DE1768595B2 - DIHALOGENPHYL- BIS- (HYDROXYARYLAETHER) AND PROCESS FOR THEIR PRODUCTION - Google Patents

Description

20th

denote, where Z is a divalent aliphatic, cycloaliphatic or araliphatic radical with 1-8 carbon atoms or -O-, -S-, -SO-, -SO ₂ - or -CO-

2. Process for the preparation of the aryl ethers according to claim 1, characterized in that one is in on known manner 1 mole of a tetrahalobenzene of the general formula

R ¹

(HaIU

The invention relates to dihalophenyl bis (hydroxyaryl ethers) of the general formula

(HaI) ₂

HO - Ar - Of Vo - Ar - OH

} ^ \ R ¹ R ²

wherein R ¹ and R ^{2 are} hydrogen atoms or identical or different alkyl or alkoxy radicals with 1-4 carbon atoms, hal chlorine or bromine atoms and Ar is the phenylene, naphthylene, diphenylene radical or a polynuclear aromatic radical of the general formula

Cydoaliphatic or aromatic radical with 1-8 carbon atoms or —O—, —S—, —SO—, —SO ² - or —CO- isJ, as well as a process for their preparation.

^^ ρ ^^ such compounds are:

t, 4-bis- {4-hydroxyphenoxy) -23-dichlorobenzene

13, bis (4-hydroxyphenoxy) -2,4-didilobenzene

13-bis (4-hydroxyphenoxy) -2 ^ -dichlorobenzene

₁ , 4. _B p3-hydroxyphenoxy) -2 ^ dichloro in _Z ol

1,4-Bis ^ <4-hydroxyphenyl-isopropyi) -phenoxyl

2 £ -dichlorobenzene

13-bis ^ 4- {4-hydroxyphenyl-sulfone) -phenoxyl ·

% 4 ^ Behlorbzo!

l ^ bis ^ 4- (4-hydroxy) diphenoxy] -2 ^ chlorobenzene

lv4-bis [4-hydroxyphenyI-isopropyl) phenoxy] -

23-dibromobenzoL

The novel halogen-containing aryl ethers are crystalline or amorphous, generally colorless materials which melt between about 50 and about 250 ⁰ C and in solvents such as methanol, ethanol, acetone, dioxane, dimethylformamide and Dimethyfculfoxid soluble. You can use plastics, e.g. B. unsaturated polyester resins and epoxy resins, for example in amounts of about 5 to about 20 percent by weight, are added to make them flame-retardant.

These new substances can be produced according to the invention by in itself as is known, t moles of a tetrahalobenzene of the general formula IH

with 2 moles of a dialkali phenolate of the general formula

MeO-Ar-OMe

Wonn Me represents an alkali metal atom and R ^1, R ^2, Hal and Ar are as described in claim 1 meanings, in a polar organic solvent at temperatures between about 6O ⁰ C and about 180 ⁰ C and acidifying the reaction mixture.

35

40

45

50

55

60

(HaIU

with 2 moles of a Dialkaliphenoiats the general ^{Formula IV}

MeO-Ar-OMe

wherein Me represents an alkali metal atom and R ^1, R ^2, Hal and Ar have the abovementioned meanings, in a polar organic solvent at temperatures between about 60 ° and about 180 ⁰ C, preferably reacted between about 90 ° and about 160 ⁰ Q and Acidified reaction mixture.

Only two of the total of 4 halogen atoms in the tetrahalobenzene react. If the tetrahalobenzene contains different halogen atoms, so will these are reacted in the order chlorine and bromine

Examples of tetrahalobenzenes are: 1 ^, 4 ^ -Tetrachlorobenzene, 1,233 tetrachlorobenzene 1.23.4-tetrachlorobenzene, I ^ AS-Tetrachlor-S.b-dimethylbenzene, 1,2,4,5-tetrabromobenzene. also tetrahalobenzenes with different halogen atoms, z. B. M-dibromo ^. S-dichlorobenzene.

