DE1468782A1 - Process for the preparation of sulfur-containing compounds - Google Patents

Description

Phillips Petroleum Company, Bartlesville, Oklahoma, USA

Process for the preparation of sulfur-containing compounds

The present invention relates to a process for the preparation of sulfides and / or polymers of aromatic compounds. One of the objectives of the present invention relates to the formation of Arylensulfidpolymerisaten by the reaction of at least one cyclic polyhalogensubstituier th Verbin dung with an alkali metal sulfide in a reaction medium which contains a polar organic compound.

Another object of the invention relates to the preparation of a diaryl or a di (alkaryl) sulfide by reacting an aryl halide or an alkali halide in a solvent consisting of an organic compound at elevated temperatures with an alkali sulfide.

809839/1449

According to a further object of the invention, the reaction with alkali sulphide is carried out after the removal of xa & v at least part of the water of hydration present in the alkali sulfide.

A variety of high polymers have been produced recently and many of them are constantly being pro-

Continuously
duziort and expelled. If such polymers are useful in many fields, a property of high polymers, particularly those of the thermoplastic type which is still in need of improvement, is the ability to withstand high temperatures. Since thermoplastic material can be quickly and satisfactorily deformed into almost any desired shape, it lends itself to mass production. A high polymer, in particular a thermoplastic material that withstands high temperatures and thus in the area of the rocket assembly, the high temperature insulation and the like could be used., Dae was goal of much research.

A variety of diaryl sulfides and di (alkaryl) sulfides are known, some of which are widely used. However, the methods currently available for making these compounds are so cumbersome and expensive that the price of these compounds has remained relatively high, which hinders their actual commercial development. For example, uiphenyl sulfide was obtained from thiophenol by reacting benzene diazonium chloride with sodium mercaptide. Another method that has been used to make this compound is that

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BATH ORIGINAL

Pyrolysis of the lead captide of thiophenol. Diaryl sulfides and Di (alkaryl) sulfides are useful as intermediates for the Manufacture of insecticides, plasticizers, high boiling solvents and the like.

These sulfides are useful as high-boiling solvents, heat-exchanging liquids, hydraulic fluids and as intermediates for the production of sulfoxides and sulfones, which themselves are used, for example, as insecticides and high-boiling solvents. For example, diphenyl sulfide f has a melting point of -21.5 ⁰ C and a boiling point at Atmoephärendruck of 296 ⁰ C. This wide liquid range, associated with its very high boiling point, renders the compound particularly suitable for use as a heat transmitting medium. Diphenyl sulfone, which is produced by the peroxide oxidation of diphenyl sulfide, is useful as an insecticide. Physical properties of other diaryl sulfides and di (alkaryl) sulfides are given in "Organic Chemistry of Bivalent Sulfur", Reid, Volume 2, Chemical Publishing Company Incorporated, New York (1960), pages 117-123. A relatively simple, economical method of making these sulfides would find immediate industrial use.

The present invention enables the production of a polymer of high temperature resistance, which is used to increase do :; Molecular weight can be treated further. Thus, the polymers may, for example, by using a dicarboxylic acid under

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Formation of bridge bonds of the polyamide type are crosslinked.

under

The polymers can be shaped, spun, ^ g high temperature conditions used and for the impregnation of materials,

tissue
such as glass wool, BKkiKiiiK »g etc., can be used.

The process according to the invention for the preparation of diaryl sulfides and / or di (alkaryl) sulfides can be used as a one-step process using inexpensive raw materials. It can be done essentially in the absence of water be performed"

The present invention thus relates to the preparation of sulfides and / or polymers from cyclic compounds by reacting certain halogen-substituted cyclic compounds with an alkali metal sulfide in a polar organic diluent as the reaction medium at elevated temperature. The temperature range is preferably about 125 ^° C. to about 450 ^° C.

Arylene sulfide polymers can be prepared by the process according to the invention in high yields by reacting at least one polyhalosubstituted cyclic compound between neighboring ring atoms has unsaturation and in which the halogen atoms are bonded to ring carbon atoms, with a Alkali sulfide in a polar epi organic solvent increased temperature. In general, the polar organic compound essentially dissolves both the alkali

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sulfide as well as the polyhalosubstituted aromatic compound, or other existing connections, as will be explained below.

The polyhalosubstituted compounds used as primary Reaction components used in the process according to the invention can be represented by the following ^ formulas:

WiHt HW _n («. ■

ΛΑ

v ° ν

(D (II)

(in)

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(χ)

t >>

(Y)

4-g

(Y)

5-e

(V)

(IV)

(VI)

in which X is a halogen atom, such as chlorine, bromine, iodine, fluorine and preferably chlorine and bromine , Y is hydrogen,

0 0 0 RO -R, -N (R) ₂ , -C-OR, -C-OM, -CN (R) ₂ , -NC-R ', -0-R',

-S-R ', -SO ₃ H and -SO ₅ M, where R is hydrogen cycloalkyl, aryl, aralkyl and alkaryl radicals with 1 to carbon atoms} R »represents alkyl, cycloalkyl

or
Aryl, aralkyl _ra <* alkaryl radicals with 1 to 12 carbon atoms dari Z means -N = and -C = j D means -0-, -S- and JL-

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G represents

_or 0 m * -S

Il

RR ¹ R 0

R. R. R ' 0 0 ι • • Ii -O-, -N-, -C-, -Si-,
ι -P-,
I. -S-

-S-

Il

dar; M means an alkali metal, such as sodium, potassium, lithium,

or
Rubidium and Cesium; η is an integer from 2 to 6; if both radicals Z of the general formula I are -C =, m = 6-n, if one radical Z of the general formula I is -C =, m = 5-n, if both radicals Z of the general formula I -N = mean, m = 4-n; b is an integer from 2 to 8 and when Z in the general formula II is -C =, a = 8-b, when Z in the formula II is -N =, a = 7-b; c represents an integer from 2 to 10; e is an integer from 1 to 3 5; g represents an integer from 2 to 4; and ρ is an integer between 0 and 1.

Those compounds of the above general formulas which contain no more than 5 halogen atoms are preferred and the dihalosubstituted compounds are particularly preferred.

Some typical examples of polyhalosubstituted compounds of the above general formulas, which after the invention: e !; _; The methods that can be used are the following:

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" ^β " «m mi

1,2-dichlorobenzene 1,3-dichlorobenzene 1,4-dichlorobenzene 2,5-dichlorotoluene 1,4-dibromobenzene 1,4-diiodobenzene 1,4-difluorobenzene 2,5-dibromaniline N, N-dimethyl-2,5-dibromaniline 1,3t5-trichlorobenzene

1,2,4,5-tetrabromobenzene hexachlorobenzene

1-n-Butyl-2,5-dichlorobenzene 1-Oyclohexyl-2,5-diiodobenzene 1-Iaooctyl-2,4-difluorobenzene 1-n-Dodecyl-2,5-dichlorobenzene 1-benzyl-2,5-dibromobenzene 1,4-di-n-butyl-2,5-dichlorobenzene 1,4 ~ di-n-nonyl-2,6-dibromobenzene 1,3 »5-trichloro-2,4,6-triphenylbenzene 1,4-dibromo 2,3-5,6-tetra- (4-ethylphenyl) benzene methyl 2,5-dichlorobenzoate Ieopropyl 2,3,5-tribromobenzoate cyolohexyl-2,4,6-triiodobenzoate phenyl-2,3,4 ·, 5 , 6-pentachlorobenzoate 2,5-dichlorobenzamide N, N-di-n-dodecyl-2,4,5-tribromobenzamide Xthyl-2,4,5-trlchloroacetanilide cyclohexyl-N-methyl ~ 2,5-dibromoacetanilide 1 , 4-dibromonaphthalene 1,4-dichloro - ?, 8-diethylnaphthalene 1-methoxy-2,5-dichlorobenzene 1-cyclohexylthio-2,5-dichlorobenzene

