DE1720826A1 - Process for the preparation of organopolysiloxane copolymers - Google Patents

Description

The invention relates to organopolysiloxane copolymers which are built up from successive blocks dzw. on processes for their production. In particular, the invention relates to copolymers in which the blocks in a previous arrangement follow one another, with at least 75 % or more to nearly 100 % of the blocks in the polymer being subject to a previous arrangement and being of a regular nature and essentially in the same order and order the same relative amount as the cyclic organotrisiloxane used to make the aforesaid polymer.

The invention also relates to those ordered block-block copolymers which have both organosiloxane segments and silicon-free segments, which are referred to herein as "organic segments" or, more precisely, all "hydrocarbon segments".

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The invention also relates to a process for the preparation of the aforementioned block-block organopolysiloxanes Causing a reaction between (A) an organolithium compound, namely (1) an organo-lithium compound, the contains at least one lithium atom bonded to a silicon atom via an oxygen atom, a (2) organo-lithium compound of the formula

(I)

and (3) a lithium-terminated macromolecular organic segment, and (B) a cyclic polysiloxane Formula:

R "

Si-O

R "

wherein said reaction is preferably, but not dingt un- ^, is carried out at least one of the reactants at a temperature below 100 ⁰ C, in an aprotic solvent for; In the aforementioned formulas, R denotes a monovalent hydrocarbon radical, R * an alkylene radical with 1 to 10 carbon atoms, R ″ an organic radical which has no aliphatically substituted halogen, namely a monovalent hydrocarbon radical, cyanoalkyl radical and halogenated aryl radical and m 0, 1 or 2.

It has been found that in the process of the present invention for the preparation of νοα block blook organopolysiloxanes from

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cyclic polysiloxanes of the formula I a certain class particularly effective and useful on organo-lithium compounds is, namely those of the general formula:

Li

_H. ti

O Si

I I

in which R '11 ^denotes the same monovalent organic radical, v / ie R "or another monovalent organic radical and XR", OH, -OR " ¹ , -OLi, -OSiR ¹¹ ', AlH. or NR""₂; R "" means the same as R ¹¹ 'or hydrogen, η an integer of at least 1, for example one from 1 to 100 or more.

After the aforementioned process has been carried out, the siloxane units of the organo-lithium compound A (1) are the Organo-nitrogen bonds of the organo-lithium compound A (2) or the macromolecular segment of the organo-lithium compound A (3) and also the siloxane units of the cyclic polysiloxane of the formula II in the resulting ordered polymer available.

The term "aprotic solvent" denotes an organic solvent that does not have active protons that interfere with the growing anionic polymerization centers. Any aprotic solvent capable of dissolving the polymer mixture by creating intimate contact with the added diorgano can be used.

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cyclosiloxane with the polymerization system. Such solvents include, for example, benzene, toluene, xylene and mesitylene. The use of solvents with different boiling points allows the method according to the invention to be carried out at different temperatures. According to a preferred Embodiments of the invention use certain dipolar aprotic solvents, the electrons donor centers own. These solvents are selected from the point of view that their metal electron donor centers are capable of To form coordination complexes with the lithium cation, thereby increasing its reactivity towards the diorganocyclosiloxane polymerization without a loss in its specific property with regard to the ring opening reactions. Preference is given to using aprotic solvents which have Lewis-Baeen characteristics, as a result of their ability to donate electrons to the lithium cation, the lithium being coordinated and thus whose reactivity is increased.

It is known that cyclic diorganosiloxanes can be produced by this can polymerize to high polymers that you can with alkaline catalysts, such as potassium hydroxide or corresponding siloxane salts heated. However, during this alkaline polymerization there is always both Breaking up of siloxane lengths with the formation of hollow polymers as well as a breakdown of high polymers taking place, formation of cyclic compounds. Because of these two competing reactions, each polymer ultimately made from a mixture of cyclic polysiloxanes contains, in random distribution, segments that are seen by the various involved Derive cyclic polysiloxanes. Sole polymers, which include copolymers, terpolymers, and even more complex combinations of siloxane units, are in their nature

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or structure largely randomly designed. This randomness or arbitrariness is often found during the copolymerization of two or more organocyclopolysiloxanes still increased as a result of the Difference in their reactivity. Furthermore, it is often difficult to carry out a polymerization without a considerable amount at the same time A large number of cyclic polysiloxanes are formed, which are an undesirable contamination of the polymerized country product mean.

One of the methods of synthesizing organosiloxane block polymers is based on the premise that homopolymer segments are to be produced separately, with subsequent Connection by means of suitable condensation catalysts.

Following the procedure of U.S. Patent 3,156,668 Polyd! Organosiloxanes with a terminal hydroxyl group the formula

'R

HO \ - Si-O ^ -R ¹

in which R, R ¹ and η can have the meaning given above, heated in the presence of lithium hydroxide or a lithium silanolate as a catalyst in order to bring about the condensation of the hydroxyl groups and the chain extension. When two different hydroxyl-endblocked polydiorganopolysiloxanes are reacted by this process, the manner in which these polymers intercondene is of an arbitrary nature. Furthermore, this process in turn leads to the undesired formation of cyclic polysiloxanes as impurities, which reduce the optimal yield of linear poly-

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Siloxahs cause a further disadvantage of the process just described is that the segments are difunctional and must be of high purity in order to obtain gel-free, linear, high molecular weight polymers. From all of these Reasons are the final structure and properties of such Copolysiloxanes still difficult to define; you can very strong even with small differences in segment length, reactivity and manufacturing conditions vary.

It has now been found that you can use block-block copolymers can produce upstream or predetermined sequence of the constituents or organo-siloxane block copolymers, under . Use of the organo-lithium compounds described above with a cyclic organotrisiloxane and a certain Class of solvents. It is also possible to use organopolysiloxanes with an extremely narrow molecular weight distribution to manufacture; it is also possible to carry out polymerisation to be carried out without equilibration, i.e. without a siloxane rearrangement. The polymer chains once formed are subject to due to their stability towards the basic lithium ion, no significant equilibration or rearrangement. As a result of their high degree of order, the polymers produced according to the invention have new and unique properties which could not be foreseen. The invention thus creates a very useful synthetic process for the preparation of blook copolymers, taking into account the properties of the Polymers by selection of the organopolysiloxane, the order of the segments and the size of the molecular weight can be varied.

The blocks that make up the polymer are not just individual ones Diorganoailoxy units t

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R.
I ■ Si - O

i
R.

M * MM

but also a plurality of diorganoailoxy units, the are linked to one another directly via oxygen atoms. These upstream blocks of diorganosiloxy units can be made from one to 1000 or more siloxy units, from derived from the lithium compound exist. Through the successive Addition of various gyclotrisiloxanes can (j the organosiloxy-ßlocks of various kinds are introduced, the properties of the end products still being modifiable are.

The possibility of producing the block-block copolymers described above with a regular sequence of the individual components was completely unexpected and surprising. First of all, it was found that the use of a lithium compound is of critical importance; namely, if other alkali metal compounds are used, for example those in which the lithium of the organolithium compound is replaced by potassium, then every reaction leads to equilibrated products with an arbitrary distribution the components. It has also been found that the use of hexaorganocyclotetrasiloxane, for example hexamethylcyclotrisiloxane, is meaningful} namely, if an octaorganocyclotetrasiloxane, for example octamethylcyclotetrasiloxane, is used at the beginning of the reaction together with the organolithium compound instead of the hexaorganocyclotrisiloxane, the reaction proceeds only slightly, if at all Measure under the desired conditions, in particular at temperatures below 100 ⁰ G. Eb is also an important part of the present invention that aprotic solvents are used, since the

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Use of other solvents that are not electron donors, for example the use of hydrocarbon solvents, at temperatures below 10O ⁰ C, leads to polymerization and condensation only to a very small extent; this is known in the art as it is the common result of the reaction of a cyclic organopolysiloxane with an alkali metal compound.

If the reaction ^{temperature is above 10O 0} C, whereby a temperature of up to about 200 ⁰ C can be maintained, the use of solvents that are not electron donors, a result that at least 75 ^ corresponds to the regularly arranged siloxane blocks, which at lower temperatures using electron donating aprotic solvents ₍ can be obtained.

It should be emphasized that the method of growing the block polymer in one direction or in two or more directions can occur, which depends on the number of lithium atoms present in the lithium compound. For example, the Reaction of lithium trimethylellanolate with hexamethylcyclotrisiloxane in an aprotic solvent to give a compound of the formula

Li - Oj - Si - O - (- Si (CH ₃ ) 3 You reaction of hexamethylcyolotrieiloxane with an organic

«9-

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see lithium compound of formula

VI (H ₅ G ₂ ) ₂ -N-CH ₂ CH ₂ -O-Li

in an aprotic solvent, leads to the formation of a Compound of formula

Li-O Si - 0

CH-

CH ₂ CH ₂ N (C ₂ H ₅ ) 2

At a molar ratio of 1 mol of lithium trimethylsilanolate to 3 moles of hexamethylcyclotrisiloxane are 9 further dimethylsiloxy units introduced into the lithium compound, which has the formula

VIII Li

CH-

-O-Si

CH,

comes to.

Corresponding results are achieved if one uses an organolite compound of the formula I or a macromolecular organic segment terminated with lithium is used.

