DE4216597A1 - Poly-cyano-arylene ether(s) useful as moulding materials - prepd. by reacting di:halo-benzonitrile(s) with di:alkali di:phenolate(s), esp. those based on 1,1-bis-4-hydroxyphenyl-alkyl-cycloalkane(s) - Google Patents

Abstract

Aromatic polycyanoarylene ethers (I) with repeating units of formula O-E-O-E1- (VII) are new; E1 = divalent cyano-aromatic residue of formula (VIIIa); -O-E-O- = diphenolate residue (IXa); 0.1-100 mole.% of residues (IXa) have the formula (Ia); R1, R2 = H, halo, 1-8C alkyl, 5-6C cycloalkyl, 6-20C aryl or 7-12C aralkyl; m = 4-7; R3, R4 = H or 1-6C alkyl (can be different for each X, but both = alkyl on at least one atom X); X = carbon. Also claimed is a process for the prodn. of (I), by reacting di-alkali diphenolates (see above) with corresp. dihalo-benzonitriles in polar solvent, e.g., N-alkyl-caprolactam or -pyrrolidone. USE/ADVANTAGE - Used for the prodn. of moulded prods. (claimed). (I) are thermoplastics with high Tg, high heat distortion temp., and good solubility, which can be processed by extrusion, injection moulding, sintering, compression moulding or film casting from soln. Low-mol. wt. (I) can be incorporated into block or graft copolymers by reaction of halo or OH end gps., or by conversion of the CN gps. into amide or COOH gps., and subsequent graft copolymerisation. Applications include electrical and electronic equipment, aerospace components, sports equipment, medical and domestic appliances, etc. (esp. for high dimensional stability).

Description

The invention relates to polycyanarylene ethers Based on special dihydroxy building blocks, preferably 1.1 Bis (4-hydroxyphenyl) alkylcycloalkanes.

Polycyanarylene ethers are known compounds and can e.g. B. from 2,6-dichlorobenzonitrile and aromatic di- or Polyhydroxy compounds such as bisphenol-A, resorcinol, Hydroquinone, naphthalenediol or dihydroxybiphenyl are obtained (e.g. EP-A 1 86 153, EP-A 4 45 840), JP-A 63-1 22 731, 63-1 89 435, 63-27 033, 63-3 058, 63-3 059 or H. R. Kricheldorf et. al. in "Macromolecular Chemistry Rapid Communications, 8, 529 (1987) ".

The products have high strength and good temperature resistance and because of the aromatic structures a good flame retardancy.

The product of 2,6-dichlorobenzonitrile and 2,7-dihydroxynaphthalene also has a high glass temperature  of 215 ° C, but is in common solvents such as acetone, Ethanol, toluene, methylene chloride or chloroform insoluble (EP-A 4 45 840).

The invention relates to polycyanarylene ethers Base of 1,1-bis (4-hydroxyphenyl) alkylcycloalkanes with high glass temperature and at the same time good solubility in z. B. solvents such as methyl ethyl ketone.

According to the invention, aromatic dihydroxydiphenylcycloalkanes of formula (I)

wherein
R¹ and R² independently of one another are hydrogen, halogen, preferably chlorine or bromine, C₁-C₈-alkyl, C₅-C₆-cycloalkyl, C₆-C₁₀-aryl, preferably phenyl and C₇-C₁₂-aralkyl, preferably phenyl-C₁-C₄-alkyl, especially benzyl and cumyl,
m is an integer from 4 to 7, preferably 4 or 5,
R³ and R⁴ individually selectable for each X, independently of one another hydrogen, or C₁-C₆-alkyl and alkyl and
X is carbon,
with the proviso that at least one atom X R³ and R⁴ are alkyl at the same time.

Preferred are at 1-2 atoms X, in particular only on an atom X, R³ and R⁴ simultaneously alkyl. More preferred Alkyl is methyl; the X atoms in the α position to the di-phenyl-substituted carbon atom (C-1) are preferred not dialkyl-substituted, but alkyl disubstitution preferred in the β-position to C-1.

Dihydroxydiphenylcycloalkanes are particularly preferred as the starting material with 5 and 6 ring carbon atoms in the cyclo- aliphatic radical (m = 4 or 5 in formula (I)) such as, for example the diphenols of the formulas

the 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (Formula II) is particularly preferred.

Dihydroxydiphenylcycloalkanes of the formula (I) can be found in in a known manner by condensation of phenols of the formula (V)

and ketones of the formula (VI)

are produced, wherein in the formulas (V) and (VI) X, R¹, R², R³, R⁴ and m are those given for formula (I) Have meaning.