1,4,7,8-tetrabromo-2,3,5,6-tetra-n-butylnaphthalene

1,315-trichloro-7-aminonaphthalene n-Octyl 2,4-dibromo-naphthalene-1-carboxylate

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N, N-Dimethyl ~ 5,6,7,8-tetrabromo-1-naphthalenecarboxamide 1-acetamido-2,4-dibromonaphththalene 8-decoxy-1,4-dlfluoronaphthalene 6,7-dibenzyl-8-methylthio-1,4 -dichloronaphthalene 1,4-dichloroanthracene 1,7-uribromo-6-oyclohexylanthracene 2,8-diiod-3,7-diethylanthracene 1-dodecyl-2,6-difluoroanthracene 1,2,4-trichloro-6-carbethoxyanthracene 2 , 6-dibromo-8-arainoanthraoene 3,7-diiodo-4-cyclohexylthioanthracene n-deoyl-3,8-difluoroanthracene-oarboxylate 1-acetaido-2,4-dibromanthraene 1O-dodecoxy-1,3,5-trichloranthracene 4, 4'-dichlorobiphenyl 3,4'-dibromo-2-aminobiphenyl 2,2 '^ - tribromo-6-acetamidobiphenyl 3,3'-dichloro-4,4'-didodeoylbiphenyl 4,4'-diiod-3-ethoxy -6-n-ο c tylbi phenyl 2,2 ·, 4,4'-tetrabromo-o-NjN-dlmethylaminobiphenyl 4,4'-diohlor-3, V -dicyclohexylbiphenyl 4,4 "-dibromo-p-terphenyl 3, 3 », 3» -triochloro-p-terphenyl 4,4 "-diochloro-3'-aoetamido-p-terphenyl

4,4 "-Difluoro-2,2 ', 2 ^M -tri-n-deeyl-3'-methoxy-p -terphenyl

4,4 "-dibromo-3'-carbbutoxy-p -terphenyl 4,4 "-Diohlor-2- (N-acetylamino) -p -terphenyl 3,4-dibromothiophene 3,4-diohlorfuran

3,4-difluoropyrrole 2,5-dibromo-4-aminothiophene 2,5-dichloro-3-ethoxythiophene 3,4-difluoro-5-aoetamidofuran 3,4-dibromo-5-carbethoxypyrrole 2,5-dichloropyridine

3,5-dibrpm-4-mi; hylpyridine 909Ö39 / 1U9

4,8-diiodoquinoline

2,3,6,7-tetrachloro-4,5-di-n-butylquinoline 1,4-dibromo-2,3,5,6-tetrafluorobenzene 4-chlorobromobenzene

2,5-dichlorobenzene sulfonic acid Sodium 2,5-dibromobenzenesulfonate 2, S-difluoronaphthalenecarbcaric acid Lithium 2,7-diiodanthracene carboxylate ρ, ρ'-dichlorodiphenyl ether ο, ρ'-dibromodiphenylumin

2,4'-difluorodiphenylmethane 3,3'-dichlorodiphenyldimethylsilane di (2-methyl-4-bromophenyl) sulfoxide Methyl di (3-ethyl-4-cilophenyl) phosphite, 4-bromophenyl-3-n-butyl-4-chlorophenyl sulfone 2,6-dichloropyrazine

According to the present invention, a process for the preparation of at least one diaryl sulphide, di (alkaryl) sulphide and / or arylalkaryl sulphide by reaction of a
Aryl monohalide and / or alkaryl monohalide with a
Alkali sulfide in a - ^ eaktionsmedium, which consists essentially of a polar organic compound, described, where-

mainly

at the polar organic compound / a jjiijcilfiijteihjejitx solvent for the reactants and essentially under the reaction conditions that generally work at
Including elevated temperature, is stable.

The reaction after which, as one can say, the inventive lake Implementation in progress is given by the following equation

909839/1449

, '1

■ t>

reproduced

2EX + M ₂ S 1 RSR + 2MX

in which R is an aryl or alkaryl radical with 6 to 18 carbons or material atoms and X a halogenator, such as chlorine, bromine or fluorine

Iodine, and M an alkali metal, such as sodium, potassium, lithium,

or
Rubidium jaxtn means cesium. Preferably X represents chlorine or

Bromine and M are sodium or potassium. Also mixtures of reaction components Any group can be used and are within the scope of the present invention, e.g., R and / or X represent a mixture.

A few examples of compounds of the general formula RX which, according to the process according to the invention, as reaction components can be used are the following:

Chlorobenzene

4-chlorotoluene

Bromobenzene

1-chloro-3-ethylbenzene

1-fluorine-3-isopropylbenzene

1-iodo-2-raeth _o 'l-4-i-ethylbenzene

1-bromo-2,4-diethylbenzene

1-chloro-3,4,5,6-tetramethylbenzene

1-chloronaphthalene

4-chlorobiphenyl

? -Bromobiphenyl

1-chloro-4-dodecylbenzene

1- 'irom-2,4,6-tri-n-butylbenzene

4-brora-p-terphenyl

6-n-octyl-1-chloronaphthalene

and da-gl., a:; chM £ ^ alicli .whose. mixtures.

The alkali sulfides which can be used in the process of the present invention can be represented by the general formula MpS, in which M is as defined above, and these include the monosulfides of sodium, potassium, lithium, rubidium and cesium, including the anhydrous and hydrated Forms of these sulfides. The preferred sulfide reagent is Na ₂ S and its hydrates. _{This sulfide is commercially available with 9 moles of water of hydration per mole of Na 2} S, or it can be obtained as a compound with about 60 to 62% by weight of Na 2 S and about 38 to 40% by weight of water of hydration.

The polar organic compounds that act as the reaction medium are used in the inventive method should for the cyclic halogen compounds and the alkali metal sulfides represent solvents or compounds in which the reaction components are at least partially soluble. Too typical Examples of such suitable classes of compounds include amides, lactams, sulfones, and the like. Specific examples of such Compounds are hexamethylphosphoramide, tetramethylurea, N.ii'-ethylenedipyrrolidone, N-methyl-2-pyrrolidone (NMP), pyrrolidone, Gaprolactam, N-ethylcaprolactam, sulfolane, dimethylacetamide, low molecular weight polyamides and the like.

The inventive method is a polar solvent at a temperature of about 125 preferably carried out by contacting the above reactants in at least to about 45O ⁰ C and protected from 175 to 35O ⁰ C. The molar ratio of

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Polyhalosubstituted aromatic or heterocyclic compounds to the MgS reaction component should be at least 0.9: 1 and generally not exceed 3.0: 1. If proportions above this range are used, the amount of unreacted polyhalosubstituted compound will of course increase and therefore require recycling. A larger excess of both reactants leads to polymers of lower molecular weight and these decreases are accelerated by increasing the reaction temperature or reaction time. If, for example, a small excess of alkali metal sulfide is used, the polymer formed is terminated with MS groups, where M denotes an alkali metal. Such a polymer can, if desired, be acidified with the formation of terminal mercaptan groups. If, on the other hand, an excess of polyhalosubstituted reactants is used, the polymer is terminated with halogen-substituted aromatic or heterocyclic nuclei. Such a polymer can, if desired, be further treated in order to convert the halogen groups into other best such as, for example, hydroxyl groups. It is within the scope of the present invention to produce polymers with such terminal groups and then to couple these polymers to form higher molecular weight polymers.

The molar ratio of RX reaction component to MgS reaction component should be at least 1.9 * 1 , whereby in general

mean the upper limit does not exceed 3 · 1. Bigger ones
Amounts of RX component can be used if desired, and the unreacted RX compound can be recovered
and returned to the reaction zone. The pressure in the reaction zone is generally autogenous, although at the reaction temperatures listed this autogenous pressure can be up to 70.3 kg / cm 2 and more, depending on the reactants chosen and the polar solvent. The reaction times depend on the reaction temperature chosen and can be in the range between 10 minutes to 50 hours. It goes without saying that, as in most reactions, longer reaction times require lower temperatures, and vice versa.

Falla desired can be relatively small amounts, generally less than 10 wt. $> The total amount of reaction components used, use of copper or a copper compound as an aid in the polymerization. To suitable
Copper compounds include copper-I and copper-II sulfide e _f halides and the like.

The amount of polar organic present in the reaction zone Solvent can vary over a wide range from about 100 to 2500 ml per mole of alkali sulfide.