When using the lithium compound described above and a multiple amount of trisiloxane, a lithium-containing polymer can be formed, which consists of polymer diorganosiloxy or other units derived from the lithium compound .

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ten also a multiple of the three siloxy groups of the cyclic Trieiloxane contains »where the number at this multiple of the Molar ratio trisiloxane / lithium compound depends.

Other blocks can also be added to the polymer of formula VIII. It can, for example, the just mentioned compound in an aprotic solvent from among the above conditions described are reacted with hexaphenylcyolotrisiloxane, an idthium compound of the formula

IX

Li - O

C ₆ H ₅ Si

• O-Si-4-CH

__J j I- _.

arises.

One can see this interaction between different trisiloxanes continue indefinitely, each time a different segment, if so desired, in a predetermined position introduces, whereby a systematically structured polymer is obtained, where all blocks are arranged in the order that the order of addition dee. corresponds to cyclic polysiloxane.

Furthermore, lithium trimethyl anolate can be used in an aprotic electron-donating solvent at low temperatures be reacted with trimethyltriphenylcyclotrieiloxane, wherein a compound of the following formula

Li

Si -

^C 6 ^H 5

0 - Si (CH ₃ )

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arises, in which m indicates the number of cyclotrisiloxane moles, which are present per mole of lithium triraethylsilanolate.

It is also possible to use lithium compounds which contain two or more lithium atoms bonded to silicon via oxygen atoms. By using such dilithium or polylithium compounds it is possible to cause growth on both or more sides of the organosiloxy unit bonded to lithium atoms are.

A suitable class of dilithium compounds is, for example, one of the general formula:

XI

Li - O -

R.
I.

S χ-Ι

O-Li

in which R has the meaning given above and ρ has a whole Number of at least 1, for example from 1 to 100, or more.

Specific examples of such dilithium compounds are those of the following formulas:

CH,

XII Li-O-Si-O-Li, XIH Li-

CH-

(CH ₂ ) ₂ -CN

■ O-Si

-0 - Li,

3 or 4

XIV Li- -

^C 6 ^H 5

O-Si-

Γ6 "5

O-Li, XV Li-O-Si-O-Si O-Li,

ii CH ₃ C ₆ H ₅

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Γ / 20826

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XVI Li4-0-Si—

I.
CH ₃

(CH ₂ J ₂ CN

-O-Si-- O-Li, XVII Li-O-Si-O-Li,

CH-:

^C 6 ^H 5

I XVIII LifO-Si

CH,

O-Li

^C 6 ^H 5

65

XIX Li-O-Si - OC ₀ H-, XX Li-O-Si -ΟΙ ²⁵ ι

Si (CH ₃ )

CH-

^C 6 ^H 5

CH

CH ₃

r -.ι -

"Α Li-O-Si - AlH. , XXII Li-O-Si-NH ₉ ,

ι ⁴ ι

CH.

CH-

CH,

XXIII Li-O-Si-CH ₃ , XXIV LiO-Si

^C 6 ^H 5 -? 6 ^H 5 "

1-110

XXV Li-O-S

Si -O-Li,

XXVI Li- + O-Si-C ₆ H ₅

10!

CH ₂ -CH ₂ - Si 0 Li

830 / 15S2

and

- sheet 13 -

In an analogous manner, by means of the lithium compounds, the Formula I lithium compounds of the following formulas are prepared:

XXVII Li-O4-Si

-Si — ΟΙ CHo

XXVIII Li-O-I- Si-

l_ ^CH 3

and

Si-O- - CH ₂ CH N (C ₂ H5)

Further classes of polylithium compounds are provided by the given in the following formulas:

XXIX
XXX

R - N 4 R'-O-Li), N {. R «-o-Li) ₅

and

where R and R ^{1 have} the meanings given above.

The following are specific examples of monolithium, Given dilithium and trilithium compounds:

H ₃ C - N -4CH ₂ CH ₂ -O-Li) _%

J ₂ - N - CH ₂ CH ₂ -O-Li C ₆ H ₅ -N- [CH ₂ -CH (CH ₃ ) J-O-Li) ₂ C ₂ H ₅ -N- (C ₆ H ₄ -O -Li) ₂ (C ₂ H _{5) 2} - N-CH ₂ - CH ₂ - CH ₂ -O-Li

-n | - <^ J ^ ~ o - Li)

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- sheet 14 -

- Li

(C ₆ H ₅ - CH ₂ ) ₂ - N - CH ₂ - CH ₂ -O-Li

XXXIII N - (CH ₂ CH ₂ -O-Li) ₃

N - [CH ₂ - CH (CH ₃ ) - O - Li N - (C ₆ H ₄ - O - Li) ₃ .

These last-mentioned compounds can be reacted with various cyclotrlsiloxanes, resulting in polymers of the following formulas, for example:

XXXIV XXXV

XXXVI

- CH ₂ CH ₂ -N- (CH ₃ )

- CH ₂ - CH ₂

N - CH,

I. 1\

O -

CH ₂ CH ₂

When the lithium siloxanolates described above have been formed, these can, if so desired, be reacted with other cyclotrisiloxanes, with the purpose of combining further trisiloxane units or multiples thereof in order to increase the chain length . It should be emphasized that if the reaction is between

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the organolithium compound and the first cyclotrisiloxane once has used, the additional action or conversion of diorganocyclotetrasiloxanes, e.g. of Octamethylcyclotetrasiloxani can take place more easily than in the event that the reaction of the cyclotetrasiloxane with the organolithium compound first takes place or should take place. Although there is still a certain risk of a certain random arrangement in the case of the polysiloxane as a result of the use of tetrasiloxane - as opposed to that large order, which is achieved in the arrangement of the constituents of the polysiloxane when using cyclotrisiloxane is due to the fact that initially cyclotrisiloxane is reacted with the organic lithium compound becomes, a very substantial decrease in arbitrariness, which in itself is caused by the involvement of the cyclotetrasiloxane will.

The lithium siloxanolates, for example those of the formulas XII to XVIII can then be reacted with cyclic trisiloxanes which have different organic groups or residues bonded to silicon (e.g. with hexaphenylcyclotrisiloxane, Hexaäthylcyclotrisiloxane and trimethyltriphenylcyclotrisiloxane) linear, ordered block-block copolymers are obtained, possess the siloxane units that are different from both the lithium compound as derived from the cyclotrisiloxane. For example, if you have equal molar amounts of Hexaphenylcyclotrisiloxan and Lithiumeiloxanolat of the formula IX reacts with one another, a compound of the following formula is obtained:

XXXVIa

CH,

- O - Si - O '

CH,

^C 6 ^H 5

Si - 0 - ^C 6 ^H 5

Li

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If a Dllithiuaellozanolat of the formula XVIII old HexaphenylcyoIotrlBlIozaa uaettst, one obtains a compound of the formula

XXXVIb

Li. O- -

-ίι - ο

r ⁵

Si - ^C 6 ^H 5

Furthermore, the lithium alkali of dimethylsilanediol [CH, J ₂ Si- (O-Li) J reacts with hexamethylcyclotrisiloxane, whereby a

ι »> * -» .ι
Compound of formula

XXXVII

Li-O--

_f 3 Si - 0

Li

arises.

These difunctional lithium elloxanes can optionally be reacted with other cyclic trieiloxanes or, under certain conditions, even with cyclic tetraeiloxanes, with the purpose of adding further trieilozane units or optionally tetrasiloxane units or a multiple of these units in order to increase the chain length.

It should be emphasized that when the reaction between the lithium compound and the cyclotrisiloxane is set in motion, a subsequent reaction of diorganocyclotetraeiloxanes takes place more easily than when the latter is attempted first with the

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Bring lithium compound to conversion.

In addition to the use of non-functional or difunctional organic lithium compounds, ie those containing 1 or 2 lithium atoms, it is also possible to use polyfunctional organic lithium compounds which have 5 to 5 or more lithium atoms, each bonded to silicon via an oxygen atom. Examples of such polyfunctional organic lithium compounds which are capable of causing the formation A of block-block copolymers along three or more axes are, for example, trilithium phenylsilanolate, trilithium methylsilanolate, tetralithium silanolate, as well as other polyfunctional organic lithium compounds which have, for example, the following formulas: Li Li

I I

0 O CH, CHo CH,

III ³ II ³

Li-O - Si-O-Si - O-Li, Li-O-Si-O-Si-O-Si-O-Li,

II 111

C ₆ H ₅ C ₆ H ₅ CH ₃ O-Li CH ₃

O-Li O-Li CHo CHo J.

I / - \ I Il ^f

Li-O - Si-^ Λ-Si-O-Li, Li-O-Si-CH ₂ CH ₂ -Si-O-Li ^CH 3 ^CH 3 CH ₃ CH ₃

If the functionality of the organic lithium compound rises above 2, ie if 3 or more lithium atoms are present in the organic lithium compound, a branch addition of the cyclic polysiloxanes will take place, dB is interesting to note that if the corresponding trifunctional organometallic compound, however, the another alkali metal, for example sodium, potassium or cesium,

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contains, instead of the aforementioned trifunctional organolithium compound, is used, gelation begins and cross-linked polysiloxanes are formed.

