DE2738962A1 - FILM-FORMING, MOLDABLE AROMATIC POLYFORMAL RESINS AND METHODS FOR THEIR MANUFACTURING - Google Patents

Description

Film-forming, moldable, aromatic polyformal resins and methods of making them.

The invention relates to film-forming poly formal resins with a intrinsic viscosity of at least 0.3 dl / g. The invention particularly relates to Reaction of methylene halide and bisphenol in a mixture containing excess methylene halide and alkali hydroxide.

So far, polyformal resins, such as for example from the U.S. Patent 3,069,386 gives by reacting a disodium diphenolate and a methylene halide in the presence of a polar one organic solvent prepared under essentially anhydrous conditions. As in this aforementioned US patent noted by Barclay, the response is great

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sensitive to small amounts of water and other impurities, Wei he contain hydroxyl groups and the undesirable Cause side reactions. As a result, have those made by the Barclay process (U.S. Patent 3,069,386) Polyformal resins have an extremely low viscosity. It was found that the poly was formally unsuitable as a thermoplastic because it was extremely brittle and very possessed poor strength properties. As a result, Barclay used the polyformal as an intermediate product for production of a polycarbonate-polyformal copolymer by a standard phosgenation process.

The present invention is now based on the finding that film-forming polyformals with an intrinsic molar viscosity up to 2.0 dl / g in chloroform at 25 ° C, which is essentially a * chemically linked units of the formula

(1) -OROCH ₂ -

consist, wherein R is a divalent ^c (^ n _O ) aromatic Resf, by reaction under essentially anhydrous conditions between methylene halide and a bisphenol of the formula

(2) HO-R-OH,

wherein R is as defined above, in the presence of an alkali hydroxide, the alkali hydroxide and the methylene halide during the intercondensation reaction in greater than stoichiometric concentrations be maintained. In contrast to the Barclay *, polyformals see the basic molar viscosity numbers of less than 0.2 dl / g and have undesirable physical properties such as brittleness, the polyformals of the present invention have Invention basic molar viscosity numbers of over 0.3 dl / g, yes even up to about 2.0 dl / g. PolyformaIe of Bisphenol-A

are derived, for example, tensile strengths of about

492 kg / cm (7000 psi) with 110 stretch and Gardner impact values by more than 320 in. lbs. exhibit. About that

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In addition, the Polyforma le of the present invention according to Standard phosgenation reagents can be converted into copolymers and they can be blended with various thermoplastic materials for improved properties to rent.

Residues that are encompassed by R in the aforementioned formulas 1 and 2 are, for example, phenylene, tolylene, xylylene, naphthalene, etc.; halogenated derivatives of such divalent aromatic hydrocarbon radicals such as chlorophenylene, bromotolylene, etc., divalent radicals such as -RQR-, in which Q is cyclohexyl, fluorene-

0 0

• I Il

nyl, -0-, -S-, -C-, -S-, -C-, and -CH ₉ - and where-

M π y «y

⁰ A

Cl Cl
at y 1 to 5 inclusive.

The present invention provides a method of manufacturing aromatic poly formal resins created, which essentially consist of chemically linked units of the formula (1) exist and which so far by reaction of an alkali metal diphenolate and a methylene halide in the presence of a polar organic solvent among substantially anhydrous conditions were produced to form a reaction mixture that is very sensitive to water and other impurities which had hydroxyl groups and undesired side reactions with the formation of polyformals intrinsic viscosity tends to be less than 0.2 dl / g. The improvement according to the present invention consists in that under essentially anhydrous conditions a reaction mixture of methylene halide, bisphenol of the formula (2), alkali hydroxide and one member selected from the class consisting of a phase change catalyst and a dipolar aprotic solvent is stirred, wherein In the Reaction mixture per mole of bisphenol more than one mole of methylene halide and more than two moles of alkali metal hydroxide are used, resulting in a reaction mixture that is less sensitive

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borrowed to water and other hydroxy containing groups and impurities and which is capable of producing film-forming, moldable aromatic polyformals which have an intrinsic molar mass Have a viscosity greater than 0.3.

