DE2117820C - - Google Patents

Description

Shark

Shark

where Hai is fluorine, chlorine or bromine, or the formula

Shark

Shark

where Hai is fluorine, chlorine or bromine, or the form hi

Shark

.V · A _r -J

Quay

where shark, fluorine, chlorine or bromine, X the direct Bond, one of the divalent residues

-SO ₂ -, - CO -, - COO - or - N = N-

and Ar denotes the o- or p-phenylene radical or the pp-diphenylene radical, are characterized, at a temperature of ¹ OO to 200 ° C and in the absence of oxygen in a polar aprotic solvent compared to the starting materials, in which the resulting polyether thioether is soluble lFt, polycondensed.

draws that as a compound of the general formula

Shark

4,4'-dichlorodiphenyl sulfone is used.

3. The method according to Aospf üchen ί and 2, characterized in that a mixture of 4,4'-dichlorodiphenylsulfone and bis- (4,4'-chlorophenylsulforiyl) -diphenyl or 4,4-dichlorobenzonhenone and 4,4-dichlorophthalopbenone is used will.

• 4. The method according to claim 3, characterized in that the two dihalogen compounds can be used in a mutual molar mixing ratio of 9: 1 to 1: 9.

5. Use of the polyether thioethers prepared according to one of claims 1 to 4 as heat-resistant ones Electrical insulation foils.

The invention relates to a process for the production of high molecular weight, heat-resistant, linear, aromatic polyether thioethers with an irregular internal structure.

Purely aromatic, linear polyethers and polythioethers have excellent thermal stability, which is characterized by continuous use temperatures of 160 to 2GO ⁰ C. A tried and tested process for the production of linear, aromatic polyethers consists in the polycondensation of aromatic bisphenoids or their alkali metal salts with aromatic dihalogen compounds (cf. d '; French patent 1 407 301 and USA patent 3 332909). In a corresponding manner, linear, aromatic polythioethers have been prepared from aromatic dithiols and dihalogen compounds (cf. US Pat. No. 3,432,468, British Pat. No. 1,160,666 and USA Pat. No. 2,822,351). While it was possible to prepare technically valuable polymers from polynuclear aromatic bisphenols or dithiols and suitable dihalogen compounds by the processes described in the patents mentioned, the polycondensation of the simplest dihydric phenols resulted in b2w. Thiols, namely hydroquinone and dithiohydroquinone, are not usable plastics. The reason for this lies in the fact that the condensation products of hydroquinone or dithiohydroquinone with aromatic dihalogen compounds are highly crystalline and consequently no longer dissolve completely even in the most effective polar solvents such as dimethylformamide or dimethyl sulfoxide. These properties already interfere with the production, which is the case with d ^; It is known that ei, en polymer types must take place in solution, in that incompletely polymerized material precipitates out before the reaction has ended. Since the required average molecular weight is not achieved in such cases, the mechanical properties of the polymer do not meet expectations either.

By special measures, for example by using a mixture of two or Several polar solvents can cause crystallization and premature precipitation of the polymers impede. By quenching the hot polymer solution. amorphous pi / ly ethers can be found in cold water or polythioethers obtained according to conventional Pressing, injecting or extruding into clear moldings. There such structures but at a higher temperature for crystallization with simultaneous deformation, cloudiness and Tending to embrittlement comes for these polymers

permanent use at temperatures between 160 and 200 C out of the question. Even in the amorphous state, the polymers mentioned are poor toxic, low-boiling and inexpensive solution

agents are insoluble, so that processing from the solution to foils and lacquers and for one Use for impregnation purposes is ruled out.

It has now surprisingly been found that easily soluble and permanently amorphous high molecular weight linear aromatic polyether thioethers with irregular internal structure by a process can produce, which is characterized in that an alkali salt of monothiohydroquinones with the equivalent amount of at least one aromatic dihalo compound, its halogen atoms are each separated by at least 3 carbon atoms and which are separated by the general formula

* but the bonds of Ar to O and S are irregular are distributed (statistical distribution). So are the nick members - O - and - S - in the polymolecule randomly distributed by adding the monothiohydroquinone to the growing chain of the polymer both by means of is attached to the OH group as well as to the SH group. So it is a matter of a polymer with irregular structure, for example the formula

Shark

Shark

Ar-O

—Ar — S

O-Ar-O

S — Ar—

With a regular arrangement of the link members, _ as in formula {II) for a non-inventive

in which Hal is fluorine, chlorine or bromine, or the 20 foils prepared according to the same Brauo formula composition as shown in (I) results in poly

mers with completely different properties.
Repeating structural units of the formula

