JPH052694B2 - - Google Patents

Description

[Detailed description of the invention]

Conix U.S. Pat. The preparation of linear polyesters of the group diphenols is described, these polyesters having relatively low molecular weights as evidenced by the low in trinsicviscosity values reported for the polyesters in the above patents.
Note that the intrinsic viscosity values reported by Konics would be smaller if reported as inherent viscosity values used in the present invention. For example, Example 6 of U.S. Patent No. 3,216,970:
1,1-bis-(4-hydroxyphenyl)-1-
For polyesters of phenyl-ethane and isophthaloyl chloride, an intrinsic viscosity of 0.7 dl/g and an elongation at tear of 17% in various tests are reported. Example 11 of the same patent reports an intrinsic viscosity of 0.83 for a polyester of 1,1-bis-(4-hydroxyphenyl)-1-phenyl-ethane and terephthaloyl chloride. The embodiment of US Pat. No. 3,351,624 is the same as Example 11 of the earlier Konics patent. Using this type of polyester it is not possible to cast films or create coatings with the desired mechanical and electrical insulation properties to be used for electrical insulation. US Pat. No. 3,546,165 to Morgan describes thermally stable polyesters of various gem-bis-phenols and various dicarboxylic acids. Encompassed within the scope of this claim are polyesters of 9,9-bis-(4-hydroxyphenyl)-fluorene and isophthalic acid and/or terephthalic acid, which are generally measured in the present invention. They generally have relatively low inherent viscosities of less than about 0.8 to 1.0 and desirable lower mechanical properties. Although a small number of high values have been reported by the above patents, applicants have not been able to obtain values greater than 1.0 by the method taught in the above patents. The object of the present invention is to provide improved polyesters with mechanical and electrical insulation properties that can be advantageously used in the electrical insulation field. Another object of the invention is to provide high molecular weight polyester films and powders having an inherent viscosity of greater than 1.8 dl/g and improved elongation at break. Another object of this invention is to provide a new method of insulating electrical conductors by providing them with a coating of the high molecular weight polyester of this invention. Yet another object of the invention is that the 9,9-bis-
An object of the present invention is to provide an electrically insulating tape comprising a film of high molecular weight polyesters of (4-hydroxyphenyl)-fluorene and isophthalic and terephthalic acids. These and other objects and advantages of the invention will become apparent from the detailed description below. The novel polyesters of the invention are terephthalic acid or its functional derivatives, isophthalic acid or its functional derivatives and 9,9-bis-(4-hydroxyphenyl)fluorene or its functional derivatives having a melting point of at least 226°C. produced by the reaction of substantially the formula -(O-X-O-Y-) in which 70 to 30% by weight of X is

[Formula] is 30 to 70% by weight.

