JPH0148286B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to tetrafluoroethylene, ethylene, hexafluoropropylene and other
The present invention relates to thermoplastic quaternary copolymers composed of copolymerizable units of different types of monomers and their uses. Copolymers composed of units of tetrafluoroethylene and units of ethylene have been known for a long time. They exhibit excellent chemical resistance, high thermal stability and good electrical properties. These can be processed from the melt by methods customary for thermoplastics and are suitable as raw materials for producing wire insulation and as raw materials for producing films and injection moldings. There is. A copolymer of tetrafluoroethylene and ethylene with a melting point of approximately 275°C exhibits poor drawing properties in the temperature range above 150°C, which must be passed in any case when processing from the melt. It has the disadvantage of showing For example 150℃ and 200℃
In the temperature range between at room temperature
The elongation at break of this polymer is more than 250%.
At ℃, it is less than 20%. To overcome this drawback, copolymers consisting of tetrafluoroethylene, ethylene, and one other type of copolymerizable vinyl monomer were created. In essence, this is a terpolymer. Such terpolymers are disclosed in U.S. Pat. No. 3,624,250 and U.S. Pat.
4166165, German Patent Application No. 2836296, and JP-A-50-143888, JP-A-50-143889 and JP-A-50-143890. A terpolymer of tetrafluoroethylene, ethylene and hexafluoropropylene is covered by a British patent no.
No. 1,355,595 and US Pat. No. 3,960,825. In particular, from U.S. Pat. No. 3,624,250, it has been found that when side chains having at least two carbon atoms are introduced into the terpolymer by means of vinyl monomers used as termonomers, It is known that significant improvements in the drawing properties of .
In short, improved properties require "minimal bulk" of the introduced side chains. Some C in the side chain
- In the case of introducing a termonomer into which only atoms are introduced, such as hexafluoropropylene, perfluoro-(methylvinyl)-ether or isobutylene, sufficient improvement in tensile strength and elongation at break can be achieved as described in US Pat. No. 3,624,250. As described in the example in the book, it cannot be obtained. This is reflected in US Patent No. 3960825 and British Patent No.
This also applies to the terpolymers of tetrafluoroethylene, ethylene and hexafluoropropylene according to No. 1355595. The tensile-elongation properties (i.e., tensile strength and elongation at break values) of this terpolymer in the temperature range between 150°C and 200°C are due to the "bulk" introduced into the chains. It is determined not only by the type and size of the side-chain groups, but is also significantly influenced by the number of side-chain groups introduced. In short, the amount of vinylic monomer incorporated as termonomer is determined given a certain predetermined tensile-elongation property and can only be reduced with a deterioration of this tensile-elongation property. Various groups of compounds have been disclosed as copolymerizable "bulky" termonomers. That is, these can be divided into fluorine-free vinyl monomers, partially fluorinated vinyl monomers, and perfluorinated vinyl monomers. In general, it can be said that the chemical and thermal stability of such terpolymers increases significantly in proportion to the increase in the degree of fluorination of the termonomer. However, in proportion to this increase in the degree of fluorination, the costs for the production of the termonomers and the associated costs for the terpolymers also increase significantly. From this point of view as well, a minimum amount of termonomer is required so that the thermal and chemical stability is affected as little as possible even with unfluorinated or partially fluorinated vinyl compounds. In addition to using expensive perfluorinated vinyl monomers, it is desirable to reduce the cost proportion of the termonomer as much as possible. Therefore, even if unfluorinated or partially fluorinated vinyl compounds are used, they do not provide a satisfactory compromise between thermal and chemical stability on the one hand and tensile elongation behavior on the other. To achieve this, tetraflu, which can be prepared using only small amounts of "bulky" vinyl compounds as the third component, has improved tensile-elongation properties when compared to conventional terpolymers. Orethylene/ethylene-based copolymers are required. The present invention has fulfilled this need by means of a fluorine-containing thermoplastic quaternary copolymer which contains from 55 to 30 mol % of copolymerized tetrafluoroethylene units. , b 60 to 40 mol% of copolymerized ethylene units, c 10 to 1.5 mol% of copolymerized hexafluoropropylene units, d 2.5 to 0.05 mol% of copolymerized units of the following groups: Unit of one type of vinyl monomer d ₁ General formula CF ₂ = CF−Rf1 (in the formula, Rf1 is 2 to 10
perfluoroalkyl group having 5 C-atoms. ) perfluorinated olefins of the general formula CF _{2 =} CF-O-Rf2, where Rf2 is a perfluoroalkyl group having 2 to 10 C-atoms; vinyl ether, _d3 general formula (wherein n=1 to 4) perfluorinated vinyl ether, _d4 general formula (wherein, n is 0 to 1), d ₅ perfluoro-2-methylene-4-methyl-1,3-dioxolane, d ₆ general formula CF ₂ =CF-O-( CF ₂ ) _o —COX ₁ (wherein X ₁ is F, OH, OR ₁ or NR ₂ R ₃ , with the proviso that R ₁ is an alkyl group having 1 to 3 C-atoms and R ₂ and _R3 each have the same meaning as a hydrogen atom or _R1 , and n means a number from 1 to 10), a perfluorinated vinyl ether represented by the general formula _d7 (In the formula, X ₂ is COOR ₄ , COOH or CN
, R ₄ is an alkyl group having 1 to 4 C-atoms and n means a number from 1 to 4. ) perfluorinated vinyl ether, d ₈ with the general formula CH ₂ =CH—Rf3 (wherein Rf3 is 2-
