DE2819582A1 - PROCESS FOR THE PRODUCTION OF POLYFORMALS AND POLYFORMAL PRODUCTS PRODUCED THEREOF - Google Patents

Description

Process for the production of polyformals and polyformal products made therefrom.

The invention relates to film-forming aromatic polyformal resins, Cyclopolyformals and Methods for Making Such Materials.

In our own older patent application P 27 38 962.4 are film-forming aromatic polyformals are described, which essentially consist of chemically linked units of the formula

(D

-OROCH ₂ -

wherein R is a divalent aromatic organic radical, the is defined in more detail below, and which are manufactured

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can by directly mixing together a mixture of methylene halide, Bisphenol, alkali metal hydroxide with either a phase change catalyst or a dipolar aprotic Solvent. Another process used for the production of low molecular weight aromatic polyformal resins is described in U.S. Patent 3,069,386 to Barclay. Barclay's process requires manufacturing of a diphenolate precursor before the condensation with methylene halide takes place.

It has now been found that, although the method according to aforementioned patent application can be used to prepare film-forming aromatic polyformals obtained Compositions up to about 50% by weight cyclopolyformals of formula 1

-JI OROCH ₂ _j_

(2)

I ^ώ I

may contain, in which R has the same meaning as in formula 1 and η is an integer equal to 2 to 25 can be inclusive.

Residues which are encompassed by R of the formulas 1 and 2 are C ^ -_ ₂₅ \ - divalent aromatic residues, for example phenylene, tolylene, xylylene, naphthalene, etc .; halogenated derivatives of such divalent aromatic hydrocarbon radicals as chlorophenylene, bromotolylene etc., divalent radicals such as -R QR, in which R is selected from C / - _ß -o \ -divalent aromatic radicals, Q can

O O

ti ti

Cyclohexyl-, fluorenyl-, -0-, -S-, -C-, -S-, and -CH ₀ -

ti y ^ y ο

and y can be 1 to 5 inclusive.

The film-forming aromatic polyformals of the present invention Invention consist essentially of chemically interrelated

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linked units of the formula (1) with an intrinsic viscosity of more than 0.3 in chloroform at 25 ° C, the are capable of being formed into a flexible film by compression molding and which can be manufactured according to a process which comprises the following process steps:

(A) Stir together a mixture that will be used as the essential ingredients a bisphenol of the formula

(3) H0-R ² -0H,

Methylene halide, alkali metal hydroxide and a member from a phase change catalyst or a dipolar aprotic solvent, wherein in the Reaction mixture per mole of bisphenol contains more than 1 mole of methylene halide and more than 2 moles of alkali metal hydroxide

2
where R comprises the R radicals defined above, such as RQ ¹ R radicals, in which Q ^{1 is} selected from Q radicals, fluorenyl, -C-, and -CH and

ti t

C C-CIo

Cl Cl

(B) Obtaining the aromatic polyformal from the mixture from step (A).

In special cases where the dipolar aprotic solvent is used in the aromatic polyformal mixture, linear aromatic polyformals can be prepared that have less than 10 wt .-% cyclopolyformal of the formula (2). Some lower cyclic aromatic polyformals have been found to have improved clarity and notched Izod values. The aromatic polyformals of the present invention which can be molded into flexible films and which comprise a Have intrinsic viscosity of more than 0.3 dl / g in chloroform at 25 ° C and essentially from chemically with each other linked units of the formula (1) consist and less than 10 wt .-% of such chemically linked

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Having units in the cyclic state can preferably be produced by the method which follows Steps includes:

(C) causing the reaction between a bisphenol of formula (3) and an alkali metal hydroxide in the presence of a mixture of methylene halide and a dipolar organic solvent and

(D) Recovery of the aromatic polyformal from the reaction mixture after stage (C),

wherein in the reaction mixture after step (C) 2 to 2.5 moles of alkali metal hydroxide per mole of bisphenol, a concentration of 20 to 50 weight percent solids and a weight ratio of 0.8 to 1.2 parts of the dipolar aprotic solvent per part of methylene halide be used.

Some of the aromatic polyformals of the present invention, such as those derived from bisphenol-A, can have tensile strengths ν & α \ * £ 92 kg / cm (7000 psi) at 110% elongation and Gardner impact values greater than 320 in / lbs . It has also been found that the polyformals of the present invention have a low degree of moisture permeability. If they are converted to copolymers by standard phosgenation processes or if they are mixed with different thermoplastic materials, it is found that they improve the same.