(H)

where Hai is fluorine, chlorine or bromine, or the Formers

Shark

35

Shark

/ Vx- _ArX y

Shark

wherein shark, fluorine, chlorine or bromine. X is the direct bond, one of the divalent residues

- CH ₂ -—C (CH ₃ J ₂ -—O —— S—,

-SO ₂ -—CO -— COO —or —N = N-

and Ar is the o- or p-phenylene or p, pD - means phenylene radical, are in inert at a temperature of 1 (K) to 20ö C., and in \ b essence of Sauerstofi in a gegenüberden starting materials polar aprotic solvent, in which the resulting polyether thioether is soluble, polycondensed.

HlIU UIIgSgVHIdXJV 'T Vl tCXIII VII TT III

The following formula is shown:

MeO

SMe + Hal-Ar-Hal

2MeHaI + polyether thioether

These polymers of the formula (II) are crystalline and insoluble in aliphatic chlorohydrocarbons (cf. Be, game 2 with example 1).
Examples of suitable dihalo compounds are

1,4-dichlorobenzene.

1,3-dibromobenzene,

1,4-dichloronaphthalene,

4,4'-dibromriiphenyl,

4,4'-dibromodiphenyl ether,

4,4'-dichlorodipbenylmethane,

4,4'-dichlorodiphenyl sulfide,

4,4'-dichlorodiphenyl sulfone,

4,4'-dichlorobenzophenone,

4,4'-diiodazobenzene,

4,4'-Dkh! Orbenzi !.

4,4'-BischlorρhenylteΓephthalophenon,

4.4'-B! SbromρhenyUsophthalophenone.

Is preferred

4.4'-dichlorodiphenyl sulfone and
4,4'-Bischlorpheny'tSiilfony! D! Pbesyl.

Suitable polar aprotic solvents are Ν, Ν-dimethylformamide. Ν, Ν-dimethylacetamide, dimethyl sulfoxide. Tetra-methylene sulfoxide, N-methyl-

phosphoric acid etnamide.

Gt ate a preferred embodiment of the In the process, the alkali salt, in particular the sodium salt, is first made from monothiohydroquinone and alkali, formed after the reaction

60

with recurring structural units of the formula HO-

-SH + 2MeOH

-O

2H ₂ O

(Me = alkali metal) formed water from the reaction mixture by distillation or azeotropic distillation with the help of an entrainer, such as. B. benzene is removed. Lithium hydroxide, sodium hydroxide, potassium hydroxide or Na ₂ CO ₃ can be used as alkalis, sodium hydroxide or sodium carbonate is preferably used.

After adding the equivalent amount of the dihalogen compound to the solution or suspension of the The alkali salt of monothiohydroquinone is heated under an inert protective gas atmosphere, e.g. B. nitrogen, Hydrogen or argon, for several hours at 100 to 200 ° C, until the desired degree of polymerization is reached

The polycondensation temperature depends on the reactivity of the halogen atoms in the aromatic dihalogen. - ·. - '' ^ ndings. While unreactive H "■ '." ^ aatoms, such as B. in 1,4-dichlorobenzene, Terni, _. Cui: ren ^{require from 180 to 200 0} C, can * "activated dihalogen compounds, such as 4,4'-DiOi _2. Diphenyl sulfone, already at 100 to 140 ° C quantitatively implemented.

Instead of just one dihalo compound, two or three of these can be polycondensed with monohydroquinone. In this way it is possible to change the melting range and the solubility of the polyether thioethers formed to a certain extent. A mixture of 4,4'-dichlorodiphenylsulfone and bis- (4,4'-chlorophenylsulfonyl) -diphenyl or of 4,4'-dichlorobenzo- 3c phenone and 4,4'-dichloroisophthalophenone, especially in a mutual mola- .en mixing ratio from 9: 1 to 1: 9. If the polycondensation according to the invention is carried out with equivalent amounts of monothiohydroquinone and dihalo compound, then it is advantageous to add a chain terminator to limit the molecular weight. For this purpose, monofunctional compounds with reactive halogen atoms, such as. B. ethyl bromide. Benzyl chloride, 4-chlorodiphenyl sulfone, etc., in amounts of 0.1 I ₁ S 1 mol percent, based on the dihalogen component used. However, the dihalogen component can also be used from the outset in a slight excess of 0.1 to 1 mol percent but the stoichiometrically necessary amount.

