolymer
Was amorphous and had a Tg of 162 ° C. Ta
-The intrinsic viscosity of the polymer is FC-75 3.33kg / m in^Threesolution
0.0734m measured at 25 ° C in^Three/ kg. Terpolymer
Is PDD / TFE / EVE = 7 as determined by F-19 NMR spectroscopy.
It had a composition of 9.5 / 16.5 / 4.0 (mol%).

Example 6 In a 2 liter horizontal reactor equipped with a paddle stirrer, 11
50 ml of deionized water, 4 g of ammonium perfluorononanoate and 1.25 g of ammonium sulfite were charged.

While rotating the stirrer at 70 rpm, 14 g of perfluoro (methyl vinyl ether) (PMVE) and 32 g of PDD (0.64
An initial charge of 3 (PMVE / PDD molar ratio of 3) was introduced into a reactor heated to 65 ° C. Next, 30 ml of a 1% aqueous solution of ammonium persulfate (APS) was added. This mixture is heated at 65 ° C for 10
Stirring for minutes, after which a continuous feed of 20 g / hr PMVE, 48 g / hr PDD and 30 ml APS solution was started and continued for 6 hours. The reactor was cooled to 30C. A dispersion containing 11.5% solids was collected.

Upon solidification of the dispersion by addition of 10 ml of concentrated nitric acid in a blender, the dispersion separated into an aqueous phase and a copolymer phase. The copolymer was dried in an oven at normal pressure at 105 ° C. for 24 hours and then in a vacuum oven at 100 ° C. to remove traces of water. The copolymer was then placed in a reactor that had been evacuated and purged with nitrogen at 25:75 fluorine.
Fluorinated with nitrogen mixture at 100 ° C. for 6 hours. This fluorine / nitrogen mixture is present in total per part copolymer.
It was passed at a rate of 0.085 parts of fluorine. The resulting amorphous copolymer had a single Tg of 173 ° C. and had a monomer composition of PMVE / PDD of 13:87 mol%.

Reference Example 8 The copolymer of 72 mol% PDD / 28 mol% TFE of Reference Example 3 is used in this Reference Example. It has a Tg of 170 ° C. This copolymer in cubic form is charged to the hopper of a crosshead extruder described in Trehu U.S. Pat. No. 4,116,654. The copolymer is extruded via a gear pump onto a core of "TO-8 commercial" fused silica to produce a 1 km continuous length of 500 micrometer diameter with a 200 micrometer diameter core. . This is performed according to the technique of Example 1 of the Teru patent. The front heating zone is at 240 ° C and the die temperature varies from 280-310 ° C. The copolymer flows smoothly and evenly without bubbles, producing a uniform coating with good adhesion to the core. This clad fiber has passed a standard strength test and has an attenuation of 120 dB / km which is suitable for many applications in automobiles and electronics. Due to the higher Tg of the clad copolymer,
The clad fiber can be used in a higher temperature environment than that of Example 11 of Squire U.S. Pat. No. 4,530,569.

Continuation of the front page (56) References JP-A-58-103385 (JP, A) JP-A-58-38707 (JP, A) JP-A-59-500769 (JP, A) US Patent 3,978,030 (US, A) US Patent No. 4530569 (US, A)

Claims (18)