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best properties.

Of the bisphenols of formula (3) used in practicing the present invention to make the Aromatic polyformals can be used, for example:

2,2-bis (4-hydroxyphenyl) propane (bisphenol-A), 2,4 * -dihydroxydiphenylmethane, Bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis- (4-hydroxyphenyl) propane, 2,2-bis- (4-hydroxyphenyl) pentane, 3,3-bis- (4-hydroxyphenyl) pentane, 4,4 * -dihydroxydipheny1, 4,4'-dihydroxy-3,3,5,5'-tetramethyldipheny1, 2,4'-dihydroxybenzophenone, 4,4 * -dihydroxydiphenyl sulfone, 2,4 * -dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfide, Hydroquinone,

Resorcinol,

9.9 * -bis (4-hydroxyphenyl) fluorene, 3,4 * -dihydroxydiphenylmethane, 4,4 * -dihydroxybenzophenone, 4,4'-dihydroxydiphenyl ether, 2,2 '- (4-hydroxyphenyl) -l, l-dichloroethylene, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3, 5-dimethylphenydpropane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3-methylphenyl-cyclohexane, bis (4-hydroxy-3,5-dimethylphenyl) sulfone, 5-chloro-2,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-2,5 * -dimethyldipheny1-ether, etc.

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Examples of methylene halides that can be used in practicing the present invention are Methylene chloride, methylene bromide, chlorobromomethane, etc. alkali metal hydroxides used in practice Potassium hydroxide, which is in the form of pellets, powder, etc. can be used, for example can, sodium hydroxide, etc.

The aromatic polyformals of the present invention can also be used to form polyformal-polycarbonate copolymers be phosgenated. The polyformals of the formula (1) and the polyformal-polycarbonate copolymers can be further used with others thermoplastic organic resins such as polycarbonate resins

(Lexan ^ i ^ resins), polyphenylene oxide resins (PPO ^ - 'resins) and, ", (r) poly-1, ^ butanedipltherephthalic acid esters. (Valox ^ i> resins), in all cases products manufactured by the General Electric Company. The blends can comprise a wide range of blends, for example 1 to 99 % of the polyformal resin can be blended with 99 to 1 % of the high performance thermoplastic organic resin. The polyformal resins of the present invention can also be blended with various fillers such as glass fibers, silicon carbide whiskers, silica fillers, etc., stabilizers, pigments, flame retardants, etc.

In the practice of the present invention, the aromatic polyformal may be prepared by reacting at a temperature of from ⁰ ° C to 100 ° C and preferably from 40 ° C to 100 ⁰ C causes intimate contact between Methylenhalogenid and bisphenol in the presence of alkali metal hydroxides . The reaction can be carried out between excess methylene halide and bisphenol until the latter has been completely converted.

Reflux temperatures at or above atmospheric pressure can be used in conjunction with vigorous stirring of the mixture. The reaction between the methylene halide and

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the bisphenol in the presence of excess alkali metal hydroxide can by using an essentially inert organic solvent in combination with methylene halide, such as a non-polar or dipolar aprotic organic solvent. Non-polar organic solvents, which can be used in the methylene halide are, for example, chlorobenzene, dichlorobenzene, benzene, Toluene, etc. Furthermore, dipolar aprotic solvents such as N-methylpyrrolidone, tetrahydrofuran, dimethyl sulfoxide, etc. Find use.

Experiments have shown that when in the absence of a dipolar aprotic solvent, methylene halide is used, effective results are obtained when a phase change catalyst is used to prevent the formation of the Alkali salt of bisphenol in place and the subsequent condensation reaction with the methylene chloride facilitate. Suitable phase transition catalysts are, for example, quaternary ammonium and phosphonium salts such as these by CM. Starks in JACS 93, 195 (1971). A proportion of about 0.01 to 0.5 moles of the phase change catalyst per mole of bisphenol provides effective results, and preferably from 0.02 to 0.10 moles of phase change catalyst can be used per mole of bisphenol.

The intercondensation reaction can be carried out in a period of 0.1 to 24 hours or longer depending from such factors as the nature of the methylene halide, the presence or absence of an organic solvent used in combination with the methylene chloride , the kind of such an organic solvent, the reaction temperature, the amount of stirring, etc. In particular In cases, for example, the more reactive methylene bromide can be used instead of methylene chloride, or a mixture can be used from chlorobenzene can be used together with methylene chloride, which boils at reflux at a higher temperature. Farther the reaction can occur at elevated pressures or in a closed

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A system can be carried out so that the methylene halide reacts with the bisphenol at a higher temperature.