The radicals represented by the symbols R and R ¹ in the preceding formulas are, for example, alkyl radicals, aryl radicals, aralkyl radicals (e.g. the benzyl and phenylethyl radical), alkaryl radicals (e.g. the ToIy1, XyIyI and ethylphenyl radical), alkenyl radicals, halogenated Aryl radicals and cyanoalkyl radicals. The presence of halogen, in particular fluorine, on an aliphatic carbon atom which is bonded to silicon increases the random nature of the structure of the polymers formed. The halogens should therefore be avoided in the cyclic polysiloxane of the formula II.

This precaution of avoiding the presence of ' Halogen on aliphatic carbon atoms does not relate to the radicals represented by the symbol R. So can organic lithium compounds of the formulas

( ₃₂ ^ ₂ NC ₂ H ₄ -O-Li and

F ₃ CN- (C ₂ H ₄ -O-Li) ₂

quite for implementation with the oyolisohen polysiloxane Formula II can be used.

Among the other lithium compounds that can be reacted with the Cyolotrisiloxane of the formula I are for example lithium trimethyl lanolate, lithium triphenyl lanolate, dilithium dibenzyl silanolate, dilithium diethyl lanolate and trilithium phenyl lanolate. The presence

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- sheet 19 -

of halogen on aliphatic carbon atoms of organic lithium compounds can be tolerated, making lithium compounds of the formulas

C ₂ H ₅

CF ₃ CH ₂ Si O-Li and (CP ₃ C ₆ H ₄ ) ₂ Si- (O-Li) ₂

C ₂ H ₅
are usable.

The lithium silanolates, to which the lithium siloxanolates belong, can be produced by one of the processes known per se. For example, one mole of a Lithiurahydroxyd ürganosilanolats with varying content of organic residues and may HydroxyIresten with at least 1 mol, and the mixture heated a half to sixteen hours at 50 ⁰ C, to obtain the desired lithium compound. More specifically, lithium hydroxide or lithium metal can be reacted with trimethylsilanol or triphenylsilanol to obtain lithium trimethyleilanolate and lithium triphenylsilanolate, respectively. Using the same method, a diorganosilanediol can be reacted with a stoichiometric amount of lithium alkyl under suitable conditions in order to obtain dilithium diorganosilanolate. Furthermore, a dihydroxy end-blocked polydimethylsiloxane, which contains, for example, 2 to 20 dimethylsiloxy groups, can be reacted with lithium hydroxide under similar conditions, a polydimethylsiloxane having a dilithium end grouping which contains lithium atoms instead of the hydrogen atoms, the number of dimethylsiloxy groups being the same as in the dihydroxy end-blocked polydimethylsiloxane. (Please see formulas XII through XVI for examples.) These procedures can be used for the purpose of manufacturing

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Position of organolithium compounds that contain more than two reactive lithium atoms.

The hydroxyl group-containing organosilicon compound that is used for Conversion with lithium hydroxide is required, can be obtained in a manner known per se. A method of manufacture of monolithium or dilithium compounds consists in that a diorganodialkoxysilane or a triorganoalkoxysilane hydrolyzed with water and partially in a mixture of water and a solvent, for example diethyl ether is condensed. On the other hand, you can also use cyclic diorganosiloxanes with steam at elevated temperatures and Implement pressure, resulting in Dlhydroxy-endblocked polydiorganosiloxanes.

If this is desired »the lithium compound can also be used to the lithium atom bonded to silicon via an oxygen atom have a terminal member, for each of which Radical or atom comes into question, which is represented by the symbol X of the formula II. Methods for making such compounds are known. For example, one can use a lithium compound of the formula

Li-O-Si AlBL

I ^C 6 »5

produced by the fact that nan lithium aluminum hydride (LiAlH.) with Diphenylilanediol implemented.

-21-

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Clearly, the number of cyclotrisiloxanes corresponding to the formula I which can be used can vary within wide limits. Examples of these cyclic trisiloxanes that can be used are the following: Hexamethylcyclotrisiloxari, hexaphenylcyclotrisiloxane, cis- or trans ^ j ^ ö-trimethyl - ^^ jö-triphenylcyclotrisiloxane, various isomers of trimethyltriethylcyclotrisiloxane, various isomers of trimethylcyclotrisiloxane, various isomers of beta-trimethyltrivinyltrivinyl -cyclotrisiloxane, trimethyltri- (4-chlorophenyl) -cyclotrisiloxane and 2,4-dimethyl-2,4fojo-tetraphenylcyclotrisiloxane.

Another surprising result of the use of lithium catalysts in aprotic solvents according to the present invention is the stereospecific opening of the siloxane ring, which is induced by the basic lithium compounds. If, for example, cis ^^ jö-trimethyl ^^ jo-triphenylcyclotrisiloxane in tetrahydrofuran is heated for two to 16 hours with a catalytic amount of n-butyllithium to a temperature below 75 ⁰ O, for example to 40 to 60 C, a non-flowing one is obtained elastic rubber which, after its isolation and implementation of a nuclear magnetic resonance analysis, shows that 60 to 65 ° A of isotactic conformation and 35 to 40 fi of heterotactic conformation is present. There may also be small amounts of syndiotactic units, but their number is so small - most of the time they are absent at all - that they do not interfere with the direction taken by the use of lithium catalyst against a majority formation of the isotactic conformation. If the same cis-cyclotrisiloxane is heated under analogous conditions with catalytic amounts of KOH, the result is according to the rules of statistical distribution

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25 i "isotactic conformation 50 i> hetero tactical conformation and 25% syndiotactic conformation.

The aprotic solvents to be used with preference include non-acidic oxygen-containing and nitrogen-containing organic solvents which are capable of coordinating with the lithium. These include, for example, tetrahydrofuran, hereinafter referred to as THi ¹ , tetrahydropyran, diethoxyethane, the dimethyl ether of diethylene glycol, dimethylacetamide, N-methylpyrrolidone, isobutylene oxide, dimethyl sulfoxide, dioxane, the diethyl ether of diethylene glycol, and various tertiary amines, such as tri-methylamine, such as dimethylamine. Solvents that contain active hydrogens or acidic hydrogen should be avoided due to the reactivity of lithium with acidic hydrogen, which would create new reaction centers and thus create an arbitrary arrangement of the components, which, in contrast to the aim of the present invention, the order of Blocks would decrease.

The fact that these electron donating solvents do so to react effectively with the lithium compound was completely unprepared visible and could not in any way from the state of the art be derived, as this teaches that lithiuraionen through the media described above are solvated to a high degree, the prior art making no difference between Lithium and other alkali metals power; it was therefore to be assumed that lithium ions would be produced in an analogous or similar manner act arbitrarily, such as sodium and potassium ions; this prior art prejudice is borne out by the present Invention overcome.

BATH ORIGINAL

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The manner in which the present invention is practiced can vary within wide limits. First, it is necessary that the active lithium ion be present in the form of the lithium compound as the first agent present. These active lithium ions can come from previously prepared lithium organosilanolates or organosiloxanolates; But they can also be formed in situ by the reaction of organocyclosiloxanes and organic or inorganic lithium compounds, for example from butyllithium, Li (OH), C (CH ₂ G ₆ H ₄ Li)., lithium aluminum hydride, and also from lithium aluminum compounds of the general formula LiAlR ^, in which R has the meaning given above, from lithium hydride and lithium metal. The main prerequisite for the production of the lithium compound in situ is that no lithium compounds may remain that would introduce an arbitrariness into the reaction, which would be caused, for example, by lithium hydroxide during the in situ formation of the organolithium compound.

Then, the organic lithium compound with the organocyclotrisiloxane in an aprotic solvent is reacted, in which at the beginning are advantageously temperatures g complied with 75 ⁰ C, for example from -50 ⁰ C to +50 ⁰ C. This initial reaction between the organic lithium compound and the cyclotrisiloxane can take place in a time of 5 minutes to 2 hours, which in individual cases depends on factors such as the temperature maintained, the lithium compound used, the type of cyclotrisiloxane, the molar concentration of the organic lithium compound and the Cyclotrisiloxane depends. You can then optionally add further organosiloxane units to the already prepared siloxane line; this is done by entering the reaction

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- sheet 24 -

tion mixture using the same aprotic Any organocyclotrisiloxane or solvent optionally also enters an organocyclotetrasiloxane, the concentration of which depends on the desired final product depends.

The conditions of the addition and reaction are ix substantially the same as in the Anfangereaktion between the lithium compound and the cyclotrisiloxane with a modification that at den'folgenden reactions advantageously higher temperatures in the order of about 100 bia 175 ⁰ C are adhered to. In any case, anhydrous conditions should prevail; it is also advisable to ensure the absence of oxygen by creating an inert atmosphere, for example by means of nitrogen or helium.

By adding the different Cyclotrisiloxanes can be polymers of any desired length be prepared, whereby the repeating units present in the polymer, their positions in the polymer and predict and predict the length of the repeating unit. The length of each segment can be predetermined and based on and in accordance with the molar concentration of the cyclotrisiloxane associated with the Lithium compound is implemented, are multiplied integrating, there can also be the block polymer reactions one after the other be performed.

The ability to predict the resulting polymers and the planned implementation of the production of such polymers makes it possible to obtain products that are unusually advanced.