The phenols of formula (V) are either known from the literature or available by methods known from the literature. (See e.g. Ullmann, Encyclopedia of Industrial Chemistry, 4th edition, volume 15, pp. 61-77.)

Examples of suitable phenols of the formula (V) are:
Phenol, o-cresol, m-cresol, 2,6-dimethylphenol, 2-chlorophenol, 3-chlorophenol, 2,6-dichlorophenol, 2-cyclohexylphenol, o-phenylphenol and o- and p-benzylphenol.

The ketones of the formula (VI) are known from the literature (see for example, Beistein's manual of organic Chemistry, 4th edition, volume 7.) A general procedure for the preparation of ketones of the formula (VI) is, for example in "Organikum" 15th edition 1977, VEB- German Publishing House of Sciences, Berlin p. 698 described.

Examples of ketones of the formula (VI) are:
3,3-dimethylcyclopentanone, 2,2-dimethylcyclohexanone, 3,3-dimethylcyclohexanone, 4,4-dimethylcyclohexanone, 3-ethyl-3-methylcyclopentanone, 2,3,3-trimethylcyclopentanone, 2,4,4-trimethylcyclopentanone, 3, 3,4-trimethylcyclopentanone, 3,3-dimethylcycloheptanone, 4,4-dimethylcycloheptanone, 3-ethyl-3-methylcyclohexanone, 4-ethyl-4-methylcyclohexanone, 2,3,3-trimethylcyclohexanone, 2,4,4-trimethylcyclohexanone, 3,3,4-trimethylcyclohexanone, 2,5,5-trimethylcyclohexanone, 3,3,5-trimethylcyclohexanone, 3,4,4-trimethylcyclohexanone, 2,3,3,4-tetramethylcyclopentanone, 2,3,4,4- Tetramethylcyclopentanone, 3,3,4,4-tetramethylcyclopentanone, 2,2,5-trimethylcycloheptanone, 2,2,6-trimethylcycloheptanone, 2,6,6-trimethylcycloheptanone, 3,3,5-trimethylcycloheptanone, 3,5,5- Trimethylcycloheptanone, 5-ethyl-2,5-dimethylcycloheptanone, 2,3,3,5-tetramethylcycloheptanone, 2,3,5,5-tetramethylcycloheptanone, 3,3,5,5-tetramethylcycloheptanone, 4-ethyl-2,3, 4-trimethylcyclopentanone, 2-isopropyl-4,4-dimethylcyclopentanone, 4-isopropyl-2,4 -dimethylcyclopentanone, 2-ethyl-3,5,5-trimethylcyclohexanone, 3-ethyl-3,5,5-trimethylcyclohexanone, 3-ethyl-4-isopropyl-3-methyl-cyclopentanone, 4-sec. Butyl-3,3-dimethylcyclopentanone, 2-isopropyl-3,3,4-trimethylcyclopentanone, 3-ethyl-4-isopropyl-3-methyl-cyclohexanone, 4-ethyl-3-isopropyl-4-methyl-cyclohexanone, 3- sec.Butyl-4,4-dimethylcyclohexanone, 3-isopropyl-3,5,5-trimethylcyclohexanone, 4-isopropyl-3,5,5-trimethylcyclohexanone, 3,3,5-trimethyl-5-propylcyclohexanone, 3,5, 5-trimethyl-5-propylcyclohexanone, 2-butyl-3,3,4-trimethylcyclopentanone, 2-butyl-3,3,4-trimethylcyclohexanone, 4-butyl-3,3,5-trimethylcyclohexanone, 3-isohexyl-3- methylcyclohexanone, 5-ethyl-2,4-diisopropyl-5-methylcyclohexanone, 2,2-dimethylcyclooctanone, and 3,3,8-trimethylcyclooctanone.

Examples of preferred ketones are

Bisphenone production generally involves 2 to 10 Moles, preferably 2.5 to 6 moles of phenol (V) per mole of ketone (VI) used. Preferred response times are 1 up to 100 hours. Generally one works at temperatures from -30 ° C to 300 ° C, preferably from -15 ° C to 150 ° C and at pressures from 1 to 20 bar, preferably from 1 to 10 bar.

The condensation generally becomes more acidic in the presence Catalysts carried out. Examples are hydrogen chloride, Hydrogen bromide, hydrogen fluoride, boron trifluoride, Aluminum trichloride, zinc dichloride, titanium tetrachloride, Tin tetrachloride, phosphorus halides, phosphorus pentoxide, Phosphoric acid, concentrated hydrochloric acid or sulfuric acid and mixtures of acetic acid and acetic anhydride. The use of acidic ion exchangers is also possible.