Examples of the bisphenols of the formula (2) are compounds such as:

2,2-bis (4-hydroxypheny1) propa η (to phe no1-Λ); 2,4 * -dihydroxydiphenylmethane;

Bis (2-hydroxyphenyl) methane;

1,1-bis (4-hydroxyphenyl) ethane; 1,1-bis (4-hydroxyphenyl) propane; 2,2-bis (4-hydroxyphenyl) pentane; 3,3-bis (4-hydroxyj _J uenyl) pentane; 4,4 · -Dihy droxydipheny1; 1,4 * -dihydroxy-3, 3 », 5, 5'-tetraraethyldipheny1;2,4'-dihydroxybenzuphenone; 4,4 * -dihydroxydiphenyl sulfone; 2,4'-dihydroxydiphenyl sulfon; 4,4'-dihydroxydiphenyl sulfoxide ;.

4,4'-dihydroxydiphenyl suIfid;

Hydroquinone; Res or ζ i no I;

9,9-bis (4-hydroxyphenyl) fluorene; 3,4 * -dihydroxydiphenylmethane; 4,4 * -dihydroxybenzophenone; 4,4 * -dihydroxy jipheny liither; 1,1-dichloro-2,2-bis (4-hydroxypheny 1) ethylene, and 1,1,1-trichloro-2,2-bis (4-hydroxyphenyl) ethane.

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Methylene halides used in the practice of The present invention can be used, for example, methylene chloride, methylene bromide, chlorobromomethane, etc. Alkali hydroxides useful in practicing the invention Potassium hydroxide, which can be in the form of pellets, powder, etc., sodium hydroxide, for example, can be used etc.

The polyforma! Resins with units of the formula (1) are thermoplastic, Injection-molded materials that can be converted into films and fibers. Preferably they are Polyformal resins, transparent, can be molded by injection molding film-forming and fiber-forming thermoplastic materials. In other cases, the polyformal resins of the present Invention translucent or cloudy materials can be 1n depending on the degree of crystallization of the obtained Polymers.

The polyformal resins of the present invention can also be phosgenated to form polyformal-polycarbonate copolymers. The polyformals of the formula (1) and the polyformal-polycarbonate copolymers can be further mixed with other thermoplastic organic resins such as polycarbonate resins (Lexan ^^ resin), polyphenylene oxide resins (PPO ^^ resin and Valox ^^ resin), in all of which Cases are products manufactured by the General Electric Company. The mixture can be used within a wide range of weights, such as from 1 to 99 % of the polyformal resin to 99 to 1 % of the weight

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high-performance thermoplastic organic resin. The polyformal resins of the present invention can also with different types of fillers such as glass fibers, silicone carbide whiskers, Silicon dioxide fill is open etc., with stabilizers, Pigments, flame retardants, etc. can be mixed.

In the practice of the present invention can Polyforma! Resin by contacting Methylenhalogenid and bisphenol in the presence of alkali metal hydroxide in a temperature range from ⁰ C to 10O ⁰ C, preferably 40 ° C to 100 C can be produced. The reaction can be carried out between excess methylene halide and bisphenol until the latter has completely reacted.

The reaction between the methylene halide and <Jem bisphenol can be carried out under essentially anhydrous conditions. There can be reflux temperatures at atmospheric pressure or above Atmospheric pressure can be used along with stirring the mixture. The reaction between the methylene halide and the bisphenol in the presence of excess alkali hydroxide can by using a substantially inert organic solvent in combination with the methylene halide, such as for example a non-polar or dipolar aprotic organic solvent. Non-polar organic solvents that can be used together with the methylene halide are, for example, chlorobenzene, Dichlorobenzene, benzene, toluene, etc. Furthermore, dipolar aprotic solvents such as N-methylpyrrolidone, tetrahydrofuran, Dimethyl sulfoxide, etc. find application.

The experiments have shown that when methylene halide is used in the absence of a dipolar aprotic solvent Effective results will be obtained if a phase change catalyst is used in place to bring about the formation of the alkali salt of bisphenol and the subsequent condensation reaction with the methylene halide. Suitable phase transition catalysts are, for example, quaternary ammonium and phosphonium salts, as they are in the

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"^ *" (1971)

publication of CM. Strong in JACS 93, 195 / are described. A proportion of about 0.01 to 0.5 moles of the phase change catalyst per mole of the bisphenol provides effective results and preferably 0.02 to 0.10 moles of the phase change catalyst are used per mole of bisphenol.