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- sheet 25 -

have gradual properties with regard to their solubility, heat resistance, the crystal ini did, the increase in strength, the temperature flexibility and the low temperature flexibility, these new properties being far above what was previously known from the copolymers of the prior art. For example, while the randomly structured polymers of the prior art are soluble in aromatic hydrocarbons, such as benzene or toluene, at ordinary temperature, the highly ordered polymers produced according to the invention are distinguished by a relative insolubility in these solvents; If you want to dissolve them, solvents such as diphenyl ether or 2,4-chloroanisole and simultaneous heating to, for example, 125 to 225 ^° C. are necessary. This resistance of the polymers produced according to the invention to solvents is probably a consequence of their crystallinity. The polymers produced according to the invention have a range of variation with regard to the crystal melting points depending on the difference in the organosiloxy segments.

The lithium block copolymers can be used in several ways treated to obtain organopolysiloxanes that no lithium atoms or no other metals or metal compounds, such as aluminum hydride (please see formula XXI). So can the recovered lithium polymer be reacted with an acid such as glacial acetic acid, the lithium atom being replaced by a hydrogen atom and a hydroxyl-endblocked polysiloxane is formed. on the other hand can be used for the purpose of making a triorganosilane or a similar organosiliciura terminal group, the lithium atom of the lithium polymer produced with, for example a triorganohalosilane such as trimethylchlorosilane or

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React triphenylchloroilane, lithium chloride and a chain-terminating triorganosilyl group being formed. This leads to stable fluids with unusual 3 θ rise adherence, especially with highly isotactic structures, where more than 65 i> isotacticity is present, as a result of the ability to the high degree of isotacticity from the reaction of the lithium compound with an cis or trans -Maintain trimers. The use of acids, such as acetic acid, also requires the removal of the aluminum hydride (AlU.-) residue and the amino residue (-NH ₂ ), leaving behind a silicon-bonded hydroxyl group. To ensure that there is complete removal of the glacial acetic acid, a wash with a 90-10 weight percent mixture of methyl alcohol and water is performed to remove any glacial acetic acid from the polymer.

The following examples serve to further illustrate the subject matter of the invention. If nothing else is said All data relating to the healing and the percentages relate to weight. Further, all responses will if nothing else is said, carried out in an inert atmosphere, for example under nitrogen. In the following For example, some lithium compounds have been used as finished products, while others have been produced in situ and reacted directly with the respective cyclopolysiloxane.

Manufacture of the lithium compounds.

The dilithiurasiloxanolate of meso-1,3-dimethy1-1,3-äiyhenyΙα isiloxane-1,3-diols was prepared by adding 2, <jg (o, ol mol) meso-1,3-diraethyl-1,3 -diphenyldisiloxane-1,3-diol with one gram (o, o395 mol) lithium hydroxide, which was in the form of dry, fresh particles, in 32 ml of anhydrous fresh

10 9830/15 52

-27-

- sheet 27 -

distilled tetrahydrofuran reacted at about 27 ° C for 18 hours. The reaction mixture was then filtered off, the lithium hydroxide residue washed with tetrahydrofuran and the combined filtrates under nitrogen in a clean and kept dry bottle, which was closed by a so-called serum stopper made of rubber. These filtrates contained substantial amounts of the desired dilithium siloxanolate, hereinafter referred to as "DL-I".

Dilithiumdiphenyldisilanolat was prepared by ^ j to 2.16 g (o, ol mol) of diphenylsilanediol dissolved in 20 ml of benzene una 7 ml of dry freshly distilled tetrahydrofuran and to the solution dropwise under nitrogen with vigorous stirring at a temperature of -35 ⁰ C o .024 mol of n-butyllithium in 15 ml of η-hexane and 5 ml of benzene were added. The reaction mixture was then warmed to room temperature, filtered off and thoroughly washed or rinsed with η-hexane to remove any excess of unreacted n-butyllithium. The dilithium diphenyl silanolate was then transferred to a reaction flask which was located in a nitrogen drying cabinet, 50 ml of dry benzene was added and the silanolate was dispersed by means of an ultrasonic mixer. The analysis of the resulting product showed that the desired lithium silanolate, which is referred to below as "DL-2", had arisen in almost quantitative yield.

The dipotassium siloxanolate of meso-1,3-dimethyl-1,3-diphenyldisiloxane-1,3-diol was produced in a manner analogous to the dilithium siloxanolate (DL-I), with the modification that instead of lithium hydroxide 0.395 moles of potassium hydroxide were used. The di-potassium epoxanolate thus obtained is referred to herein as "DL-3".

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In the following examples different block-block * Copolysiloxanes described, the polymers being designated by letter combinations, for example by AB, ABBA, ACBBCA, ABCCBA, where the letters have the following meanings:

A - [(C ₆ H ₅ J ₂ SiO] _x .

B * [(CH ₃ J ₂ SiO] _x

C - [(CH ₆ H ₅ ) (CH ₃ ) SiO] _x

where χ means the value 3 or a multiple of the value 3, depending on the molar concentration of the cyclic polymers which are reacted with the lithium compound, i $ s is to emphasize that in the following examples the letters indicating the type of polymer that is obtained do nothing about indicate the presence of organoailoxy contents that originate from the lithium compound for the reason that the amount of such organosiloxy units generally is so small that it has little effect on the properties of the final polymer. Of course, this is not supposed to means that organolithium compounds are not used in a sufficient amount with regard to their organosiloxy content can, -affect the properties of the finished Exercise Polymers.

However, it should be emphasized that the starting point for the production of the blocks of the block copolymers begins with the organosiloxy units of the lithium compound and that, as the case may be. whether the lithium compound is oriented in one direction or in several directions, a determination has been made, whether the added block polymers, starting with the organosiloxy unit of the lithium compound, are in or in orientate in several directions. For this purpose, a

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Example given: If the original realization is between LL-I and HexamethylcyclotriBiloxane takes place and then with Hexaphenylcyclotrisiloxane is implemented, this results in a Determination to the effect that a compound of the following formula is formed before the lithium atoms are removed:

CH-, CEL
II ³

Li-O-AB-Si-O-Si-BA-Li I I

^C 6 ^H 5 ^C 6 ^H 5 I.

For the sake of simplicity, however, when specifying the obtained polymers omitted the organosiloxy units derived from the lithium compound by letters will; it can be assumed that the position of the lithium atom is occupied by a substituent, for example a hydroxyl group, which in the individual case depends on the way in which the lithium atom of the find polymer was removed.

Example 1:

This example describes the preparation of poly-bis g (diphenyl-block-methylphenylsiloxane-dimethylsiloxane-block * (ACBBCA). 5 g (o, o225 mol) of hexamethylcyclotrisiloxane with 2.2 ml of dry tetrahydrofuran and o, O71 x 10 "^ Moles of DL-I mixed. The mixture was then refluxed for 135 minutes and then 5 g (0.12 moles) of ice, trans-2,4,6-trimethyl-2,4,6-triphenylcyclotrisiloxane in 10 ml of benzene from a Calip suspension added to the reaction mixture. The reaction was then allowed to proceed on the steam bath for about 2 hours and then 5 g (0.084 moles) of hexaphenylcyclotrisiloxane dissolved in 30 ml of benzene were added in the same way, then the solvent was added thereby resulting from the reaction odor

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ferrite that nitrogen was passed through the slightly heated reaction mixture for one hour. The reaction mixture was ^{then heated to 125 °} C. for 15 minutes and then to 200 ^° C. for 4 hours in order to ensure that the reaction was complete. The product was then extracted from the reaction mixture first with glacial acetic acid and then with benzene, a solid, white hydroxyl-end-blocked polymer whose siloxane blocks were arranged according to the following system; ACBBA.

Example 2:

In this example, the same procedural steps and Procedures as carried out in Example 1, with the modification that DL-I first with ice, trans-2,4,6-trimethyl-2,4,6-triphenylcyclotrisiloxane, then reacted with hexamethylcyclotrisiloxane and finally with hexaphenylcyclotrisiloxane, after removal of the lithium atoms and formation of the hydroxy1-endblocked linear polysiloxane, a block copolymer that corresponds to the following system: ABCCBa.

Example 3:

This example describes the synthesis of poly (dipaenylsiloxane-block-dimethylsiloxane-block-diphenylsiloxane). As were 9 g (o, o4o5 mol) of hexamethylcyclotrisiloxane with 3.8 ml of dry Tetrahydrofuran and o, oool21 mol DL-I in one reaction vessel, which was equipped with a reflux condenser, mixed, can refluxed the reaction mixture gently for 2 hours boil, practically a complete conversion with the Kexamethylcyolotrisiloxan took place. Then 6 g (o, ol mol) hexaphenylcyclotrisiloxane, dissolved in 30 ml of dry benzene, slowly added to the reaction gel and that The latter refluxed for another 30 minutes. At-

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Finally, the solvent was slowly removed by a stream of nitrogen and the temperature increased, and the reaction was carried out. 30 minutes iSrhitzen to 125 ⁰ C, and then 4 stundiges Brhitzen to 200 ⁰ C continued. The product obtained, which consisted of a solid white elastomer, was then extracted with hot glacial acetic acid, washed acid-free with methanol and finally dried ^{at 50 ° C. in vacuo.} The polymer was obtained in a yield of 99 "ß> and corresponds to the formulation ABBA.

While the Met hy 1 proton signal this polymer is measured very much in a Varian A-60 nuclear magnetic resonance spectrometer was sharp, showed copolymers of random structure prepared by the usual coreaction technique were, for example, by the reaction of hexamethylcyclotrisiloxane with hexaphenylcyclotrisiloxane, with respect to the methyl protons broad paramagnetic resonance signals.