ι- ■ · "■ -

ζ ■ Through a suitable choice of the polyhalogen-substituted aromatic reaction components, the polymers can be modified,

i "SÖÖ839 / U4Ö

so that one polymers of different crystallinity, different Degree of crosslinking and different molecular weight. For example, according to the method according to the invention a highly crystalline, high melting point poly (phenylene sulfide) from p-dichlorobenzene and sodium sulfide in a polar solvent such as IT-methylpyrrolidone. Using a mixture of p-dichlorobenzene and 1,2,4-trichlorobenzene you can greatly increase the degree of crosslinking of the polymer. On the other hand, when a mixture of p-dichlorobenzene and dichlorotoluene is used, the crystallinity of the polymer is reduced and thus the melting point and the shear ' Viscosity of the polymer changed »

As a further correct modification of the present invention one can use polyhalosubstituted aromatic compounds which contain other substituents through which at further implementation, cross-linking can be achieved »This is how ZoB. the reaction of sodium sulfide with a mixture of p-dichlorobenzene and 2,5 ~ dichloroaniline a phenylene sulfide polymer, which contains amino groups on some aromatic nuclei, which depends on the type of dichloroaniline used. Am Such a polymer can be crosslinked by using a dicarboxylic acid, with crosslinking of the polyamide type being formed will"

909839/1443

BATH ORIGINAL

As another important modification of the present invention, a small amount of a monohalosubstituted aromatic Compound, e.g. monochlorobenzene, etc., as a chain terminator are used, so that one has a means of limiting the molecular weight of the polymer formed at hand.

The polymers produced by the process of the invention can vary considerably, depending on the reactants used. Some are high-melting thermoplastic materials with excellent high temperature resistance, while others can be much lower molecular weight, including liquids and fat-like materials. The melting point or softening point of these polymers can range from melting at 25 ⁰ C liquids to polymers which melt about 40O ⁰ O, rich. These polymers can be heat treated, either in the absence of oxygen or with an oxidizing agent, either under vacuum or at atmospheric or higher than atmospheric pressures, njyi in order to increase the molecular weight either by lengthening a molecular chain or by cross-linking or by a combination of both possibilities, to improve properties such as tensile strength. Such a treatment can be carried out, for example, by heating the polymer, preferably to a temperature above its melting point, in some cases up to 250 to 500.degree. Such a heat treatment can be carried out while the polymer is in contact with air or under vacuum or under an atmosphere of an inert grass such as nitrogen, 909839/1449

The polymers produced by the process of the present invention can be molded into a variety of useful articles by known molding techniques. The deformation should be carried out above the melting point or softening point, but below the decomposition point of the specific polymer to be deformed. As suitable molding process may be injection molding, compression molding, vacuum forming, extrusion and the like mentioned. _C The polymers can directly after recovery from the reaction zone in which they are formed, be deformed, or it can be subjected even before the deforming a heat treatment as described above, will. As a further option, a heat treatment below the softening point can be used for deformed articles o

The polymers produced by the process according to the invention are used wherever a high melting point and / or high temperature resistance are desired. These polymers can be mixed with fillers, pigments, stabilizers, plasticizers, extenders and other polymers will. As fillers, graphite, carbon black, titanium oxide, glass fibers, metal powder, magnesium oxide, asbestos, clays, wood flour, ■ Cotton flakes, <χ -cellulose, mica and the like. Used will. A more complete list of fillers will be given in "Modern Plastics Encyclopedia", 41, No. 1a, September 1963, pages 529-536. If necessary, such can Fillers poured into the polymerization reaction vessel

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will. Such polymers treated with filler are in particular for applications in the ultra-high temperature range, e.g. suitable as ablative nose cones.

When shaping the sulfides, the anhydrous form of the alkali sulfides is preferably used. The sulfides can be found in this Form can be introduced into the resection zone, but they can can also be introduced into the reaction zone in a hydrated form, the RX reaction component being

™ kung a drying process to remove the water of hydration is subjected. For example, the hydrate form of an alkali metal sulfide can be used to remove water while at the same time Beating nitrogen through the solution in a polar organic solvent. This removal of the Water can be effected in the reaction zone prior to the introduction of the RX reactant, but it can also be effected in a separate zone are carried out, followed by a solution of the anhydrous sulfide in a poleren organic

* Solvent is introduced into the reaction zone.

The reactions can be carried out batchwise or as a continuous process. Each completion of the implementation e.g. common methods for the production of diaryl sulfides, Di (alkaryl) sulfides, arylalkaryl sulfides and / or their Mixtures are used. After completion of the reaction, the reaction mixture is generally of the reaction temperature

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BATH ORIGINAL

cooled down, filtered to remove the alkali halides and then to recover the sulphide product. steps such as distillation, crystallization, extraction and the like.

The description and the following examples show that the method according to the invention is a relatively simple and ■ Commercial process for the production of diaral sulfides, Di (alkary ^ sulfides, arylalkaryl sulfides and / or mixtures thereof represents. Typical sulfides that can be prepared by the process according to the invention can be mentioned v / earth:

Diphenyl sulfide

Di (4-methylphenyl) sulfide

Di (3-ethylphenyl) sulfide

Di (2-methyl-4-isopropylphenyl) sulfide

Di (2,4-diethylphenyl) sulfide

Dinaphthyl sulfide

Phenyl-4-methylphenyl sulfide

Di (2-ethyl-4-n-decylshenyl) sulfi d

Phenyl naphthyl sulfide

Di (4-biphenylyl) sulfide

Di (4- / p, P ^f -terphenylyl7) sulfide

4-biphenylyl phenyl sulfide

example 1

An initial etch is filled in, in which poly (phenylene sulfide) by Un-s «± tzun £ - of p-dichlorobenzene with sodium sulfide in -I.ieth; / lpjrr (, xidon made v.urde.

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In this approach 60 grams of Na ₂ SoQH ₂ O in 100 ml of N-methylpyrrolidone were charged to a glass flask and heated under a nitrogen stream to 160 ⁰ C. This preliminary heat treatment served to remove the water of hydration from the sodium sulfide. 36.7 g of p-dichlorobenzene were then added to the resulting solution and the resulting mixture was melted into a glass tube. This mixture was then heated for 44 hours at 231 ⁰ C, then 20 hours at 225 ° C and then 24 hours at 260 ⁰ O. Then a polymer was obtained with a Schirielzpunkt between 275 and 285 ⁰ C from the pipe, which could be deformed at 29 ° C ⁰ to a hard Piim.

Because of the pressure applied in the implementation, all of the following approaches in which NapSv and p-dichlorobenzene were implemented were carried out in a stainless steel bomb unless otherwise stated. Each batch was the desired amount SoSHpO in the desired amount of reaction diluent

^{heated to 190 °} C. under a stream of nitrogen in order to remove the water of hydration. The resulting solution was then introduced into a stainless steel bomb together with the desired amount of p-dichlorobenzene. The contents of the bomb were then ^{heated to approximately 250 0} C during the desired reaction time, after which dif; Bomb opened, the polymer removed and washed with water and acetone. The polymer was then dried and the melting point and the shear viscosity were determined. The determination of the shear viscosity was carried out according to the method of R.Ll. I.IcGlanery and AoA. Harban performed that in the

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te chili s ciien lecture of the "Society of Plastics Engineers, Inc.", j3, Section 21, Publication Mr. 3 »presented in January 1962 at the Annual PES Technical Congress in Pittsburgh, Pennsylvania, The results of these runs are shown in Table I.

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Table I.

Gram gram used

73.4

73.4 240.2 240.2 240.2 240.2 240.2

_ _middle tenzol

Volume absorption solder temperature medium ο _Λ ml

Reaction time,
Hours.
in the
Reaction temp.