The person skilled in the art readily recognizes that, for example, the methylene halide even if it is in excess quantities is used, can serve as a suitable organic solvent as well as a reaction component.

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 pellets, 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 refluxed heated and stirred under a nitrogen atmosphere for 21 hours. 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 an intrinsic viscosity in chloroform at 25 ° C. of 0.60 dl / g. The precipitate was then monitored on a gel permeation chromatograph analyzed. It was found to contain aromatic cyclopolyformal. More specifically, it was found that the precipitate consisted of about 8.7% by weight cyclic polyformal and the remainder of the product a linear polyformal which consists essentially of chemically linked units of the formula

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-Λ

C - / oV-

CH

OCHj

where η had an average value of 65.

The polymer was at 160 ° C with the formation of a tough,
colorless, flexible transparent film deformed by compression. A
Part of the precipitated polymer was further analyzed with a high pressure liquid chromatograph. A cyclic dimer with a melting point of 279 ° C was found, which had the following formula:

—0- / 0V cYoV 0CH2—

CH- J_

To a concentrated methylene chloride solution of the above polyformal dimer, a diethyl ether-BFg complex was added to give a 1% by weight complex solution. The mixture was stirred with a metal spatula. On the metal spatula was
found a solvent-resistant coating after its removal from the mixture and air drying. It had
a crosslinking of the dimer has taken place, which is also due to the
nuclear magnetic resonance spectrum NMR was confirmed.

A cyclic trimer was also found using high pressure liquid chromatography, which is one of the following
Formula corresponded to

CH

yy

^J 3

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The trimer had a melting point of 200 ° C to 250 ° C. The cyclic trimer and higher cyclic compounds in which η is up to 20 in formula (2) have also been found to be useful for the preparation of coating compositions for metals when the same with a Lewis acid catalyst such as FeCl ₃ , H ₂ SO ₄ , etc. . were used.

Typical physical properties of the aforementioned linear polyformal produced by the above method are the following:

Tensile strength until it yields

(psi at yield) 7000-8000 492-562 kg / cm ²

Tensile strength to break

(psi at break) 7100-7500 499-527 kg / cm ²

Extensibility (%) 110

Density (g / cm ³ ) 1.10

Flexural Strength (psi) 14,300 1005 kg / cm ²

Blegemodul (10 ⁵ psk 73 ° F) 4.0

Gardner Impact Strength 320 in. Ib.

Example 2

A mixture of dimethyl sulfoxide, methylene chloride, potassium hydroxide, bisphenol-A and Aliquat was stirred for 4 hours at a temperature of 6O ⁰ C under substantially anhydrous conditions. The mixture had a solids content 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 of bisphenol-A was used in the mixture, while aliquat was present in a ratio of about 0.1 mole of aliquat per mole of bisphenol-A. A polyformal with an intrinsic viscosity in chloroform at 25 ° C. of 0.548 dl / g was obtained. On-

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because of the manufacturing process, the polymer essentially passed from chemically linked bisphenol A units and formaldehyde units. By high pressure liquid chromatography and gel permeation chromatography showed that the polymer had about 5.1% cyclic groups under the Formula (2). A tough, flexible film was obtained by compression molding using the procedure of Example 1 found or the film being cast from a chloroform solution.

Example 3

A mixture of chlorobenzene, methylene chloride, potassium hydroxide pellets, Bisphenol-A, tetrabutylammonium bromide and 1.9% by weight Water was stirred for about 50 minutes at a temperature of 75 ° C. The mixture had a solids content of 19% by weight, wherein the chlorobenzene was used in a proportion of about 9 parts of chlorobenzene per part of methylene chloride, while about 2.6 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 per phase change catalyst Moles of bisphenol-A present.

A yield of 36 % polyformal was achieved from the aforementioned mixture with an intrinsic viscosity of 0.519 dl / g in chloroform at 25 ° C., which essentially consisted of chemically interconnected bisphenol A units and formaldehyde units. High pressure liquid chromatography and gel permeation chromatography showed that the polymer contained 27.6% by weight of cyclic groups within the framework of the formula (2).

