JPS58145710A - Ethylene/tetrafluoroethylene or chlorotrifluoroethylene copolymer - Google Patents

Abstract

PURPOSE:A copolymer whose high-temperature strength and elongation and stress cracking resistance are improved without detriment to its properties, containing ethylene, tetrafluoroethylene or chlorotrifluoroethylene and a specified fluorovinyl ether. CONSTITUTION:A copolymer containing ethylene, tetrafluoroethylene or chlorotrifluoroethylene and a vinyl ether of the formula, wherein X is H, F or Cl and n is 1-10. Monomer contents are as follows. Namely, the molar ratio of ethylene to tetrafluoroethylene or chlorotrifluoroethylene is 40:60-60:40 and the vinyl content is 0.1-10mol%. The above copolymer can be produced by copolymerizing the above three kinds of monomers in the presence of a polymerization initiator (e.g., peroxide). Any polymerization systems can be used, but an aqueous suspension polymerization method is preferred.

Description

[Detailed description of the invention] Or related to chlorotrifluoroethylene-based compounds,
For details, see Ethylene, Tetrafluoroethylene V7 Maft.
The present invention relates to a novel ethylene-tetrafluoroethylene or chlorotrifluoroethylene copolymer comprising chlorotrifluoroethylene, chlorotrifluoroethylene, and certain fluorovinyl ethers.

Ethylene-tetrafluoroethylene or chlorotrifluoroethylene copolymer p (hereinafter referred to as E(C)T I″E
That's what it means. ) has excellent chemical resistance, heat resistance, electrical properties, etc., and is also easy to process by hot bath melt molding.
It is used in a wide range of fields as a material for various molded products, wire coverings, linings, coatings, etc.

To improve the customization of E(C)'rFE, especially its high-temperature mechanical properties, it has been proposed to add and copolymerize E(C)'rFE as various cell-modifying agents. and fluoroethylene or chlorotrifluoroethylene, and the formula [wherein, ] It is characterized in that the molar ratio of ethylene and tetrafluoroethylene or chlorotrifluoroethylene is 40+60 to 60:40, and the content of vinyl ether is 0.1 to 10 mol%. It consists of ethylene-tetrafluoroethylene or chlorotrifluoroethylene copolymers.

The fluorovinylethe/l/(di) used in the present invention is a known compound and can be easily synthesized, for example, by ester/ether exchange reaction of vinyl acetate and a suitable fluoroalcohol. Examples of fluoroalcohols include HCF2CH20H, H(CF2)2(:H20H,
H(CF2)4CH20H, H(CF2)acH20i
(, CF CH20H-CF3CF2CH20H,F
(CF2)8CH20H, IcI-CF2CH20
H-CI (CF2)2C1(20H,C,1(CF2
)8C; H20H and the like are preferably mentioned. In fluorovinylethe/I/(■), if n is too large, the original physical properties of E(C)TFE tend to be impaired and the copolymer reaction rate decreases, so those with n of 11 or more are It's not light and heavy.

The fluorovinyl ether (I) is copolymerized in a proportion of 01 to 10 mol % based on the total copolymer K.

If the weight of fluorovinyl ether (I) is less than this limit, the high-temperature strength and elongation of the obtained copolymer and the severe stress cracking property will not be sufficiently improved; (C) The excellent physical properties of the TFE salvage are impaired, and the copolymerization rate decreases, making it uneconomical.

The copolymer of the present invention can be produced by copolymerizing the above three monomers in the presence of a polymerization initiation source. Polymerization methods include bulk polymerization, liquid polymerization, @turbidity polymerization,
Either emulsion polymerization or gas phase polymerization can be used, and aqueous suspension polymerization is especially light and heavy.

Polymerization initiation sources include peroxides, azo compounds, ultraviolet light,
It may be appropriately selected from ionizing radiation etc. depending on the polymerization method. Light and heavy polymerization initiation sources include peroxides, especially peroxides F (e.g. di(chlorofluoroacyl) peroxide, di(berfluoroacyl) peroxide,
peroxyesters (such as [-butylperoxyisobutyrate) and peroxycarbonates (such as diisopropyl peroxydicarbonate) It is.

1-7 When using a solvent or a dispersion medium during copolymerization, for example, in the case of solution polymerization or suspension polymerization, halogenated hydrocarbons such as trichlorofluoromethane, dichlorodifluoromethane, dichlorofluoromethane, chlorodifluoromethane , trifluoromethane, trichlorotrifluoroethane, dichlorotetrafluoroethane,
Chloropentafluoroethane, difluoroethane, water, and the like are preferably used, and these can be used alone or in combination.

A chain transfer agent may be used to adjust the molecular weight of the copolymer, and preferred chain transfer agents include 1. Examples include halogenated alkinopeparaffins, Al]-w%, esters, ethers, and mercaptans.

The polymerization temperature is usually 0 to 100°C, preferably 10 to 70°C.
It is ℃. Polymerization is usually carried out under pressure.1. <Ba1~40
It is carried out under pressure of about i(9/C?JG).

In addition to the three monomers listed above, other monomers may be added to the copolymer of the present invention to avoid adverse effects on the resulting copolymer.
Examples of these other monomers include propylene, hexafluoro I-copropylene, trifluoropropylene, and butenes (1-butene, isobutyne, fluorinated butene, halogenated butene, etc.). can.

The flow value of the copolymer of the present invention produced in this manner was measured at 300°C using a nozzle with a Koka-type Flotenutor with a total load of 12, a load of 7 to 9, a diameter of 2 mm, and a length of 8 mm. It is usually 0001 to 0.1 ac/min.