Grams of dry polymer recovered

yield

fo the
theory

45

45 147 147 147 147 147

N-methylpyrrolidone

N-methylpyrrolidone

200 260-265 41.5
200 260 91

IJ-Me thy lpyrr o- 1000 lidon

Dimethylformamide 1200

N-methylpyrrolidone

N-methylpyrrolidone

ÜT-LIe thy! Pyrrolidon

1000

1000

1000

17th
16
17th

17th
17th

96.3

59.9

91.0

90.7

91.2

Melting point of the polymer ο «

Shear viscosity at 303

Poise

79

60.5

not calculated

not calculated

84.2 84.0 84.5

275 8.80

248.5-252

275

240

282.5-. 40.08 285.5

286-291, 37.30 284-287 37.8

Sine sample of the polymer from run 32 of Table I was molded at 310 G ⁰ and brittle found "Another sample was heated under vacuum for 3 hours at 340 to 36O ⁰ C" to give na.eh the deforming at 310 ⁰ C a brittle plate. a sample was then placed on a hot plate and melted and processed in the molten state with a Spr.tel. This sample was tough and was not brittle "a further sample was hot between two plates provided with a Glasfasergewebescliicht at 338 ⁰ C overnight deformed this deformed sample was processed with a hammer without having fallow another sample of this mixture was applied to a hot plate on which an air stream was about blown for 20 minutes, and then at 310 ⁰ C and 843 , 6 kg / cm deformed. The Shore D hardness of this sample was 85, while the tensile strength

P sample

strength at break was 713.1 kg / cm. One more »

"pressed was melted on a hot plate on two layers of glass fiber fabric and between two hot plates at 33O ⁰ C for 15 hours this plate was then re-formed in a Polynerisationspresse at 31o ° C and 843.6 kg / cm. This material had a Shore D hardness of 85, a tensile strength of 1068.6 kg / cm and an elongation at break of 1.5 % . Another sample from batch 32 was ^{heated on a hot plate at 371 °} C. for about 10 minutes in air. Each cooling, the polymer vrurde ⁰ C and 843.6 kg / cm deformed and then quenched in ice-water »The measured shear viscosity of this material at 3O3 ° C was 1.01 χ 10 poisse at 34O.

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~ 24 -

Example 2

In another approach, sodium sulfide and p-dichlorobenzene were converted into suIfolane. In this approach, 200 ml of sulfolane and 15.5 g of NapS placed in a bomb and added to this mixture 29.2 g of p-dichlorobenzene were added. The mixture was then Heated to 250 0 for 17 hours, then the bomb was opened and the reaction product was removed. The product of this approach was found to be a black, tar-like product suitable for coating of pipelines, etc., can be used, for example, to impart resistance to corrosion.

Example 3

An approach was carried out in which no attempt was made to remove the water of hydration from the sodium sulfide prior to the reaction with p-dichlorobenzene. In this approach was 1 1 I-Iiethylpyrrolidon, 147 g of p-dichlorobenzene and 240.2 g NapS.9HpO heated for 17 hours at 250 ⁰ G in a sealed bomb "The product consisted of two phases, namely from a rigid polymer and a dark colored liquid. The polymer was separated off by filtration, washed three times with water and once with methyl alcohol and then dried. The weight of the dry polymer was 45.8 g. A solid cake of polymer was also obtained from the bomb. This cake was ground with water in a mixer, filtered and dried. This material weighed 31.7 g, which gives a total yield of 77.5 g of polymer (corresponding to

71.8 ^c / o of theory).

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A sample of the polymer from the solid cake was used in 334 G melted and quenched overnight. Slow cooling of the molten polymer resulted in a brittle interior, while the quenched polymer was flexible "

Example 4

In two other approaches, separate drying of the sodium sulphide was effected before the reaction in order to reduce the influence of this To show the drying process »

In the first batch, 1 liter of IT methylpyrrolidone and 200 ml of xylene were heated to boiling under reflux, and 240.2 g of sodium sulfide nonahydrate were added to this solution. For 1.5 hours heating this mixture at reflux temperature resulted in the removal of significant amounts of water The remaining material was placed in a bomb with 147 g p-dichlorobenzene, after 17 hours' reaction at 25O ⁰ C the bomb was cooled, the dark-colored polymer removed and how worked up in Example 1. The polymer weighed 74.8 g. This polymer had a melting point of 281.5 to 286 ° C. and a shear viscosity of 2.68 poise, measured at 303 ⁰ O ₀

In the second approach, were heated for 5 hours at 200 ⁰ C under vacuum and held during the removal of the vacuum under nitrogen atmosphere 441.3 g NaPS ^ HPO, which had been kept under vacuum at room temperature for one week "compartment of this method were 282, 5 g of water removed. 80 g of this dried

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Natriumsulf ids, 1 1 E-methylpyrrolidone and 151 g p-Diclilorbenzol were under a nitrogen stream in a bomb introduced The sealed bomb was then heated 17 Stun.Ien to 25O ⁰ G, and the resultant polymer v / ie processed in Example 1 "This Polymer weighed 73.4 g, melted at 273 to 277.5 ° C and had a shear viscosity at 3O3 ° C of approximately 2 poise «

Example 5

Under the influence of an additive according to the invention and the oxygen

To show the flow of x & adädic when in contact with the polymer, a number of runs were carried out using the procedure of the runs outlined in Table I, with the exception that copper or a copper compound was added to the reaction vessel. For each of these runs, the feed contained 11 H-methylpyrrolidone, 240.2 g Fa ₂ S.9H ₂ O, and 147 g p-dichlorobenzene. The sulfate and sulfide were heated to 186 ° 0 for about 1 hour with stirring and a nitrogen purge to remove the water of hydration. The resulting material was then introduced into the bomb together with the p-dichlorobenzene and the desired amount of copper or copper compound. Each test mixture was heated 17 hours euf 250 ⁰ O, after which the polymer was recovered by Mitra ion and subsequent stitches as in Example. 1 The results of these test batches Kr. 37 to 4C are shown in Table II.

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Table II

copper source used

CuCl

CuCl

Copper tube

CuCl

Gram gram cutting point shear viscosity

used copper source obtained dry Pclymeri- tat at 303 ⁰ C

Polymer sats ⁰ C poise

2 4

327.5 cm long, 0.635 cm inner diameter; Copper pipe snake

92 ,8th 282 , 5-286 , 5 18th , 5 92 • 6 285 , 5-286 »5 52 , 4 98 ,8th 276 - 280 56 , 3 89 , 6 282 , 5-285 , 5 12th A.

One sample of the polymer from run 38 and 39 of Table II was applied to a hot plate in an aluminum foil and heated for 5 hours and 55 Hinuten at 340 ⁰ C. Measurements of the shear viscosity of the heated samples were then made «. The original polymer from run 38 was at 303 ⁰ O showed a shear viscosity of 18.5 poise and after heat treatment ", this polymer has a shear viscosity at 3O3 ° C of 139» 6 Poise * the original polymer from run 39 had a shear viscosity at 303 ⁰ O of 52.4 poise, while the shear viscosity at 3O3 ° C after the heat treatment was 3320 poise

A 23.5 g sample from Run 40 of Table II was placed in a glass tube which was then placed in an electric oven. After the polymer had melted, air was slowly passed through the melt. The air is brought to 310 ⁰ C and passed 2 hours through the polymer, after which the temperature con 355 ⁰ C. Then the tube was cooled and it was found that the polymer adhered to the glass ,, The glass was broken and a sample of the polymer obtained. The shear viscosity of the material was 5930 poise at 303 ⁰ C.

Example 6

Comparative tests were carried out on the heat treatment of poly-

(phenylene sulfide) in air and in nitrogen. at

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Two glass tubes were charged to these batches with polymer from batch 38 of Table II and a gas inlet device was inserted into each tube so that nitrogen or air could be passed through the polymer. The two tubes were placed in an oven and nitrogen was passed through the other polymer while the polymer was heated above its melting point. After 2 hours at 340 ^° C., the samples were removed from the oven and cooled. No weight loss occurred in any of the samples with this treatment. The original polymer before the treatment had a shear viscosity at 303 ⁰ O of 52.4 poise. The sample heated in nitrogen showed a shear viscosity at 303 ⁰ O of 84.2 poise,

while the shear viscosity at 303 ⁰ O of the air-treated sample was 2860 poise. Both samples were deformed into a 3 µm ^{at 340 ° G;} The nitrogen treated sample was brittle, while the air treated sample was flexible and much stronger than the nitrogen treated sample.

Example 7

Bs were carried out two approaches in which a lot of Monochlorobenzene was used together with p-dichlorobenzene, to modify the polymer and cause a reduction in molecular weight.