The polyether thioethers produced by the process according to the invention are obtained by pouring them into them the viscous solution in water as a colorless, fibrous falver. One can also proceed in this way that part of the solvent is distilled off and the very viscous solution is added through a nozzle a 3 to 4 mm thick strand, solidified in water and granulated. The granules are removed from the rest The alkali salt and solvent were freed by extraction with water and dried.

The linear structure and the high molecular weight of the polymers result from the fact that they in organic solvents, such as. B. methylene chloride, chloroform or tetrachloroethane, soluble and give high values of the reduced specific viscosity. The reduced specific viscosity (RSV) is defined by the equation

RSV = ^r ^ ~ - ,
c

where) / “, the relative viscosity and c is the concentration of the polymer in g / 100 ml of solvent. All RSV values used here relate to chloroform or N-methylpyrrolidone as solvent, a polymer concentration of 0.2 g / 100 ml and a measuring temperature of 20 ° C. The aromatic polythioethers prepared in the manner described give RSV values of 0.4 to 2.0. Particularly favorable processing properties are achieved with polymers of RSV from 0.5 to 0.8.

The surprising properties of the polyether thioethers produced according to the invention, namely their Solubility in chlorinated aliphatic hydrocarbons and their permanently amorphous character a consequence of the irregular arrangement of the bridge links along the polymer chain. You can do this Designate the effect as "internal copolycondensation". In contrast, hydroquinone or Dithiohydroquinone and aromatic dihalogen compounds only polymers with a regular arrangement of the bridge members are preserved. This results in crystalline polymers that are aliphatic Chlorinated hydrocarbons are insoluble, as shown in Table I.

The polyether thioethers produced according to the invention can be processed by injection molding or extrusion to give moldings, foils, sheets, pipes and endless profiles of all kinds, which are characterized by high long-term temperature resistance. Heating such shaped bodies for several months in the presence of air to temperatures of 180 to 200 ^° C. does not cause any significant change in the physical properties. In particular, the clearly transparent character of the molded body is retained. The only change found in some representatives of this class of plastics was a slight discoloration of yellowish to light brown shades.

ιaoere

Polyethers, polythioethers and polyether thioethers derived from hydroquinone, dithiohydroquinone. Monothiohydroquinone and the dichloro ^{compounds DDS +} ) and DCPSD * ⁺ )

Condensation products

Hydroquinone + DDS *)

Hydroquinone + DCPSD *) ..
Dithio ^ / droquinone + DDS *)

Distribution of

Bridge links along

the polymer celt

regularly regularly regularly

λ the obtained Polymers kris'allinc
Melting point
° C 310 350 223 I nslichkit in
aliphatic chlorine
kohk'iiA.ivicrstoflen '* * insoluble insoluble insoluble

continuation

Properties of the polymers obtained

KondCT & atiorispröduide from

- ^ Distribution of the bridge links along the polymer chain more crystalline
Melting point
'' ⁰ C

: Solubility in aliphatic chlorinated carbons WASSCrStOfTeH ⁺ * ⁺ J

Dithiohydroquinone + DCPSD *)

Monothiohydroquinone A- DDS **), ...
Monothiohydroquinone + DCPSD **)

regularly

irregular

irregular - r; 362

amorphous

amorphous

., insoluble "soluble soluble

20th

DDS - AA -thdilotäiphcnyhuUon I) CPSU = ßiv (4 / i'-dicblorphen} lsu! Ionyl] -d] phefiyl methylinchloride, chloroform or telechloroethane. Comparative products not manufactured according to the inventive method. Products according to the invention.

Since the polyhydric ethers have excellent electrical properties, they are ideally suited for the production of temperature-resistant insulating materials. which are preferably used in the form of foils. Are preferably produced during films of 100 to 500 α strength after Extrusion- or Blasverfahien, can be thin films up to down to 10 μ thickness without Sch "iengkeilen from 10 to 30% solutions of the polymers in Melhylenchlorjd pour. The electrical properties of such a cast film. dk was produced according to Example 5, the table 11 shows.

example 1

3 °

Table II

Electrical properties of a cast film made from the polycondensation product of monothiohydroquinone and 4,4'-Dschlordipbedylsu! foa

Volume resistance.

23 C 12 / cm 12 κ Itf ¹³

Likewise after

24 hours water storage 23 α 10 ¹⁵

Surface resistance,

23 Γ ti Ll κ i & -

Dcsgleidien after

24 hours water

storage 1-4 κ 10 "

Dielectric strength.