Example 4 _v

A mixture of 140.5 parts of N-methylpyrrolidone, 120.6 parts Methylene chloride, 21.8 parts of potassium hydroxide pellets, and 34.25 parts of bisphenol-A were added for 39 minutes at 70 ° C below substantially stirred anhydrous conditions. The polymerization

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mixture had about 17.7 percent solids based on the weight of the mixture and a ratio of about 2.6 moles of potassium hydroxide per mole of bisphenol-A. A polyformal was obtained which consists of chemically linked bisphenol A units and Formaldehyde units with an intrinsic viscosity of about 0.50 dl / g. By high pressure liquid chromatography and gel permeation chromatography showed that the polymer contained 26.4 weight percent cyclic units. By casting as described above or by compression molding a tough, flexible film was obtained from the polyformal.

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 were used. About 1.16 parts of N-methylpyrrolidone per part of methylene chloride were also used, wherein the amount of solvent used was such that a mixture with about 24.3 wt .-% solids based on the weight of the mixture was obtained. After about 1 hour, there was a 66% yield of a polyformal with an intrinsic molar Viscosity number of 0.80 dl / g obtained. High pressure liquid chromatography revealed that the polyformal had about 5.2 weight percent cyclic units.

Example 6

The process according to Example 4 was repeated with the exception that 1% by weight of p-t-butylphenol, based on the Weight of bisphenol-A was used. Furthermore, a sufficient amount of bisphenol-A and potassium hydroxide are used to make about 18% solids by weight in the mixture the mix, to get. It did not become an allquat phase transition catalyst used. It became a polyformal with an intrinsic viscosity of 0.352 in chloroform at 25 ° C obtained, which consisted essentially of chemically linked bisphenol A units and formaldehyde units

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and which with p-tert-butylphenol units for chain termination had been brought. The polyformal obtained had about 27.2% by weight of cyclic units of the formula (2) and was poured or converted into a tough, flexible film by compression molding.

The above procedure was repeated except that 2% by weight of the chain terminator was in the intercondensation mixture were used. It was found that the intrinsic viscosity of the polyformal was reduced to 0.273 dl / g was. Another intercondensation reaction was attempted without chain terminators present, with stoichiometric Amounts of potassium hydroxide and bisphenol-A were used. However, it was found that even after the mixture was heated and stirring at 70 ° C. for two hours, the intrinsic viscosity of the polyformal obtained was 0.227. The low basal molar Viscosity number of the polyformal indicated that more than a stoichiometric amount of the potassium hydroxide was required to polyformal with an intrinsic viscosity of at least 0.3 dl / g to produce.

Example 7

A mixture of methylene bromide, potassium hydroxide pellets, bisphenol-A, and aliquat phase change catalyst was 10 Heated at 96 ° C for minutes under essentially anhydrous conditions while stirring the mixture. The mixture contained 11 weight percent solids and the potassium hydroxide was in a ratio of 4 moles of potassium hydroxide per mole of bisphenol-A used, while the phase change catalyst applied in a ratio of 0.1 mole of catalyst per mole of bisphenol-A became. A polyformal was obtained which essentially consists of bisphenol-A units chemically linked to one another 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 casting or compression molding.

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Example 8

A mixture of methylene chloride, N-methylpyrrolidone, potassium hydroxide pellets and 9,9-bis (4-hydroxyphenyl) fluorene, "BPF", became essentially anhydrous for 66 minutes at 70 ° C Conditions stirred. A polyformal was obtained with an intrinsic viscosity of 0.638, which essentially of chemically linked formaldehyde units and units of the formula

duration. The polyformal was obtained in a yield of 63% and formed a flexible, tough one upon casting or compression molding Movie. It had a glass transition temperature T of 221 ° C.

Example 9

A mixture of 2.3 parts (0.01 moles) of bisphenol-A, 1.7 parts (0.026 mole) of 85% powdered potassium hydroxide, 0.47 part (0.001 mole) of Aliquat 336, and about 53 parts of methylene chloride was stirred at room temperature under essentially anhydrous conditions for 18 hours. The reaction mixture was then washed with water until neutral. Methanol was then added to the mixture, causing a precipitate of the product. It became a 49% yield of polyformal obtained, which had an intrinsic viscosity of 0.31 dl / g. The polyformal possessed due to the G.P.C. determination 42.9% by weight of cyclic groups with C-2 to C-17.