In the first batch, 200 ml of N-methylpyrrolidone and 75 g S.9HgO placed in a flask and placed under a stick

909839 / U49

material stream heated ^{to 190 0} C to remove the hydration water. This LIc.terial was introduced together with 23 p-Q Diehlorbenzol and 35 "2 g Ghlorbenzol in a stainless StPlilbombe. This mixture was then heated to 25 ° C. for 17 hours, after which the bomb was opened and the product obtained. The recovered material contained a dark liquid and a solid. The solid material, namely 2Tatriim! Chloride, was filtered off "The liquid was then extracted with chloroform and benzene"

In the second batch, the loading material was the same as in the first batch above, with the assumption that 2 g of CuCl were added. In turn, a liquid product was obtained which was soluble in acetone. On cooling this material, some white, crystalline material separated out.

Example 8

An approach was carried out in which: a small amount of o-chloroaniline was used in order to riodify the characteristics of the polymer. In this approach, 73.2 g of F. ^ S.9KJ ^ ' - * - ⁿ 400 ml of ET methylpyrrolidone were heated to 190 ⁰ C to remove the' .Tassers. This material was then placed in a bomb along with 41 g of p-dichlorobenzene and 6.4 g of 2-chloroaniline. The sealed bomb v / urde there; nn 17 hours to 250 ⁰ G heated, after which the polymer is recovered and worked up as in Example. 1 24.4 g of the polymer with a melting

909839 / U49

point of 283 Ms 286 ⁰ C were gained. The shear viscosity
at 303 C of this material was 52 poise.

Example 9

Two approaches were carried out in which dichlorotoluene
used vmrde to unite the characteristics of poly (plienylene sulfide)
modify «In the first approach mirdeii 240 g ITa ₀ S ₀ 9HpO in 1 1
IT-Kethylpyrrolidoii heated to 19O ⁰ C to remove Y / water. This material was combined with 73 »5 g of p-dichlorobenzene and
80.5 g of 2,4-Bichlortoluol in the bomb introduced The sealed bomb was heated 17 hours at 250 ⁰ C, whereafter the reaction vessel vrarde cooled. In this approach, all of the polymer appeared to be in solution. After filtering off the sodium chloride, the piltrate was poured into 2 liters of water, which resulted in the formation of an emulsion. Then 200 ml
Acetic acid was added to coagulate the polymer, after which the polymer obtained was heated on a steam bath for 2 hours
became. The resulting polymer was viscous, but was pourable at the boiling point of water. After drying under vacuum overnight at 125 ° C., 100.3 g (corresponding to 89.5 ° / ° der
Theory) of the polymerisivts obtained. This polymer melted
under IfO ⁰ C to a viscous liquid. At room temperature the material was a hard, brittle solid.

I; .i second approach were 24 ^f -, 2 g Na ₂ S.9HgO in 1 1 U-MethyI-

lntfemunf for /: of V / ater to 190 ⁰ C heated. Df.s

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BATH

Material held was placed in a bomb together with 103 g of p-dichlorobenzene, 40.3 g of 2,4-dichlorotoluene and 6 g of 1,2,4-trichlorobenzene (as a crosslinking agent). Compartment 17 hours heating to 250 ⁰ G has been opened the bomb and taken out and the polymer worked up as in Example. 1 33something additional polymer was in solution and this material was obtained by pouring the filtrate into 2 liters of water and adding 200 ml of vinegar. acid was added to precipitate the polymer. After drying, the insoluble polymer resulted in 47.9 g, while the polymer obtained from the solution was 49.1 g. The insoluble polymer melted to 215 C.

Example 10

A number of experiments were carried out in which various Amounts of 1,2,4-trichlorobenzene together with the p-dichlorobenzene were added to crosslink the polymer.

For each batch, 240.2 g of Na ₂ S.9HgO in 1 1 of IT-methylpyrrolidone were added under a stream of nitrogen to remove the water of hydration.

sers heated to 190 ⁰ O.

In the first approach, the dehydrated sulfide mixture was put together men with 132.1 g of p-dichlorobenzene and 12 g of 1,2,4-trichlorobenzene placed in the bomb. The mixture was heated at 250 ° C. for 17 hours, then cooled and recovered as in Example 1. The dry polymer obtained was 84.6 g and melted

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at 25O ⁰ Co A sample of the deformed film was heated in air for 4 hours at 340 G and quenched into ice water. This sample was tough and very difficult to break,

In the second approach, the dehydrated sulfide mixture was introduced into the bomb together with 117.8 g of p-dichlorobenzene and 24 g of 1,2,4-trichlorobenzene. Bach 17 hours at 25O ⁰ O was recovered and the polymer washed as in Example 1, - 85.1 g were being of dry polymer having a melting point of 37o C ⁰ obtained.

"In the third approach, the dehydrated mixture sulfide 81.4 g of dry polymer was combined with 139.8 g of p-Mchlorbenzol and 6 g of 1, 2,4-trichlorobenzene was 17 hours at 25O ⁰ C in the bomb introduced by having a melting point of 265 ⁰ C.

A sample of this polymer from the third batch was ^{melted at 316 °} C. in an aluminum dish. This material was quenched in water and made a brittle material. This brittle sample was applied to a hot plate at 316 ^° C. and heated over power in air. A very tough sample was obtained which could not be broken with a hammer. A sample of this material was ^{re-deformed between aluminum foils at 295 0} O and 1265 kg / cm. A flexible tough film was obtained.

90 983 9 / H4 9

The use of. Trihalobenzene causes crosslinking, and an increase in the amount of trihalobenzene leads to polymers of increased hardness.

Example 11

In order to determine the changes in molecular weight due to the use of different amounts of trium sulfide, additional experiments were carried out as in Example 1, in which the amount of sodium sulfide was changed slightly. After dewatering, the reaction "was effected for 17 hours at 250 G ^0. The following table shows the decrease of shear viscosity at 3O3 ° G in poise at the use of large quantities of sodium sulfide"

Mole ratio shear viscosity

NaoS / p-dichlorobenzene at 303 ° C (poise)

1.00 37.3

1.02 6.4

1.04 4.8

1.05 7.1

Example 12

11 N-methylpyrrolidone and 720.6 g Na ₂ S.9H ₂ O were placed in a glass flask and heated with stirring to de-distill the water of crystallization. This distillation v / are removed 517.6 g, together with some N-methylpyrrolidone. The remaining material was placed in a steel reaction vessel together with 441 g of p-dichlorobenzene. This mixture was 17 hours

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- 55 -

heated at 226.7 ° C, after which the reaction vessel is opened and

solid polymer removed \, urde. This polymer was washed three times, 2 liters of methanol and then 2 liters of water being used in each washing process. This polymer weighed 285 g after drying. The polymer was heat-treated by being heated under vacuum at 620 ⁰ O 24, hours, after which it was allowed to cool to 3O2 ° C and 703 kg / cm deformed and Zi ■ iiaertemperatur. This polymer possessed the following properties:

Flexural modulus 33700 kg / cm ²

Shore D hardness 85

Tensile strength at the yield point 870 kg / cm elongation at break 12 $

Example 15

In another experimental approach, 1 liter of IT-methylpyrrolidone and 720 g of Na ^ S.9HpO were heated under a nitrogen atmosphere to remove water by overhead distillation. After 550 g had been removed by overhead distillation, the resulting mixture was placed in a steel reaction vessel together with 485 g of p-dichlorobenzene and heated at 252 to 238 ° C. for 17 hours. The stitching temperature was then increased to 260-295 ° C for 2 1/2 hours. After washing, which was carried out according to the method described in Example 12 above, and subsequent drying, 298 g of dry polymer were obtained. PolymeriBat was at 538 ⁰ O for 24 hours under a vacuum tip ^ jDehrndelt. During the heat treatment, 94.9 g only 3.1 g

909839/1449 BAD ORJGiNAl.

lost This is an astonishingly low loss when you consider that the polymer was ^{heated under vacuum at 338 0} O for 24 hours. The electrical properties found in this example were determined according to ASTM Method DT 531-61. This heat-treated polymer was then molded at 310 ° C. and 1406 kg / cm, after which the electrical properties of the polymer were determined.

