DE1905651A1 - Polymers and process for their preparation - Google Patents

Description

DR.-ING. WALTER. ABITZ DR. DIETER MORF

Patent attorneys

8 Munich 27, Pienzenauerstraße 28 Telephone 483225 and 486415 Telegrams: Chemindus Munich

5th February 1969

F-1896

"EI. DU PONT DE MEHOUES AED OQlWAM 10th and Market Streets, Y / ilraington, Delaware, 19898, V

Pol'.merioa.te and ancestors for their manufacture

The present invention meets new polyketones and mixed • polylcetones av.t der Baais from Ä'.ibenso-p-ilioxin (DliD)? the as Kochteinperatur-j [ß ;. ^! li.erung are brewable.

i & e have already been described several times, for which reference is made to British patents 971 227 and 1 019 226 yerv7io3cn - «r. In ilsi * holländischGii patent specification 6 611 019 and in Belgian patent specification 689 509, phenodioxin and oxy-bis ~ £ 4-4'-benzotrichloride) or the

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speaking acid is mentioned in an example, but none are A donkey or results given.

The present invention provides polymers, polyketenes and mixed polyketones, suiting the repeating structural unit

il

v / orin the phenylene radical is either p-phenylene, m-phenylene or mixtures thereof, in which the polymer contains a sufficient number of units to provide a polymer with a logarithmic viscosity number of at least 0.3 su, göaesse-n at a 0 _? 5 gevr .- ^ igen solution in concentrated sulfuric acid or another solvent boi 30 ⁰ G.

The extremely useful polymers of the present invention are prepared from IDibenso-p-dioxin and terephthaloyl halide (T) ₇ isophthaloyl halide (i) or mixtures thereof or the sritopreuhsnüen carboxylic acids. \! enia equal Säursohloride the bevorsugten halides, yet also .8äyrebror "are ide useful. If mixtures of halide or acid reagents are required, each can

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desired ratio of "Sere" - au "Iso" components used will. The process conditions are conventional and can be, for example, as described in US Pat above Dutch patent specification 6 611 019 and Belgian patent 689 509, to which Beaug can be referred. Anyone can participate in the process customary Friedel-Crafts catalysts are used, including Aluminum chloride, aluminum bromide, boron trifluoride, hydrogen fluoride, Iron (III) chloride, tin (IV) chloride; Titanium tetrachloride and the like belong. Aluminum chloride is a preferred catalyst and mixtures of hydrogen fluoride and boron trifluoride are very preferred.

The amount of, for example, the preferred catalyst is usually at least one molar equivalent of boron fluoride per carbonyl group in the monomeric reagents. An excess up to about 50 or 75 moles of boron fluoride per carbonyl group in the starting reagents can be used. the The amount of hydrogen fluoride is more than a molar equivalent of HF based on the amount of boron fluoride used, i.e. they is from about 2 to about 10 or more moles of hydrogen fluoride per mole of boron fluoride.

The polymerization reaction proceeds within a fairly wide range of temperatures, ranging from only a few degrees above the freezing temperature of the reagents up to 100 or 150 ⁰ C, and it is generally for a few minutes to several hours, usually at the autogenous pressure, performed. Other conditions can also be used.

The new polymers according to the invention have good thermal stability, hydrolytic stability, and oxidation resistance and good electrical insulating properties. Your glass

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Mnfriertemp era doors be at least about 200 ⁰ C. In FiImform they show good toughness, clarity, flex life, tensile strength, good modulus and good elongation. The polymers are useful in a variety of applications. At viscosities of about 0.3 or more, they can be used as coatings on various substrates, for example on other polymers and metals, including copper, aluminum, nickel, silver and the like. At higher logarithmic viscosity numbers, ie at about 0.5 and higher, they form tough films and are lasers. These materials are particularly useful as electrical insulation *

Poly (isophthaloyldibenzo-pr.dioxin) (DBD / l) can be converted into useful molded articles, for example films, by melt pressing. Copolymers containing up to about 50 * f Terephthaloylrcste addition to Isophthaloylresten may also in'der melt are compressed. All polymers according to the invention can be cast into films from a solution in suitable solvents, such as liquid hydrogen fluoride. The DBD / l polymer and the DBD / TjI mixed polymer (50:50) can be cast into a film from solution in sym-dichloroteträfluoroacetone hydrate,

The polymers are particularly useful as electrical insulation. They have high specific resistances. Their dielectric constants and their dielectric loss factors determine their classification in the class of good electrical insulators. They retain these good properties up to the glass freezing temperature, which has been found to be very high, as shown in Table I. The excellent electrical high-temperature properties of DBD / ΐ are excellent, as its glass freezing temperature is 26O ⁰ C,