Furthermore, the reaction can be carried out by adding cocatalysts such as C₁-C₁₈ alkyl mercaptans, hydrogen sulfide, Accelerated thiphenols, thioacids and dialkyl sulfides will.

The condensation can be without solvent or in the presence an inert solvent (e.g. aliphatic and aromatic hydrocarbon, chlorinated hydrocarbon) be performed.

In cases where the catalyst is used simultaneously as dehydrating agent acts, it is not necessary  use additional dehydrating agents, the latter, however, is to achieve good sales in any case advantageous if the one used Catalyst that does not bind water of reaction.

Suitable dehydrating agents are for example:

Acetic anhydride, zeolites, polyphosphoric acid and phosphorus pentoxide.

The preparation of the diphenols correspond to formula (I) described in German patent application P 3 83 296.6 and is illustrated by Example 1.

This invention relates to aromatic polycyanaryl ethers with the recurring structural unit

-O-E-O-E¹- (VII)

wherein -E¹- is a divalent radical of an aromatic cycnaryl of formula (VIIIa)

and in what

-O-E-O- (IXa)

is a divalent diphenolate residue, which is characterized are that from 0.1 mole% to 100 mole%, preferably from 3 mol% to 100 mol% and in particular from  10 mol% to 100 mol% of the diphenolate residues (IXa) of the formula (Ia)

where X, R¹, R², R³, R⁴ and m are as in formula (I) are defined.

The polycyanaryl ethers of the invention have preferred average molecular weights w (weight average) of 758 up to 500,000, in particular from 3,000 to 200,000 and especially from 5000 to 100,000.

The polycyanarylene ethers according to the invention can also be produced by this method, being polar Solvent preferred on nitrogen C₁-C₅- alkyl-substituted caprolactam, such as N-methyl-caprolactam, N-ethyl-caprolactam, N-n-propyl-caprolactam, N- Isopropyl caprolactam, preferably N-methyl  caprolactam, and preferably on nitrogen C₁-C₅- alkyl substituted pyrrolidones such as N-methylpyrrolidone; N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, Diphenyl sulfone, sulfolane or tetramethyl urea, be used. Proportionally z. B. 0.1 up to 200 wt .-% based on the weight of the polar solvent other less polar solvents used z. B. aromatic hydrocarbons such as Toluene, xylene, mesitylene, chlorobenzene, or aliphatic Hydrocarbons such as gasoline, cyclohexane.

This invention also relates to a method for Preparation of the polycyanaryl ethers according to the invention with the structural unit (VII) by reacting dialkalidiphenolates (IXb)

Alkali-OEO-alkali (IXb)
with dihalobenzonitrile (VIII)

in which
Hal is halogen, preferably fluorine, chlorine and bromine,
in polar solvents, which is characterized in that from 0.1 mol% to 100 mol%, preferably from 3 mol% to 100 mol% and in particular from 10 mol% to 100 mol%, of the dialkalidiphenolates (IXb) of the formula Ib

correspond,
wherein X, R¹, R², R³, R⁴ and m are as defined in formula (I), and that the reaction is carried out in polar solvents such as N-alkylated caprolactams or N-alkylated pyrrolidones, preferably in N-alkylated pyrrolidones.

Suitable diphenols of formula (IX) are e.g. B .:
Hydroquinone,
Resorcinol,
Dihydroxybiphenyls,
Bis (hydroxyphenyl) alkanes,
Bis (hydroxyphenyl) cycloalkanes,
Bis (hydroxyphenyl) sulfides,
Bis (hydroxyphenyl) ether
Bis (hydroxyphenyl) ketones,
Bis (hydroxyphenyl) sulfones,
Bis (hydroxyphenyl) sulfoxides,
α, α′-bis (hydroxyphenyl) diisopropylbenzenes
and their nuclear alkylated and nuclear halogenated compounds.

These and other suitable other diphenols (IX) are e.g. B. in US-PS 30 28 365, 29 99 835, 31 48 172,  32 75 601, 29 91 273, 32 71 367, 30 62 781, 29 70 131 and 29 99 846, in German Offenlegungsschriften 15 70 703, 20 63 050, 20 63 052, 2 21 10 956, the French Patent 15 61 518 and in the monograph "H. Schnell, Chemistry and Physics of Polycarbonates, Interscince Publishers, New York 1964 ".