Electrical Properties

Dielectric constant

100 kHz 2.3337

1. MHz 2.3335

Loss factor (dissipation

factor)

100 kHz 0.000379

1 MHz 0.000454

Example 14

An experimental approach was carried out in which p-dichlorobensol and ITodium sulfide by the process of the present invention were implemented using hexamethylphosphoramide as the reaction solvent "

In this approach, 120 g (0.500 Hol) hydrate, 500 ml of hexamethylphosphoramide and 200 ml of toluene were in a 1 liter three-necked flask, placed under nitrogen. Dpc The resulting mixture was heated by distillation to drive off the water and heating was continued with stirring,

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BATH

had until the vapor temperature reaches 238 ⁰ G, "The intestinal fluid was cooled to about 13O ⁰ G and 73.5 g (0.50 mol) of p-dichlorobenzene was added. The mixture was then heated to reflux at a liquid temperature of 226 to 239 G for 24 hours, and the Dps mixture then left to stand over a weekend was then diluted with water, filtered, washed twice with water, flushed three times with nitrogen and ^{dried at 70 °} C. under vacuum. The weight of the dry polymer - sats was 44.3 g 'which corresponds to 82 ^c ß> conversion. The melting point of this polymer was 260 to 265 C.

Example 15

Bs an approach was carried out in which p-dichlorobenzene with Sodium sulfide using tetramethylurea as solvent was implemented.

In this approach, 27.75 g (0.345 mol) of anhydrous Na ₂ S, 50.7 g (0.345 mol) of p-dichlorobenzene and 400 ml of tetramethyl urea were placed in a stirred, stainless steel autoclave and left at 250 for 21 hours ⁰ G heated. The reaction mixture was then poured into water and the brown solid polymer present was isolated and dried under vacuum. After drying, the weight of the polymer was 28.5 g, corresponding to a yield of 76.5 "/> of theory. This polymer had a softening point of 280-285 ⁰ G.

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BAD ORiGINAL

J & Vtiw '

Example 16

An approach was carried out "in which it was attempted p-Dichlorbeiizol vilt ITodium sulfide using To implement 1-methylnaphthalene as a reaction solvent » In this experiment 33.7 g of anhydrous Ha are used. S, 61 g p-dichlorobenzene and 580 ml of 1-methylnaphthalene together 300 C heated for 28 hours ο It did not react. « This approach shows that a polar organic solvent is necessary in the process according to the invention.

Example 17

A test was carried out in which a polymer according to the inventive method by reacting Sodium sulfide and m-dichlorobenzene produced in H-diethylpyrrolidone became.

! In this approach were 480.4 g Hatriumsulfidnonahydrat 1 and 1 IT-Ke thy pyrrolidone were charged and heated until 385 g Y / ater by ijberkex'fdestillation v eh separated in a 3 liter flask, were orden. The remaining katorial was poured into a stainless steel bomb and 294 g of m-dichlorobenzene was added to the bomb. The bomb was then sealed and attached to a lip and heated to 227 ° C. for 17 hours while shaking it.

The deep action mixture was then washed four times with Vifu-ser, after each V / at-ch process filtered and the isolated Folyneriprt

909839 / U49

BATH ORIGINAL

was dried under vacuum overnight dry polymer was 217 g.

Example 18

In another experimental approach, a polymer was prepared by reacting 4,4'-dibromobiphenyl with sodium sulfide in H-methyl-pyrrolidone. In this approach, 1 liter of IT methyl 1-pyrrolidone and 240.2 g of sodium sulfide nonahydrate were placed in a 3 liter flask and heated until 215 g of v / water had been removed by overhead distillation. This mixture was then placed in a bomb and the solution allowed to cool, and 312 g of 4,4'-dibromobiphenyl were added to v.-onB.ch. The bomb was then sealed and placed on a seesaw and ^{shaken at 30O 0} O for 3 hours. After the polymer had been washed three times with water, it was dried in a vacuum oven at 125 ° C. 184 g of dry polymer were obtained. The melting point was 431 ⁰ O and the VerJ determined by differential thermal analysis,

The melting point was 431 ⁰ O and the solidification peak 395 ⁰ O,

Example 19

In another approach, the polymer was prepared by reacting 2,5-dibromothiophene with sodium sulfide. This Anaatz vurde by the same I.Iethode such as Bosch rubbed in Example 18 carried out using 1 H-1 and IIethylpyrrolidon 'r.'4 ^(j,' ri g Hfvfcriumsulfidnonahydrat used v;. Ere The amount of by t'borkoijfdestillation separated ^{T 'r} water during drying was 186 g. The amount of 2,5-dibromo added

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BAD ORlO (NAi.

thiophene was 240 g, with the reaction taking 17 hours
227 ° ö was carried out »Subject isolation of the polymer by the method described in Example 18 was 56 g
dry polymer obtained.

Example 20

A smoke batch was carried out in which a polymer was prepared by reacting 4,4'-bis-p-bromophenyl ether with sodium sulfide in N-methyl pyrrolidone. In this approach, 7312 g of sodium sulfide nonahydrate and 400 ml of N-methylpyrrolidone is heated under nitrogen flow to remove water at 19O ⁰ O were. The resulting solution was together with 100 g
bis-p-Bromphenyläther in a bomb, and heated 17 hours at 25O ⁰ G "After washing, filtering and drying
according to the method described in Example 18, 47.1 g
solid polymer obtained. The melting point of this polymer was 195 to 200.5 ⁰ C

Example 21

In a further approach, a polymer was prepared by reacting 2,5-dichlorobenzenesulfonic acid with sodium sulfide in N-methylpyrrolidone by the process according to the invention.
In this batch, 93 g of sodium sulfide nonahydrate in 500 ml of N-methylpyrrolidone was added under a stream of nitrogen for removal
of approximately 70 ml of water was heated to about 190 ° C. by overhead distillation. The remaining material was 101.9 g

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bath

2,5-dichlorobenzenesulfonic acid and mixed together for 4 hours heated to 200 ° C for a long time. A water-soluble polymer was obtained =,

Example 22

A test was also carried out at at ζ, in which a polymer was produced by reacting 2,4-diohlortoluene with sodium sulfide in ίΓ-Iüe thylpyrrolidon. In this approach, 1 liter of M-methylpyrrolidone and 1 LIoI of sodium sulfide nonahydrate were introduced into a glass flask and heated with stirring until 200 ml of water and N-IJe thylpyrrolidone had been removed by overhead distillation. The remaining material was placed in a bomb and to this mixture was added 1 pint of 2,4-diehlortoluene. The resulting mixture was heated for 15 hours at 232 ⁰ O and 2 hours at 260 ⁰ C, whereafter the reaction vessel was cooled and opened "The polymer product was soluble in N-Kethylpyrrolidon. The solution was poured into 2 l of water, which resulted in the precipitation of the polymer. The precipitated polymer was heated wurde'auf a steam bath and to the extraction of the polymer 2 1 of chloroform were added · c The polymer solution was then poured into methyl alcohol to precipitate the polymer, after which the polymer was laughs dried under vacuum at 125 ⁰ C. The polymer resulted as a clear resin at room temperature and melted under 1GO ⁰ G to a viscous liquid. The weight of the polymer was 84 g and the product was soluble in benzene. A sample of this polymer was taken for 3 hours

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BATH

Vacuum heated at 327 ⁰ O, which resulted in a hard crosslinked material which ^{could not be deformed at 310 0} O and 1546.6 kg / cm, since the polymer did not melt under these conditions. This heat-treated polymer was insoluble in hot benzene.

Example 23

A number of experiments were carried out in which p-dichlorobenzene was reacted with phosphorous sulfide in IT-methylpyrroliaon at various reaction times and temperatures. In ; Each of these approaches has been one liol sodium sulfide and 1 1 ir-Metliylpyrrolido.il with simultaneous introduction ve ^η: -TiC]; ~ material through the material to remove the -lydratr.tionswaesor '? heated to 190 ^{0 G.} After essentially the entire Vfesser had been removed, 1 LIoI of p-dichlorobenzene was added to the mixture and the mixture was heated to a temperature above 2CO " ¹ C. After the reaction time given in the table, the polymer was isolated, Washed twice with 7 / water and once with Leths.nol and dried overfold under vacuum The results of these approaches are given in the following table.