Other diphenyldimethyl block copolysiloxanes of type A33A were prepared in the same manner as described in Example 3, then the effects of molecular weight and the segment lengths (molar concentrations) were determined. The following table I gives an overview of the properties such block copolymer:

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- sheet 32 -

link

Hol

73
80

* 84.25
91.5
96

27
20th
15.75

8.5

TABLE I. Segment length

(CH ₅ I ₂ SiO

14th

4th
η

150
150
150
150
150

(CH ₆ H ₅ I ₂ SiO

75
50
67.5
18.8
8.5

xlO "

375 250 185 100 42

Tm., ⁰ C

(C ₆ H ₅ J ₂ SiO (CH ₃ J ₂ SiO

237

236

228

228 (210J

⁺ Cooling

Explanation: D ₆ = hexamethylcyclotrisiloxane

DP_

= Hexaphenylcyclotrisiloxane = mean molecular weight

«Average degree of polymerization (number of through χ symbolized units in the representation of the polymers in unit letters)

* Melting point of the crystals

"•" Cooling with differential calorimetric determination.

The crystal melting points given in Table I cause the unusual for these block copolymers Solubility Properties and Strength These Block Copolymers own.

Comparative example;

If DL-I is reacted in a similar way as described above, but this time octamethylcyclotetrasiloxane instead of hexamethylcyclotrisiloxane, no reaction occurs even if the mixture is kept boiling for 48 hours under reflux conditions and then left at room temperature for another 25 days. This shows very clearly the importance of teaching that one first

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the lithium compound has to react with a gyclotrisiloxane, if you want to get blockic copolymers.

Example 4:

This example describes the manufacture of polymer segment blocks in one direction and specifically the production of poly-CMethylphenylsiloxane-block-diphenylsiloxane). It was First a prepolymer is prepared by adding 5 g of trans-2,4,6-Triinethy 1-2,4,6-triphenylcyclotrisiloxane with 10 moles of n-butyllithium in 5 ml of dry tetrahydrofuran Reacted for 16 hours at ordinary temperature, using a compound of the J formula

Li

CH ₃

• 0 - Si

3η

was obtained in which η is the number of moles of the aforementioned jsiethylphenylcyclotrisiloxane. 3 g (0.05 moles) of hexaphenylcyclotrisiloxane were then added to this reaction mixture. The reaction mixture was then heated on the steam bath for one hour, some of the tetrahydrofuran escaping. Subsequently, the reaction mixture was 15 IJinuten at 125 ⁰ C, then for 15 minutes at 150 ⁰ G and heated to 200 ⁰ C, finally for 30 minutes. The mixture was then extracted with acetic acid and treated, as in the previous examples, with ethanol. The product obtained consisted of a white, rubber-like solid which was insoluble in benzene, but soluble in diphenyl ether at 200 ° C., and which had a crystalline structure, as could be determined by measuring the diffraction or scattering of X-rays using the Debye-Scherrer method . This polymer could be made into firm, flexible

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ο films are pressed at a temperature of around 300 0,

ea corresponds to the formulation AB.

Example 5 (comparative example):

This example describes the result of a reaction which is similar to that of Example 3, but this time using the corresponding potassium siloxanolate instead of lithium siloxanolate. 3 g (o, ol35 mol) of hexamethylcyclotrisiloxane were allowed to react with o, o2 χ 10 "mol of DL-3 in 1.3 ml of dry tetrahydrofuran for one hour under reflux conditions. The reaction mixture was then cooled to room temperature and 2 g (o , oo36 mol) hexaphenylcyclotrisiloxane in 2o ml of benzene added. the resulting reaction mixture was then held for one hour mild under reflux conditions at the boiling point and subsequently removing the solvent. by introducing a nitrogen stream Then the reaction mixture was 3o minutes at 125 ⁰ C and finally two hours heated to 200 ^0G. the polymer was soluble in benzene. "They solved it in benzene, which contained a small amount of glacial acetic acid for removal of potassium, and precipitated it by adding! ethanol again. this gave in 60% yield of a randomly built-up copolymer which, in contrast to the flexible and solid polymer of Example 3, looked slightly cloudy and was stiff in nature. If this resinous structure is treated at elevated temperatures with an organic peroxide or with benzene bis-sulfonazid deformed, you got a weak PiIm one

2 Tensile strength from 3.5 to 7 * 0 kg / cm, whereas the tensile strength of the polymer prepared according to Example 3 at 35 to 42 kg / cm lies.

The following example shows the result of the attempt to combine a lithium compound with a mixture of cyclic organopoly-

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to implement siloxanes, with the order of addition opposite the procedure described above has been changed.

Example 6 (comparison example):

There were 5.96 g (o, ol46 mol) eis, trans-2,4,6-trimethyl-2,4,6 ~ triphenylcyclotrisiloxane melted and mixed with 26 g o2 (o, o438 mol) hexaphenylcyclotrisiloxane at 210 ⁰ C in mixed in a reinforced air oven. Then there was 2.4 x 10 "" moles of lithium methyldiphenylsilanolate of the formula

CH-

I ³

Li-O-Si (C ₆ H ₅ ) ₂

added and mixed thoroughly with the reaction mass, and then the reaction mixture ^{heated to 210 0} G for 5 hours. The reaction product was then cooled, giving a hard, brittle, white resin-like structure which, after being crosslinked at elevated temperatures by means of benzene-bis-sulfonazide, has a tensile strength of 7.0 to 10.5 kg / cm. Its solution of the polymer in hot diphenyl ether was analyzed using the nuclear magnetic resonance% spectroscopy method. The magnetic resonance spectra of the methyl protons gave an extraordinarily large number of signals with respect to the methyl region, which indicates an arbitrary structural arrangement.

Example 7:

This example describes the non-equilibration properties of lithium ions when used in accordance with the method of the present invention. Bs, 5 g (o, ol23 mol) eis, trans-2,4,6-trimethyl-2,4,6-triphenylcyclotrisiloxane at 125 ⁰ C is melted and mixed with 8.31 x 10 ~ mol of DL-I. Then became

1 09830/165 2

-36-

- sheet 36 -

the reaction mixture is ^{heated to 125 °} C. for 24 hours while stirring. A certain portion of the polymer, which will be referred to as "portion 1", was then diluted with 10 ml of tetrahydrofuran and left to stand for 16 hours before glacial acetic acid was added to replace the lithium atom with a silicon-bonded hydroxyl group. Another portion, namely "portion 2", was then taken off and the polymerization was terminated immediately by adding benzene containing glacial acetic acid. Then each polymer was treated with methanol in order to remove traces of acetic acid which would interfere; this was followed by drying ^{at about 60 ° C. in vacuo.} The total yield of <polymers was approximately 99 # of theory. DiB intrinsic viscosities of the two components in benzene at 25 ⁰ C were as follows

certainly: M. * o, 35 dl / g Share 1 W. = o, 38 dl / g Share 2

These results clearly indicate the non-equilibration characteristics of the lithium ions under the conditions listed above. Under comparable conditions of polymerizations with sodium or potassium instead of lithium, the dilution effect is that the ring-chain equilibrium is shifted towards the rings, with the yield and the molecular weight of linear polymer falling. ,

Example 8:

This example describes the crosslinking of some of these block copolymers, yielding products that are unusual Have tensile strengths and extensibility, even in the unfilled state. 100 parts of the block copolymer of the composition ABBA, which was prepared according to Example 3, were produced

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was, on mixing rolls at a temperature between 140 and 150C with a weight percent (based on the copolymer) of benzene-meta-disulfonazid (BMDSA) were mixed and the mixture then for 30 minutes at a temperature of 175 ⁰ C and a pressure!: deformed into leaves by 350 kg / cm. Then the leaves were removed from the mold and subjected to two hours in an air circulating oven at 175 ⁰ C a reheating. An additional crosslinking of this polymer was carried out, similar to that described above, but this time 1 percent by weight of di- (ot -Cumyl) peroxide was used as the crosslinking agent.

The following table II gives the properties of the crosslinked polymers, the starting polymer being composed of about 80 mol- # dimethylsiloxy units and 20 mol- ^ diphenylsiloxy units. The tensile strength and extensibility of the cured polymers were measured ^{both at normal temperature (about 27 °} C.) and at 125 ^{° C.} Sin sample (No. 2) contained 20 parts of fumed silica (= silicon dioxide obtained from the gas phase) per 100 parts of polymer as a filler.

Networking
middle TABiSLLiS II 125 ⁰ C Percentage
Extensibility 111
146
200 template
No. Di- (Oi -Cumyl) -
peroxide
Il
BMDSA filler 30.1
27.3 usually _Ί οςθ '
Temp. ¹ ^ ° 1
2
3 0
20 parts
0 Tensile strength in 152
120
270 usually
Temp. 29.4
43.4
39.2

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Example 9:

According to this example, a poly (diphenylsiloxane-blockdimethylsiloxane-block-diphenylsiloxane) polymer of the ABBA type was prepared similarly to Example 3, with the modification that this time the blocks in the molar concentration 75 ώοΐ-τέ dimethyl and 25 mol ¹ ^ diphenylsiloxy units were present. Using the BMDSA, a portion of this polymer was cured using the same cyclic compound as in Example 6 and the samples tested for physical properties. In another experiment, a sample of this ABBA polymer was dissolved in hot diphenyl ether before curing and then precipitated with methanol for the purpose of converting the polymer from an elastomer into a resin. BMDSA was then added to this resin and cured in a manner similar to that described in Example 8. One weight percent BMDSA based on the weight of the polymer was used as the curing agent in each pail.