KV cm 17 (Hf-FoHe) - -DesHle check

6 M <-.ztcn at 200 "'C 1 720
fcelasi.i iJielectricity-

constanle 15

VcrlusifafcloT Ig at

2Ϊ Γ 50Hz 0.0013

500 Hz 0.00082
500OHz 0.0009
50000 Hz 0.0017
500000 Hz 0.0029

The formulations of aromatic polyethioethers Chlorinated aliphatic hydrocarbons are also suitable for diactiating and for fmprag.ijcning and cover for paper and textile fabrics of all kinds. Received by the latter Treatment does not only indicate insulating properties. but at the same time they become wakeful fianimfest gemachi.

In a 250 ml three-necked flask equipped with a stirrer. Dean-Stark attachment and gas inlet tube, 12.6Ϊ6 g (0.1 mol) of monothiohydroquinone in 80 ml of xylene dissolved and treated with 22.1 ml of aqueous sodium hydroxide solution (362 mg of NaOH'ml, 0.2 mol). Under Introduction of nitrogen, the mixture is heated to the boil. The water distilled as Azeotrope with the xylene from iü · - 'becomes in 2 hours separated quantitatively. After the xylene has been distilled off, the disodium salt of monothiohydroquinone is: as white crystal powder. 28.716 g (0.1 mol) of 4.4'-dichlorodiphenyl sulfone are entered and the mixture in 100 ml of anhydrous dimethyl sulfoxide geiösi. The reaction mixture is now heated to 160'C, with temporarily a orange-red coloring occurs. After about 30 minutes the color and the viscosity of the Solution increases slowly with the separation of fine-grained sodium chloride. After A highly viscous, slightly yellow-colored reaction mass is present for 6 hours. The solution is made with 100 ml Diluted dimethyl sulfoxide, »freed from sodium chloride by filtration and the polycondensate through Dropping into water precipitated. The fibrous, voluminous product is boiled in water and then dried in a high vacuum at 150'C.

The reduced specific viscosity of the polymer.

is 0.65 (measured in chloroform at 20 "C, 02 g 100 ml solvent). Da., Product dissolves excellently in methylene chloride. Such solutions

are stable and can be stored for several weeks without any changes. After the Casting processes can produce colorless films of excellent transparency and high mechanical Strength can be produced.

The glass transition temperature 7 ^ of the polymer is at 17Γ C (determined by a Perkin-Elmer differential Scanning Calorimeter DSC-I). The excellent thermal stability of the polymer emerges from the thermogravimetric analysis:

Cumulative weight loss after heating for 2 hours in air at the following temperatures:

55

60

65 Weight Loss. %

Temperature. "'C

200

0.9

250

1.5

300

2.0

350

2.1

400

30 »627AOf

Comparative example

The production of a polymer of the same gross composition as in Example 1, but with a regular sequence of the - ö - and - S - bridges is described.

in a 250 ml-Dreihälskolben equipped with a stirrer, and Rmkflußkühler GaseinldtUrtgsrqrii ^1, - ', 18.844 g (0.05 mol) of 4-Mer pio ^ ^' - {p-chloro - 'phenylsulfonylj-diphen: läthsr and 3.498 g anhydrous? Submitted sodium carbonate and replaced with 20 ml of NN-dimethylformamide \. The reaction mixture is heated to 140 ° C. for 4 hours, the viscosity gradually increasing. The viscous reaction mass is added to a Turmix mixer in Wa <w> er, the polymer precipitates as a flaky, white powder. After boiling out several times in water, the product is ^{dried at 140 °} C. in a high vacuum.

The reduJerte specific viscosity of the polymer is 0.35 (as measured in N-methylpyrrolidone at 20 ⁰ C, 0.2 g / 100 ml). In contrast to the polymers described in Example 1, stable solutions in methylene chloride or chloroform cannot be prepared from this product. Although temporarily seeking clear solutions. Crystallization starts after just a few minutes. and the polymer precipitates fine-grained. The crystalline product only dissolves in N-methylpyrrolidone at 200PC. The crystalline melting point of the polymer is 225 ° C. (determined on the Perkin-Elmer Deterential Scanning Calorimeter DSC-I).

Example 2

The corresponding disodium salt is prepared according to the method given in Example 1 from 12.616 g (0. ί mol) of monothiohydroquinone entered and mixed with 100 ml of dimethyl sulfoxide. At 150 ^° C. rapid polycondensation occurs. The mixture is continued at this temperature for 4 hours. The product is isolated and worked up in the manner indicated ^{in Example 1.}

The white, coarse-grained polymer has an RSV of 0.78 (measured in N-methylpyrrolidone at 20 ^° C., 0.2 g / 100 ml of solvent).