(57) [Claims] 1. The following formula derived from 65 to 99 mol% of perfluoro-2,2-dimethyl-1.3-dioxole: In the repeating units (I) represented, b) below derived from chlorotrifluoroethylene formula -CF ₂ -CFCl- (IIb) represented by the repeating unit (IIb), c) the following equation derived from vinylidene fluoride - A repeating unit (IIc) represented by CH ₂ —CF ₂ — (IIc); d) the following formula derived from hexafluoropropylene In represented by the repeating unit (IId), e) the following formula -CHF-CF ₂ derived from trifluoroethylene - (repeating unit represented by IIe) (IIe), f) formula CF ₂ = CFOR _F [wherein, R _F is a normal perfluoroalkyl group having 1 to 3 carbon atoms], and the following formula derived from perfluoro (alkyl vinyl ether) G) a formula CF ₂ CCFOQZ wherein Q is a perfluorinated alkylene group containing 0 to 5 ether oxygen atoms, wherein Q is
The sum of the C and O atoms in is 2-10; and Z is-
COOR, -SO ₂ F, -CN, a group selected from the group consisting of -COF and -OCH _3, where R is a C ₁ -C ₄ alkyl]
The following formula derived from fluorovinyl ether of H) a repeating unit (IIh) represented by the following formula —CH ₂ —CHF— (IIh) derived from vinyl fluoride; and i) R _f CH = CH ₂ [wherein R _f is a C ₁ -C ₈ normal perfluoroalkyl group], which is derived from (perfluoroalkyl) ethylene An amorphous copolymer with at least one supplementary amount (35-1 mol%) of a repeating unit selected from the group consisting of repeating units (IIi) having a glass transition temperature of at least 140 ° C; the maximum mole percent of repeating units in the copolymer;
M _b ... M _i are b) with respect to the repeating unit (IIb) derived from chlorotrifluoroethylene, M _b = 30, c) the repeating unit (II) derived from vinylidene fluoride
For c), M _c = 20, d) for the recurring unit (IId) derived from hexafluoropropylene, M _d = 15, e) for the recurring unit (IIe) derived from trifluoroethylene, M = 30, f) respect repeating unit (IIf) derived from _{CF 2 = CFOR F, M f} = 30, g) with respect to the repeating units derived from CF ₂ = CFOQZ (IIg), repeat derived from M _g = 20, h) vinyl fluoride respect units _{(IIh), M h = 25} , and i) with respect to the repeating units (IIi) derived from _{R f CH = CH 2, M} i = 10; , as described above, and the case of copolymers having more repeating units than 1 Wherein the amount of each repeating unit is the corresponding maximum percent, mole percent relative to M _b ... M _i ,
A _{copolymer wherein} the sum of the ratios of m _b ... m _i , S is an amount that satisfies the following formula: S = m _b / M _b + ... + m _i / M _i ≦ 1. 2. At least 180 ° C., preferably at least 2
S has a glass transition temperature of 20 ° C. and S is less than 1 when the copolymer comprises more than one comonomer copolymerized with perfluoro-2,2-dimethyl-1,3-dioxole. 2. The copolymer according to 1. 3. A composition comprising at least one comonomer selected from the group consisting of chlorotrifluoroethylene, vinylidene fluoride, perfluoro (propyl vinyl ether), perfluoro (methyl vinyl ether), hexafluoropropylene and trifluoroethylene, and perfluoro-2,
3. The copolymer according to claim 1, which is a dipolymer with 2-dimethyl-1,3-dioxole. 4. The copolymer according to claim 3, which is a dipolymer of vinylidene fluoride, chlorotrifluoroethylene or perfluoro (methyl vinyl ether) and perfluoro-2,2-dimethyl-1,3-dioxole. 5. An optical fiber comprising a core and a clad, wherein the clad is the amorphous copolymer according to any one of claims 1 to 4. 6. The cladding is a dipolymer of a comonomer selected from the comonomer listed in b), d) and f) according to claim 1 with perfluoro-2,2-dimethyl-1,3-dioxole. An optical fiber according to claim 5. 7. A self-supporting film of the amorphous copolymer according to claim 1. 8. Polishing agent for a chemical reactor, made from the amorphous copolymer according to claim 1. Description: 9. A composite substrate for the production of circuit boards, produced from the amorphous copolymer according to claim 1. Description: 10. An optical lens made from the amorphous copolymer according to claim 1. 11. At least two layers thermally laminated to each other
A layered structure consisting essentially of a single film or sheet, wherein at least one of these layers is a layered structure.
A structure which is a film or sheet of an amorphous copolymer of perfluoro-2,2-dimethyl-1,3-dioxole according to any one of the preceding claims. 12. The structure of claim 11, wherein said amorphous copolymer of perfluoro-2,2-dimethyl-1,3-dioxole is reinforced by a fibrous material. 13. A polymer sheet having a coating of an amorphous copolymer of perfluoro-2,2-dimethyl-1,3-dioxole as defined in claim 1 on at least one of its faces. the film. 14. A metal sheet having a coating of an amorphous copolymer of perfluoro-2,2-dimethyl-1,3-dioxole according to any one of claims 1 to 4 on at least one side thereof. Or foil. 15. The method according to claim 1, wherein at least one of the surfaces in contact with the fluid is perfluoro-2,2.
Pipes, tubes, fittings, pump housings, pump impellers, valve bodies, valve stems, valve seals, diaphragms, tanks, made of amorphous copolymers of 2-dimethyl-1,3-dioxole
An article for handling or treating a fluid selected from the group consisting of trays, pipettes and laboratory vessels. 16. A container or part of a transport system suitable for holding or transporting an object in contact with a corrosive fluid, wherein the container is a perfluoro-2,2 according to any one of claims 1-4. A container or part made of an amorphous copolymer of dimethyl-1,3-dioxole. 17. A current carrying component comprising at least one insulating element made from an amorphous copolymer of perfluoro-2,2-dimethyl-1,3-dioxole according to claim 1. Or equipment. 18. A protective coating of the amorphous copolymer of perfluoro-2,2-dimethyl-1,3-dioxole according to claim 1 on at least one of its exposed surfaces. Electronic circuit articles to be provided.