Example 10

A mixture of 3600 parts of methylene chloride, 119 parts (0.238 mol) of Aliquat 366, 542 parts (2.37 mol) of Bisph ^ nol-A and 400 parts

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len (6.2 mol) of potassium hydroxide pellets was stirred in a closed system at 6O ⁰ C. The mixture was stirred for about 115 minutes to form a polyformal having chemically linked bisphenol A units and formaldehyde units, which had 6.7% by weight of cyclic units of the formula (2).

Example 11

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

O> -c- < O

CH,

I '

CH-

existed and which had an intrinsic viscosity of 1.48 and a glass transition temperature of 86 ⁰ C.

Example 12

A mixture of methylene chloride, N-methylpyrrolidone, bisphenol-A, o-Hydroxyäthylresorzinol and potassium hydroxide pellets were used at a temperature of 70 ° C for 90 minutes under substantially anhydrous conditions. The mixture was a solid content of 19 wt .-% and there was a ratio of about 78 parts of methylene chloride per 91 parts of the N-methylpyrrolidone

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and a ratio of about 2.6 moles of potassium hydroxide per mole of bisphenol-A per mole of o-hydroxyethylresorzinol was used. It was used obtained a polyformal, which essentially consists of chemically linked bisphenol A units and formaldehyde units existed and the chain termination was made with units of the formula

achieved. The polyformal had an intrinsic viscosity of 0.471 dl / g.

Example 13

A mixture was obtained under essentially anhydrous conditions from methylene chloride, N-methylpyrrolidone, potassium hydroxide pellets and 3,3-bis (p-hydroxyphenyl) pentane at a temperature of 70 ° C for about 42 minutes. The mix had a solids content of about 18 wt% and a ratio of about 52 parts of methylene chloride per 60 parts of N-methylpyrrolidone and a ratio of about 2.6 moles of potassium hydroxide per mole of the 3,3-bis (p-hydroxyphenyl) pentane. It became a polyformal obtained which had an intrinsic viscosity of 0.831 dl / g, a glass transition temperature T of 91 C. and which consists essentially of chemically linked formaldehyde units and units of the formula

-0- <o) -c

CH,

CH,

c- <O> -o-

CH, CH.

duration.

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Example 14

A mixture of methylene chloride, chlorobenzene, potassium hydroxide pellets, Bisphenol-A and Aliquat, the phase change catalyst Example 1, manufactured by General Mills Company, Chemical Division, was heated and kept at a temperature of Stirred at 60 ° C under a nitrogen atmosphere for 7.4 hours. The solids content of the mixture was about 20% by weight and it was a molar ratio of 2.6 moles of potassium hydroxide per mole Bisphenol-A used. There was also a ratio of about 1140 parts of chlorobenzene to 901 parts of methylene chloride in the mixture used. Furthermore, the ingredient "Aliquat" was in the mixture in a ratio of 0.1 mol Aliquat per Moles of bisphenol-A used.

Following the procedure described in Example 1, a 58% yield of a polyformal with an intrinsic viscosity obtained in chloroform at 25 ° C of 0.735 dl / g, which 11 wt .-% cyclic polyformal units in the context of Formula (2) included. By pouring the polymer from a chloroform solution or by compression molding at 150 ° C., the Polymers obtained a clear film. The film was tough and flexible and had a Gardner Impact Value of more than 320 in. Ib. on.

Example 15

The procedure of Example 14 was repeated with the exception that 4 moles of sodium hydroxide were used instead of the potassium hydroxide were used. In addition, a ratio of about 68 parts of chlorobenzene per 20 parts of methylene chloride was used. The intercondensation reaction was carried out at a temperature of 75 ° C and completed within 4 hours. It a 75% yield of a polyformal was obtained, which essentially consists of chemically linked formaldehyde units and bisphenol A units existed, as already shown in Example 1 and which had an intrinsic viscosity of 0.422 dl / g. By pouring the polymer

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a tough, flexible film was obtained from chloroform or by compression molding according to the procedure described in Example 1.

Example 16

The procedure of Example 7 was carried out using

thylenbroraid repeats with the exception that instead of the Bisphenol-A the compound

CH- CH,

3 3

HO- / 0V S - / θ V-OH / N

CH /

was used. It became a polyformal with a glass transition temperature T of 175 ° C obtained, which essentially «from chemically linked units of the formula

OCH ₂ -

duration.

The polyformal was found to be highly insoluble in non-polar organic solvents.