Perfluoroalkyl group with 10 C-atoms. ), d ₉ 1,1,1-trifluoro-2-(trifluoromethyl)-4-penten-2-ol, d ₁₀ allyl-hydroxyhexafluoroisopropylidene Ether, d ₁₁ General formula CH ₂ = CR ₅ —CH ₂ —O—CF ₂ —
CFX ₃ H (wherein X ₃ is F, Cl or trifluoromethyl and R ₅ is H or CH ₃
It is. ) Fluorinated allyl ether represented by d ₁₂ fluorinated vinyl ether represented by the general formula CH ₂ = CH-O-CF ₂ -CFX ₃ H (wherein X ₃ is F, Cl or trifluoromethyl) , d ₁₃ General formula CH ₂ = CR ₆ - CH ₂ - OCO - R ₇ (wherein R ₆ is H or CH ₃ and R ₇ is 1
It is an alkyl group having ~3 C-atoms. ), d ₁₄ general formula CH ₂ =CH—O—CO—R ₈ (in the formula,
R ₈ is an alkyl group having 1 to 3 C atoms. ) and has a melt index of 5 to 200 g/10 minutes (measured by applying a load of 11 kg at 300° C.). Surprisingly, the inventors have found that, in addition to the "bulky" vinyl compounds, 1.5 to 10 mol %, in particular 3 to 8 mol %, in particular 3 to 5 mol % of copolymerized hexafluor When lupyropyrene units are incorporated into the copolymer, the tensile-elongation behavior of such copolymers of the ethylene/tetrafluoroethylene system, in short its tensile strength and especially its elongation at break, is again substantially improved. I found out that it can be done. This finding suggests that, in accordance with the behavior of known terpolymers, hexafluoropropylene lacks "bulkness" and is therefore able to withstand tensile stress in the temperature range between 150°C and 200°C.
This is surprising since it would have been expected not to contribute substantially to improving elongation properties. Even when the "bulky" vinyl monomers are incorporated in equal amounts, the quaternary copolymers of the present invention exhibit a high tensile strength and It is superior to known terpolymers in terms of elongation at break. In particular, the greatly improved elongation at break at high temperatures can be achieved by moldings, such as injection moldings or wire coatings, produced from the quaternary copolymers of the invention at such temperatures. This allows them to be exposed to high mechanical stresses and therefore reduces the occurrence of tears during their manufacture and use. If we predetermine a specific value of elongation at break at a temperature between 150 and 200 °C as the desired target, this value is determined in the case of the quaternary copolymers of the invention by a small amount of “ This can be achieved using bulky vinyl monomers. This fact is clear from the values in the table. In Table 1, one is the quaternary copolymer of the present invention (Example 1).
~18) and the other are the tensile strength and The elongation at wave break (measured at 23°C and 160°C) is listed. The terpolymer and quaternary copolymer to be compared were produced under the same polymerization conditions. The table shows that the quaternary copolymers of the present invention additionally containing hexafluoropropylene units are coarsely loaded with the "bulky" vinyl monomers used in each case. 160℃ even at room temperature
The results also show that the copolymers invariably give a better elongation at break than corresponding terpolymers of the same composition without hexafluoropropylene. On the other hand, the quaternary copolymer of the present invention is
It also exhibits much better tensile-elongation behavior than known ternary copolymers composed of tetrafluoroethylene, ethylene and hexafluoropropylene (compare Example 4 with Comparative Example E in Table 1). . Furthermore, from the table, in order to achieve a constant elongation at break at 160°C, in the case of a terpolymer produced without using hexafluoropropylene, compared to the quaternary copolymer of the present invention, and many times the “bulk”
It turns out that a vinyl component must be incorporated. For example, when comparing Example 4 and Comparative Example A in Table 1, it is found that when an elongation at break of 500% at 160°C is to be achieved, in the case of the terpolymer, the quaternary copolymer of the present invention It is found that approximately 2.5 times the amount of perfluoro-(propyl vinyl)-ether must be incorporated. Example 13 and Comparative Example I in Table
and J that in order to achieve an elongation at break of 600% at 160°C, approximately twice the amount of tetrafluoroethyl allyl ether must be introduced in the case of a terpolymer, and the same amount. It is shown that when incorporated, only an elongation at break of 25% at 160°C is achieved. These comparisons show that the incorporation of additional hexafluoropropylene units into the copolymer according to the present invention surprisingly makes it more “bulky”.
It has been shown that the amount of vinyl compound introduced can be reduced and that despite this reduction in content, a product with good elongation at break and little brittleness at high temperatures can be obtained. I have to. A wide variety of compounds having one vinyl group can be used as the "bulky" vinyl monomer to prepare the quaternary copolymers of the present invention.
These include the following groups of vinyl monomers: d ₁ of the formula CF ₂ =CF-Rf1, where Rf1 has 2 to 10, in particular 2 to 5 C-atoms. A perfluorinated olefin represented by a perfluoroalkyl group. Particularly advantageous compounds include perfluoropentene, perfluorohexene and perfluoroheptene. Processes for producing such long-chain perfluorinated olefins are known and are described, for example, in US Pat. No. 2,668,864. d ₂ formula CF ₂ = CF-O-Rf2 (in the formula, Rf2 is 2 to 10
, especially 2 to 4 C atoms. ) perfluorinated vinyl ether. Perfluor-n-
Mention may be made of the ethyl, perfluoro-n-butyl and especially perfluoro-n-propyl groups. The method for producing such perfluoro-(alkyl vinyl)-ethers is described in U.S. Patent No.
