DE1595789A1 - Arylolpolysiloxanes and processes for their preparation - Google Patents

Description

fiFPHAPn RAT7FI 68 Mannheim ι, August 26th

. ^ SKttAKU KAI ^ tL ICQC ₇ OQ Sed.nheimerStr.tte Tel. (0621) 406315

PATENT Attorney I 0 »0/83 .11

PoiUelitckkonto. Frankfurt / M. No. 2" I · it k 1 DtvtMlM lank Mannheim No. Π / 000 « Ttlcgr.-Cod · ι Gtrpat

GENERAL ELECTRIC COMPANY 1 River Road
Soheneotady, New York / USA

Arylolpolysiloxanes and processes for their preparation

The present invention relates to arylolpolysiloxanes which contain chemically linked siloxyarylol units, and a method for their production.

These organopolysiloxanes, which can be designated as arylolsiloxanes, correspond to the formula

R »

(1) [horr] H _b si o ₍₄ _ _a _ _b _ _c) a - ~ "7

in which R is a divalent aryl radical, R ^{1 is} a divalent saturated aliphatic radical with at least three

-2-

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- Sheet 2 -

Carbon atoms, R "a monovalent saturated hydrocarbon remainder, a halogenated monovalent saturated Is a hydrocarbon radical or a cyanoalkyl radical, a is a Value from 0.002 to 1, b a value from 0 to 0.1, c a value Has a value from 0 to 2.5 and the sum of a, b and c has a value from 1 to 3.

The radicals encompassed by R are, for example, divalent aromatic hydrocarbon radicals and halogenated divalent aromatic hydrocarbon radicals, such as phenylene, Chlorophenylene, tolylene or xylene radical; bivalent allcoxy-substituted aromatic hydrocarbon radicals, such as the methoxyphenylene, ethoxyphenylene or ethoxytolylene radical; nitrated divalent aromatic hydrocarbon radicals, such as the nitrophenylene, nitrotolylene or nitroxylylene radical.

Radicals that are encompassed by R ¹ are, for example, divalent aliphatic radicals, such as the propylene, butylene or pentylene radical. Residues which are encompassed by R ″ are, for example: monovalent aryl radicals and halogenated monovalent aryl radicals, such as the phenyl, chlorophenyl, toly1 or naphthyl radicals; aralkyl radicals, such as the benzyl or pnenylethyl radical; saturated aliphatic radicals , cycloaliphatic radicals or halogenated aliphatic radicals, such as, for example, alkyl radicals or haloalkyl radicals, such as the methyl, ethyl, propyl, chloropropyl, trifluoropropyl, butyl, pentyl, hexyl or octyl radical; cycloaliphatic radicals, such as the Cyclobutyl, cyclohexyl or cycloheptyl reed; cyanoalkyl reed, such as cyanoethyl, cyanopropyl or cyanobutyl reed.

By the method according to the invention it was found that that an addition of the siloxane hydride of the formula:

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- Sheet 3 f

< ^H ) a ^{Si 0} (4-ac)

to the aliphatically unsaturated arylol of the formula (3) R " ¹ ROH

what is hereinafter referred to as "unsaturated arylol", found, whereby a carbon-silicon bond is formed between the aliphatically unsaturated R ¹¹ '-.lest of the formula (3) and the siloxanhydride, without a reaction between the hydroxyl radical of the unsaturated Arylene and the siloxane hydride takes place. In the preceding formulas a and c have the meaning given above, the sum of a and c has the value 1 ois; and R ¹¹ 'is a monovalent aliphatic radical having at least 3 carbon atoms and aliphatic unsaturation in

the end position. This result was not expected, because Andrianov and coworkers, Izvestia Akademii name, SSR. Otdelenie Khemicheskikh Naulc No. 11, pp. 1039-2046 teach that the addition between triethoxysilane and o-allylphenol based on the conversion of the hydroxyl group of the phenol, as well as on the double bond of the allyl radical of the phenol.

It has now been found that Arylolsiloxane of formula (I) can be prepared by reacting up to 115 ⁰ C (A) at temperatures of a siloxane hydride of formula (2) and (B) an unsaturated Arylol of formula (3) in the presence of a effective amount of a platinum catalyst.