Example 17

A mixture of 30 parts (0.1 mol) of 3,4-bis (p-hydroxyphenyl) -3,4-hexanediol, 14.6 parts (0.26 mol) of KOH pellets, 81 parts of methylene chloride and 93 parts of N-methylpyrrolidone were stirred and heated to reflux (70 ° C). After 81 minutes, an additional 11 parts (0.2 mol) of KOH pellets were added. After 92 minutes it was the very viscous reaction mixture was poured into methanol to recover the polymer. It became a film-forming polyformal obtained, which consisted of formaldehyde units, the

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chemically with the structural units:

C-OH

I.
high

CHj / oV-O-

^L 3

were connected. The polymer had an intrinsic viscosity of 0.564 dl / g and a glass transition temperature T of 67 ° C.

Although the N-methylpyrrolidone was used to make the aforementioned Polyformal can be produced according to the present invention, the most diverse dipolar aprotic Solvent in the polyformal reaction mixture 25 ° C to 100 ° C can be used in amounts of 5 to 95 wt .-%, based on the total weight of the mixture.

Example 18

There were initially 9.65 parts of 98.8% strength by weight sodium hydroxide pellets added to a stirred mixture consisting of 53.5 parts of methylene chloride, 20 parts of 4,4'-thiodiphenol and 16.5 parts N-methylpyrrolidone existed. The resulting mixture was stirred and refluxed. Then there were three more Portions of the sodium hydroxide were added at the rate of 9.65 parts per 20 minutes. The intrinsic viscosity of the mixture built up in about 71 minutes and the reaction continued for an additional 40 minutes. The mixture was then allowed to cool and about 150 parts of methanol were added.

An 81% yield of the product was obtained, which with Water and methanol was washed. Due to the manufacturing process, the reaction product is a poly

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formal, which essentially consists of chemically linked Units of the formula

OCHo-

duration. The polyformal was found to be insoluble in chloroform, but could be dissolved in hot tetrachloroethane. It had an intrinsic viscosity of 0.71 dl / g. It was easily converted to a clear film by compression molding and had a glass transition temperature T of 50 ° C

and a T value of 154 ° C. Part of the film made up a ra

crystalline product after standing for 12 hours at room temperature in chloroform solution.

Example 19

There were 13.17 parts of 88.5 wt% potassium hydroxide pellets to a stirred mixture of 20 parts of 4,4'-SuIfOHyIdI-phenol, 100 parts of methylene bromide and 61.5 parts of N-methylpyrrolidone given. Three more portions of potassium hydroxide pellets at 13.17 parts per portion were then added to the stirred mixture added at 20 minute intervals while mixing was heated to reflux. After the mixture was refluxed for 3 hours, it was cooled left and poured into methanol. A 62% yield of a product was obtained which had an intrinsic viscosity of 0.75 dl / g, a glass transition temperature T of 177 ° C and a T value of 406 ° C. Because of the

Manufacturing process, the product is a polyformal, which is essentially made up of chemically with each other connected units of the formula

0
duration. The polyformal was molded at 232C

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(45O ° F) converted to a clear film. Part of the film was allowed to stand in chloroform at room temperature for several days. A crystalline product was formed.

Example 20

A mixture of 5 parts bis (4-hydroxyphenyl) methane, 1.23 parts 89.9% Aliquat 336, 4.12 parts 88.5% potassium hydroxide and 63 parts of methylene bromide was stirred and refluxed heated. After refluxing the mixture for 15 minutes it was allowed to cool and then poured into methanol. A product was obtained which is insoluble in chloroform and could be dissolved in hot N-methylpyrrolidone.

[· Value of 54 ° C and a T g m

The product had a T value of 54 ° C and a T value of 190 ° C. Acts on the basis of the manufacturing process? it is with the product is a polyformal, which consists essentially of chemically linked units of the formula

-0- <O V-CH ₂ -CO> - OCH ₀ -

duration.

Although the foregoing examples are directed to only a few of the very numerous variables involved in practical Implementation of the present invention can be used, it should be expressly noted that the present Invention is directed to a method of making a much broader class of polyformals, which are essentially consist of chemically linked units of the formula (1) and CyclopoIyformaleη of the formula (2) as well as film-forming poly forma! - compositions containing less than 10% of the chemically linked units of the formula (1) in the usual form. The cyclic polyformals of the formula (2) Can be used to against organic solvents Manufacture durable wire coating formulations by such cyclic polyformals are used in combination with a Lewis acid catalyst and an organic solvent will.