The intercondensation reaction can be carried out within 0.1 hour to 24 hours or more depending of such factors as the nature of the methylene halide used, the presence or absence of an organic solvent in combination with the methylene halide, the Kind of such an organic solvent, the temperature of the reaction, the degree of stirring, etc. In special cases One example is the highly reactive methylene bromide instead of the methylene chloride or it can be a mixture of chlorobenzene with methylene chloride at a higher temperature be refluxed. In addition, the reaction can take place at elevated pressures or in a closed system carried out to a reaction of the methylene halide to effect with the bisphenol at a higher temperature. Otherwise, the person skilled in the art knows that, for example, when using of the methylene halide in excess amounts as a suitable organic solvent as well as a reaction component can serve.

The following examples are given to illustrate the invention without, however, affecting the invention in any way Way intended to restrict. All parts are based on weight, unless otherwise stated.

example 1

A mixture of 114 parts (0.5 moles) bisphenol-A, 95 parts (1.7 moles) KOH peIlets, 23.3 parts (0.05 moles) Aliquat 336 (95% active monomethyltricaprylylammonium chloride), a phase change catalyst manufactured by General Mills Company and 1.009 parts of methylene chloride were heated to reflux and stirred for 21 hours under a nitrogen atmosphere.

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Then water was added to the mixture and the organic phase was separated off and washed with water. It was a 70% yield of the polymer obtained in-which the organic Layer added to methanol and the resulting precipitate was filtered off and dried at 60 ° C. The polymer had a glass transition temperature T of 85 ° C and a base molar Viscosity number in chloroform at 25 ° C of 0.6O dl / g. The polymer was compression-molded at 160 ° C. to form a tough, colorless, flexible, transparent film. It could can also be poured from chloroform. Acted on the basis of the elemental analysis and the nuclear magnetic resonance spectrum the polymer is a polyformal with the formula:

CH

^CH j

where η had an average value of 65.

The polyformal had the following physical properties:

until you give in
Tensile strength (psi at yield /) 7-8000

until it breaks
Tensile Strength (psi at break /) 71OO-7000

Extensibility (%) 110

Density (g / cm ³ ) 1.10

Flexural Strength (p.s.i.) 14,300 Flexural Modulus (10 ⁵ psi 73 ° F) 4.1 Gardner Impact Strength> 320 in. Ib. Example 2

A mixture of dimethyl sulfoxide, methylene chloride, potassium hydroxide, Bisphenol-A and Aliquat were made at one temperature stirred at 60 ° C for 4 hours under essentially anhydrous conditions. The mixture had a solids content

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of 22% by weight and a ratio of about 110 parts of dimethyl sulfoxide per 90 parts of methylene chloride. Furthermore, a ratio of 2.6 moles of potassium hydroxide per mole was used in the mixture Bisphenol-A was used while Aliquat was used in a ratio of about 0.1 mole of aliquat per mole of bisphenol-A. It was a polyformal with an intrinsic viscosity in chloroform at 25 ° C of 0.548 dl / g obtain. Due to the manufacturing process, the polymer consisted essentially of chemically bonded together Bisphenol A units and formaldehyde units. By compression deformation a tough, flexible film was obtained using the method of Example 1 or the film was poured from a chloroform solution.

Example 3

A mixture of chlorobenzene, methylene chloride, potassium hydroxide pellets, Bisphenol-A, tetrabutylammonium bromide and 1.9

Water was stirred for 40 minutes at a temperature of 75 ° C. The mixture had a solids content of 19% by weight Chlorobenzene was used in a proportion of about 3 parts of chlorobenzene per part of methylene chloride about 2.2 moles of potassium hydroxide per mole of bisphenol-A were used. Furthermore, the tetrabutylammonium bromide was in the mixture in an amount of about 0.1 mole of phase change catalyst present per mole of bisphenol-A.

A yield of 36 "l polyformal was obtained from the above mixture with an intrinsic viscosity of 0.519 dl / g in chloroform at 25 ° C., which essentially consisted of chemically linked bisphenol A units and formaldehyde units. By pouring or by compressing the polymer by the method described above, a tough, flexible film was obtained.