Examples of dihydric phenols are: hydroquinone, resorcinol. Dihydroxydiphenyls and dihydroxynaphthalenes and bisphenols of the formula V

65

mean, where Z is a divalent aliphatic. wherein Z is a divalent aliphatic, cycloaliphatic

see or araliphatic radical with 1-8 carbon atoms or -O-, -S-, -SO-, -SO ₂ - or -CO-

Examples of such bisphenols are:

Bis (4-hydroxyphenyl) methane,
U-bis- (4-hydroxyphenyQ-cyclohexane,
Bis (4-hydroxyphenyl) phenylmethane,
4,4'-dihydroxydipheny & ther,

-sulfide, -sulfoxide, -benzophenone,

but especially 2i-sis- {4-hydroxyphenyl) propane and

4,4'-dibydroxydiphenyl sulfone.

The cations for the diphenolates are those of the metals of the first main group of the periodic table in question. The sodium and potassium salts are preferably used.

Suitable polar organic solvents are, for example, diethyl sulfoxide, dimethyl sulfone, Diethyl sulfone, diisopropyl sulfone and tetramethyl sulfone. but preferred dimethyl sulfoxide (DMSO) called

The dialkali salts of the diphenols can be prepared by known methods before the actual implementation produce by mixing the respective diphenol in an inert organic solvent with the corresponding Reacts alkali metal, alkali alcoholate or alkali hydroxide and then the solvent with the alcohol or water which may have been liberated during the salt formation is distilled off

However, it is simpler and more expedient for the subsequent condensation reaction to use the respective To prepare dialkali phenolates in situ by the salt formation and the condensate reaction with the Tetrahalogen compound run in the presence of the polar solvent simultaneously or sequentially leaves.

To do this, molar amounts of the tetrahalogen compound are dissolved with twice the molar amounts of the diphenol in a sufficient amount of the polar solvent, gives the stoichiometric amount Add alkali hydroxide in solid form or as a concentrated aqueous solution and heated under inert gas, e.g. B. Nitrogen, gradually to reaction temperature. The reaction time is then, depending on the reaction temperature and the water content of the mixture, about 2 - 20 hours. After cooling, the reaction mixture is mixed with acidified water, whereupon the reaction product separates out and can be separated off. Impurities can optionally remove by falling over, washing out or recrystallization from a suitable solvent.

If the tetrahalobenzene tends to sublimate, only the diphenol and the Alkali hydroxide with heating in the polar solvent cools this mixture to room temperature and then heated gradually to the reaction temperature after adding the tetrahalobenzene with stirring. In such a case it is also possible to work under an inert gas pressure of about 1-2 atmospheres. In order to achieve high yields and to shorten the reaction time, it can be advantageous for the condensation the dialkali phenolate with the tetrahalobenzene lowers the water content of the reaction mixture keep. To do this, the diphenol is dissolved in a sufficient amount of the polar solvent

the stoichiometric amount of alkali metal hydroxide in solid form or as a concentrated aqueous solution are added and the mixture heated for some time, for example 2-6 Standen, under inert gas to about 110 ° to about 150 ⁰ C and S while distilling the existing and the liberated in the water Phenolatbfldung , expediently with the concomitant use of an entrainer such as benzene, toluene, xylene or chlorobenzene, largely from the mixture. Subsequently, the tetrahalogen compound is added, whereupon the actual condensation reaction is carried out by a z. B. '/ 2-8 hours of heating to the reaction temperatures mentioned takes place

Another simple method of removing most of the water from the reaction mixture consists

ι S therein, the diphenol and the alkali hydroxide below Heat in a sufficient amount of the polar organic solvent and then dissolve distilling off about 10-20% by volume of the polar solvent before adding the tetrahalogen compound, expediently under vacuum. Here, the water distills azeotropically with the portion of the polar solvent from the reaction mixture. The tetrahalogen compound is then added, whereupon condensation sets in with further heating.

Compared to the halophenyl ethers of the French patent specification 15 14 721, the invention, OH-containing aryl ethers have the technical advantage that they are added to polyesters, for example to thermoplastic, aromatic polycarbonates neither sweat out of the polycarbonate melt still crystallize.

Another technical advance of the invention OH-containing aryl ethers compared to the halophenyl ethers of FR-PS 15 14 721 consists in that the OH group-containing aryl ethers according to the invention alone or together with others Bisphenols, for example, condense or form special polycarbonates with reduced flammability. (»Let condense.