909839/0620

Claims (1)

Claims Process for making a polyforeal resin having an intrinsic viscosity greater than 0.3 in Chloroform at 25 C, which can be molded into a flexible film by compression molding, characterized in that it comprises the following steps: (1) Stirring a mixture containing methylene halide, bisphenol, alkali metal hydroxide as essential ingredients and one member selected from the class consisting of a phase change catalyst and a dipolar aprotic solvent, contains and (2) Obtaining the polyformal from the mixture according to stage (1), wherein more than 1 mole of methylene halide and more than 2 moles of alkali metal hydroxide per mole of bisphenol in the reaction mixture be used. 2. Process according to claim 1, characterized in that in the reaction mixture a phase change catalyst is used. 9O9B3S / O02O 3. The method according to claim 1, characterized in that in the reaction mixture a dipolar aprotic solvent is used. 4. The method according to claim 1, characterized in that in the reaction mixture a substantially inert non-polar organic solvent is used. 5. The method according to claim 4, characterized in that in the reaction mixture Chlorobenzene is used. 6. The method according to claim 3, characterized in that in the reaction mixture N-methylpyrrolidone is used. 7. The method according to claim 3, characterized in that in the reaction mixture Dimethyl sulfoxide is used. 8. The method according to claim 1, characterized in that a temperature range from 25 ° C to 100 ° C is used. 9. The method according to claim 1, characterized in that the alkali metal hydroxide Is potassium hydroxide. 10. The method according to claim 1, characterized in that the alkali metal hydroxide Is sodium hydroxide. 11. A method for producing a polyformal resin which essentially of chemically linked units of the formula 909839/0620 28T9582 consists, characterized that it includes the following procedural steps: (1) Stirring a mixture containing as essential ingredients methylene chloride, bisphenol-A, potassium hydroxide and one member selected from the class consisting of N-methylpyrrolidone and a phase change catalyst, contains at a temperature in the range from 25 ° C to 100 ° C and (2) Obtaining the polyformal resin from the mixture according to step (1), more than 1 mole of methylene chloride and more than 2 moles of potassium hydroxide are used per mole of bisphenol-A. 12. The method according to claim 11, characterized in that in the reaction mixture Monomethyltricaprylylammonium chloride is present. 13. The method according to claim 11, characterized that N-methylpyrrolidone is used in the reaction mixture. 14. The method according to claim 11, characterized that chlorobenzene is used in the reaction mixture. 15. Cyclopolyformals of the formula -I OROCH ₂ -JI 909839/0620 281S582 where R is a divalent aromatic organic radical and η is an integer from 2 to 25 inclusive represents. Cyclopolyformal of the formula - - o - \ o \ - c - \ o \ - ochH- CH 2 Cyclopolyformal of the formula r ~ \ · ^Η ν-Λ 0— ( O V- C - / O V-OCHj- Uli ο "* Process for the production of a polyformal which essentially of chemically linked units of the formula -OROCH ₂ - and less than 10% by weight chemically with one another of linked units in a cyclic state, characterized by the following Process steps: (C) causing the reaction between a bisphenol of formula (3) and an alkali metal hydroxide in the presence a mixture of methylene halide and a dipolar organic solvent and (D) Recovery of the aromatic polyformal from the reaction mixture after stage (C), wherein in the reaction mixture after step (C) a ratio of 2 to 2.5 moles of alkali metal hydroxide per mole 909839/0620 2879582 Bisphenol-A is used during a concentration from 20 to 50 weight percent solids is maintained and a weight ratio of 0.8 to 1.2 parts of the dipolar aprotic solvent per part of methylene halide Applies. 19. Polyformal, characterized in that that it consists essentially of chemically linked units of the formula -OROCH ₂ - and has an intrinsic viscosity in chloroform at 25 ° C of at least 0.4 and is suitable to be formed into a flexible film by compression molding and has less than 10% by weight of such chemically linked units in the cyclic state, in which R is a C, _β ".valent aromatic radical selected from phenylene, tolylene, xylylene, naphthalene and -R QR -, where R is a C, g- ₁₃ \ divalent radical and Q is a cyclo 0 0 M Il hexyl, fluorenyl, -0-, -S-, -C-, -S-, and -CH ₀ - ι · y ^ y ο and y is 1 to 5 inclusive. 20. Polyformal according to claim 19, characterized that the chemically linked units have the formula CH ₃ -o- / o \ - c - / o \ -ocH ₂ - CH ₃ exhibit. 909839/0620