Example 4 A mixture of N-methylpyrrolidone, methylene chloride, potassium

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- Vb -

hydroxide pellets and bisphenol-A were taken at 70 ° C under essentially stirred for 39 minutes in anhydrous conditions. The N-methylpyrrolidone and the methylene chloride were in approximately equal parts by weight used in the polymerization mixture, which is about 19% by weight. Contained solids. The mixture contained a Ratio of 2.0 moles of potassium hydroxide per mole of bisphenol-A. It a polyformal was obtained which consisted of bisphenol A units and formaldehyde units chemically linked to one another and an intrinsic viscosity of about 0.50 dl / g exhibited. According to the casting or compression molding techniques described above the polyformal became a tough, flexible one Film received.

Example 5

The procedure of Example 4 was repeated with the exception that instead of the potassium hydroxide, 2.1 moles of sodium hydroxide per Moles of bisphenol-A use). After about 1 hour there was a 66 '(yield of a polyforma Is with an intrinsic molar Viscosity number of 0.80 dl 'g obtained.

Example 6

The procedure according to Example 4 was repeated with the assumption that that in the mixture 1 part by weight of p-t-butylphenol, based on the Weight of bisphenol-A, was used and the mixture was added Heated to 70 ° C for 105 minutes. There was no aliquat phase transition catalyst used. It became a polyformal with an intrinsic molar viscosity of 0.352 dl / g in chloroform obtained at 25 ° C, which consists essentially of chemical Interconnected bisphenol A units and formaldehyde units and which had been chain terminated with p-t-butylphenol units.

The obtained polyformal was made by molding or compression molding converted into a flexible, flexible film.

The above procedure was repeated with the exception

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that 2 parts by weight of the chain terminator ^ in the intercondensation mixture were used. It was found that the round molar viscosity number of the polyformals was 0.273 dl / g was diminished. Another intercondensation reaction was attempted without chain terminators present using stoichiometric amounts of potassium hydroxide and Bisphenol-A. It was found, however, that even after the mixture was heated and stirred for two hours at 70.degree The viscosity number of the obtained polyformal was 0.227. The low intrinsic viscosity of the polyformal indicated that although the intercondensation reaction mixture was free of chain terminators and had been heated for 2 hours » more than a stoichiometric amount of potassium hydroxide was required to make polyformal with an intrinsic viscosity of at least 0.3 dl / g.

Example 7

A mixture of methylene bromide, potassium hydroxide pellets, bisphenol-A, and aliquat phase change catalyst was heated to 96 ° C for 10 minutes under essentially anhydrous conditions while stirring the mixture. The mixture contained 11% solids by weight and the potassium hydroxide was used in a ratio of 3/4 moles of potassium hydroxide per mole of bisphenol-A, while the phase transition catalyst was used in a ratio of 0.1 mole of catalyst per mole of bisphenol-A. A polyformal was obtained which essentially consisted of chemically linked bisphenol A units and formaldehyde units and which had an intrinsic viscosity in chloroform at 25 ° C. of 1.9. The polymer was transformed into a tough, flexible film by its or compression deformation.

Example 8

A mixture of methylene bromide, 1,1-dichloro-2,2-bls (4-hydroxyphenyD-ethylene, Potassium hydroxide pellets and aliquat phase conversion catalyst was heated and at 9G ° C for 75 minutes

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- la -

stirred under essentially anhydrous conditions. A polyformal was obtained which essentially consists of formaldehyde units consisted chemically with the units of the formula:

were connected and which had an intrinsic viscosity owned by 0.441. The polymer was easily converted into a tough, flexible film through its chloroform solution or through Compression deformation converted. It had a glass transition temperature

temperature T of 115 ⁰ C-.
G

The film obtained above had valuable dielectric and flame retardant properties, thereby making the polyformal as a flame retardant additive for injection molding Removable plastics proved. The film oxygen index was 37.

Example 9

A mixture of 15 parts (0.05 mol) of 2,2-bis (p-hydroxyphenyl) -}, l, l-trichloro * than, 11 parts (0.195 mol) of KOH pellets, 56 parts of methylene bromide and 66 parts of N-Vethylpyrrolidon was on Stirred under reflux at 70 ° C. After 13 minutes one showed up vigorous reaction which was obviously exothermic and a resulted in increased viscosity of the reaction mixture. After 51 minutes the reaction mixture was poured into methanol and the polymer was isolated in the usual way. It turned out to be a 75Tige Yield of polyformal obtained, which essentially consists of Formaldehyde units 1 »? Stood chemically with the units the formula:

Cl '

'N / A

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-VX-

were pre-bonded and which had an intrinsic viscosity of 0.745 dl / g.