It is known from specification No. 3180895. d type ₃ (wherein n is 1 to 4, in particular 1 or 2). A method for preparing such perfluorinated vinyl ethers is known from US Pat. No. 3,450,684. d ₄ type (In the formula, n is 0 or 1, especially 0.)
Perfluorinated vinyl ether represented by
Methods for making these monomers are disclosed in US Pat. No. 4,013,689. d ₅ perfluoro-2-methylene-4-methyl-
1,3-dioxolane. A method for making this is known from US Pat. No. 3,308,107. d ₆ General formula CF ₂ = CF - O - (CF ₂ ) _o - COX ₁ (wherein, X ₁ is F, OH, OR ₁ or NR ₂ R ₃ ,
However, R ₁ is an alkyl group having 1 to 3 C-atoms, R ₂ and R ₃ are each a hydrogen atom or have the same meaning as R ₁ , and n is 1 to 10
means the number of ) perfluorinated vinyl ether. A method for preparing such monomers is known from GB 1145445. X=
Particular preference is given to OH or _OCH3 . d ₇ type (wherein, X ₂ is COOR ₄ , COOH or ON, where R ₄ is an alkyl group having 1 to 3 carbon atoms, and n means an integer of 1 to 4) Fluorinated vinyl ether. A method for preparing such copolymerizable monomers is disclosed in US Pat. No. 4,138,426. X ₂
Particular preference is given to COOH or _COOH3 . d ₈ formula CH ₂ = CH−Rf3 (in the formula, Rf3 is 2 to 10,
In particular perfluoroalkyl radicals having 2 to 6 carbon atoms. ) A perfluoroalkyl-substituted vinyl compound. Such partially fluorinated olefins are disclosed in U.S. Pat.
It is prepared by addition of ethylene to a perfluoroalkyl iodide and subsequent dehydrohalogenation with alkali hydroxide as described in US Pat. No. 3,535,381. d ₉ 1,1,1-trifluoro-2-(trifluoromethyl)-4-penten-2-ol: A method for making this is known from US Pat. No. 3,444,148. d ₁₀ Allyl-hydroxyhexafluoroisopropylidene ether It is obtained by adding allyl alcohol to hexafluoroacetone, as described in French Patent No. 2,178,724. d ₁₁ General formula CH ₂ = CR ₅ ―CH ₂ ―O―CF ₂ ―
CFX ₃ H (wherein R ₅ is H or CH ₃ and X ₃
is F, Cl or trifluoromethyl, especially F. ). Such monomers can be prepared by adding the corresponding fluoro- or chlorofluoro-olefin to allyl alcohol as described in US Pat. No. 2,975,161. d Formula ₁₂ CH ₂ = CH-O-CF ₂ -CFX ₃ H (in the formula, X ₃
is F, Cl or trifluoromethyl, especially F. ) fluorinated vinyl ether. These can be manufactured according to US Pat. No. 2,631,975. d Formula ₁₃ CH ₂ = CH-CH ₂ -O-CO-R ₅ (In the formula, R ₅
is an alkyl group having 1 to 3 C atoms, especially a methyl group. ) Allyl or methallyl ester. d ₁₄ General formula CH ₂ = CH-O-CO-R ₆ (wherein, R ₅
is an alkyl group having 1 to 3 C atoms, especially a methyl group. ) vinyl ester. Among the above groups, d ₁ ), d ₈ ), d ₉ ), d ₁₁ ) and
Preference is given to the group d ₁₂ ), especially the groups d ₂ ), d ₃ ) and d ₄ ). Mixtures of such "bulky" vinyl monomers which collectively form the fourth component can also be incorporated. However, in that case the entire polymer may also consist of more than four types of monomers. Each of the vinyl monomers mentioned above is generally sufficiently telogenically inert to form quaternary copolymers within a molecular weight range suitable for thermoplastic processing. is important. The side chain bulk introduced by these vinyl monomers necessarily affects the crystallization behavior of the copolymer. This is the case if side chains with at least 2 carbon atoms are introduced. If the emphasis is solely on improving the tensile-elongation behavior, there is no criticality in the type and nature of the "bulky" side chains introduced. If good chemical and thermal stability of the copolymer is additionally required, highly fluorine-substituted, especially perfluorinated, vinylic monomers are preferred. Generally, 3 to 5 mol% in the quaternary copolymer
By introducing copolymerized hexafluoropropylene units, the content of "bulky" vinyl monomers can be reduced by 2 compared to the corresponding terpolymer.
It can be said that it can be reduced by a factor of ~3.5. The content of "bulky" vinyl monomers in the quaternary copolymers of the invention is determined first of all by the desired product properties. It is derived from one of the "bulky" vinyl monomers mentioned above.