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DBD / Τ DBD / l DBD / Τ, Ι (50:50)

TABLE I. more crystalline
Melting point Glass freezer
temperature 525 ⁰ C
43O ⁰ C
44O ⁰ C 260 ⁰ C
200 ⁰ C
235 ⁰ C

The physical properties of the polymers are also remarkable. Pur the poly (terephthaloyl-dibenzo-pdioxin) polymer this results in the following picture:

Tensile modulus (kg / cm)
Tensile strength at break (kg / cm ^)
Elongation at break

TABEL II 23 ⁰ C 155 ⁰ C 200 ⁰ C 24 700 17th 870 H. 780 520 338 254 kg / cm) 2.4 5, 8th 10, 8th

The above properties ε-ind as well as those in the
the following examples
Standard tests determine rfc. The procedures for the physical properties are described, for example, in US Pat. No. 3,179,634, column 9 »lines 24-45, while the electrical properties are described in accordance with US Pat.

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2 787 603 tests described in writing 2 787 603 can be determined.

The following examples are intended to further the invention illustrate. The parts and details are weight-related, Unless otherwise stated or evident ο

B ^ e ia pi e 1 1

1.84 g (0.01 mole) dibenao-p-dioxin, 1.01 g (0.005 mole) lerephthaloyl chloride and 1.02 g (0.005 mole) isophthaloyl chloride are placed in a jacketed 130 ml stainless steel pressure vessel and the Container is closed. It is cooled in a solid carbon dioxide / Acetonbau to about -60 ⁰ C and evacuated. Immediately thereafter, 10 g (0.5 mol) of anhydrous hydrogen fluoride and 17 g (0.25 mol) of boron trifluoride are condensed into the container by transferring them from storage bottles through a stainless steel hot tub. The reaction vessel is placed on a shaker and placed at Sigendrucl; Heated to 25 ^° C. for 1 hour and to 50 ^° C. for 1 hour. The vessel is cooled to about 1O ⁰ C and then ventilated for degassing, after which the suriickbloibande reaction mixture into a saturated aqueous llatriumace did solution is drained. The precipitate formed is collected by filtration and washed successively with washer * 5 aqueous sodium bicarbonate solution and water, then heated for 30 hours in similar water, further collected by filtration and immediately dried. The polymer has a logarithmic viscosity number of 0.72, poured on a 0.5 gev /.- JÜgen solution in ayni-üichlortetra-

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BATHROOM OHiGiSNAL

j? -189S *

fluoracetonhydrat at 5O ⁰ C. The polymer has a glass-measured glass transition temperature of 235 ⁰ O and a crystalline melting point of 44 ⁰ C-O calorimetrically. It is converted by 15 ~ sekünäiges Schiaelspressen with 18120 kg pressure both at 405 ⁰ G and at 425 ⁰ C in a Piim. Under such conditions, a sample is melt-pressed into contact with poly (based on pyromellitic dianhydride and 4,4'-diamioiodiphenyl ether) and firmly bonded to it.

A solution of 1 g of the polymer in 9 ml of sym-diehlortetrafluoroacetone hydrate is prepared and a film is cast from this solution using a 508 m doctor blade. If you dry it, you will get a closer, foldable picture. Other equally cast films are used for the measurement of various properties of this polymer. The PiIm shows a module of 31,200 kg / cm, an elongation of $ 3.6 5 and a toughness of 766 kg / cm. The X-ray analysis shows that the polymer is completely amorphous. Programmed thermogravimetric analysis in air shows the occurrence of the main decomposition between 425 and 500 ⁰ C.

At ε ρ χ el

Using a procedure as described in Example 1, a 150 ml stainless steel pressure vessel is filled with 1.84 g (0.01 mol) of mbenzo-p-dioxin, 2.03 g (0.01 mol) of isophthaloyl chloride, 20 g ( 1.0 mole) hydrogen fluoride and 34 g (0.5 mole) boron trifluoride charged. While aur Be vegiing shaken *, the container is heated for 2 hours at 25 ⁰ C, then cooled and vented for degassing. The remaining viscous, purple-colored material

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is emptied into a 1: 1 Hischirag (volume ratio) of pyridine and methanol at ⁰ ° C., which is stirred with a high shear mixer. The precipitate formed is collected by filtration, then heated for 2 hours in a boiling vessel, again collected by filtration and dried ^{in vacuo at 50 0 O.} The polymer has an inherent Yiskositätssahl O ₉ 67 »measured on a 0.5 wt .- $ strength by weight solution in concentrated sulfuric acid at 30 ⁰ G. The polymer is soluble in sym-Diehlortetrafluoracetonhydrat and in concentrated sulfuric acid. It is insoluble in Ιί, Η-DimethylforiBamid, HjH-Dimethylacetamid, Dimethylsulfoxyd and Srifluoroacetic acid. Its infrared spectrum shows a large peak at 6.03 / u, a medium-sized shoulder at 6.14 / u and a very small shoulder at 5.80 / u.