The polymer is very soluble in a mixture of methylene chloride and chloroform (1: 1) up to a concentration of 25 to 30%. Solcae solutions can be kept for several weeks without any cloudiness. The glass transition point Tg of the amorphous polymer is 245 ° C.

Example 3

It is the production of a polymer from monothiohydroquinone and two different dihalogen compounds described.

The corresponding disodium salt is prepared from 12.616 g (0.1 mol) of monothiohydrocbinone as described in Example 1. There are 14,358 g (0x15 moles) of 4,4'-dichlorodiphenyl sulfone and 25.172 g (Oj05MoI) of 4,4'-bis- (4-Chiorphenylsulfonyl) biphenyl, followed by lOOml Dimeihylsulfoxyd added and the mixture was reacted at 150 ⁰ C for the polycondensation. The reaction is complete after 4 hours. The hot, viscous mass is diluted with 100 ml of dimethyl sulfoxide and nitrated under pressure. The further work-up takes place according to Example 1.

The dried product is white and grainy. The reduced specific viscosity is. 0.58 (measured in chloroform at 20 ° C, 0.2 g / 100 ml solvent). The polymer has an excellent solubility in methylene chloride, chloroform, methylene chloride-methanol (9: 1), tetrachloroethane and in N, N-di - 'rnethylformamid. Since the polymer does not crystallize, ro ¹ Sj ₁ Id, the solutions virtually indefinitely. Thin films of high mechanical strength and excellent electrical properties can be cast from these solutions.

The ulas transition temperature of the polymer is 210 ° C (differential calorimetrically determined). At 280 to 300 ^° C., the polymer can also be processed thermoplastically. At 300 ⁰ C pressed clear, colorless films are characterized by high flexibility and mechanical strength. The vorzügliehe Dauerwärmebes'ändigkeit is apparent from the fact that after omonatiger heat aging at 200 ⁰ C in air, no decrease in the mechanical and electrical properties is detectable.

Application example

The production of a cast film is described. 240 g of the RSV 0.72 polymer mentioned in Example 3 are dissolved in 800 ml of methylene chloride on a pouring machine to remove dust particles, the solution is filtered back. A water-clear solution is obtained with a viscosity of 2200 cP (measured with an Epprecht viscometer at 2Cr ¹ C).

The solution is poured with the help of a hand pouring device. To get a bubble-free film, the atmosphere above the freshly cast film is saturated with methylene chloride. After 10 minutes the film can be lifted from the glass base

and is ^{completely dried at 160 °} C. in a strong stream of air. The thickness of the crystal clear, colorless film is 40 to 50 μ.

The following film properties are determined:

Light transmission 89%

Residual moisture 0.03%

Tensile strength 9.1 kg / mm ²

Elongation at break 12%

Shrinkage

at 150 ° C 1.0%

at 180 ° C 2.8%

at 200 ° C 6.2%

Electrical breakdown

strength 142 KV / mm

Example 4

The disodium salt is prepared in the usual way (see Example 1) from 12.616 g (0.1 mol) of monothiohydroquinone. 12.555 g (0.05 mol) of 4,4'-dichlorobenzophenone and 17.761 g (0.05 mol) of 4,4'-dichiorisophthalophenone are added and 100 ml of tetramethylene sulfoxide (tetrahydrothiophene-1,1-dioxide) are added. The polycondensation is carried out ^{at 180 ° C. for 3 hours.} The dark yellow reaction product is precipitated in water and repeatedly boiled with water until the washing machine

water no more chlorine ions are detected The polymer katin at? 80 ° C to clear form-

it can. After drying in a high vacuum, pieces are to be pressed. Because of the amorphous cha

a granular, yellow-colored product, whose redü- rakters of the polymer remain sblcne pellets ituch

The specified specific viscosity is 0.69 (measured after weeks of heat aging completely clear and

generally chloroform at 20 ° C. 0.2 g / 100 ml solvent), 5 fiexible.

Claims (1)

Patent claims: 1. Process for the production of high molecular weight, heat resistant, linear aromatic Polyether thioether with unregulated inner Structure, characterized in that one is an alkali salt of monothiohydroquinones with the equivalent amount of at least one aromatic dihalo compound, its halogen atoms are each separated by at least 3 carbon atoms and which are separated by the general formula