In the two cases mentioned, the technical one is based Progress of the aryl ethers according to the invention over the aryl ethers of FR-PS 15 14 721 on the phenolic OH groups of the aryl ethers according to the invention.

The OH group-containing aryl ethers according to the present invention have compared to other halogen-containing Compounds with phenolic OH groups. the halogen atoms and phenolic OH groups on

5v carry the same aromatic core (see DTPS 11 29 957), for example 2,2-bis- (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane. 2,2-bis- (3-bromo-4-hydroxyphenyl) per pan or 2,2-Bi :-( 3-ehlor-4-hydroxyphenyl) -propane, the surprising technical progress that they are polyesters, For example, polycarbonates added, no depolymerization or darkening of the polycarbonates cause. The structural difference of the aryl ethers according to the invention, the OH groups and Carrying halogen on various aryl radicals apparently favors these compounds in a surprising manner compared to comparable known OH groups and halogen on the same aromatics bearing Links.

fts This surprising finding is illustrated by the following Comparison confirmed (tests 1 to 7):

By condensation of bisphenol A (2,2-bis- (4-hydroxyphenyl) -propane) with phosgene was known

ter method (ζ. B. H. S c h η e U, Chemistry and Physics of Polycarbonates, New York, 1964) produced a high molecular weight polyester (polycarbonate) This polycarbonate was dissolved in methylene chloride. Samples of this solution have been given various flame retardants making additives and investigating their effects. The amount added was the same in each case and was 7 % By weight, based on the dissolved polyester. Films were cast from the polymer solutions, their physical Properties before and after brief melting and re-pouring (for imitation of the injection molding process) were compared with non-doped polycarbonate. In detail, the following were Results obtained demonstrating the superiority of the invention Products show:

Polyester film Before melting

Aus Molgew. Fractional plane M rotation Notched impact toughness DIN 53435 (22 ° C)

After melting Appearance molecular weight Fracture-

rotation

Notched impact strength DIN 53435 (22-C)

1. Polycarbonate without additives

color 210 000 110%

Come on,

clear

also 210,000 104%

2. Polycarbonate with additive
of 1,4-bis [4- {4-hydroxyphenyl-isopropyl) -phenoxy] -2,5-dichlorobenzene

3. Polycarbonate with additive
of 1,4-bis [4- {4-hydroxyphenyl-isopropyl) -phenoxy] -2,5-dibromobenzene

4. Polycarbonate with additive
of £ 2-bis (3-chloro-4-hydroxyphenyl) propane

5. Polycarbonate with additive
of 2 ^ -Bis- (3-bromo-4-hydroxyphenyl) -propane

6. Polycarbonate with cover
of 2,2-is- {3,5-dichloro-4-hydroxyphenyl) propane

7. Polycarbonate with the addition of the same 210,000 92% of 2,2-bis- (3,5-dibromo-

4-hydroxyphenyl) propane

The fire behavior of the products from tests 1 to 7 was 10 cm long and 2 cm wide

also 210,000 102%

also 210,000 101%

also 210,000 98%

also 210 000 96% colorless,
clear

colorless,
clear

colorless,
clear

yellow-brown

210000 110% 80

210,000 102% 71

210,000 101% 68

146,000 86% 22

74% 16

dark- 128 000

Brown,

clear

black- 44 000 28% 4.2

Brown,

cloudy

black- 42 000 26% 3.8

Brown,

cloudy

Film strips examined For this purpose, the film strip was initially 5 see with one end in an open one Flame held, then removed from the flame and his further behavior observed

Polyester film

Film properties
before
Melting after
Melting Fire behavior
before
Melting after
Melting colorless,
crystal clear colorless,
crystal clear burns with
bright flame burns with
bright flame colorless,
clear colorless,
clear goes out
after 3 seconds goes out
after 3 seconds colorless,
clear colorless,
clear goes out
after 3 seconds goes out
after 3 seconds colorless,
clear
colorless,
clear yellow-brown,
clear
dark brown,
clear goes out
after 5 seconds
goes out
after 3 seconds goes out
after 12 seconds
goes out
after 9 seconds colorless,
clear black-brown,
cloudy goes out
after 3 seconds goes out
after 6 seconds colorless,
clear black-brown,
cloudy goes out
after 3 seconds goes out
after 5 seconds