0.05 to 2.5 mol%, especially 0.1 to 1 mol%, especially 0.2 to 1 mol%
It is 0.8 mol% of copolymerized units. The content of copolymerized tetrafluoroethylene units is 55 to 30 mol%, especially 55 to 40 mol%, and the content of copolymerized ethylene units is 60 to 40 mol%, especially 55 to 45 mol%. It is. In order for the quaternary copolymer of the present invention to be processed from the melt according to thermoplastic molding methods, its molecular weight must be
The melt viscosity measured at 300° C. under a shear stress of 1×10 ⁵ Pa should be adjusted to be in the range of 4×10 ² to 2×10 ⁴ PaS. Melt index (MFI value) is generally used as a measure of polymer fluidity.
use. The melt index measured at 300℃ and under a load of 11Kg is 5 to 200g/10 minutes, especially
It should be within the range of 10-100g/10 minutes. Copolymers with a melt index of 15 to 50 g/10 min are suitable for producing coatings for electric wires. The quaternary copolymers of the invention have melting points (determined as the minimum of the melting curve by differential thermal analysis) between 245 and 280 DEG C., depending on their chemical constitution.
The melting point decreases within this range in inverse proportion to the increase in the content of copolymerized hexafluoropropylene units in the quaternary copolymer. The quaternary copolymer of the present invention can be produced according to known polymerization methods. That is, it can be carried out by solution polymerization, suspension polymerization, emulsion polymerization, bulk polymerization or gas phase polymerization. Preference is given to preparing them by polymerization in organic solvents or by suspension or emulsion polymerization in an aqueous phase. In addition to organic solvents and water, mixtures of organic solvents and water are also suitable as reaction media. Preferred organic solvents are fluoroalkanes or chlorofluoroalkanes having 1 to 4 C atoms. Polymerization in chlorofluoroalkane as a solvent is described, for example, in U.S. Pat. It is disclosed in Publication No. 49-24295. The copolymerization can also be carried out in a mixture of tert-butyl alcohol and water, as is known, for example, from US Pat. No. 2,468,664. Copolymerization in a pure aqueous reaction medium is known from US Pat. No. 3,859,262. The reaction conditions for carrying out the copolymerization depend on the polymerization method chosen. Reaction temperature is usually -50℃~+150℃
℃, especially in the range from +20°C to +100°C. If the copolymerization is carried out in organic solvents, such as in particular fluoroalkanes or chlorofluoroalkanes, the customary free-radical-releasing organic peroxide compounds or azo compounds are particularly used as polymerization initiators. It is also possible to initiate the polymerization by energy-rich radiation, for example gamma radiation from radioactive elements. If the copolymerization is carried out in an aqueous medium, customary radical-forming water-soluble polymerization initiators such as ammonium persulfate can be used. Particularly advantageous initiators for copolymerization in aqueous media are manganese acids and their salts, as disclosed in US Pat. No. 3,859,262. The copolymerization resulting in the quaternary copolymer of the present invention is
It is carried out under a total monomer pressure within the usual range of 50 bar. The composition of the polymer is conventionally controlled by the molar ratios of the monomer components to each other. In the polymerization reactor, the molar ratio of the sum of tetrafluoroethylene and hexafluoropropylene to ethylene is
It should be in the range 60:40 to 85:15, especially 65:35 to 75:25. The “bulky” vinyl monomer is
1.05 for the desired amount incorporated into the copolymer
A ~5-fold excess is introduced over the course of the polymerization. In order to obtain a unitary composition of the quaternary copolymer, the ratio of each monomer is preferably kept constant by metering each monomer during the entire polymerization period. Unreacted monomers can be recovered after copolymerization according to known methods. Customary chain transfer agents are added during the copolymerization in order to adjust the molecular weight or the melt index obtained therefrom. If the copolymerization is carried out in an organic solvent or a mixture thereof with water, these include the known hydrogen-containing organic compounds, such as cyclohexane or acetone. When working in aqueous systems, dialkyl esters of malonic acid are particularly advantageous. If the copolymerization is carried out in an aqueous phase according to an emulsion polymerization method, the quaternary copolymers of the invention are colloidal with a polymer solids content of 15 to 30% by weight relative to the aqueous medium. Occurs in the form of an aqueous dispersion. The dispersed particles have an average particle diameter of 0.05 to 0.35 μm, in particular 0.10 to 0.25 μm. The particle size distribution of the dispersed particles is very narrow and each particle has a spherical shape. Furthermore, it has a viscosity in the range from 2 to 4 mPas (measured with a rotational viscometer at 20 DEG C.) and a very high stability against the influence of shear forces. Polymer solids can be obtained from such dispersions by customary coagulation methods, such as stirring or addition of coagulants and then by drying. The quaternary copolymers of the present invention can be processed from the melt into films, tubes, rods, injection molded articles and other molded bodies by thermoplastic molding methods. Furthermore, they are suitable for producing single fibers with good mechanical properties that can be processed into textiles with good thermal and chemical stability. 15-50g/10
The quaternary copolymers according to the invention having a melt index of 11 kg (11 kg load) are suitable for producing coatings for electrical conductors. Wire coatings made from this quaternary copolymer are not brittle even at high temperatures and do not exhibit a tendency to crack. “Bulk”
Even with the same content of vinyl monomers, wire coatings made from the quaternary copolymers of the invention show better results in the "stress-cracking" test than the corresponding terpolymers. and has higher elongation at break and tensile strength. Furthermore, thin wire insulation made from the quaternary copolymers of the present invention exhibits less flaws and dielectric breakdown than coatings made under the same conditions from corresponding terpolymers. The quaternary copolymers of the present invention differ substantially from the corresponding terpolymers without hexafluoro-propylene in their wide-angle X-ray spectra.