[Formula], and Y is the formula

An organic high molecular weight polyester having the formula and containing chain members of 60% by weight of phenol and 40% by weight of 1,
100ml mixture of 1,2,2-tetrachloroethane
have an inherent viscosity of greater than 1.8 dl/g as measured at 30°C in a solution of 0.5 g of the polyester described above in a solution of 0.5 g of the above polyester in solution, and the film cast from a chlorinated organic solution has an inherent viscosity of greater than 1.8 dl/g as measured in accordance with ASTM D-882-75b. The above polyester has an elongation at break of at least 20%. The polyester of the present invention has many desirable physical properties that make it valuable for electrical dielectric breakdown. These properties include high tensile strength, excellent dimensional properties,
High temperature stability, good flame retardancy, good adhesion to metals, dielectric strength and dissipation
good electrical insulation properties and good mechanical properties as well as good water absorption properties. A novel method for producing polyesters with inherent viscosity greater than 1.8 dl/g is based on pure 9,
It consists of reacting 9-bis-(4-hydroxyphenyl)-fluorene or a functional derivative thereof with terephthalic acid or a functional derivative thereof and isophthalic acid or a functional derivative thereof in a suitable organic solvent. The functional derivative of diphenol can be an alkali metal diphenolate such as sodium, potassium or lithium, and the functional acid derivative can be an acid halide. This method is fully described in US Pat. No. 4,430,493. In order to obtain polyesters with as high an inherent viscosity as possible, 9,9-bis-9,9-bis-
It was found necessary to use (4-hydroxyphenyl)-fluorene. The process for producing phenol-aromatic ketone condensation products by reaction of phenols and ketones in the presence of gaseous hydrogen halides described in U.S. Pat. A valent or tetravalent metal halide is added in a catalytic amount up to a molar amount based on the above ketone, gaseous hydrogen halide is introduced, and after the end of the condensation reaction water is added to the reaction mixture and the purified condensation product 9,9-bis-(4-hydroxyphenyl)-fluorene monomer having a melting point of at least 226°C containing traces of residual metal catalyst and 1, having a melting point of at least 189°C.
It consists of producing 1-bis-(4-hydroxyphenyl)-1-phenylethane. The dicarboxylic acid is most preferably used as a mixture in the proportion of 70-30% by weight of terephthalic acid and 30-70% by weight of isophthalic acid, in order to obtain the polyesters of the invention with higher values of elongation at break. used as an equimolar mixture of The polyester of the present invention can be produced with a thickness of 0.010 mm to 0.25 mm, for example, by the known method of dissolving the polyester in a suitable organic solvent, forming a film of the solution on a smooth surface, evaporating the organic solvent, and removing the resulting polyester film. ,Preferably
It can be in the form of a thin film with a thickness of 0.020-0.150 mm. As mentioned above, the polyester films of the present invention have excellent electrical insulation properties and more importantly excellent mechanical properties as demonstrated by elongation at break and dimensional stability. Furthermore, good mechanical properties allow for the production of films of good quality regardless of manufacturing-related variations. In the polyesters of the present invention, the inherent viscosity of the polyester is highly dependent on the purity of the monomers, and even relatively small variations in the purity of the diphenol monomer can cause large variations in the inherent viscosity values. 1.8
Elongation at tear values for polyesters with inherent viscosities between dl/g and 2.4 dl/g do not appear to change as rapidly with increasing inherent viscosity as at lower inherent viscosities. As a result, the elongation at break value may be more consistent under actual manufacturing conditions. Polyesters with inherent viscosities greater than 2.5 dl/g are impractical as they are usually obtained only with diphenols of very high purity and these polyesters are not suitable for film castings of the desired optimum viscosity in chlorinated organic solvents. Not soluble enough to obtain solution. The polyester films of the present invention have a higher limiting oxygen index as measured by ASTM D2863-77 than prior art polyesters having lower inherent viscosities. Polymers with a high oxygen index become more important, especially in applications where the thermal decomposition of the polymer, especially the smoke generation and toxicity of the flame-induced decomposition products, cannot be tolerated. The polyesters of the present invention have a very high degree of thermal stability, which is a desirable property for electrical insulation purposes. The polyester of the invention may be of the formula where R is selected from the group consisting of alkyl, acyl, cycloalkyl, aryl and halogenated methylene and other hydrocarbon groups as described in U.S. Pat. No. 3,216,970. It may also contain small amounts of compounds, ie 10% by weight, preferably 5-8% by weight. The coated electrical conductor of the present invention has a 1.5 dl/
Inherent viscosity greater than g and at least 20%
an electrical conductor with an electrically insulating layer of the polyester of the present invention having an elongation at break of . Said layer may be applied, for example, by wrapping the electrical conductor, preferably when it is in the form of a wire, with a polyester film or adhesive tape, especially pressure-sensitive tape, or by wrapping the heated conductor in a fluidized bed of polyester powder. The extrusion may be applied in any suitable manner by placing the material in the mold or by other known means such as hot melting. At least some of the polyesters of the present invention contain not only high molecular weight components, but also small amounts of low molecular weight components that are believed to increase the adhesive properties of the polyester and make it more useful in the electrical insulation field. An interesting bimodal distribution (bimodal
distribution). The invention is illustrated by some preferred embodiments in the following examples. However, it should not be understood that the invention is intended to be limited to that particular embodiment. Reference example 1 1051 g (3.0 mol) of 9,9-bis-(4-hydroxyphenyl)-fluorene was dissolved in sodium hydroxide.
264g, isopropanol 2.5 and distilled water 5.0
After dissolving in a solution of at 70°C and cooling the mixture to room temperature, 1 part of distilled water was added to the disodium phenolate solution. The resulting solution was added to a coolable reaction vessel equipped with a high-speed stirrer, thermometer and metering pump, followed by 34.5 g (0.15 mol) of benzyltriethylammonium chloride in distilled 1,2-dichloroethane 15 and 200 ml of distilled water. A room temperature solution of was added. A solution of 304.5 g (1.5 mol) of isophthaloyl chloride and 304.5 g (1.5 mol) of terephthaloyl chloride in 1,2-dichloroethane 20, stored under anhydrous conditions while maintaining a temperature below 40°C, was prepared in 25 minutes. The mixture was stirred vigorously while being added gradually. The mixture was stirred for 45 minutes, during which time the viscosity increased. The resulting mixture was allowed to stand for 15 minutes to form an aqueous phase and a highly viscous organic phase, and the aqueous phase was discarded. The organic phase was washed three times with 30 parts of water each time and then stirred vigorously with 30 parts of isopropanol, after which time the desired polyester was precipitated. Strain the mixture and add 30 ml of isopropanol to the polyester product
mixed with. The mixture was centrifuged and the recovered product was washed twice with 10 volumes of water each time to remove residual inorganic salts. The resulting polyester product at 130℃
The polyester was dried in a circulating air oven for 15 minutes to give a constant weight product of 1.383 g (96% yield) of polyester.
The inherent viscosity is 60% by weight of phenol and 1,
It was determined to be 1.73 dl/g at 30 DEG C. (capillary constant - 0.011) using a solution of 0.5 g of polyester in 100 ml of a 40% by weight mixture of 1,2,2-tetrachloroethane and an Utsuberohde viscometer. Example 1 9,9-bis- with a melting point range of 226-230°C
(4-hydroxyphenyl)-fluorene 1.051g
(3.0 mol) was added to a solution of 264 g of sodium hydroxide, 3.0 g of dioxane and 5.0 g of distilled water at 70° C., and after the mixture had been cooled to room temperature, 1 portion of distilled water was added thereto. The process was then repeated as in Reference Example 1 to obtain 1.368 g (95% yield) of the desired polyester with an inherent viscosity of 23 dl/g. Reference Example 2 A solution of 5.75% by weight of the polyester of Reference Example 1 in 1,2-dichloroethane was used as a coating solution in a film casting machine.
A polyester film was formed having a thickness of 0.040 mm. ASTM elongation at break of film
Determined to be 22% by D882-75b. 0.125
Another film of the polyester of Reference Example 1 having a thickness of mm was prepared from the same casting solution and the oxygen index of the film was determined to be 33% by ASTM D2683-77. Reference Example 3 To demonstrate the advantageous properties obtained by using purer monomers, the melting point range 224-230°C
(Product A), 224-230°C (Product B) and 225-
9,9-bis-(4-
Hydroxyphenyl)-fluorene (2 moles) and 2 moles of an equimolar mixture of isophthaloyl chloride and terephthaloyl chloride were reacted in the presence of benzyltriethylammonium chloride and isopropanol as a catalyst, and the inherent viscosity and elongation at break were expressed. The corresponding polyester shown in 1 was obtained.