1. Polycarbonate without additives

2. Polycarbonate with the addition of 1,4-bis- [4- (4-hydroxyphenyl-isopropyl) -phenoxy] -2,5-dichlorobenzene

3. Polycarbonate with the addition of 1,4-bis- [4- (4-hydroxyphenyl-isopropyl) -phenoxy] -2,5-dibromobenzene

4. Polycarbonate with the addition of 2,2-bis- (3-chloro-4-hydroxyphenyl) propane

5. Polycarbonate with the addition of 2,2-bis- (3-bromo-4-hydroxyphenyl) propane

6. Polycarbonate with the addition of 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) propane

7. Polycarbonate with the addition of 2,2-bis- (3,5-dibromo-4-hydroxyphenyl) propane

*) The halophenols added in experiments 4 to 7 relate to comparison compounds.

7 8 *

example 1
1,4-bis [4- (4-hydroxyphenyl-isopropyl) -phenoxy] -2,5-dichlorobenzene

HO

OH

114, lg (0,5MoI) of 2,2-bis (4-hydroxyphenyl) propane bisphenol A) and 40 g (1 mol) of sodium hydroxide are dissolved in 600 ml dimethyl sulfoxide by heating under an inert gas atmosphere (nitrogen) Add 150 ml > S benzene added and heated for 6 hours at 110 ° - 120 ⁰ C. it distills the water in the reaction mixture azeotropically with benzene in a water separator, vährend the benzene in the mixture flows back after the removal of the water is allowed *> the reaction mixture Cool to 70 ^° C. and add 54.0 g (0.25 mol) of 1,2,4,5-tetrachlorobenzene with stirring. The mixture is heated under reflux of benzene for a further 2 hours. Then distilled from the benzene and the mixture is left for 6 hours at 150 ° -160 ⁰ C to react further. Finally, the reaction product obtained is precipitated as a snow-white powder by pouring into acidified water. After filtering off, washing neutral and drying, a yield of 145 g is obtained. If the product is colored, it can be recrystallized with activated charcoal from a mixture of glacial acetic acid and water or from a mixture of dioxane and water. Slight proportions of higher condensation can be removed "by falling over from dilute sodium hydroxide solution. The product melts at 96 ° -98 ° C.

Elemental analysis for C36H32O4CI2:

Calculated: C 72.0, H 5.4, O 10.7, Cl 11.9; Found: C 71.5, H 5.4, O 10.8, Cl 11.9.

Wt% phenol. OH:

Calculated: 5.3;
found: 5.4.

Example 2
1,3-bis [4- (4-hydroxyphenyl-isopropyl) -phenoxy] -2,4-dichlorobenzene

HO

CH CH ₃

CH,

45.6 g (0.2 mol) of 2,2-bis (4-hydroxyphenyl) propane and 16 g (0.4 mol) of sodium hydroxide are dissolved in 300 ml of dimethyl sulfoxide with heating , 1 mol) 1.23.4-tetrachlorobenzene was added. The mixture was heated for 16 hours to 120 ° - 140 ⁰ C, and then pours the reaction mixture into acidic water. The white powder obtained is taken up in dilute sodium hydroxide solution while warming, filtered and precipitated by pouring into acidified water. Filtration, neatrical washing and drying - a yield of 48 g is obtained. The white powder melts at 1OP-102 ° C.

Elemental analysis for C36H32O4CI2:

Calculated: C 72.0, H 5.4, O 10.7, Cl 11.9; found: C 71.2, H 5.4, O 10.7, Cl 11.7.

Wt% phenol. OH:

Calculated: 53;
found: 5.5.