The following Table III gives the results of the tests carried out on the individual samples.

III

template tensile strenght in kg / cm Percentage Extensibility Mr. ordinary
temperature 125 ⁰ C. ordinary
temperature 125 ⁰ C. 4th
⁺ 5 40.25
77.6 28.1
37.8 275
209 302
247

⁺ Precipitated from diphenyl ether with methanol.

BATH ORIGINAL

-39-109830 / 1552

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Example IQ;

4.08 g (o, ol mol) of ice, trans-2,4,6-trimethyl-2,4,6-triphenylcyclotrisiloxane were obtained dissolved in 25 ml of dry tetrahydrofuran in a reaction vessel under a nitrogen atmosphere. Then 6.2 ml (o, ol mol) of n-butyllithium in a small Amount of η-hexane added to the siloxane solution with stirring. After stirring for two hours, a lithium compound was obtained, which corresponds to the following formula:

Li

CH ₃
O - Si -

^C 6 ^H 5

C ₄ H ₀

Then 0.1 ml (0.029 × 10 moles) of this solution were added to 2.5 g (0.1 mol moles) of hexamethylcyclotrisiloxane dissolved in 2 ml of dry tetrahydrofuran. The reaction mixture was refluxed for 2 hours to ensure complete copolymerization of the hexamethylcyclotrisiloxane. Then 2.5 g (0.042 mol) of hexaphanylcyclotrisiloxane in 10 ml of dry benzene were added and mixed thoroughly with the polymeric composition already formed; the mass was then heated under reflux conditions while at the same time the tetrahydrofuran solvent was removed under a stream of nitrogen. After most of the solvent had been removed, the reaction mixture was heated for a further 30 minutes to 125 ⁰ G. and then for 4 hours to 200 ⁰ G. For the purpose of removing the lithium, the reaction product was then mixed with a sufficiently large amount of glacial acetic acid to produce a to ensure complete reaction between this and the lithium; the lithium acetate was then removed by filtration

109830/1552

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- sheet 40 -

ferrite. The residue product was then washed with ethanol, to remove any trace of acetic acid. The received The product consisted of a solid white crystalline elastomer, which consisted of linearly constructed polydiorganosiloxane, whereby the one chain end from a silicon-bonded hydroxyl group and the other chain end from a silicon-bonded one Butyl group; the yield was 90? »; this polymer corresponds to the formulation AB.

Example 11:

10 g (0.417 mol) of lithium hydroxide were slurried in 50 ml of 3enzol and then by heating, under a stream of nitrogen «Removes the benzene.

Then 4.08 g (o, oil mol) of ice, trans-2,4,6-triniethyl-2,4,6-triphenylcyclotrisiloxane in 25 ml of dry tetrahydrofuran were added and the resulting slurry was stirred for about 18 hours at ordinary temperature. The excess lithium hydroxide was then removed by filtration and the filtrate was stored under nitrogen. This filtrate, which, as determined by acid titration, o, χ o32 10 * "^ li contained on a basic lithium ion, corresponded to the formula:

O -

CH,

I "

Si- I

OH

This is equivalent to one cyclopolyeiloxane ring opening per any active lithium in the reaction product.

-41-

109830/1552

- sheet 41 -

About 0.08 ml (o, o25 χ 10 mol) of the aforementioned lithiura compound in tetrahydrofuran were added to 2.5 g (o, oll mol) of hexamethylcyclotrisiloxane in 2 al dry tetrahydrofuran and the mass was heated under reflux conditions for 2 hours, the copolymerization of the Hexamethylcyclotrisiloxane took place. Then 2.5 g (0.042 mol) of hexaphenylcyclotrisiloxane dissolved in 10 ml of benzene were added to the reaction product with stirring and the reaction mixture was heated to boiling under reflux conditions for 50 minutes, the solvent being removed in a stream of nitrogen. The mixture is subsequently heated the reaction mixture 30 minutes 125 ° C and 4 hours at 25O ⁰ O and the resulting product treated subsequently with Bisessig and then with methanol *, in the same manner as described in the previous examples. ! .lan obtained a solid, white elastomer, the yield was more than 90 i ° of theory. This product corresponds to the formulation AB, with both chain ends of this polymer having hydroxyl groups.

Example 12;

6 g (0.1579 mol) of lithium aluminum hydride were suspended together with 4.08 g (0.15 mol) of ice, trans - ^^ jö-trimethyl - ^^ o-triphenylcyclotrisiloxane in 45 ml of dry tetrahydrofuran by making the ingredients Mixed for 18 hours under nitrogen at ordinary temperature. The resulting reaction mixture was filtered to obtain a lithium compound represented by the formula

Li

-42-

109830/1662

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is equivalent to. 0.1 ml (0.025 10 mol) of this lithium compound were added to 2.5 g (0.025 mol) of hexamethylcyclotrisiloxane in 2 ml of dry tetrahydrofuran and the reaction mixture was slowly heated and kept at the boil for a total of 2 hours under reflux conditions, with the copolymerization proceeded. Then 2.5 g (0.042 mol) of hexaphenylcyclotrisiloxane in 15 ml of dry benzene were added and the reaction mixture was also diluted with 20 ml of benzene and then heated with stirring until complete solution was achieved. The solvent was then removed by introducing a stream of nitrogen and the reaction mixture was heated to 125 ^° C. for 30 minutes and then to 200 ° C. for 4 hours Described in the previous examples, represented a polymer which corresponds to the formulation AB, the yield was more than 90 -β> of theory. This linear polysiloxane had a silicon-bonded hydroxyl group on both ends.

Example 13;

4 »8 g (0.6 mol) of freshly ground lithium hydride was under Nitrogen together with 4.08 g (o, ol mol) of ice, trans-2,4,6-trimethyl-2,4,6-triphenylcyclotrisiloxane slurried in 30 ml of dry tetrahydrofuran. After looking at the ingredients After mixing for 18 hours at ordinary temperature, the slurry was diluted with 10 ml of dry benzene and filtered off. The filtrate contained a lithium compound of the formula:

Li

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One ml of this solution of the lithium compound was added to 2.5 g (o, oll ^ 5 mol) of hexamethylcyclotrisiloxane in 2 ml of dry tetrahydrofuran; the mixture was then heated to boiling under reflux conditions for 5 hours in order to bring about complete copolymerization. Then 2.5 g (o, oo42 IvIoI) hexaphenylcyclo-trisiloxane in 15 ml benzene were added to the reaction mixture and this was heated gently to remove the solvent while a stream of nitrogen was introduced at the same time. Then, heating the reaction product verblieoene 30 Ivlinuten at 125 and then for 4 hours at 200 ⁰ C. i <ian extracted the product with glacial acetic acid and then treated, similarly as described in the previous examples, with ethanol, a solid, white elastomer being obtained, the yield was significantly more than yO γο of theory. This linear organopolysiloxane, which corresponds to the formulation AB, had a silicon-bonded hydroxyl group at one end of the chain and a silicon-bonded hydrogen atom at the other end of the chain.

This example illustrates the important advantage of successive Addition of cyclopolysiloxanes to a lithium compound; In contrast to this, a product of random or random structure is obtained if one uses the cyclopolysiloxanes copolymerized at the same time.

Example 14;

A block copolymer which corresponds to the formulation ABBA was prepared by adding 5 g (o, ol225 mol) of ice, trans-2,4,6-trimethyl-2,4,6-triphenylcyclotrisiloxane with o, ol g (3.31 x 10 ^-5 mol) of DL-I was heated for 16 hours at 125 ⁰ C. After cooling the reaction mixture, 5 ml

109830/1552

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- sheet 44 -

Tetrahydrofuran was added together with 5 g (0.0843 mol) of hexaphenylcyclotrisiloxane and the reaction mixture was heated to boiling for one hour under reflux conditions. Subsequently, the tetrahydrofuran removed by Löeungsmittel .Einleiten a stream of nitrogen and then heated to 125 C residue 15 minutes, then 15 minutes at 150 ⁰ C, and finally 15 to 20 minutes at 200 ⁰ C. The resulting product consisted of white from one, rubber-like mass that was hard and solid at ordinary temperature..Bas product was extracted with glacial acetic acid and treated with ethanol in a similar way to that described in the previous examples, a product which was insoluble in benzene was obtained. The proton magnetic resonance spectra of this product indicated that no equilibration or rearrangement occurred during the block copolymerization. An X-ray examination using the Debye-Scherrer method showed that the product is highly crystalline.

Comparative example:

For comparison, copolymerization was carried out under random conditions. To this end, 5 g (0.0225 mol) of ice, trans-2,4,6-trimethyl-2,4,6-triphenylcyclotriloxane were mixed with 5 g (0.0843 mol) of hexaphenylcyclotrisiloxane in 50 ml of dry benzene and dissolved . The mixture was then melted together at 210 ⁰ C, purged with nitrogen, and the polymerization by the addition of 3 x ΙΟ ^"5 mol of DL-I set in motion. The reaction was continued for 5 hours at 210 ⁰ C to ensure a complete polymerization of the product The product finally obtained consisted of a rigid, resinous body which is soluble in benzene and which was determined by nuclear magnetic resonance spectroscopy to be a copolymer with an arbitrary structure.

