JPS59113030A - Insulated electric conductor and manufacture - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an electrical conductor, and more particularly, to an electrical conductor insulated by a single aromatic polyketone.

Recently, aromatic polycarbons have attracted widespread interest because of their resistance to thermal degradation. Y4 flavors are gathered in ~n. U.S. Patent No. 3.065
According to No. 205, the polyketone having the above-mentioned repeating unit is a Friedel-based polyketone of Honugen and Diphenylny7/Shito.
It can be produced by catalytic polymerization. Identical repeating units are further described in British Patent No. 1,086,021 by polycondensation of diphenyl ether-4-carbonyl chlorite and reaction of diphenyl ether with diphenyl ether-4,4'-dicarbonyl chloride. It has been obtained.

A number of patents have been granted for improved methods of making such polyketones. The analogy is U.S. Pat.
The processes disclosed in No. 41,538 and No. 3,442,857 fully demonstrate the advantage of using boron trifluoride catalysts enhanced with hydrogen fluoride.

The molten metal characterized by the repeating unit
The production of the most important polymers was carried out by Klaus J. Tarr.
U.S. Patent Application No. 218.46 filed January 17, 972
He is being harassed by No. 5, where he is also admonished about Iya's techniques.

Aromatic polyketones containing other repeating units have also been reasonably well studied. Commonly processed ρI-capable polyketones with repeating medium: H≧HIOOG■- are described in Krauss J., US Pat. No. 218,466, for example biphenylyloxybenzoyl Obtained by polymerization of chloride using l-I F7 B F 3 catalyst.

According to British Patent No. 1,078,234, the repeating unit is: D OOO<=>GO-k, and 350
Polymers having a melting point of 0.degree. C. can be produced from the reaction of hydroquinone and 4.degree. 4-difluorobenzophenone.

It would be a substantial advantage if aromatic polyketones with favorable properties could be obtained by using as a reaction component a material that is more common and less expensive than those previously used. .

Medium repeat: , -C) , 516°966,
It has been reported that 1-17B F3 catalytic polymerization of the above reaction components gives a melt-unstable product. Accordingly, in that patent all copolyketones having a significant content of isophthaloyl residues are prepared and the products are reported as melt-stable. According to our studies, although the process of the US patent gave polymers of satisfactory molecular weight, the compacted slabs showed signs of excessive gel content and a significant degree of thermal crosslinking during melt processing. . We have therefore determined that diphenyl ether is unstable in HF/B F 3 yarns under the conditions selected by the U.S. patent, leading to as yet undetermined and uncertain side reactions. Ta. By carefully selecting the attack conditions for reaction component 2, a new and economical aromatic polyketone was obtained using the I-I F/BF3 contact platform, and the inherent viscosity of this polyketone was 410. 5 at °C
It has been found that compression molding at, for example, 10.0 QQ psi for minutes is essentially unaffected, and that this polyketone is an excellent electrically insulating material.

According to the present defense, an electrical conductor and a substantially ramid polyketone comprising repeating units of the formula %, under Friedel-Krach Jv=w reaction conditions, have the formula: The nucleophilic reaction component shown and the electrophilic reaction component shown by the formula: are reacted, if necessary, in the presence of other nucleophilic reaction components 2 or nucleophilic reaction components. The resulting insulated electrical conductor comprising an insulating layer of polyketone having an inherent viscosity of at least 0.04 is separated.

(In the formula, each of X, In and n is O or 1,
P is an integer from 1 to 4, and when X is 1, n is O,
When P is greater than 1, 1n is 1 and X is 0 and 8. CUR represents a carboxylic acid chloride group or an ether group. ).

The inherent viscosity of this polyketone is, for example, 1o,
Compression mold at 410° C. for 5 minutes at o o o psi.

The quality of the wood is not affected by this.

Representative co-reacting components useful in forming homopolymers suitable for the practice of this invention are all listed in the table below. Each 4 is
This is a compound of known compound 1, which is prepared using standard procedures described in the literature.

εI-1-C) O a. l -@ = M x - Electrophilic 1 Regarding the bioanti-J-centered component, the dissolving group may be other than the above, such as nodoxy, hydroxyl, etc., or is preferably chlorine. For the case where P is 2.3 or 4, the optional electrophilic reactants can be used with tetra- and penta-butahexaphenylene ethers, respectively. The reactant components are obtained by a combination of 2 moles of phenol and 1 mole of 4.4-sidaromosifenyl ether. Pentaphenylene ether m, 1,4-cyclomobenzene (1 mol) and 2 mol of 4-hydroxycyphenylene ether are produced by injecting them. It is easily synthesized by condensation of 4'-cybromone phenyl ether (1 mole) with 2 moles of 4-hybromone phenyl ether.