The copolymer of the present invention has the excellent properties of E(C)TFE, has significantly improved properties in high-temperature strength and elongation and stress crack resistance12, has little deterioration during molding, and has heat resistance. The quality has also been improved.

It is lightly used for coatings, tubes, sheets, films, block nuts), coach ink 2 (for example, kimono; fist coach ink), linings, bright line coatings, etc.

Next, the present invention will be explained in detail, omitting examples.

In the Examples, the flow value, high-temperature strength and elongation, and stress crack resistance were measured according to the following booklet: J-based on the flow value before flow value.

Strength and Elongation at Temperature The strength and elongation of JI No. 83 tanbells were measured in accordance with AS-rM D' 638 in a temperature atmosphere of 180° C. at a tensile rate of 20 Q jlm 1 minute.

Anti-Nutrene Cracks 1 Growth Length 3 B ynnr x Width 13 MITI x Thickness 2
JLM's tenuto sample was notched and placed in a folding holder (according to ASTM D 1693) was heated in air at a rate of 2°C/min, and cracks were observed 5□□
□, Oh, yeah. '' Example 1 12 J of deoxygenated and demineralized water was put into a polymerization tank V made of galanu lining with an internal volume of 307 cm, and after replacing the internal air with total nitrogen, it was evacuated and dichlorotetrafluoroethane 10
7jA (i'''15℃) in the tank under sufficient stirring.
I kept it. To this, fluoroalkyl vinyl ether C
l-42=CH5651ket0CH2(CF2)4H, then add ethylene/tetrafluoroethylene mixture (molar ratio 18:82) to k6.8 and 9/cyJG
Press-in I at t. n-pentane 28 as a molecular weight regulator
After adding 0ml, cy(0)-hydroperfluoroheptanoyl) peroxide 22゜4y as a polymerization initiator.
k was added. As the pressure decreased as the polymerization progressed, ethylene/Te1-rafluoroethylene/fluoroalkyl vinyl ether (molar ratio 48:50:2) was additionally injected to maintain the pressure k 6.819/cyAGvc. 442 polymerization initiators were added every 5 hours.

281 After dark, the monomer and dichlorotetrafluoroethane were removed from the tank to form a white powdery compound 4600P.
I got it. Copolymerization composition: ethylene/tetrafluoroethylene/fluoroalkyl vinyl ether-48:50:
2o melting point 266°C. Flow value 1.28 x 10 c
c/min.

A stress crack resistance test was conducted on a sheet molded from the Kono copolymer, and as a result, no cracks occurred even when the sheet was heated to a melting point of V.

Example 2 In actual mm 41, initial charge of fluorovinyl ether 76.55', amount of n-pentane added 170-1
Additional 7Jl] Total molar ratio of the monomer mixture to be press-fitted: 47:50
:3, and the same procedure was repeated except that the polymerization was continued for 34 hours to obtain 47402 white powdery copolymers. Copolymer composition: ethylene/tetrafluoroethylene/fluoroalkyl vinyl ether-47:50:3° melting point 2
61°C, flow value 056 x 10 Dc/min.

A stress crack resistance test was conducted on a sheet formed from this composite material, and as a result, no cracking occurred until the melting point was reached.

Comparative Example 1 In Example 1, the polymerization pressure was set to 4'9/cl G,
A white powdery ethylene/tetrafluoroethylene copolymer 12601 was obtained by repeating the same procedure except that n-pentane was charged at 200 rnl and fluoroa I lekyl vinyl ether was not charged. pA! l!
, 287°C, flow 1 shift 0.61X1000/min.

As a result of conducting a Strenu crack resistance test on a sheet molded from this copolymer, cracks were observed to occur at 135°C.

In Example flI3, fluorovinyl ether was converted to CH2=
CH, the initial charge amount is 0CI-12(CF2)20 258g, and the polymerization pressure is 6'? / C2ΔG and the polymerization time was 6 hours in total, but the same procedure was repeated to obtain 940 g of a white powdery copolymer. Co-ranking group 1,
Ethylene/tetrafluoroethylene/fluoroalkyl vinyl ether = 48: 50: 2° Melting point 266
℃. Flow value 0.77 XI OCo/min.

Example 4 In Example 1, fluorovinyl ether was converted into GH2=
CH, the initial charge amount is 0CH2(CF2)2F 287g, and the pressure is 6K? A white powdery copolymer 8309 was obtained by repeating the same procedure except that the reaction time was 5 hours. Copolymer composition.

Ethylene/tetrafluoroethylene/fluoroalkyl vinyl ether-48:50:2°, melting point 265°C. Flow 1 Straight 0.60 x 10 CC/Relaxation Table F shows the surface strength and elongation of the copolymers obtained in Example 1, Wild Goose Example 2, and Comparative Example 1.

Table 1 Patent Applicant Daikin Industries, Ltd. Agent Patent Attorney Seihaku Ao (and 2 others) Continued from page 1 Inventor Kozo Asano 4-5-13 Kitakasugaoka, Ibaraki City

Claims (1)

[Claims] ■, ethylene, tetrafluoroethylene, fc (rl, cx, rottrifluoroethylene, and formula CI (2=CH 0CH2 (CnF2 n )X [wherein, X is hydrogen, fluorine or chlorine, and n is represents a number of ¥1 to 10.] The ethylene and tetrafluoroethylene mixture has a molar ratio of chlorotrifluoroethylene of 40:60 to 60:40, and a vinyl ether content of 0. An ethylene-tetrafluoroethylene or chlorotrifluoroethylene copolymer characterized in that the amount thereof is from . The first one in which X in the formula ll”r is fluorine
Copolymer described in section.