Preferred other diphenols (IX) are, for example:
4,4'-dihydroxybiphenyl,
2,2-bis (4-hydroxyphenyl) propane,
2,4-bis (4-hydroxyphenyl) -2-methylbutane,
1,1-bis (4-hydroxyphenyl) cyclohexane,
α, α′-bis (4-hydroxyphenyl) -p-diisopropylbenzene,
2,2-bis (3-methyl-4-hydroxyphenyl) propane,
2,2-bis (3-chloro-4-hydroxyphenyl) propane,
Bis (3,5-dimethyl-4-hydroxyphenyl) methane,
2,4-bis (3,5-dimethyl-4-hydroxyphenyl) -2-methylbutane,
1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane,
α, α′-bis- (3,5-dimethyl-4-hydroxyphenyl) -p-diisopropylbenzene,
2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane,
2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane and
4,4'-dihydroxydiphenyl sulfone.

Other particularly preferred diphenols are, for example:
2,2-bis (4-hydroxyphenyl) propane,
2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane,
2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane,
2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane and
1,1-bis (4-hydroxyphenyl) cyclohexane and
4,4'-dihydroxydiphenyl sulfone.

They can be used individually or in a mixture.

Formula IXa and IXb represent in by removing 2 H atoms formed residues of these diphenols respectively the alkali salts of these compounds.

Suitable dihalobenzonitriles of the formula (VIII) are e.g. B .:
2,6-dichlorobenzonitrile,
3,5-dichlorobenzonitrile,
2,3-difluorobenzonitrile,
2,4-difluorobenzonitrile,
2,5-difluorobenzonitrile,
2,6-difluorobenzonitrile,
3,4-difluorobenzonitrile,
3,5-difluorobenzonitrile,
preferably 2,6-difluorobenzonitrile,
particularly preferably 2,6-dichlorobenzonitrile.

As alkali in the dialkaliphenolates (Ib) and (IXb) preferably serves sodium and potassium.  

Preferred polycyanaryl ethers according to the invention are those which are at least 10 mol% of recurring unit

included, and a weight average molecular weight of have over 3000 g / mol.

According to the invention, the polycyanarylene ethers can be used at temperatures from 120 ° C to 320 ° C, preferably 135 ° C to 280 ° C and at pressures of 0.8 to 10 bar, preferably 1 to 3 bar especially at atmospheric ambient pressure getting produced.

The molar ratio of alkali diphenolates (Ib) and (IXb) to the dihalobenzonitriles (VIII) between 0.5 and 2, preferably 0.8 and 1.2, particularly preferred 0.95 and 1.05, being for high molecular weights a ratio of 1 or close to 1 can be selected got to.

The amount of polar solvents is 0.5 to 50, preferably 2 to 20 parts by weight based on the total weight of the polycyanarylene ether formation components.  

The polycyanarylene ethers according to the invention can be as follows can be obtained from the reaction mixtures obtained.

The reaction mixture is diluted, especially if very highly viscous solutions are available, e.g. B. with the polar Reaction solvent or another solvent for the polyethersulfone, and filtered. To Neutralization of the filtrate with a suitable acid, e.g. B. acetic acid, the polycyanaryl ether is poured in a suitable precipitation medium, e.g. B. water, Alcohols (such as methanol, isopropanol) or water Alcohol mixtures, e.g. B. H₂O / methanol 1: 1, precipitated, isolated and then dried.

The polycyanarylene ethers according to the invention are thermoplastic Plastic with high heat resistance.

For example, they can be processed by extrusion, Injection molding, sintering or pressing.

Any shaped body can be produced. These can be used wherever polycyanarylene ethers are higher Dimensional stability are required, for example the field of electrical engineering and electronics, vehicle construction including aerospace, for sports equipment, functional parts and dishes for microwave shelves, sterilisable medical devices, coffee machine parts, Egg cookers, hot water tanks, pipes and pumps, Hair dryer and the like.

Because of their good solubility, they are ready for manufacture well suited for cast films.  

The polycyanarylene ether according to the invention can also be conventional Additives such as plasticizers, mold release agents, stabilizers such as B. UV absorbers or antioxidants, Intumescent aids (flame retardants), reinforcing fibers such as glass fibers, carbon fibers or aramid fibers, Fillers, inorganic and organic Pigments, ceramic raw materials, carbon black etc. added are, preferably in amounts of 0 to 80, preferably 0 up to 60% by weight, based on polyether sulfone = 100%, Appropriately before processing the invention Polyether sulfones to molded articles.