The siloxane hydride of the formula (2) can be a linear polymer or a cyclic, branched or crosslinked structure. £ 8 can be obtained by equilibration of Siloxyhydrid units of

909887/1521 BAD ORIGINAL

-4-

Formulas

R "
t

(4) HSiO ₁ cj HSIO j HSiO _n , -

R "

with up to 10,000 moles of siloxy units of the formulas

(5) SiO ₂ ; ^Rt ' ^SiO i, 5 i R " ₂ Si0; Rn ₃ SiO _{0 5}

per mole of said siloxyhydride units, whereby a product is formed in which the ratio of the sum of the hydrogen atoms bonded to the silicon and the R ^M radicals per silicon atom in the said siloxanhydride is 1 to 3.

The accessibility of the hydrogen atoms on silicon of the siloxane hydride of the formula (2) for coupling with the unsaturated one Arylene bound may be of the type of siloxy units of the formulas (4) and (5) used for the preparation of the siloxane hydride used depend, as well as on the structure of the obtained siloxane hydride. For example, if coupling takes place between the unsaturated arylol and a highly crosslinked or branched siloxane hydride should, accessible siloxyhydride units can through a digestion technique will be introduced that will support the use of diorganohalosilanes of the formula

R "

(6) HSiX ₁
R "

includes, in which R "has the above meaning and ϊ a halogen

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- sheet 5 -

atom is. The re-etching can occur between accessible silanol residues of such resinous materials and diorganohalogeno be effected in the presence of an acid acceptor.

Aliphatically unsaturated arylols _t encompassed by formula (3) are, for example: 2-allylphenol, 2-allyl-4-methylphenol, o-allyl ^ -chlorophenol, 2-allyl-4-nitrophenol, 6-allyl-2- methoxy-4-methylphenol, 6-ally1-2,3-methylenedioxyphenol, 2-allyl-l-naphthol, l-allyl-2-naphthol, 3-allyl-4-hydroxybiphenyl, 3-allyl-2-hydroxybiphenyl, 4- Allyl-2,6-dichlorophenol, 4-allyl-2,6-dimethylphenol, 4-allyl-2-methyl-6-methoxyphenol, 2- (1-butenyl) -phenol, 6- {l-pentenyl) -2- methoxy-4-methylphenol or 2-methoxy-4-allylphenol.

The siloxane hydrides of the formula (2) are cyclic Substances of the formula

comprises, in which R ^{N has} the meaning given above, d is an integer from 1 to 20, e is an integer from 0 to 19 and the sum of d and e is 3 to 20. This also includes linear polymers which have at least one chemically linked siloxyhydride unit of the formula (4), consisting essentially of 10,000 chemically linked siloxy units, namely.

R * R »

SiO or SiO, and the Ktttenabbruch by a

Y R *

909887/1521 -

■ * o—

R "

Siloxy unit of the formula SiY is caused, in which Y

H"

Is hydrogen or an R "radical. In addition, also silo anhydride resins of the formula

< ^H > a ^Si0 (4-ad) 2

can be used in the practice of the invention where R ^N and a are as defined above, d has a value from 1 to 1.7998, and the sum of a and d is 1 to 1.8.

The siloxane arylols can be used as foam generators, lubricants and intermediates for silicon-organic copolymers be used. They can also be used as dye intermediates and for breaking oil emulsions will.

In the practice of the invention, the reaction at temperatures is effected all the way up to 115 ⁰ G between the siloxane and the unsaturated Arylol in the presence of a Piatinkatalysetors. Although the recipe for combining the hydride, arylene, or catalyst is not critical, it has been found that effective results can be achieved if a stoichiometric excess of the arylol is maintained at all times during the addition. Optimal results can be achieved if the hydride is added to the arylol at a rate which is not greater than that which is required to keep the reaction mixture obtained during the addition so that an “in effective” concentration of at least 5 If aryl is present per mole of hydride.

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A temperature in the range of 70 ⁰ C to 115 ° C provides effective results, although a temperature in the range of yO ° C to 105 ⁰ C is preferred. It has been found that the use of a suitable organic solvent facilitates the reaction between the hydride and the arylol, although at the same time the temperature of the reaction is moderated. Any solvent which is inactive with respect to the starting materials during the reaction can be used as a suitable organic solvent. Examples of suitable solvents are toluene, benzene, dioxane and bis (methoxyethyl) ether. Various catalysts can be used, such as a platinum alcoholate coraplex compound as described in U.S. Patent 3,220 or a platinum-olefin complex compound as described in U.S. Patent 3,159,601. The separation of the arylolsiloxane from the reaction mixture obtained can be carried out in accordance with conventional separation and withdrawal processes *. The following examples illustrate the invention. All parts are parts by weight.