Example 3
1.4 ^ Bis ^ 4- (4-hydroxyphenyl-isopropyl) -pheQoxy> 2 ^ -dibromobenzene

CH ₃

OH

OH

CH ₃

114 ,! g (03 mol) of 2J-bis (hydroxvphenyi 4, the water in the reaction system propan virtually and 6435 g (1 mole) 865% aqueous potassium hydroxide solution 65 removed completely dissolved after cooling to 6O ⁰ C is in 700 ml of dimethyl sulfoxide 1,2,43-tetrabromobenzene (0 £ 5 mol) one blast to the 983 g addition reaction vessel with nitrogen and distilled in and the reaction mixture heated under normal pressure for 8 vacuum 100 ml of dimethyl sulfoxide from. this will hours at 130 ° -140 ⁰ C After Termination of

Condensation, the reaction product is precipitated by stirring into acidified water. For purification, it is reprecipitated twice from dilute sodium hydroxide solution. After filtering off, washing neutral and drying, 128 g of a white powder with a melting point of 80 ° - 81 ° C. are obtained.
Elemental Analysis for C ₃₆ H ₃₂ O ₄ Br ₂ : Calculated: C 62.8, H 4.7, O 9.3, Br 23.2; Found: C 62.1, H 4.6, 0 9.1, Br 22.9.

Wt% phenol. OH:

Calculated: 4.95; found: 4.9.

Example 4 1,3-bis [4- (4-hydroxyphenylsulfone) phenoxy] -2,4-dichlorobenzene

Cl

50.1 g (0.2 mol) of 4,4'-dihydroxydiphenylsulfone and 25.74 g (0.4 mol) of 87.2 ^o / oiges aqueous potassium hydroxide are dissolved in 400 ml of dimethyl sulfoxide are added, 175 ml of benzene and heated for 2 hours at 110 ° -120 ⁰ C. After removal of the water is allowed to cool, the reaction mixture to 70 ° C. and 2s, with stirring, 21.6 g (0.1 mol) of 1,2,3,4-tetrachlorobenzene added. The mixture is heated for a further 4 hours under Benzolrückfluß, the benzene is distilled off and the reaction mixture is continued for 4 hours at 140 ° - react further 15O ⁰ C. The reaction product obtained is then precipitated by pouring it into acidified water. It is purified as in Example 1 to give 49 g of a beige powder \ om melting point 77 ° -78 ⁰ C.

Elemental analysis for C ₃₀ H _{20 OgS 2} Cl ₂ :

Calculated: C 56.0, H 3.1, O 19.9, Cl 11.0, S 10.0; Found: C 55.4, H 3.1, O 19.6, Cl 10.8, S 9.9.

Wt% phenol. OH:

Calculated: 5.3; found: 5.2.

Example 5 1,4-Bis [4- (4-hydroxy) diphenoxy] -2,5-dichlorobenzene

Cl

HO

111.7 g (0.6Mo!) 4,4'-DihydroxydiphenyI and 77.4 g (1.2 mol) of 87% aqueous potassium hydroxide are dissolved in 500 ml of DMSO and heated to 140 ° C. In the hot mixture is a Solution of 64.8 g (03 mol) of 1,2,4,5-tetrachlorobenzene in 250 ml of chlorobenzene added dropwise. After the addition of the chlorobenzene solution, the reaction mixture is heated to reflux temperature for 1 hour and the chlorobenzene is then distilled with the water contained in the reaction mixture. The temperature rises towards the end of chlorobenzene distance to 160 ° -170 ⁰ C. The reaction product obtained is then precipitated by pouring it into acidified water. It is cleaned as in Example 1. 141 g of a white powder with a melting point of 206-208 ° C. are obtained.

Elemental Analysis for C ₃₀ H ₂₀ O ₄ Cl ₂ : Calculated: C 69 £, H & 9, O 12.4, Cl 13.8; found: C «& H 3 $, 012 & Cl 13.7.

Wt% phenol. OH:

Calculated: 6.6; found: 6.7.

Claims (1)

Patent claims: LDiiudo ^ npbenyMjis-ihydroxyarymthe ^ deraU-common ronnel ίο in which R 'and R ^{2 are} hydrogen atoms or identical or different alkyl or ABcoxy radicals τφ- | -4 C atoms, Hal chlorine or bromine atoms and Ar is the phenylene, naphthylene, diphenylene radical or a polynuclear aromatic radical of the general formula 15th