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BATH

5 temperature Tabel Viscosity "at Time 5 Weight of 303 ⁰ O Poise Ötd. 250 ⁰ O dry
Polymer 35.1 42 250 ⁰ G 92.5 29.1 7, 30C ⁰ C 86.2 6.50 7, 25th 250 ⁰ O 92.4 28.9 1 3C0 ° 0 90.4 2 300 ° 0 10.60 1 3C0 ° C 88.3 13.33 <-f heated up 89.5 8.76 300 ° 0 88.3

then cooled

Beiopiel 24

An etching process was carried out for 2s, in which large amounts of P-dichlorobenzene and large amounts of sodium sulfide were brought into contact in 1 liter of IT-ethylpyrrolidone. In this approach, 3 l-iol of ifetrium sulfide nonahydrate were added to 1 l N-IIethylpyrrolidone and the mixture was heated to 190 ° under a stream of nitrogen to remove the water of hydration. 517.6 grams of the material was removed by overhead distillation during this drying step. The obtained mixture γ / was introduced into a small reaction vessel together with 3 mol of p-dichlorobenzene. The Ilischung obtained Roll 17 i'itunden at 227 ⁰ G heated, after which the Polymerient isolated and six times alternately with 2 1 of methanol and 2 1 water / -ownsehen, said first methanol was used "The polymer was then vacuum dried overnight and yielded

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BATH

285 g dry polymer. This polymer had a melting point of 276 ^° C. and a shear viscosity of 639 poise, which was determined at 303 ^° C.

Example 25

Two approaches were made in which fillers were introduced into the polymerization zone. In one approach was a mixture of 1 1 N-methylpyrrolidone and 720.6 g of sodium sulf idnonahydrate distilled up to 520 g of material by overhead distillation were separated. This mixture was then together with 441 g of p-dichlorobenzene and 100 g of graphite powder in dropped a bomb. This mixture was then shaken on a seesaw for 17 hours at 227 ° C., after which the polymer separated and five times with 2 l of water and once with 2 l of methanol was washed. The dry polymer contained a homogeneous dispersion on graphite.

This approach was repeated with the exception that the amount of material separated from the drying step by overhead distillation was 480 g and 485 g of p-dichlorobenzene and 30 g of _{molybdenum disulfide were introduced into the reaction area instead of the graphite, and 0} 344 g of dispersed molybdenum disulfide were added to the polymer won.

Example 26

Uodium sulfide was with chlorobenzene according to the invention

Process for the production of diphenyl sulfide implemented.

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BATH ORIGINAL

240.2 g Na ₂ S.9H ₂ O were heated to 190 ⁰ C while introducing nitrogen in 1 1 N-Methylpyrr.olidon. The purpose of this pretreatment was to remove essentially all of the water of hydration. The resulting solution was placed in a stainless steel bomb and, after cooling, the bomb was charged with 255 »1 g of chlorobenzene.

The mixture was then heated to 250 ° C. and left at this temperature for 17 hours. The bomb was then cooled and opened, and a light green colored liquid containing τΐ undissolved sodium chloride was isolated. Analysis with the aid of gas-liquid chromatography indicated a yield of about 74 (xe-Wo '/ o diphenyl sulfide and the presence of about 26% unreacted chlorobenzene. After the salt was filtered off, the mixture was distilled and the diphenyl sulfide at 162 ° C. ... of absolute pressure of 15 mm mercury collected a total of 116.6 g of diphenyl sulfide was recovered Gasi'lüssigkeitsChromatographie showed a purity of 97 $ for this material to infrared analysis confirmed - that ea concerns with the product to Elementarcnalyse diphenylsulfide. this material gave the following results:

Elemental analysis

Clement, wt. <$> Calculated: C 77.5 H 5.4 S 17.1 #

found: 76.9 5.5 15.1; S.

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BADOFtIGINAL

Example 27

A number of experiments have been carried out, '-ei those either chlorobenzene or bromobenzene with sodium sulfide in a polar solvent by the process of the invention implemented.

1o) 13, C g of sodium sulfide (60 </ <>) , 31.5 g of bromobenzene and 150 λΙ IT-methylpyrrolidone were eir. Put in a 500 ml flask, which was equipped with a thermometer in the steam region and a condenser, which was connected to a device for use under a nitrogen atmosphere. Diece's feed contained 0.2 part of bromobenzene and 1.0 part of Ha ^ S. The entr.tr nC.ene solution was heated to boiling under reflux for 38 hours. The mixture was left to cool, after which it was diluted with 80 ml of water and the aqueous phase was extracted with two 200 nJ portions of ether.

The ether layers were combined and then dried and the Ither distilled off ₀ The remaining material v / urde then through a "Vigrepux column" distilled and a fraction boiling the absolute at 120 to "121 ⁰ C" 5 mm of mercury pressure, <vurde This fraction was 5.6 g and had a refractive index n ^ of 1.6295. This corresponds to a yield of 30 ⁶ yes bxi diphenyl sulfide ο

The sample of diphenyl sulfide was dissolved in 75 ml of acetic acid and treated with 10 ml of 30% hydrogen peroxide. The peroxide

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BAD ORIGtNAL

Sulphide genius was heated on a steam bath for 1 hour and then poured into bis. The resulting white precipitate was filtered off, washed with ater ^r Y and dried. After Uinkristallisation from ethanol a tjchmelzendes at 124 to 126 ⁰ C material was recovered, wherein the melting point for comparatively diphenylsulfone 125 ⁰ O is specified.

2.) To show the influence of drying the alkali sulfide hydride before the reaction, the same loading material as described under 1.) was used, except that the sulfide and. The solvent was added to the flask and heated to 195 ° G to remove the water before adding the bromobeiiaol. Approximately 125 ml of N-diethylpyrrolidone dripped off with the water, so that an equivalent amount of the material was reintroduced. The mixture was ^{cooled to 100 0} G and bromobeiizol was added. The resulting mixture was heated under reflux for about 24 hours to boiling left (about 180 C), after which the material to cool over a weekend

worked up
and as under 1.) ^ kü3 & ismcf & i% && filt & was. The yield was 7.9 g of an absolute at 110 to 123 ° C with 5 mm of mercury

OR

Pressure boiling material, with a refractive index of nt of 1.6275 ° This corresponds to a yield of 42.5 ° and clearly shows that drying of the iosodium sulfide hydrate improved the yield

In Annex 3, the procedure described under 2.) was used / ended, except that 150 ml of 2 - pyrrolidoh were used. To

909839/1449

The reaction mixture was worked up as in the previous batches by boiling under reflux at 185 ° C. for 27 hours. 2.4 g of the ^{material boiling at 111 °} C. with 5 mm of mercury with a

25th
A refractive index of n ^ of 1.6560 were obtained. This corresponds to a yield of $ 13 diphenyl sulfide and again proves the advantage of the previous drying of the sulfide hydrate before the addition of halobenzene.

Another experimental batch 4 was carried out at to which the previous drying step was applied. This Approach was carried out according to the method described under 2.X, except that 22.5 g (0.2 mol) of chlorobenzene were used. In addition, 100 ml of benzene was added to the feed material, to aid in the removal of water during the drying step. After refluxing for 50 hours at a] liquid temperature of 185 to 193 ° C, the Reaction mixture worked up as in the previous batches. A yield of 2.8 g of the at 110 to 115 ° 0 at 5 mm Mercury of absolutely boiling material with a refractive index of n-Q of 1.6200 was obtained. This corresponds to a yield from 15? 'j.

In batch 5, 150 ml of potassium methylpyrrolidone, 100 ml of benzene and 13 g (0.1 hol) of sodium sulfide from the previous batches were distilled until di <| Vapor temperature reached 200 ⁰ C, was and the mixture cooled and put into a 300 ml-Autoklcvender with a magnetic stirrer, was introduced.