The low molecular weight polycyanarylene ethers according to the invention are suitable due to their functional end groups (Halogen or OH) also for incorporation in block copolymers in Connection with other co-condensable components.

They also have a functional group on the polymer backbone (nitrile group), which is analogous to polymer Reactions in other functional groups such as Amide or carboxyl groups can be converted. Such polyarylene ethers are particularly good for construction of graft copolymers.

Examples Example 1 Preparation of a biphenol of formula (A)

7.5 mol (705 g) of phenol and 0.15 mol (30.3 g) of dodecanethiol and at 28 to 30 ° C. with dry HCl are in a 1 liter round-bottom flask equipped with a stirrer, dropping funnel, thermometer, reflux condenser and gas line tube. Gas saturated. A mixture of 1.5 mol of dihydroisophorone (210 g) and 1.5 mol (151 g) of phenol is added dropwise to this solution at 28 to 30 ° C. in the course of 3 hours, HCl gas still being passed through the reaction solution. After the addition has ended, a further 5 hours of HCl gas are introduced. To complete the reaction, the mixture is left to stand at room temperature for 8 hours. Excess phenol is then removed by steam distillation. The remaining residue is extracted twice with 500 ml of petroleum ether (60-90) and once with 500 ml of hot methylene chloride and filtered off.
Yield: 370 g corresponds to 79%;
Melting point: 205-207 ° C.

Example 2 Preparation of a polycyanarylene ether according to the invention

In one equipped with a water separator and be stirred with nitrogen purge 155.21 g (0.5 mol) of the bisphenol of formula A. (TMC bisphenol), 86.01 g (0.5 mol) of 2,6-dichlorobenzonitrile and 89.84 g (0.65 mol) of anhydrous K₂CO₃ submitted in 1 l of N-methylpyrrolidone and 500 ml of toluene.

The reaction solution is dewatered and with the decrease in toluene the internal temperature 185 ° C increased. At this temperature, 6 h and stirred at 195 ° C for an hour.

Then it is precipitated in approx. 16 l of water acidified dilute phosphoric acid, electrolyte-free washed and precipitated again in methanol. After filtration and drying in a water jet vacuum 192 g of a polycyanaryl ether with a glass transition temperature of 239 ° C (determined by DSC, second heating) receive.

The product has a molecular weight Mw of 53,000 (GPC, PS calibration) and is in methyl ethyl ketone very soluble.  

Examples 3 and 4

Polycyanarylene ethers were obtained in an analogous manner, which in addition to the bisphenol of formula A (TMC bisphenol) still have bisphenol-A as a di-component.

Claims (6)

1. Aromatic polycyanarylene ethers with the recurring structural unit -OEO-E¹- (VII) wherein -E¹- is a divalent radical of an aromatic cyanaryl of the formula (VIIIa) and in what
-OEO- (IXa) is a double-bonded diphenolate residue,
characterized in that from 0.1 mol% to 100 mol% of the diphenolate residues (IXa) are those of the formula (Ia) wherein
R¹ and R² independently of one another are hydrogen, halogen, C₁-C₈-alkyl, C₅-C₆-cycloalkyl, C₆-C₂₀- aryl and C₇-C₁₂-aralkyl,
m is an integer from 4 to 7,
R³ and R⁴ individually selectable for each X, independently of one another hydrogen or C₁-C₆-alkyl, and
X is carbon,
with the proviso that on at least one atom X R³ and R⁴ simultaneously mean alkyl. 2. Aromatic polycyanarylene ether according to claim 1, characterized by average molecular weights w from 758 to 500,000 g / ml. 3. Aromatic polycyanarylene ether according to claim 1, characterized characterized in that from 3 mol% to 100 mol% the diphenolate residues (IXa) diphenolate residues the Formula (Ia) are.   4. Aromatic polycyanarylene ether according to claim 1, characterized characterized in that from 10 mol% to 100 mol% the diphenolate residues (IXa) diphenolate residues the Formula (Ia) are. 5. A process for the preparation of the polycyanarylene ethers of claim 1 by reacting dialkalidiphenolates with dihalobenzonitriles (VIII) Hal is halogen, characterized in that from 0.1 mol% to 100 mol% of the dialkalidiphenolates are those of the formula (Ib) are,
wherein X, R¹, R², R³, R⁴ and m have the meaning given for formula I in claim 1, and that the reaction is carried out in polar solvents such as N-alkylated caprolactams or N-alkylated pyrrolidones. 6. Use of polycyanaryl ether according to claim 1 for the production of moldings.