Preferably, all repeat units in the polymer are lignically oriented. In this case, the woody combination of 1 heather is characterized by a meta-bond on the interfering link, such as occurs when a mixture of terephthaloyl and inphthaloyl chloride is used as an electrophilic reaction component. It is thought that it exhibits better thermal stability than coalescence. Of course, even when only terephthaloyl chloride or similar para-reactive components are used, a small number, for example, a few percent of the repeating units may form electrophilic reactive components at positions other than the para-position, resulting in long polymers. It seems inevitable that it includes a different combination of payoffs that arises from attacking the service.

In general, the polyketone used herein may be a copolyketone containing primarily a single repeating unit according to the above-described formula. The following nucleophilic co-reacting components are exemplified among the components suitable for co-composition: Cyphenyldulphide 4,4-cyphenogysibiphenyl P-phenoxyphenol 2,2-diphenoxybiphenyl P-
Phenylphenol 1.2-Diphenoxybenzenedibenzofuran 1.3-Diphenoxybenzenethene 7threne 1-Phenoxynaphthalenephenogisatin 1.2-Diphenoxynaphthalenephenonoxin Siphenyl ether diphenyl 7 1.5-
The following are examples of electrophilic co-reacting components suitable for copolycarbonate formation: Honugen, carbonyl difluoride, inphthaloyl chloride, benzene-1,4-(sulfonyl) chloride), pensene-L3-(sulfonyl chloride), 2-chlorobenzene-1,4-disulfonyl chloride, thio-beef (4,4'-benzoyl chloride), oxy-bis(4,4'-benzenesulfonyl) chloryl chloride), benzophenone-4,4-cy(carbonyl chloride, -benzenesulfony /L' 70 phyto], Sipheni J Le 3.3
~Si(carbonyl chloride 3-benzoyl chloride), sulfonyl-bis(
4, 4'-'>: yyilchloraien, nulfonyl rubis (3.3'-benzoyl chloride), sulfonyl-bis (3.4'-benzoyl chloride), thio-his (3.4'-benzoyl chloride), diphenyl -3.4'-(sulfonyl chloride), oxybis[4,4'-(2-chlorobenzoyl chloride)]
], naphthalene-1,6-di(-carbonyl chloride), naphthalene-1 + 5-di(carbonyl chloride), naphthalene-2.

6-C (carbonyl chlorite), naphthalene-1, 5
-C(nulfonylchloride l'), OxyvinuC
7.7'-naphthalene-2,2'-7 (sword luponyl chlorite)], thiohihis8.8'-naphthalene-1,
l-(carbonyl chlorite)], 7,7-pinaphthyl-2,2'-(carbonyl chloryl chloride) Honyl chlorite-ra],
Sulfonyl-bisC6,6'-naphthalene-2.

2-(carbonyl chloride), ), dibenzofuran-2.7-(carbonyl chloride).

In another embodiment of the invention, the repeating unit is: ) is primarily, and most preferably, consists essentially of a linear, crystalline bath-stable undercarriage. Such a person 8
Polymers are made in exactly the same manner as the whole bulk polymers, except that a portion or all of the electrophilic terephthaloyl chloride and esters are replaced with inphthaloyl chloride. The use of terephthaloyl P and isophthaloyl chloride as a footrest causes the humidity of the song at 271 to 360°C to rise to the surface, and this type of joint gas gives a large correction area due to the extrusion temperature. I was able to do it, and when I was in agony with the last April, I was left with a long life, and I was given 7
Special effects 2 can be obtained, for example plasticization. Another advantage that may arise from such a departure from the whole bulk polymer system is the crystallization properties of -2 ashing P in adults. The effect of this is Kanakura.

The preferred reaction conditions can be used to form homoconjugates (many of which are novel) from the coreactants mentioned above. The copolyketone coreactants are more abundant than the dinuclear ones. If the copolyketone preferably has a
It should contain repeating units corresponding to the general structural formula given above.

Preferably, the polymers used in the invention have at least about 0
4, preferably from about 0.5 to about 20, and most preferably from 0.72 to 15. Molecular weight can be adjusted by caraping as taught in US Patent Application No. 136,236. Favorable character pink agents contain ketone bonds, such as 4-
It is phenoxybenzophenone.