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BATH ORIGINAL

31.4 g (0.2 hol) of bromobenzene were then added to this mixture. After 4 hours at 235 ° G, the mixture was cooled and diluted with 1000 ml of water. The aqueous phase was extracted three times with ether, a total of 400 ml of ether being used and the combined extracts were washed with water and dried. The ether was expelled and the residue distilled to give 12.3 g of a at 105 to 11O ⁰ C at 4.5 mm ^ uecksilber were absolutely obtained. This material had a refractive index n ^ of 1.6292 and was equivalent to 66% yield of diphenyl sulfide.,

Sin further Versuchsansätζ 6 was carried out in an autoclave like Anoatz 5 except that 0.2 mol of chlorobenzene and the Reaktionsbedingungenj were applied for 90 minutes at 210 ⁰ C and 3 »5 hours at 220 to 224 ° C," A yield of 11 ° / o obtained from diphenyl sulfide. In this approach, a lesser amount of the heavier material was examined by infrared analysis and found to contain diphenyl disulfide.

In batch 7, the conditions from batch 5 were repeated with 0.2 mol of bromobenzene, but a reaction time of 5 hours at 230 to 250 ^° C. was used. Diphenyl sulfide was obtained in 60% yield.

The approaches described above are given below in the form of a T & belle summarized.

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BATH ORIGINAL

approach
Ur. used
Halo. ^ Enbenzene conditions yield
Get y> 1 Bromobenzene no drying 30th 2 Bromobenzene prior drying 42.5 3 Bromobenzene Pyrrolidone as a solution
medium, dry 13th 4th Chlorobenzene Benzene at the dry
step 15th '"' 5 Bromobenzene 4 hours at 235 ° C 66 6th Oleobenzene 5 hours at 210-225 ° C 11 7th Bromobenzene 5 hours at 230-25O ⁰ O 60

Example 28

39 g (0.5 mol) of anhydrous Ka ₂ S, 113 g (1.0 hol) of chlorobenzene and 500 ml of dimethylacetemide were heated to 30 ° C. for 3.5 hours. The Rea.l: tion mixture was then diluted to 1500 r.il with water, after which the mixture extracted three times with ether vvas ... The ether extracts were combined, washed twice with ^T 7asser washed, dried and distilled under vacuum to isolate the diphenyl sulfide. The yield of the material boiling at 117 to 119 ° 0 at 3 mm Hg absolute pressure was 34 g, which corresponds to a yield of 36.6 ^c / o of theory.

This approach was repeated except that 5CO ml tetramethylurea were used as the polar organic! Solvent, and the mixture was heated 27 hours at 232 ⁰ C. The washing, extraction and the entire work-up was carried out as described above and the yield of diphenyl sulfide, which boiled at 115 to 117 ° C at 3 mm Hg absolute pressure, was 15 g,

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BAD ORlQtNAL

what 16 ^c / o corresponds to the theory »

It was yet performed, another approach to the same procedure aussei ¹ that 500 ml hexamethylphosphoramide used v / ere and da.s mixture was heated for 3 hours "at 300 ⁰ C. Analysis of the reaction product with gas Flüssigkeitschrornatographie revealed that the reaction product of 68 weight This analysis was carried out after removing the reaction solvent

The three approaches above show that besides N-methylpyrrolidone also other polar organic solvents in the case of the invention Procedures can be used.

Example 29

A mixture of 11 B-methylpyrrolidone and 240.2 g of sodium sulfide nonahydrate was heated in order to remove water by overhead distillation cool to about 25 ° 0 left "Then, v / ere 253.2 gp-chlorotoluene introduced into the bomb and the contents were heated to 293 ⁰ C and kept at this temperature for 1.5 hours with shaking on a YfiDpe. The reaction vessel was then cooled and 2 liters of water and 1 benzene were added to the reaction mixture. The hydrocarbon layer was separated, washed with water and at a

90983 9 / U49

BATH

- ■ 52 -

Distilled pot temperature of 250 ⁰ G. Needles of di (p-tolyl) sulfide crystallized in the still of the distillation column »Some product was lost during mechanical handling, but 72.1 g of di (p-tolyl) sulfide were obtained»

According to the present invention are within the scope of the preceding Description and the following claims considerable variations and modifications are possible, but it is essential that polymers by reacting at least one polyhalosubstituted cyclic compound with an alkali metal sulfide be prepared in a polar organic solvent using the methods described, and that diaryl, Di (alkaryl) ~ and arylalkaryl sulfides by converting an aryl or alkaryl monohalide and sodium sulfide into a polar one organic solvents can be obtained at elevated temperature «

909839 / U49

Claims (8)

Claims 1 process for the preparation of a sulfur-containing compound, a so-called polymeric compound, thereby indicates that at least «one halogen-substituted cyolieche Connection, the unsaturation between neighboring Ringatoaen and contains halogen bonded to carbon with an Alkali Sulfld In a polar organic medium at increased Temperature is implemented 2. The method according to claim 1, characterized in that as polar organic medium pyrrolidone, oaprolaotam, N-Xthylcaprolactaa, SuIfolan, Dinethylacetainid, Tetramethylharnetoff, Hexamethylphosphoraiaid or Ν, Η'-Xthylenedipyrrolidone used will· 3. Method according to claim 1 or 2, characterized in that that N-Hethyl-2-pyrrolidone is used as the polar organic medium will· 4 · Method according to one of the preceding claims «, characterized characterized in that the alkali sulfide la hydrated form brought in and aindeetens tellweiee is drained before the unit. 909839 / U49 BAD ORiGfNAU 5 · Method according to one of the preceding claims, drdtirch characterized) that the reaction mass before the implementation of Water frees v / earth » 6. The method according to any one of the preceding claims, dr through marked that the amount of polprera organic! cdiuia Alkalieulfid varies between 100 and 2500 ml per hol. 7 · Method according to one of the preceding claims, characterized characterized that an Arylmonohaloiseniä or Alkarylmcno- halide with an alkali sulphide to form a dinryl sulphide 7) i (alk & ryl) »sulphide or an arylalknryloulphide is implemented. 8. The method according to one of claims 1 to 6, characterized in -jekennaeiohnet, that a plyhalosubstituted cyclic compound with 1 to 3 eromatic or heterocyclic hangings with an alkali sulfide in a polar organic ileum will. 9 »The method according to claim 8, characterized in that as aromatic compound Compounds of the general formula
uses \ verdent 909839/1449 BATH , tv- * C C - e.g. C C (Y) _a (X) C C C σ ζ II (Y) 10-0 C C C C 'C ^ C "^; C. CC C C C C C III C. CC C C 5-β (χλ C C C C (Y) (X) IY 909839/14 4 9 C. C C C C 5-β BATH <*> e ft). c. c cc cc CC CC C C C ... C cc VI in which X is a halogen atom, such as chlorine, bros, iodine and fluorine and preferably chlorine and bromine »Y means hydrogen, 0 0 0 RO -Kt -K (R) ₂ , -C-OR, -C-OM, -CK (R) ₂ , -If-S-R ', -0-H «, -KH ¹ , - OjH or -; OjM, where -R is Waeeeretoff or alkyl, cycloalkyl, aryl, aralkyl or alkaryl radicals with 1 to V carbon atoms} R \ is alkyl, cycloalkyl, aryl, aralkyl or alkaryl atoms of 1 to 12 carbon atoms; Z means -N »or -C * rf I) means -0-, -r- or RjO means -N- 90 9 8 39 / H, ^ 9
BATH R-- ft Ε » • 0 O ι ι »» η Κ—, ~ G-j -P-, -ε ι ', ι H H 0
- "» - ι H-emphasized an alkaline tall, like Iistriuia, Kaliur: ,, MtM iR, Rubidium Cäaiunj η ie-t eise integer yen <? bio 6; when both best in-fo-ZXELe ..! I ~ C »bejd; one _t lot ra equals 6-n» if a 2 in formula I means -G *, let m glelcsli 5-n, if both R & ste Z in formula I mean -N =, then m equals 4- n; b -is a number from 2 to 8, land if Z in ^ epriiel II -G * means "a equals 8-b, v.if Z in Fonael II -ίί" means, let a equals 7-bj c let a whole Number from 2 to 10 and an integer from 1 to 5 »β is an integer from 2 to 4 and ρ is a number from O to 1; the wit a pi alkaline acid in a poleren organic compound at elevated temperature long enough for the production of the polyerizate by _i; : is replaced 10 · ,, Yetzttumtn according to in «-spring S oÄer 9» characterized in that there is a small amount of ^^^ conn * - all means for at least one part of the reaction Let the limitation of the permissible molecular weight be denied. 9O9839 / 1449 BATH ORIGINAL