109830/1652 -

—4P—

- sheet 45 -

Example 15:

This example illustrates the preparation of a Bloek block copolymer, which is derived from a trifunctional organiscaen lithium compound.

First there was a trilithium phenylsiloxanolate of the formula

C ₅ H ₅ -Si- (O- Li) ₃

prepared by dispersing 1.56 g (o, ol mol) of phenylsiloxanetriol with partial dissolution in 20 ml of freshly distilled tetrahydrofuran and this then under nitrogen with a stirred solution of n-butyllithium (o, o36S mol) in 20 ml Benzene and 23 ml of η-hexane at a temperature between 0 and 25 ⁰ O added. A lithium salt precipitated for 13s and was collected on a filter in a drying cabinet filled with nitrogen and washed several times with 5 to 10 ml portions of benzene. This trilithium salt thus prepared was stored under nitrogen at ordinary temperature. This product had a purity of more than 95 "A and corresponds to the formula of trilithium phenyl trisiloxanolate.

A mixture of 5.15 g (0.0222 mol) of hexameth cyclotrisiloxane and 0.0269 g of the one prepared as described above was then prepared Prepared trilithium phenyl trisiloxanolate (1.54 x 10 moles) in 2.4 ml of dry tetrahydrofuran and heated the mixture to near boiling temperature under reflux conditions for 45 minutes. Then there was 5.15 grams (0.087 moles) of hexaphenylcyclotrisiloxane dissolved in 30 ml of dry benzene and this was added to the reaction mixture together with 10 ml of benzene. The reaction mixture was then heated to boiling under reflux conditions for one hour with thorough stirring. The solvent was then removed by introducing it

10983Q / 1562

-46-

- sheet 46 -

a dry stream of nitrogen and heated the reaction mixture for 30 minutes to 125 ⁰ G and then for 4 hours at ⁰ C. The 2OQ solcherraaseen product consisted of a hard, rigid and opaque polymer was branched into three directions. This product can be referred to by the following j? Orael, this j? Ormel image showing the αβη core, which is derived from the trilithium phenyl trisilanolate:

- Si

O-Si

O-Li

3n

-J 3

In this formula, η and m are the molar concentrations of the starting cyclopolysiloxanes. Without answering aes core tcann the polymer using the formula symoles explained above

AWAY

be identified by the following formulation: A3 BA.

Example 16:

Yg of hexainethylcyclotrisiloxane were mixed with 3.33 ml of dry tetrahydrofuran and 0.27 ml of DL-2 and the reaction mixture was heated to boiling for about 2 hours under reflux conditions; then 6 g of hexaphenylcyclotrisiloxane dissolved in 30 ml of benzene was added to the reaction product, the first reaction product being prepared in the tetrahydrofuran initially present. The reaction mixture was then used. treated with 10 ml of benzene and slowly removing the solvent by carefully heating under a stream of nitrogen; then heated to 125 ⁰ C for 20 minutes and finally

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borrowed 4 hours to 20O ⁰ G. iv; an obtained a solid block-block copolymer in more than 90% yield which corresponds to the formulation A3BA.

The lithium polymer obtained, recognizable by the existing ones. Diorganosiloxy groups including those derived from DL-2 Proportions, corresponds to the formula

Li

C Hc, 6 5

Si-T

^C 6 ^H 5

CH.

-0-Si-

CH.

, 6 5 • O-Si— 0-

^C 6 ^H 5

~ CH
3 - - C. H 5 -0- -Si -Si
I. CH ₃ 3 I.
^C 6 - "" 3

Examples 17 to 21 below explain uie practical implementation of the present invention, using an organic lithium compound of the formula I.

When carrying out these processes, traces of water should also be avoided and preferably completely anhydrous Conditions and inert atmospheres both in the preparation of the organic segment polymer and in the coreaction are adhered to with the cyclic polysiloxane. Other reaction conditions, for example the presence of Carbon dioxide, acids and compounds that produce acids Containing groups should also be avoided, otherwise the lithium catalyst will be destroyed could or takes place and a tendency to terminate the polymerization is created.

This process, namely both the homopolymerization of the unsaturated monomer and the block copolymerization

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dee lithium derivative dee organic polymer segment with the cyclic polysiloxane is preferably conducted at ordinary temperatures and advantageously at temperatures in the range of 10 to 35 ⁰ C. In general, the normal atmospheric pressure will exist, although the use of overpressure or underpressure and also that of higher or lower temperatures is not excluded.

The block copolymers have polyorganosiloxane iändsegmente due to the fact that they are ultimately formed by the co-reaction of the lithium derivative of the organic segment with the cyclic polysiloxane. These block copolymers have individual polyvinyl or polydiene segments between these JändSegmenten or polysiloxane segments, which alternate with polyvinyl or polydiene segments between the iändsegmenten, if so desired, other polymer segments can be between the polyorganosiloxane and the polyvinyl - or polydiene segments are inserted. The weight ratio of the individual polyorganosiloxane segments in the block copolymer can vary within wide limits. In general, the percentage by weight of the organic segments, ie the polyvinyl or polydiene segments, should be at least two or three percent in order to ensure an influence on the properties of the block copolymer and in addition to create areas through which hardening or Vulcanization by means of peroxides, sulfur or high energy radiation can take place. On the other hand, the percentage by weight of one or more polyvinyl or polydiene segments can be up to 95 i>.

If only extremely low percentages of the polysiloxane are present, the organic segment will be large in general hardly significantly due to the extremely small amounts influenced by the polysiloxane segment. However, if the amount of Polyeiloxane increases and the value of about 5> 4, based on the

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- ³ latt 49 -

Total weight of the segments, the properties of the block copolymers are significantly influenced, especially what the water-repellent properties and the frictional properties concerned.

However, it should be emphasized that the presence of small percentages on polysiloxane segments, especially terminal ones Polysiloxane segments, a unique option for represents further chemical reactions. For example, the polysiloxane segment can have a terminal Si — OH group be a useful means of preparing ordinary temperature curable compositions, for the most part organic segments and only to a small extent polysiloxane segments contain.

The organic lithium compounds of formula I can on can be made in any manner known in the art. For example, you can use at least 1 ivlol lithium hydroxide with 1 mole of an organic nitrogen compound of the formula

mix, wherein R, R ¹ and m have the abovementioned meaning, and then the mixture is heated for half an hour to 8 hours at 50 to 7O ⁰ C, is produced whereby the desired organic lithium compound. Instead of lithium hydroxide, lithium metal can also be used to produce the organic lithium compound.

Another special example is the reaction between lithium hydroxide and a stoichiometric amount of triethanol amine, N-Methyethanolamine, N, If-Dimethyethanolamine indicated; in every case, organic lithium compounds are formed which the

109830/1552

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Formula I correspond.

Comparative example A Production of a lithium-ion connection of the formula II.

2oo ml (0.3 mol) of n-butyllithium in η-hexane were together with 5o ml benzene and 5ο ml diethyl ether slowly to 13.3 ml (ο, Ι ί ο1) Triethanolamine added and the Reaictionsgemisca 1 hour stirred for a long time; The precipitate formed was allowed to dissolve drop. The liquid above was removed and the precipitate was washed twice with benzene and then dried; 15 »1 g of a compound of the formula were obtained

(Li-OC ₂ H ₄ J ₃ N

which had a melting point of 195 to 215 C.

Example 17;

0.97 × IQ mol. of the lithium salt of triethanolamine, which had been prepared according to the preceding comparative example A, were stirred with 5 g of hexamethylcyclotrisiloxane in 2 ml of dry tetrahydrofuran. After the mixture of ingredients had been heated to boiling for two hours under reflux conditions, an organopdlysiloxane was obtained which corresponds to the following formula, where m and η in this formula and in the formulas of the following examples are the number of moles of hexamethylcyclotrieiloxane or hexaphenylcyclotrisiloxane used indicate:

7 *

Si

CH.

C ₂ H ₄ -

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- sheet 51 -

This polymer could with 3 uol trimethylchlorosilane per IvIoI on polymer of formula XVII treated v / ground, wooei a chain-terminated Organopolysiloxane of the formula

[CH ₃ ]

Si

CH

-Si-

as well as lithium chloride was formed.

Example IS:

A block-block copolymer was prepared from the organic lithium polysiloxane compound of the formula given in Example 17 by adding 5 g of hexaphenylcyclotrisiloxane dissolved in 30 ml of benzene with the reaction mixture (including the THF solvent) enjoyed in Example originated from the reaction of hexamethylcyclotrisiloxane with aem lithium salt of triethanolamine, reacted. The suspension of the ingredients was kept boiling for 3 ½ minutes under reflux conditions, the solvent being removed under a nitrogen blanket. Then the reaction mixture was heated initially for 30 minutes at 125 ° G and then for 4 hours at ⁰ C. 2Ou läan received hieroei a branched. Block-block copolymer of the formula

? 6 ^H 5

0 - Si

^C 6 ^H 5

3n

CH

• O-Si

CH.

O - C ₂ H ₄

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Π20826

-Sheet 52 -

By treating this polymer with acetic acid or anhydride the lithium atoms can be removed using a hydroxy1-endblocked polysiloxane of the formula

^C 6 ^H 5

0 - Si

^C 6 ^H 5

3n

CH-

0 - Si

CH;

0 -

receives.