Example 10

A mixture of methylene chloride, N-methylpyrrolidone, potassium hydroxide pellets and 9,9-bis (4-hydroxyphenyl) fluorene or "BPF" was stirred for 66 minutes at 70 ° C under essentially anhydrous conditions. It became a polyformal with a intrinsic molar viscosity of 0.638 dl / g obtained, which essentially consists of chemically linked formaldehyde units and units of the formula:

duration. The polyformal was obtained in 63% yield and formed a tough, flexible film. It had a T value of 221 ° C.

Example 11

A mixture of 2.3 parts (0.01 moles of bisphenol-A, 1.7 parts (0.026 moles) of 85 tiger powdered potassium hydroxide, 0.47 Parts (0.001 moles) of Miquat 33Π and about 53 parts of methylene chloride was stirred at room temperature under essentially anhydrous conditions for 1P hours. The reaction mixture was then washed with water until neutral. Methanoi was then added to the mixture resulting in precipitation of the Product. There was a 49 day yield of polyformal obtained, which had an intrinsic viscosity of 0.31 dl / g and was essentially composed of chemically interconnected Bisphenol - \ - units and formaldehyde units consisted.

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- 1 «* Example 12

A mixture of 3600 parts of methylene chloride, 119 parts (0.238 moles) of Aliquat 336, 542 parts (2.37 moles) of bisphenol-A and 400 parts (6.2 moles) of potassium hydroxide pellets were stirred in a closed system at 60 ° C for about 115 minutes. Ks a poly forma I was obtained, which essentially consists of chemically linked bisphenol A units and formaldehyde units and which had an intrinsic viscosity of 0.551 dl / g.

Example 13

A mixture of methylene chloride, N-methylpyrrolidone, potassium hydroxide pellets and 2,2-bis (4-hydroxyphenyl) butane was stirred for 30 minutes at 70 ° C. under essentially anhydrous conditions. The mixture had a solids content of about 15% by weight and for the animal husbandry a ratio of about 52 parts of methylene chloride per 60 parts of N-methylpyrrolidone and a ratio of 2.6 moles of potassium hydroxide per mole of the 2,2-bis (4- hydroxyphenyl) butane has been used. A polyformal was obtained which essentially consists of chemically linked formaldehyde units and units of the formula:

CH

CH ₉
CH ₃

and which had an intrinsic viscosity of 1.48 dl / g and a T value of 86 ° C.

Example 14

A mixture of methylene chloride, N-methylpyrrolidone, bisphenol-A, o-Hydroxyäthylresorzinol and potassium hydroxide was stirred for 90 minutes under substantially anhydrous conditions at a temperature of 70 ⁰ C. The mixture had a solids content of 19 parts by weight and a ratio of about 78 parts of methylene chloride per 91 parts of the N-methylpyrrolidone and a ratio of about 2.6 mol was used for its preparation

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Potassium hydroxide per mole of bisphenol-\ and a ratio of about 35 moles of bisphenol-A per hol O-HydroxySthylresorzinol used. A polyformal was obtained which essentially consists of chemically linked bisphenol units and Formaldehyde units and the chain ended with units of the formula:

HIGH ₂ CH ₂

and the polyformal had an intrinsic viscosity of 0.471 dL / g.

Example 15

A mixture of methylene chloride, N-methylpyrrolidone, potassium hydroxide pellets and 3,3-bis (p-hydroxyphenyl) pentane was added under essentially anhydrous conditions for 42 minutes stirred at a temperature of 70 ° C. The mixture had a solids content of about 18% by weight and was used for production a ratio of about 52 parts of methylene chloride per 60 parts of N-methylpyrrolldone and a ratio of about 2.6 moles Potassium hydroxide is used per mole of the 3,3-bis (p-hydroxyphenyl) pentane. It became a polyformal with an intrinsic viscosity of 0.831 dl / g and a T value of 91 ° C and the polyformal consisted essentially of chemically bonded Formaldehyde units and units of the formula:

Example 16

A mixture of methylene chloride, chlorobenzene, potassium hydroxide pellets, Bisphenoi-Λ and Aüquat, the phase transition catalyst

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tor vegetables example was l.der been by General Mills Company, Cheaical Division hergestelii, 7.4 hours was heated under a nitrogen atmosphere to a temperature of 6O ⁰ C for. The solids content of the mixture was about 20% by weight and a molar ratio of 2.6 moles of potassium hydroxide per mole of bisphenol-A was used. A proportion of about 1110 parts of chlorobenzene to 901 parts of methylene chloride was also used in the mixture. In addition, Aliquat catalyst was used in the mixture in an amount of 0.1 mole of Aliquat per mole of bisphenol-A.

Using the procedure according to Example 1, a 58 "'yield was obtained of polyformal with an intrinsic viscosity of 0.735 dl / g obtained in chloroform at 25 ° C. By pouring the polymer from a chloroform solution or by compression molding a clear film was obtained at 160 ° C. The film was partial and flexible and had a Gardner Impact Rating greater than that than 320 in. Ib. on.

Example 17

The procedure of Example 16 was repeated with the exception that 4 moles of sodium hydroxide were used in place of the potassium hydroxide became. In addition, a proportion of about 68 parts of chlorobenzene to 20 parts of methylene chloride was used. The intercondensation reaction was carried out at a temperature of 75 C and it was completed within 4 hours. It was obtained a 75% yield of polyformal, which is essentially consisted of chemically linked formaldehyde units and bisphenol-A units, as in Example 1 is explained and softes an intrinsic viscosity of 0.422 dL / g. By pouring the polymer from chloroform or by compression molding according to the method of Example 1 a tough, flexible film was obtained.

Example 18

The procedure of Example 7 was followed using methylene bromide repeated except that instead of bis-

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- YT - phenol- \ a compound of the formula:

was used. It became a polyformal with a _Tr value of

175 C obtained, which consists essentially of chemically linked Units of the formula:

-ο- / ο V- s - / ο V-OCH ₂ -H ₃ d ^δ ^ a ₃

duration.

Example 19

A mixture of 30 parts (0.1 mol) of 3,4-bis (p-hydroxyphenyD-3,4-hexanediol, 14.5 parts (0.26 mol) of KOH pellets, 81 parts of methylene chloride and 93 parts of N-methylpyrrolidone were stirred and heated to reflux to 70 ° C. After 81 minutes, parts (0.2 moles) of additional KOH pellets were added. After 92 minutes the very thick reaction mixture was poured into methanol to recover the polymer. It became a film-forming polyformal obtained, which consisted of formaldehyde units, the chemise, with the units of the formula:

CH-

I J

CH ₂ C-OH

HOC- (O> -0-CH,

were connected.

The polymer had an intrinsic viscosity of 0.564

rt from G7 ° C.

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dl / g and a T value of G7 ° C.

Although for the production of the aforementioned polyforraals N-methylpyrrolidone had been used, so the present looks Invention but the use of a large variety of dipolar aprotic solvents used in the poly forma I reaction mixture at 25 ° C to 100 ° C can be used in amounts of 5 to 95 parts by weight, based on the total weight the mix.

Although the preceding examples are not directed to just a few of the very rich variables involved in the practical implementation of the present invention can be used, it should be expressly noted that the present Invention relates to a much broader class of polyformals encompassed by formula (1) and also the processes for the preparation of these materials than those listed in the description and the preceding examples are.

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Claims (1)