In addition to the viscous, The pressure vessel contains the purple-colored reaction product After washing with water, there is still a clear, colorless IPiIm that adheres to the inside of the container. The infrared spectrum of this film shows peaks corresponding to the Peaks are identical to those in the above-described polymer sample to be observed.

example

! The reaction of Example 2 / v repeatedly ill, but all of 2 hours, heated to 5O ⁰ C for this 3 times "ventilating the reaction vessel leaves a dark green liquid The bulk of this liquid is in a 1:. 1- Mixture (volume ratio) of pyridine and

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Poured methanol with O ⁰ G, which is stirred with high shear. The remainder of the dark green liquid is poured onto a stainless steel sheet to cast a film directly from the crude reaction mixture. After rinsing the reaction vessel with a mixture of pyridine and methanol, several small pieces of pilm are also found on the inside of the reaction tube. The main part of the product precipitated in pyridine / methanol is left in this mixture for 5 layers and then heated in boiling water for 2 hours. The polymer is then collected and dried at 6O ⁰ C in vacuo. The films obtained above are dissolved in water 5 Sage allowed to soak and then heated for 2 hours in water at reflux, after which they are likewise dried at 60 ⁰ C in vacuo.

This polymer does not melt up to 360 ⁰ G. It iet soluble in concentrated sulfuric acid and has an inherent viscosity of 1.00, measured in a 0.5 weight 5aigen solution in concentrated sulfuric acid at 3O ⁰ C. The infrared spectra of both the downcast Powder and film samples are essentially identical, showing major peaks at 6.00 to 6.05 / u and 6.13 to 6.15 / u and a very small peak at 5.80 m . The polymer has a glass transition ^{temperature of about 200 °} C. and a crystalline melting point of e 'by thermal differential analysis.

a crystalline melting point of about 430 ⁰ C, - measured

Example 4

The reaction of Example 2 is repeated except that the 2.03 g of isophthaloyl chloride is replaced by 2.03 g

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Ierephthaloyl chloride can be replaced. The reaction mixture is ^{heated to 25 °} C. for 2 hours. After venting the reaction vessel, a dark, viscous liquid remains. The majority of this liquid is poured into a 1: 1 mixture of pyridine and methanol at ⁰ ° C., stirring with high shear. The remaining small portion of the viscous liquid is cast into a film using a 508 / U doctor blade on a stainless steel sheet, which is quenched in a pyridine / methanol mixture to give a clear yellow film after drying. The main part of the product precipitated in pyridine / methanol is collected by filtration, then heated for 2 hours in boiling water, again collected by filtration and dried ^{at about 50 ° C. in vacuo.} The polymer is soluble in concentrated sulfuric acid and insoluble in H, N-diethylformamide, ΙΙ, Ιί-diinethylacetamide, dimethyl sulfoxide, trifluoroacetic acid and sym-dichlorotetrafluoroacetone hydrate. The polymer has an inherent viscosity of 0.93, measured on a 0.5 "- # solution in concentrated sulfuric acid at 30 ⁰ C. The polymer does not melt up to 475 ° C

The infrared spectrum of the obtained in the manner described above Filmes shows a large sharp peak at 6.02 / U, a sharp medium shoulder at 6.15 / rev and a very small shoulder at 5.80 / rev. .

example

Using the same general procedure as described in the previous examples, a 150 ml Pressure vessel with 3.68 g (0.02 mol) of dibenzo-p-dioxin, 4.06 g

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(0.02 hol) terephthaloyl chloride, 40 g (2.0 moles) hydrogen fluoride and 68 g (1.0 mole) boron trifluoride. The container is ^{heated to 25 °} C. for 2 hours, then cooled and ventilated for degassing. Any remaining viscous purple liquid is cast directly onto a series of films using a 254 / u doctor blade on stainless steel plate. After most of the hydrogen fluoride has evaporated, the films are strong enough to be stripped from the support and they are placed in Ν, Η-dimethylacetamide (DMAC) at room temperature. This treatment changes the purple color of the films to yellow. During soaking in DMAC, small portions of the film are placed in water to determine whether the film obtained from such treatment is cloudy or clear. Although some of the first samples become cloudy, all such films transferred into water remain clear within one minute. Hence v; After 1 to 2 minutes in DMAC, all films are attached to racks, transferred to water and washed in running tap water for 1 day. During the first few seconds (about 10 seconds) in water, pulling of the films on the racks occurs in a tensioned state. Uach washing with water, the films are for 5 hours under vacuum at 122 ⁰ C and then for about 7 hours: dried in vacuum at 180 ⁰ C. At this point, the films are light yellow in color. The inherent viscosity of the polymer film is 0,8i, measured on a 0.5 wt .- # solution in concentrated sulfuric acid at 30 ⁰ C.