TABLE The results in the table clearly show that the higher the purity of the starting diphenol monomer, the better the properties of the polyester obtained as shown by the higher inherent viscosity and percentage elongation at break. Example 2 In order to demonstrate the advantageous properties of the polyesters of the invention, films made respectively from polyesters with an inherent viscosity greater than 1.8 dl/g and polyesters with an inherent viscosity less than 1.8 dl/g were subjected to a series of tests. and the results are reported in the table below. dielectric constant
constant) and dielectric facator
was determined according to DIN53483, and the key measurement, dielectricstrength, was determined in volts per mil. The ultimate oxygen index is
The elongation at break and tensile strength were determined by ASTM D2863-77 for a 0.025 mm thick film, and the elongation at break and tensile strength were
determined by DIN53455, and the elastic modulus is
Determined by DIN53457. Gel permeation chromatography was also determined along with thermogravimetric analysis. Puncture resistance and extent of high temperature film shrinkage and film weight loss and water absorption were also determined. All samples tested were 50% terephthalic acid-50
% isophthalic acid and have the inherent viscosities listed in the table.

【table】

[Table] From the values in the table above, elongation at break, ultimate oxygen index,
High temperature film shrinkage, high temperature film polymerization losses, tensile strength and modulus values are very good for films with high inherent viscosity. Modifications may be made to the products and methods of the invention without departing from the spirit or scope of the invention, and it is intended that the invention be limited only by the scope of the claims. should be understood.

Claims (1)

[Scope of Claims] 1. Terephthalic acid or a functional derivative thereof, isophthalic acid or a functional derivative thereof and at least 226
prepared by the reaction of 9,9-bis-(4-hydroxyphenyl)fluorene or a functional derivative thereof having a melting point of 70 to 30% by weight of X is [formula], 30 to 70% by weight is [formula], and Y is an organic high molecular weight polyester containing chain members of formula [formula], and 60% by weight of phenol and 40% by weight of 1,
100ml mixture of 1,2,2-tetrachloroethane
have an inherent viscosity of greater than 1.8 dl/g as measured at 30°C in a solution of 0.5 g of the polyester described above in a solution of 0.5 g of the above polyester in solution, and the film cast from a chlorinated organic solution has an inherent viscosity of greater than 1.8 dl/g as measured in accordance with ASTM D-882-75b. and an elongation at break of at least 20%. 2. The polyester according to claim 1, wherein 50% by weight of 2X is terephthaloyl and 50% by weight is isophthaloyl. 3 10% by weight of the second condensable diphenolate
The polyester according to claim 1, which contains up to 4. The polyester according to claim 1, containing a residual amount of metal catalyst.