T. ΓβΓ. nat. Horst Schuler ^ ⁰⁰⁰ FwnMurVMain 1.29 August 1977 f ATf MTAHWAlT Kab.rs * o »· 41 Dr. Sch / Hk Telephone (0611) 235555 Telex: 04-16759 mapat d Postal check account »282420-602 Frankfuii / M. Bank account ι 225/0389 Deutsche Bank AG, Frankfurt / M. 4379-RD-8971 GENERAL ELECTRIC COMPANY 1, River Road
Schenectady, NY, USA Claims 1. Aromatic poly formal, characterized in that it consists essentially of chemical connected units of the formula -OROCII ₂ - exist and have an intrinsic viscosity in chloroiorm at 25 ° C of at least 0.3 dl / g and which can be shaped by pressure or cast into films, where R is a divalent C / _ß 3q) ~ aromatic radical. 2. PolyformaI according to \ nspruch 1, marked thereby inet that R is the formula CH
CH ₃ having. 3. Polyformal according to claim 1, characterized that R is the formula 809819/0570 ORIGINAL INSPECTED Il Clf ^S C1 having. 4. Poly forma I nacii claim 1, characterized that R is the formula having. Process for the preparation of aromatic polyformal resins by reaction between a mkalidiphenolate and a Methylene halide under essentially anhydrous conditions and in the presence of an organic solvent, which leads to a reaction mixture that is highly sensitive to water and other impurities containing hydroxyl groups and tends to enter into undesired secondary reactions with production a poly formal resin with an intrinsic molar viscosity of less than 0.2 dl / g, characterized that a reaction mixture of methylene halide, bisphenol, alkali hydroxide and a member selected from the class consisting of a phase change catalyst and a dipolar aprotic solvent, is stirred under essentially anhydrous conditions, with more than one mole of methylene halide per mole of bisphenol in the reaction mixture and more than two moles of alkali hydroxide are used and a reaction mixture is obtained which is less sensitive to water and other impurities containing hydroxyl groups and is a film- 809819/057 0 ™ »5" forming polyformal resin with an intrinsic molar viscosity fits number supplies. tSte count of more than 0.3 dl / g in chloroform at 25 ° C 6. The method according to claim 5, characterized in that the methylene halide is methylene chloride is. 7. The method according to claim 5, characterized in that the methylene halide is methylene bromide is. 8. The method according to claim 5, characterized in that the bisphenol is bisphenol-A. 9. The method according to claim 5, characterized in that the bisphenol has a compound the formula H0- / OV-C- <O) -0H Il Cl '% 1 is. 10. A method for producing a polyformal resin with an intrinsic viscosity in chloroform hot 25 ° C of more than 0.3 dl / g, which results in a flexible FlIn is compressible and essentially made of chemically connected units of the formula -OROCH ₂ - consists, characterized in that a mixture that serves as essential ingredients Methylene halide, bisphenol, alkali hydroxide and a Member selected from the class consisting of one Phase conversion catalyst and a dipolar aprotic Solvent1, consists, under essentially water- 809819/0570 free conditions is vigorously moved, being in the Reaction mixture per mole of bisphenol more than 1 mole of methylene halide and more than 2 moles of alkali metal hydroxide can be used, resulting in a reaction mixture that is less sensitive to water and others Hydroxy group-containing impurities and a film-forming poly formal resin results, which a intrinsic viscosity in chloroform at 25 ° C of more than 0.3 dl / g. 11. The method according to claim 10, characterized in that a phase change catalyst is used in the reaction mixture. 12. The method according to claim 10, characterized that in the reaction mixture an essentially inert, non-polar organic Solvent is used. 13. The method according to claim 12, characterized in that chlorobenzene in the reaction mixture is used. 14. The method according to claim 12, characterized in that N-methylpyrrolidone in the reaction mixture is used. 15. The method according to claim 10, characterized that dimethyl sulfoxide is used in the reaction mixture. 16. The method according to claim 10, characterized in g e that a temperature in the range of 40 ° C to 100 ° C is used. 809819/0570 17. Process for the production of polyformal resin from im essential chemically damaged units of the formula: CH -0- <O> -C- <O> -OCH ₂ - CH, characterized in that a mixture with Hen essential ingredients: methylene chloride, bisphenol-A, potassium hydroxide and a member selected from the class consisting of N-Methy! pyrrolidon and MonomethyltricapryIylammoniumchlorid, at a temperature in the range of 0 ⁰ C to 100 ° C below is subjected to vigorous agitation in substantially anhydrous conditions, more than 1 mole of methylene chloride and more than 2 moles of potassium hydroxide being used per mole of bisphenol-Λ. 18. The method according to claim 17, characterized that monomethyltricaprylylanunonium chloride is present in the reaction mixture. 19. The method according to claim 17, characterized that N-methyl! pyrrolidone in the reaction mixture is used. 20. The method according to \ nspruch 17, characterized that chlorobenzene is used in the reaction mixture. 809819/0570