Evaluation of this spectrum reveals that the crystal structure of the quaternary copolymer is significantly different from that of the terpolymer. Further advantageous industrial properties of the quaternary copolymers of the invention are attributable to the changes in crystal structure caused by the additional incorporation of hexafluoropropylene. The fillers and/or fillers customary in the quaternary copolymers of the invention
Alternatively, pigments may be mixed. For example, the quaternary copolymer can be reinforced with 5 to 50% by weight of glass fibers, optionally previously treated with a silane binder. Each parameter indicating the characteristics of the quaternary copolymer of the present invention and the terpolymer produced for comparison, which are described in the specification and examples, was measured by the following measurement method. : 1 Fluorine Content The fluorine content (% by weight) of the copolymer is determined by calcining in a Wickbald apparatus and then titration with thorium nitrate in a potentiograph. 2 Content of hexafluoropropylene Content of hexafluoropropylene (weight%)
The measurements are for 100~
This is done by IR analysis of a 300 μm thick film. Thickness measurements are made with a micrometer screw. Analysis by Nicolet
Company's HX-1 type Floril Transform.
IR spectrophotometer (Fourier)
Performed with Transform-IR-Spektrofotometer). For correction, similar films of copolymers consisting exclusively of tetrafluoroethylene and ethylene are used. Evaluate the band of ν = 490 cm ^-1 . The hexafluoropropylene content is calculated by the following formula: Hexafluoropropylene (wt%) = Absorbance at 490 cm ^-1 / Thickness (mm) x 3 3 “Bulk” Vinyl Content of monomers The amount of "bulky" vinyl monomers of groups _d1 ) to _d14 ) to be incorporated is determined by measuring the total amount introduced into the reactor and determining the amount of monomers copolymerized in the reactor. It is determined by the material balance by subtracting the amount of monomer remaining. 4 Content of tetrafluoroethylene The content of tetrafluoroethylene is calculated from the analytically determined fluorine content, which is based on the fluorine content attributable to hexafluoropropylene and the respective “bulky” vinyl monomers. It is obtained from the value of fluorine by subtracting the percentage of . 5 Density These measurements were made on 2 mm extruded from melt
In accordance with DIN standard 53479 with a cord of thickness. 6 Melt Index These measurements were made at 300°C and a load of 11 kg with a nozzle of 2.1 cm diameter and 8 mm length.
Carry out according to DIN standard 53735-70. 7 Melting Points Melting points are given as the minimum value of the melting range determined using a "differential scanning" calorimeter. 8 Elongation at break and tensile strength The elongation at break and tensile strength are 95 ×
ASTM punched from a board with dimensions of 95 x 2 (mm)
Measured using a test specimen according to D-1708. This board is
It is produced by heating 38 g of copolymer powder or copolymer granules obtained from the melt to 300° C. for at least 1 hour and cooling under a pressure of up to 200 bar. A pressure of 200 bar is reached during 5 minutes. Elongation at break and tensile strength are 23
and 160°C according to ASTM D-638. 9 "Stress-Crack" - Test Electrical wires with a 250 μm thick coating of each copolymer are heat treated at 200° C. for 3 hours. Next, wrap this wire around its own diameter by 5
Wrap it around. Five parallel specimens are produced in this way. 200 for another 3 hours with the wire wrapped around it.
Heat treatment at ℃. The roll is then unwound and tested for cracking and dielectric strength. 10 Testing of the mechanical properties of wire sheathing Tests of the mechanical properties of wire sheathing are carried out in accordance with VDE - Test Regulations No. 0472 and No. 0881. The invention will be explained in more detail by the following examples: Examples 1 to 12, Comparative Examples A to H Quaternary copolymers of the invention of Examples 1 to 12 and ternary copolymers of Comparative Examples A to H The polymer is prepared under the following reaction conditions: total volume equipped with a buffer and an impeller stirrer.
485 in 190 enamelled polymerization reactors
g of diammonium oxalate monohydrate,
120 in which 485 g perfluorooctanoic acid and 135 g malonic acid diethyl ester are dissolved.
Fill with demineralized water. Air in the remaining gas space of the polymerization reactor is carefully eliminated by blowing in nitrogen and then tetrafluoroethylene. The stirring speed is adjusted to 235 rpm. In the case of Examples 1 to 4 and 7 to 12,
Example 5 1500g of hexafluoropropylene
400g in the case of and in the case of Example 6
Add 3000g of hexafluoropropylene in advance. Comparative Examples A to D and F to H are carried out without the addition of hexafluoropropylene.