Example 1:

A mixture of 15 parts methyltrichlorosilane, 45 parts Phenyltrichlorosilane, 18 parts of dimethyldicalorsilane and 27 parts of diphenyldichloroilane in toluene were slowly under Stir in 400 parts of water. After the resulting mixture was stirred for a few minutes, it would settle calmly. The organic layer was separated and stripped to 90 # solids. That Organopolysiloxane resin obtained by the Zerewitinoff method 1.24 percent by weight of silicon-bonded hydroxy residues, based on the total weight of the organopolysiloxane resin.

15 parts of dimethylchlorosilane were added to 300 parts of a 20 #

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-8th-

- sheet 8 -

A solution of the above-described resin in toluene containing 20 parts of pyride was added, the resulting mixture was stirred for 1 hour and then sealed and aged at a temperature of 25 ° C. for 18 hours. The mixture was then extracted twice with dilute acetic acid and twice with water to remove salts and the excess pyridine. The mixture was concentrated ^{to 100 ° C. by prolonged heating.} Based on the manufacturing process and the infrared analysis, a clear, sticky, solid siloxane hydride of the following composition was obtained:

^(H) 0.0795 ^(CH 3 ⁾ 0.712 ^(C 6 ^H 5 ⁾ 0.737 ^SiO 1.236

24.2 parts of the above Siloxanhydridβ was added to a mixture of 6 parts of 2-allylphenol, 25 parts of toluene and 0.0028 part of platinum, which was in the form of a platinum alcoholate catalyst. The mixture was ^{heated to 107 °} C. to HO ^° C. for 13.5 hours, with an instantaneous starting peak of 115 ^° C. After heating for 13.5 hours, the infrared analysis of a sample showed that the mixture was free of silicon hydride. A quantitative yield of product was obtained from the mixture by Devolatilisation at 100 ⁰ C in the form of a clear solid. Based on the method of manufacture and the infrared spectrum, the product was an arylolsiloxane of the composition:

^(CH 3O.712 ^(C 6 ^H 5O.737 ^Si0 1.236 0.0795

-9-909887 / 1521

Example 2:

üJin organopolysiloxane resin became equimolar by cohydrolysis Amounts of phenyltrichlorosilane and dimethyldichlorosilane in toluene manufactured. The resin solution obtained was washed free of HCl and by azeotropic distillation of a portion of the toluene dried. The resin obtained contained according to the Zwerewitinoff method 4 »47 percent by weight of silicon-bonded hydroxyl radicals, based on the total weight of the organopolysiloxane resin.

41.4 parts of dimethylchlorosilane were added within 50 minutes added to a solution of 138 parts of the above resin, 200 parts of toluene and 65 parts of pyridine. The mixture was then Heated under reflux for 3 hours, cooled, washed and concentrated as in Example 1. According to the method of manufacture became a clear, homogeneous siloxane hydride of the formula

^(H) 0.204 < ^0H 3> 1.205 'W

obtain.

45.8 parts of the above siloxane hydride were added to a mixture of 32.8 parts of eugenol, 210 parts of toluene and 0.0014 parts of platinum, which was in the form of a platinum alcoholate catalyst. The mixture was ^{heated to HO 0} G to 112 0 for 5 hours. At this time, the infrared analysis no longer showed any silicon hydride. The product was freed from the solvent and concentrated ^{at 100 ° C. in vacuo.} A clear, soft resin was obtained in 95% theoretically possible yield. Kach. According to the manufacturing process and infrared analysis, the product obtained was an arylolsiloxane of the formula

- «0.204

909887/1521

-10-

- sheet 10 -

Example 3:

72.6 parts of a liquid hydroxy-end-blocked linear polyorganosiloxane with 9 dimethylsiloxy units per CH ₅ Si (H) 0 unit were added to a mixture of 32.8 parts of eugenol, 0.0014 parts of platinum in the form of a platinum Added alcoholate complex compound and 200 parts of toluene. The addition was carried out in a temperature range from 105 ° C to 112 ⁰ G. The mixture was heated another 9 hours 11O ⁰ G to 112 ⁰ C. The product was ^{treated at 100 °} C. in a vacuum in order to remove excess eugenol and toluene. Eb a clear homogeneous liquid was obtained in a practically quantitative yield. After the method of manufacture and infrared analysis, the product was an arylolsiloxane of the formula:

HO—

9 ^H 3 |

SiOj-CH ₃ I,

/ ^w 3

4- I-H

J3s was added 1 part of the above copolymer to a mixture of 20 parts of water and 4 parts of a polydimethylsiloxane which had a viscosity of 1000 centipoise at 25 ⁰ C. By vigorously stirring the mixture, a dispersion of polydimethyleiloxane in water is formed, which does not settle when standing.

Example 4:

iSs 6 parts of 1,3,5,7-tetramethylcyclotetrasiloxane to a solution of 13.42 parts of 2-allylphenol and 0.00011 parts of platinum in the form of a platinum alcoholate catalyst

909887/1521

-11-

- sheet 11 -

Compound, given in toluene. The mixture was heated to 100 ⁰ G and held for 3 hours at this temperature until the infrared spectrum of a sample of the mixture showed no more silicon hydride absorption. After concentration in vacuo at 100 ⁰ G 92 #ige yield of product was obtained. According to the method of manufacture, the product was a cyclic arylene siloxane of the formula:

Example 5;

A liquid organopolysiloxane, which consists essentially of chemically linked methylsiloxyeinholes with hydrogen bonded to silicon, is prepared in the following manner: A mixture of 96.5 parts of liethyldichlorosilane is hydrolyzed with 5.5 parts of trimethylchlorosilane, whereby a linear polymethylsiloxane is formed, which on average 26 chemically linked Siloxyhydrid units and a viscosity of 75 centipoise at 25 ⁰ C possesses.

12 parts of the above polymethylsiloxane were added to a mixture of 53.6 parts of 2-allylphenol, 0.0014 part of platinum in the form of a platinum alcoholate complex compound, and 300 parts of toluene. The addition was carried out in a temperature range of 110 to 112 ⁰ G ⁰ O. The mixture was then reacted at a temperature of 115 ⁰ C. for a further 8 hours. After concentration in vacuo at 10O ⁰ C, the excess 2-allylphenol to remove the product in 98 #iger yield.

909887/1521

-12-

- sheet 12 -

According to the method of manufacture and the infrared spectrum the product was an arylolsiloxane of the average formula:

(CH ₃ ) ₃ Si

-Si (CH ₃ J ₃

Example 6:

12 parts of the polymethylsiloxane from Example 5 were added to a mixture of 65.6 parts of eugenol, 0.0014 parts of platinum, in the form of a platinum alcoholate complex compound, and 300 parts of toluene. The addition was carried out in a temperature range from HO ⁰ C to 112 ⁰ C; the mixture was then held at the same temperature for an additional 5.6 hours. After the evaporation carried out as in Example 5, a clear liquid was obtained in a practically quantitative yield. Based on the manufacturing process and infrared spectrum, the product was an arylolsiloxane of the average formula:

(CH ₃ ) ₃ SiO

Si (CH ₃ I ₃

Example 7t

Yes, a mixture of 1332 parts of Oc tame thy Icy clot etrasiloxane, 124 parts of sym-tetramethyldisiloxane and 35 parts of 86 #iger

909887/1521

-13-

- sheet 13 -

aqueous sulfuric acid was left at room temperature for 17 hours long stirred. The acid layer was carefully separated. The oily layer was made with 25 parts of sodium bicarbonate

Stirred for 1 hour, filtered and stripped off in vacuo to an internal temperature of 150 ⁰ O at 3 torr. By method of manufacture and infrared spectrum, the product was a polydimethylsiloxane that had an average of 18 chemically linked dimethylsiloxy units and terminal dimethylsiloxyhydride units.