In preparing the polymers used in the present invention according to the preferred procedure, equimolar weights of the nucleophile and cyclolide co-reacting components are supplemented with a small amount of the monofunctional capacitor, if desired, Add a sufficient amount of anhydrous HF at 0°C for 10 m.
Prepare a bath of 0% at -20°C to 10°C, preferably 0°C, first at a temperature of J-I Ct;
Generate, lack, BF3'fc 30 ps i
Add under pressure, let the ingredients react for about 6 hours, and then remove the liquid. Footstool 〒502 or additional 1. -IF and interpret it β
) Form a melt containing 5% solids. Recovery is done by one-member fog drying or by sieving the rice or water (waring) in tutanol (-78°C).
! ! By sinking υQ in the ILj table, it is now possible. The 91'J system and borax-containing substances in the product were reduced by washing with water, and the substances were heated for 3 to 51 hours at 150°C for 20 nm.
Main line with reduced pressure F of 4 Hg. All reactions are carried out in an atmosphere free of all transition metals.

An example of producing a preferable polyketone used in the present invention is shown below.
As long as there are no other incumbents, part 2 is the Emperor I! ivC
Based on.

Production Example 1 1.29 to 50-polychlorotrifluoroethylene pipe
81 (4,95 mmol) of 1,4-Schiff-enoxybenzene, 1.0049 P (4,95 mmol) of terephthaloyl chloride, 0.00279 (0,01 mmol) of 4-phenoxybenzophenone (capping agent). ] 2 and a stirrer were charged.

A 20-degree anhydrous fluorinated water system was gradually added to the mixture. Connect the tube to polychlorotrifluoroethylene s empty line (
Toho Kasei Kogyo Co., Ltd., Osaka, Japan]
Purged with nitrogen while cooling to .degree.

Boron trifluoride was added and the reaction mixture was kept at a pressure of 30 PSi for 6 hours until a total of 4 cycles was obtained. Excess boron trifluoride was removed from the reaction thread, and the polymer solution was diluted with diluted fluoride water and then poured into cold (-78°C) methanol with rapid stirring.

The resulting product was filtered, washed with water and tanol, and dried at 180°C to obtain a colorless substance. This for 20 minutes 1
Annealing was performed at J230°C. Tables 2 to 4 show the inherent viscosity before and after indentation, the base composition of the resin, and the physical customization, respectively. In this example and Example 2, almost colorless flexible slabs were prepared by molding at 410° C. for 5 minutes at 10,000 PSl. It is a shame that the inherent viscosity is essentially unaffected in compression molding.In the relevant large bags, diphenyl ether and terephthaloyl chloride are all reacted by the procedure I11.11 below and the heald unit: all In the latter case, the inherent viscosity of the powder was 0.53, which was smooth and narrow (
Mountain bark id 0.49 and Metsu 1ζ. All inhesin l-
J-Divination is Preparative Method's
of Polymer Chemistry
Sorenson's method as described in Interscience (4968) Publishing, page 44 [100% sulfur at 25°C. 0 in the z solution. This is the average value calculated according to M's total salary. I used a Perkin-Elsimer differential scanning calorimeter to calculate 7 rules for one point.

Production Example 2-5 Produced according to the procedure of Ike no Rigoitai Kai Production Example 10 listed in Table 1. Its properties are shown in Tables 2-4.

In the case of manufacturing crisis case 5, all 7 high points were not located, or 3 substances were
If the temperature is within the range of 00°C to 350°C, it will be evaluated as 1 song.

Polymerization of 114-diphenoxybenzene with inphthaloyl chloride The entire borofluoride mixture was saturated with pentafluoride series V at -23°C for 4 hours at a pressure of 30 psi. 50-116' degree l
/i:l,4-diphenoxybenzene 1.3050F (
4975 mmol], inphthaloyl chloride 1.0
151S' (5 mmol), P-phenoxybenzophenone (J, 0137P (1 mol%) was charged with LUPi stirring. To this mixture was added cold (-78°C) trifluoride water 1 10. Add slowly to Z' and connect to the reaction tube complete line. Boron trifluoride is added at a pressure of 30 Psi and a viscous orange bath solution is produced.
The chassis was kept at O℃ for 6 hours. Excess boron trifluoride was removed from the reaction thread, diluted with total hydrogen oxide in a bathtub, and then pressed into rapidly stirred cold (0°C) water. One bottle of the obtained lily was completely filtered, washed with water, and then heated to 150℃/
Drying with 201+a+Hg left a colorless brush-like substance.