In the case of Comparative Example E, the recipe for Examples 1 to 12 is followed, but in this case, in addition to tetrafluoroethylene, ethylene and hexafluoropropylene (1500 g pre-charged), No additional monomers added. Tetrafluoroethylene is then injected to a total monomer pressure of 13.7 bar, and then ethylene is injected to a total monomer pressure of 17 bar. Thereafter, the amounts of each of the "bulky" vinyl monomers listed in Sections and Tables are added. 20g of KMnO per 1 water with ₄
Polymerization is initiated by introducing a solution of potassium permanganate containing . The supply of potassium permanganate after the start of polymerization is approximately 60 to 100 g/・
Adjust the polymerization rate to achieve the desired polymerization rate. The polymerization temperature is 26-27°C. The heat of polymerization produced is carried away in the form of a cooling medium via a cooling jacket of the polymerization reactor. A total monomer pressure of 17 bar is maintained by continuously metering in a tetrafluoroethylene/ethylene mixture in a molar ratio of 1:1. In the case of Examples 1 to 4 and 7 to 12 according to the invention and Comparative Example E, 3100 g of hexafluoropropylene (1200 g in the case of Example 5 and 6400 g in the case of Example 6) were used during the polymerization. Hexafluoropropylene) and the respective vinyl monomers in the amounts specified in Tables 1 and 2 are metered in continuously. The reaction is stopped at a solids content of 20-22% by weight, based on the aqueous medium, by releasing the monomer mixture by releasing pressure. The polymer is produced in the form of an aqueous dispersion which is subsequently solidified by stirring. The resulting polymer solids were separated from the liquid, washed several times with water, and then incubated under a nitrogen atmosphere for 200 min.
Dry for 15 hours at °C and then melt granulate. The amounts of polymer solids obtained in each case are listed in Tables 1 and 2. Furthermore, Tables 1 and 2 also list the following parameters characterizing the inventive quaternary copolymers of Examples 1 to 12 and the copolymers of Comparative Examples A to H: fluorine content;
Melting point and density by “differential scanning-calorimeter” method. Examples 13-18, Comparative Examples I-L Total volume with buffer and impeller type stirrer
In 18 enamelled polymerization reactors,
Add 1,1,2-trichlorotrifluoroethane (4.8) in advance. The air in the reaction vessel is replaced with ethylene. The stirring speed is 100 revolutions/min.
Dispense the following into the reaction vessel: 290 g
of hexafluoropropylene (Examples 14 and 18)
580g), 10g of the vinyl monomer listed in Section 1 and the table respectively (20g in Comparative Example J) -
These are dissolved in 100 ml of 1,1,2-trichlorotrifluoroethane - and the amounts of cyclohexane given in Tables 1 and 2 respectively - which are also dissolved in 10 ml of 1,1,2-trichlorotrifluoroethane. It's dissolved. The reactor contents are heated to 65° C. and the stirrer speed is increased to 250 revolutions/min. Tetrafluoroethylene is then forced in to a total pressure of 7.8 bar, and then ethylene is forced in to a total pressure of 10.7 bar. Thereafter, 1 g of bis-(4-tert-butylcyclohexane peroxy-dicarbonate) was added to 300 ml of 1,
A solution dissolved in 1,2-trichlorotrifluoroethane is metered in. After the start of the polymerization, a mixture of ethylene and tetrafluoroethylene in a molar ratio of 1:1 is fed into the reaction vessel while maintaining a constant total monomer pressure of 10.7 bar. The copolymerization reaction is stopped at a copolymer content of approximately 6% by weight, based on the 1,1,2-trichlorotrifluoroethane used. The reaction contents are then cooled to about -5°C, unreacted monomers are released by pressure relief, the reaction contents are poured off, and the solvent is removed along with any vinyl monomers still dissolved in the solvent. To leave. The resulting copolymer is then heated to 100° C. in a nitrogen atmosphere for 12 hours. The partially caked product is then ground in a hammer mill to a powder with a particle size of 300-400 μm. The amounts (Kg) of copolymer powder obtained in each case are shown in Tables 1 and 2. In addition, the fluorine content, differential scanning calorimeter melting point and density are also given as characteristic parameters in the table. The table summarizes the tensile strength and elongation at break values at 160°C and 23°C, comparing the quaternary copolymers of the invention with the respective structurally corresponding terpolymers. . Comparative Example E shows the properties of a terpolymer of tetrafluoroethylene, ethylene and hexafluoropropylene.
Furthermore, the table shows the composition of the copolymer (copolymerically incorporated units of each monomer: mole %) and the melt index - measured at 300°C under a load of 11 kg. There is.

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[Table] Weight for
amount%)

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【table】

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[Table] F113 = 1,1,2-trichlorotrifluoroethane Example 19 A wire coating with a thickness of 250 μm is produced from the granules produced from the melt of the product of Example 1 under the following conditions: Extrusion. Molding machine: Go¨ttfert Extrusiometer,
Measurement temperature: 340℃, wire material: silver-plated Cu
Wire (AWG24/1), preheating of electric wire: 80 to 150℃,
Nozzle diameter: 5.5mm, mandrel diameter: 3.5mm, nozzle temperature: 340℃, extrusion speed: 36m/min. The resulting sheathed wire is subjected to a "stress-cracking" test at 200°C. Five pieces of wire tested parallel to each other passed this test. The wire coating is pulled out and tested for tensile strength and elongation at break at room temperature.