Einhundertsiebenundvierzig parts of the above polydimethylsiloxane was carefully added to a mixture of 30 parts of 2-AlIyIphenol and 0.0028 part of platinum, in the form of a platinum alcoholate catalyst, if at a temperature of 9O ⁰ C. After the addition, the mixture became wider

Heated to a temperature of 90 ^° C. to 100 ^° C. for 2 hours. The oily layer was dried; an infrared inspection of part of the product showed that it was free of silicon hydride. The product was washed several times with 80% aqueous methanol to remove the excess allyl phenol. A small amount of methylene chloride was then added to facilitate phase separation. After treatment in vacuo, 148 parts of product were obtained, which corresponds to a yield of 85 % , based on the starting materials. According to the method of preparation, the product was an arylolsiloxane of the average formula

909887/1521

-14-

-HUt * M- ^Ί595789

A block copolymer was prepared by introducing phosgene into a mixture of 57 parts of 2,2-bis (4-hydroxyphenyl) propane, 70 parts of pyridine, 1300 parts of ethylene chloride, 100 parts of the above arylolsiloxane and 2.95 parts of 2-allylphenol . The mixture was phosgenated until unreacted phosgene appeared in the exhaust gases. Excess 2-allyl phenol was then added to the mixture to react with any excess phosgene or chlorocarbonate end groups. The copolymer was precipitated by adding methanol. Bb 150 parts of a copolymer were obtained, the terminal

P,
Oc-0-

CH ₂ = CHCH ₂ ^ y radicals. The yield was 88 -ji, based on the starting materials. The copolymer had terminal polydimethylsiloxane blocks

CH3 Q r

- °? ^ic 3 ^H 6 - J { \ units that were chemically linked with polycarbonate blocks.

/ Claims

909887/1521

Claims (8)

Claims in II a divalent aryl radical, R 'a divalent Saturated aliphatic radical with at least 3 carbon atoms, R "a monovalent, saturated one Hydrocarbon residue, a halogenated, monovalent, saturated hydrocarbon radical or an oyanalkyl radical a is a value from 0.02 to 1, inclusive. b a value from zero "up to and including 0.1, c a Has a value from zero to 2.5 inclusive and the sum of a, b and c has a value of 1 to 3 inclusive 3 has. 2. arylolpolysiloxanes according to claim 1, characterized in that the sum of a, b and c has a value of 1 up to and including 1.0. 3. Cyclic arylolpolysiloxanes, characterized by the formula of claim 1. 4. Linear arylolpolysiloxanes, characterized by the Formula of claim 1. New Unteriaoen im. 7 $ ι From ₆ .2 ^^ ^^ + ^ 0 * ^ k V ^ J .m ΦΛ ΛΛ wr. 1 ν 4 a \ mn agen i% ι From ₆ .2 wr 909887/1521 BATH ORIGINAL - patent claims - 5. arylolpolysiloxanes according to claim 1 or 2, characterized by the formula (H) _b (R " in which a has a value from 0.002 up to and including 1, b has a value from zero up to and including 0.1, c has a value Value from zero up to and including 2.5 unu R "the methyl or phenyl radical or a mixture of these Leftovers is. 6. Cyclic Orgaiiopolysiloxan according to claim 1 to 3, gekennzeiclinet by the Porinel 7 · Linear or ^ anopolysiloxane according to claim 1, 2 or 4 »identified by the formula CH ₃ SiO CH ₃ 18th CH ₃ SiC ₃ H ₆ . CH ₃ BATH ORIGINAL 909887/1521 -At. 8. Process for the preparation of Arylolpolyeiloxanen the formula [~ horr · Ί a ^H b ^Si0 (4-abo) by reacting a siloxane hydride with an aliphatic unsaturated compound in the presence of a platinum catalyst and subsequent separation of the product obtained, thereby characterized in that the hydride is a compound of the formula R » _c and an aliphatically unsaturated arylol of the formula · as the unsaturated compound. R ¹ x ¹ RAW used and the reaction is carried out at temperatures up to 115 ⁰ C, where R is a divalent aryl radical, R ^{1 is} a divalent saturated aliphatic radical with at least three carbon atoms, R "is a monovalent saturated hydrocarbon radical, a halogenated monovalent saturated hydrocarbon radical or a cyanoalkyl radical, a has a value from 0.02 to 1 inclusive, b has a value from 0 up to and including 0.1, c has a value from 0 up to and including 2.5 and the sum of a and b and c has a value from 1 up to and including 3 Has. 909887/1521