The substance is iI8! I showed 136 sessions of mucinous skin. 400 for 5 minutes
Compression molding at 0.degree. C. produced an iJ visibility slab with an intrinsic viscosity of 1.37. A differential scanning calorimeter showed a glass normal temperature of 153°C and a crystal melting temperature of 271°C (transverse strain rate: 20°C/min). Heat void hoe in all air 4/
? Loss of 10 double stars at 600℃ (scanning 4 degrees = 20℃)
/min). By molecular spectroscopy, the following data are consistent with the repeating unit:
Infrared (film canut from hydrogen fluoride): 1655 m-1 (ketone bond), 1235 cm-1 (I knee y
Ultraviolet (concentrated sulfuric acid) λmax, 4
07nm (ε, 4.8X104): nuclear faE co%
((VCF2-COCF CiD O/CL)C13=
I: 1): δ+ PP”2: 7.18 (2 ml!, 41 (, J=9Hz), 7
．． 28 (Koume, 4H), [proton at ortho position to ether linkage 8] Near, 82 (single wire, 3H), 8
08 (double jealousy, 4 H, J = 91 (z), 8.
18 (Single chain, IH) Proton production near C ketone bond Example 7 1,4-Diphenoxybenzene with terephthaloyl chloride/isophthaloyl chloride mixture Main base with terephthaloyl chloride and inphthaloyl chloride I returned the stock V using the same procedure as in the previous example, except that I used the footrest proboscis. The ratio of Yabu chloride and the rate of special first grade of the imperial government official are highlighted on the other side.

The polyketone used in the present invention is a film 2 and a fibrous-forming compound which are used in a tonne A type by extruding the polyketone on electrical appliances, cables, etc. A favorable combination results in a crystalline material that crystallizes at temperatures in the range of 340-404°C. Those in which the carphonyl moieties are present in a greater number than the ether acids, for example poly(benzophenone ether), are expected to crystallize substantially faster, and the latter is expected to crystallize more rapidly than in the extrudates. If the annealing process is performed with tensile strength 1 strength 2 and edge wear
Rather than giving money to properties such as resistance to eclipse, it is best to eliminate them. The wide-spread steel plate used in accordance with the present invention has a temperature on the order of 400°C or higher at one point.
It is advantageous in that it prevents deterioration of insulation properties due to contact with the soldering iron due to the total pressure when it is used for swollen operation.

The present invention includes the following embodiments.

(2) Polyketone is contained as a single repeating unit sound of the sake formula: (in the formula, each of m.n and Absolute #J drowsiness specialty consisting of a truss-shaped car combination.

(3) The insulating draft according to item (2) of MiJ, wherein the height of the chassis is 2, rn is 1, and the valley of n is 0.

(4) If there are 3 in the repeating unit of the chassis, m−nJ? Yohi

(5) The polyketone can be produced by a total of 1 unit or 1 reflow type (in the formula m-
When each of nB and X is 0 or 1 and X is 1, n is O
It is necessary. ) - A conductor consisting of a boyish jealous monomer.

- a monomer union of at least about 0.04 and preferably about 0.05;
+4iJ (
The insulated electrical conductor according to item 5).

(7) Homo 厘合I4- is one in which all of the repeating units are of the phosphorus type. ) Homo car combined salary is essentially the same as the one in which all of the repeating units are in the reconnaissance style.
Don't hesitate.

(9) Homo Rindaiki is essentially a gvc from all of the early attacks or 4 second crisis formulas. .

■ All of the repeating units are horizontally curved, and the woody VC is an insulated electrical conductor.

口υ Homopolymerization is an insulated electrical conductor described in Mekuji (6) Uta, which essentially consists of all of the repeating units or those in the customer shield type.

Patent applicant Ray Chem, Corporation agent Patent attorney Maeda Ao (2 others) 207-

Claims (1)

[Claims] l An electrical conductor, made of a linear polyketone containing repeating units of the formula: Under Friedel-Kraf contact reaction conditions, an electrical conductor of the formula: The electrophilic reaction component represented by the formula: is obtained by reacting the electrophilic reaction component represented by the formula: in the presence of another nucleophilic reaction component 2 and/or an electrophilic reaction component, if necessary, and at least An insulated electrical conductor comprising an insulating layer of polyketone having an inherent viscosity of
is an integer from 1 to 4, when X is 1, n is O, and when P is greater than 1, m is 1 and X is O. C
OR represents a carboxyl group, an acid chloride group or an ester group. ). . 2. A substantially linear polyketone comprising a repeating unit represented by the formula: is placed on a free flow conductor, and under free flow flow catalytic reaction conditions, a J nuclear reaction represented by the formula: Components and formulas: All of the electrophilic 1 bioreactive components represented by, if necessary, also the nucleophilic catalytic component 2, which can be reacted in the presence of an electrophilic or nucleophilic reactive component, and at least A method for producing an insulated electrical conductor, comprising melt-extruding a polyketone km having an isoherent viscosity of 0.4 to form an insulating layer, where x, m and n, i/I-4, O'!7'j
P is an integer from 1 to 4, and when X is 1, n is O, and when P is much larger, rrl is 1 and X is O. CUR represents a carboxyl group, an acid chloride group, and a Xf7:poeneter group. ).