The procedure of the previous paragraph is repeated and in this case the logarithmic viscosity

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number of polymer files obtained 0.79 · A sample of this film is analyzed for carbon and hydrogen. The following picture emerges:

Analysis of CoqH-jqO. :

C II

76 C. 3 II calculated: 76 43 3 _f 21 found: 18th , 52

The Mim also is found still a Pluorgehalt of $ 0.11 and a boron content of 0.05 i *.

The polymer shows a glass Binfriertemperatur of about 26O ⁰ C and a crystalline melting point of etv on / a 525 ⁰ G, as determined from results of the theriaischen differential analysis. The zero jPestigkeitstGiapex-ature of the polymer is ia: found lt approximately 67o ⁰ G. The / Uiftreten of decomposition d © 3 polymer v / ith durcli tiiermograviiDetrische analysis in the range of 450 to 55O ⁰ C and by thermal Differentialanal3 '"se at about 565 ⁰ C found. The polymer has a density of 1.365 g / esr. The Rontgsnstralilenanalyse exhibits a very low degree of crystallinity, which can be increased by heating to one fourth above the glass freezing porature.

Films made from this polymer turn out to be in Air at 220 ° 0 for more than 17 weeks, still as foldable, which shows their good thermal oxidation resistance.

They have good hydrolytic stability of the Polymerisatfilisss goes au ε out the fact that this after more than 18 weeks of aging in 0.1 η sulfuric acid at 10O ⁰ C is foldable. Even =

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so the film remains folded after more than 18 weeks of aging in 0.1N iTatriuinhydroxydlösung at 100 ⁰ C.

example

The procedure of Example 5 is repeated, with the Au si * ·: ιγ.ι3 that the 4 "06 g of terephthaloyl chloride are replaced by 4.06 g Isop ι ühaloylchlorid, and the mixture is heated at 50 ⁰ 2 StuLidan C instead of 25 ⁰ C heated. As in Example 5, the entire viscous crude product is cast into mimes with a 254 μ Halcel on steel plates free of residues, 33is cast films are immersed in II, li ~ di-ethylacetamide and kept there for about 60 hours. Then they are attached to racks and immersed in running tap water for a day. If some of these films tear due to shrinkage during water treatment, other films are washed in water for a maximum of 30 seconds and then placed on racks and placed in running water for a day. The latter films do not tear allowed to air dry. They have Polymerieatfilme a logarithmic viscosity of 0.61, measured on a 0.5 wt .- ^ solution in concentrated sulfuric acid at 30 ⁰ C. Biese'Polymerisatfilme be at 300 ⁰ C with 1-iainüVfciges melt pressing 18 120 kg of Sruok transferred to other films.

Based on the above detailed description Lie gen: Ur skilled in the art, numerous changes and modifications obvious without from the scope of Erfindimg r adopted.

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Claims (4)

5 ο February 1969 claims: 1. Usually solid polymers with the repeating Structural unit wherein the phenylene radical is p-phenylene, m-phenylene or mixtures of which means " 2. A polymer as claimed Anopriieh 1 wherein Oine sufficient number existing in the polymer, the repeating units present to sine logarithiniacbe Viskoaitätszahl to provide at least 0.3 _f geneesen to eiitier 0.5 gsw.-jSigen LöBimg in konssntrierter Som / afelsäura at 30 ⁰ C. 3. Polymers according to claim 2 in the form of a self-supporting Film, a 3? Aer or a Pormkörpers. 4. Process for the production of mixed polyketone polymers, those in the main from the knowledge-recovering Structural units 909835 / U42 ßÄD ORIGINAL 3P-1896 Persisti characterized in that one is in the presence of 3? riedel grafts catalyst essentially equimolar Amounts of dibenzo-p-dioxin and (1) terephthaloyl halide or! terephthalic acid or (2) isophthaloyl halide or Isophthalic acid or (3) mixtures of (1) and (2). - 15 -909835 / UA2