A tensile strength of 47 N/mm ² and an elongation at break of 250% were measured. Comparative Example M From the granules produced from the melt according to Comparative Example A, a wire coating with a thickness of 250 μm is produced as described in Example 19. This wire was also subjected to a "stress-crack" test at 200°C. Two of the five wire pieces tested in parallel had cracks in the insulation. The remaining three specimens exhibited dielectric breakdown during electrical testing. The drawn wire coating exhibits a tensile strength of 45 N/mm ² and an elongation at break (measured at 23° C.) of 185%. As can be seen from the comparison of the results of Example 19 and Comparative Example M, the wire coating made from the quaternary copolymer according to the invention shows that even when perfluoropropynyl ether is comparatively introduced. , exhibits better "stress-cracking" behavior and better tensile strength and elongation at break than wire coatings made from corresponding terpolymers. Examples 20 and 21 In Examples 20 and 21, Examples 4 and 15
The granules produced from the melt of the product are processed into wire coatings with a thickness of 125 μm under the following conditions: extrusion machine; Gettfeld Extrusiometer; wire material: silver plating. Cu wire (AWG24/1), wire preheating: 80 to 150℃, nozzle diameter: 5.5mm, mandrel diameter: 3.5mm, nozzle temperature: 34℃, extrusion speed: 60
m/min. Electrical defects are tested on the wire sheathing immediately after manufacture at a test voltage of 8KV. Examples 20 and 21
A wire coating produced according to the method shows no dielectric breakdown over a wire length of 1000 m. Comparative Example N As a “bulky” third component in addition to ethylene and tetrafluoroethylene Contains a vinyl monomer of 37g/10
Minute melt index (300℃, load 11Kg),
Melting point of 277°C (differential scanning - calorimeter),
A commercially available terpolymer having a fluorine content of 60.7% and a density of 1.713 was processed into a 125 μm thick wire coating under the conditions described in Examples 18 and 19 and free from electrical defects. test. Between 40 and 140 breakdowns per 1000 m were found during five tests. Even if the processing temperature is increased or decreased by 10°C, it is not possible to obtain a wire coating without dielectric breakdown. Example 22 From the quaternary copolymer of Example 10 to Example 19
A wire coating with a thickness of 250 μm is produced and then the coating is drawn. For this item, 56N/at 23℃
A tensile strength of mm ² and elongation at break of 215% were determined. After storing this wire coating at 190° C. for 10 days, a tensile strength of 38 N/mm ² and an elongation at break of 200% were measured at 23° C., respectively. In the "stress-cracking" test at 200 DEG C., no cracks or dielectric breakdown were observed in the five wire pieces tested in parallel. Furthermore, a wire coating with a thickness of 125 μm is produced from the quaternary copolymer of Example 10 according to Example 20. It did not have any electrical defects over a length of 1000 m.

Claims (1)

[Scope of Claims] 1 a 55 to 30 mol% of copolymerized tetrafluoroethylene units, b 60 to 40 mol% of copolymerized ethylene units, c 10 to 1.5 mol% of copolymerized units. units of hexafluoropropylene, d 2.5 to 0.05 mol % units of one type of copolymerized vinyl monomer from the following group d ₁ General formula CF ₂ = CF−Rf1 (wherein Rf1 is 2～10
perfluoroalkyl group having 5 C-atoms. ) perfluorinated olefins of the general formula CF _{2 =} CF-O-Rf2, where Rf2 is a perfluoroalkyl group having 2 to 10 C-atoms; vinyl ether d ₃ general formula (wherein n=1 to 4) perfluorinated vinyl ether, _d4 general formula (wherein, n is 0 to 1), d ₅ perfluoro-2-methylene-4-methyl-1,3-dioxolane, d ₆ general formula CF ₂ =CF-O-( CF ₂ ) _o COX ₁ (wherein X ₁ is F, OH, OR ₁ or NR ₂ R ₃ , with the proviso that R ₁ is an alkyl group having 1 to 3 C-atoms and R ₂ and _R3 each has the same meaning as a hydrogen atom or _R1 , and n means a number from 1 to 10), a perfluorinated vinyl ether represented by the general formula _d7 (In the formula, X ₂ is COOR ₄ , COOH or CN
, R ₄ is an alkyl group having 1 to 4 C-atoms and n means a number from 1 to 4. ) perfluorinated vinyl ether, d ₈ with the general formula CH ₂ =CH—Rf3 (wherein Rf3 is 2-
Perfluoroalkyl group with 10 C-atoms. ), d ₉ 1,1,1-trifluoro-2-(trifluoromethyl)-4-penten-2-ol, d ₁₀ allyl-hydroxyhexafluoroisopropylidene Ether, d ₁₁ General formula CH ₂ = CR ₅ —CH ₂ —O—CF ₂ —
CFX ₃ H (wherein X ₃ is F, Cl or trifluoromethyl and R ₅ is H or CH ₃
It is. ) Fluorinated allyl ether represented by d ₁₂ fluorinated allyl ether represented by the general formula CH ₂ = CH-O-CF ₂ -CFX ₃ H (wherein X ₃ is F, Cl or trifluoromethyl) vinyl ether, d ₁₃ general formula CH ₂ = CR ₆ —CH ₂ —OCO—R ₇ (wherein R ₆ is H or CH ₃ and R ₇ is 1
It is an alkyl group having ~3 C-atoms. ) Allyl or methallyl
Ester, d ₁₄ general formula CH ₂ = CH—O—CO—R ₈ (in the formula,
R ₈ is an alkyl group having 1 to 3 C atoms. ) and has a melt index of 5 to 200 g/10 minutes (measured by applying a load of 11 kg at 300°C). Polymer. 2 a 55-40 mol% of copolymerized tetrafluoroethylene units, b 55-45 mol% of copolymerized ethylene units, c 8-3 mol% of copolymerized hexafluoropropylene units. The fluorine-containing thermoplastic according to claim 1, which comprises copolymerized units of one type of vinyl monomer from the group _d1 ) to _d14 ), d1 to 0.1 mol%. Plastic quaternary copolymer. 3 a 55-40 mol% of copolymerized tetrafluoroethylene units, b 55-45 mol% of copolymerized ethylene units, c 5-3 mol% of copolymerized hexafluoropropylene units. The fluorine-containing thermoplastic according to claim 1, comprising units of copolymerized vinyl monomers of one type from the group _d1 ) to _d14 ), with d ranging from 0.8 to 0.2 mol %. Quaternary copolymer. 4 Component d) is expressed by the formula CF ₂ = CF−Rf1 (where Rf1 is 2
means a perfluoroalkyl group having ~5 C-atoms. ) The fluorine-containing thermoplastic quaternary copolymer according to any one of claims 1 to 3, which is a perfluorinated olefin represented by: 5 Component d) is expressed by the formula CF ₂ = CF-O-Rf2 (where Rf2
is a perfluoroalkyl group having 2 to 4 C atoms. ) The fluorine-containing thermoplastic quaternary copolymer according to any one of claims 1 to 3, which is a perfluorinated vinyl ether represented by: 6 Component d) is the formula (wherein, n means 1 or 2). Polymer. 7 Component d) is the formula The fluorine-containing thermoplastic quaternary copolymer according to any one of claims 1 to 3, which is a perfluorinated vinyl ether represented by: 8 Component d) is a perfluoroalkyl-substituted vinyl compound of the formula CH ₂ =CH-Rf3 (wherein Rf3 means a perfluoroalkyl group having 2 to 6 carbon atoms); A fluorine-containing quaternary copolymer according to any one of claims 1 to 3. 9 Component d) is 1,1,1-trifluoro-2-
The fluorine-containing thermoplastic quaternary copolymer according to any one of claims 1 to 3, which is (trifluoromethyl)-4-penten-2-ol. 10 Component d) has the formula CH ₂ = CR ₅ -CH ₂ -O-CF ₂
-CFX ₃ H (wherein R ₅ is H or CH ₃ and X ₃
is F, Cl or _CF3 . ) is an allyl ether represented by ) The fluorine-containing thermoplastic quaternary copolymer according to any one of claims 1 to 3, which is an allyl ether represented by: 11 Component d) has the formula CH ₂ = CH-O-CF ₂ -CF ₃ H
The fluorine-containing thermoplastic quaternary copolymer according to any one of claims 1 to 3, which is a vinyl ether represented by: 12 15-50 g/min melt index (300
Measured by applying a load of 11 kg of material at ℃. ) The fluorine-containing thermoplastic quaternary copolymer according to any one of claims 1 to 3. 13 a 55-30 mol% of copolymerized tetrafluoroethylene units, b 60-40 mol% of copolymerized ethylene units, c 10-1.5 mol% of copolymerized hexafluoropropylene units. unit, d 2.5 to 0.05 mol % of units of one type of copolymerized vinyl monomer from the following group d ₁ General formula CF ₂ = CF - Rf1 (wherein Rf1 is 2 to 10
perfluoroalkyl group having 5 C-atoms. ) perfluorinated olefins of the general formula CF _{2 =} CF-O-Rf2, where Rf2 is a perfluoroalkyl group having 2 to 10 C-atoms; vinyl ether, _d3 general formula (wherein n=1 to 4) perfluorinated vinyl ether, _d4 general formula (wherein, n is 0 to 1), d ₅ perfluoro-2-methylene-4-methyl-1,3-dioxolane, d ₆ general formula CF ₂ =CF-O-( CF ₂ ) _o —COX ₁ (wherein X ₁ is F, OH, OR ₁ or NR ₂ R ₃ , with the proviso that R ₁ is an alkyl group having 1 to 3 C-atoms and R ₂ and _R3 each have the same meaning as a hydrogen atom or _R1 , and n means a number from 1 to 10), a perfluorinated vinyl ether represented by the general formula _d7 (where X ₂ is COOR ₄ , COOH or ON
, R ₄ is an alkyl group having 1 to 4 C-atoms and n means a number from 1 to 4. ) perfluorinated vinyl ether, d ₈ with the general formula CH ₂ =CH—Rf3 (wherein Rf3 is 2-
Perfluoroalkyl group with 10 C-atoms. ), d ₉ 1,1,1-trifluoro-2-(trifluoromethyl)-4-penten-2-ol, d ₁₀ allyl-hydroxyhexafluoroisopropylidene Ether, d ₁₁ General formula CH ₂ = CR ₅ —CH ₂ —O—CF ₂ —
CFX ₃ H (wherein X ₃ is F, Cl or trifluoromethyl and R ₅ is H or CH ₃
It is. ) Fluorinated allyl ether represented by d ₁₂ fluorinated allyl ether represented by the general formula CH ₂ = CH-O-CF ₂ -CFX ₃ H (wherein X ₃ is F, Cl or trifluoromethyl) vinyl ether, d ₁₃ general formula CH ₂ = CR ₆ —CH ₂ —OCO—R ₇ (wherein R ₆ is H or CH ₃ and R ₇ is 1
It is an alkyl group having ~3 C-atoms. ) Allyl or methallyl
Ester, D ₁₄ General formula CH ₂ = CH—O—CO—R ₃ (wherein,
R ₃ is an alkyl group having 1 to 3 C atoms. ) and has a melt index of 5 to 200 g/10 minutes (measured by applying a load of 11 kg at 300°C). A coating material for electric wires whose main ingredient is a polymer.