Example 19:

The dilithium salt of N-methyl-diethanolamine of the formula

(Li-O-

- ^CK

is shown similarly as in Comparative Example A, with the change that instead of using triethanolamine, this time N-methyl-diethanolamine with n-3utyllithium implements. Using the conditions shown in Examples 17 and 18, 5 g of hexaraethylcyclotrisiloxane are initially obtained with the dilithium salt of N-Iüethyl-ciäthanolamin reacted in 2 ml of dry tetrahydrofuran and then react the resulting product with 5 g of hexaphenylcyclotrisiloxane left, the conditions of Example 18 being met again became. This gives a block-to-block copolymer the formula:

^C 6 ^H 5

0 - Si

^C 6 ^H 5

0-Si

CH.

3n

0 -

N-CH.

BATH ORIGINAL

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172U826

- sheet 53 -

This composition can be used for the purpose of removing the lithium atoms be treated as described above, optionally one or both lithium atoms by an iriorganosilyl radical, replaced by hydrogen or by other organosilicon radicals.

Example 20:

The monolithium salt of Ν, Ν-dimethylethanolamine of the formula

Li-O- G ₂ H ₄ - K (CH ₃ ) ₂

is shown similarly as in Comparative Example A, with the modification that instead of using triethanolamine this time Ιί, Ν-dimethylethanolamine with n-butyllitnium implements. In compliance with those shown in Examples 17 and 18 Conditions are 5 g of kexamethylcyclotrisiloxane initially with the monolithium salt of Njlf-Dimethyiäthanolarain and 2 ml reacted dry tetrahydrofuran; the product obtained is then added to 5 g of trimethyltriphenylcyclotrisiloxane to, again adhering to the conditions of Example 18. In this way, a block-bloek copolymer of regular construction is obtained the formula

CH.

0 - Si

^C 6 ^H 5

CH,

-0 - Si

O - C ₂ H ₄ -N (CH ₃ ) ₂

3q

where q indicates the number of moles of methylphenyl trimer used. This composition can then be treated again as described above, in order to remove the lithium atom and replace it with a

109830/1552

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Triorganosilyl radical, hydrogen or another organosilicon radical to replace.

Example 21;

3 »34 g of the lithium salt prepared according to Comparative Example A. of the formula XVI were suspended in 150 ml of freshly distilled tetrahydrofuran and then 26.6 g (0.12 1.I0I) Hexamethylcyclo.trisiloxane added; it was under worked under a nitrogen atmosphere and then 6 hours heated to boiling for a long time with stirring and reflux conditions. The reaction mixture was then filtered off The filtrate evaporated to an oily liquid, this was redissolved in benzene, washed with water and the organic Layer separated. This organic splint was dried and a liquid polymer was also obtained here, aas has the general average formula as follows:

H-

0 - Si

CH.

0 -

■ N

/ 3

JSs found that this polymer has an i.iolecular weight in benzene of about 1240. This liquid had a decided tendency to stabilize and form Causing foam. If you add a few drops of this liquid to a benzene-water emulsion, then ergao that the jämulsion full 4 days by the presence this polymer was stable. In the absence of this polymer, this emulsion ruptured within a few hours.

109830/1552

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This polymer is useful for production, for example of foams made of polyurethane, which can then be heated, for the purpose of producing rubber-like polyurethane foams with uniform pore size.

According to one embodiment of the present invention, oei the a macromolecular organic segment with terminal: lithium is used, becomes an olefinically unsaturated one iilonomer (this term includes lithium polymerisers organic compounds with one or more £ -CH = GH groups) initially in the presence of lithium or one polymerized organic lithium compound under conditions in which the i'.Ionomer in an organic polymer is transferred, which has arisen in one or more places ig the aforementioned lithium atom or xäthiumatome. This polymerization with the lithium coating (it is So here not only elemental lithium painted, but also lithium derivatives, such as organolithium compounds, capable of polymerizing unsaturated .lonomers to effect) can be used in any solvent for such purposes be carried out, iiin solcaes usable Solvent for the production of polymers in the presence of a lithium compound is any solvent which has both towards the reactants as well as the reaction product is inert to, for example n-eexane and benzene.

Various methods of polymerization are known in the art unsaturated organic monomer with alkali metal compounds known.

The organic polymer with terminal: lithium is then reacted with the cyclic trisiloxane of the formula II, preferably in the presence of an aprotic solvent,

BATH ORIGINAL

109830/1552

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- sheet 56 -

for the purpose of obtaining a block copolymer which consists of organic, i.e. hydrocarbon segments and organosiloxanes is constructed.

Among the lithium compounds that are used in addition to elemental lithium for Production of the organic polymers terminated with lithium can be used «the following may be mentioned by way of example: Lithium naphthalene, lithium anthracene, butyllithium, lithium stilbene, 9-fluorenyl lithium, diphenyl lithium, 1,4-dilithium benzene, 1,5-di-lithium pentane, 15-dilithium naphthalene, 1,2-dilithium-1,3-triphenylpropane, 1,3,5-trilithium pentane and 1,3,5 -Trilithium benzene.

The unsaturated olefinic organic monomers which can be used and from which block copolymers can be prepared include both vinyl and diene monomers, for example styrene, butadiene, isoprene, 2,3-dimethylbutadiene, 1,3-pentadiene, chlorine butadienes, methyl methaorylate, methyl acrylate, O-methylstyrene, 2,5-dichlorostyrene, vinyl toluene, allyl benzoate, allyl acetate, croton nitrile, acrylonitrile, methacrylonitrile, vinylidene chloride and acrylamide. It should be emphasized that many other vinyl and diene monomers can also be used. Eb homologues of the aforementioned monomers, including the alkyl- and aryl-substituted homologues, can also be used

The lithium compound can be present in a very small amount that is still sufficient to prevent the polymerization of the To effect monomer, for example ο, οοοοΐ bit * o, 3 mol Lithium catalyst or initiator per mole of unsaturated monomer

The unsaturated monomer, which should be practically anhydrous and oxygen-free, is mixed with the lithium compound, whereby one then the polymerization in an inert atmosphere and suitable Temperatures can take place, for example at temperatures from -50 to - »- 20 °; the reaction time can be between a few minutes

109830/1552

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and lie for several days.

The lithium solution of the organic polymer is then added to the cyclic trisiloxane in the aprotic solvent the ingredients of the resulting mixture are left together react, advantageously normal temperature and preferably one below 100 ° 0 prevails.

This type of reaction can take a few minutes to several days before the block copolymer has formed. The mixture of ingredients is then heated for a few minutes to several hours to a temperature of 100 to 200 ^° C. in order to ensure that the reaction is complete; the polymer is then isolated in a manner known per se, it being possible to use various solvents for this purpose. Small traces of bound lithium can be tolerated in many applications and processing methods of the polymer, since the terminal lithium ions can be easily removed and are therefore relatively uninvolved in the reaction described below.

Example 22;

Production of a macromolecular organic segment with terminal lithium.

45 g (0.433 mol) of styrene were distilled over calcium hydride in vacuo and stored in a pyrex flask fitted with a break-lock. The styrene was then mixed with 50 ml of anhydrous, degassed cyclohexane which contained 1.67 × 10 ^J mol of n-butyl lithium . The reaction mixture was closed in a flask with a round bottom by means of a Bruohversohlusses and allowed to polymerize for 4 days while shaking at -4O ^{0 C.}

109830/1552

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Polymerization of organosiloxanes.

The polystyryllithium active solution thus obtained was used to prepare a terpolymer as described below. 6 g (o, o27 mol) Hexamethylcyclotrieiloxan dry, freshly distilled tetrahydrofuran were added in Io m. Dissolved and then distilled off by heating a few milliliters of tetrahydrofuran. A further 8 ml of dry tetrahydrofuran and 1/3 of the above-described active poly styryl-lithium solution were then added to the reaction mixture. The reaction mixture was then shaken for 15 hours, a block copolymer of the polystyrene and the hexamethyltrisiloxane segment being formed. At this point, the block copolymer can be represented by the following formula:

- CH.

CH,

-Si- I. CH.

.Li

in which χ and y indicate repeating polystyryl or siloxane units. Then 4 g (o, oo675 mol) of hexaphenylcyclotrisiloxane, which had been dissolved in 20 ml of benzene (distilled over calcium hydride), were added to the reaction mixture and this was heated to boiling for 1 hour with simultaneous stirring and under reflux conditions. Ansohliessend the solvent was removed and the Miβοhung heated for 4 hours at ⁰ C 2uo. The reaction product was cooled and then dissolved in heissera benzene and then precipitated with methanol, with 90 i of "a Blook terpolymer precipitated, which consists of a white, was hard resin. This polymer can be represented by the following formula

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- sheet 59 -

172Ü826

CH -

Si 0

^C 6 ^H 5

-Li

in which χ and y have the meaning given above; ζ indicates the molar concentration of diphenylsiloxane blocks introduced into the polymer. As a result of the use of lithium, no random arrangement could be found in the terpolymer; the segments were present in the same position and order in which they were introduced; they are also present in practically the same amounts in which they were introduced under the reaction conditions described above.

If, on the other hand, you use potassium instead of lithium, for example, you get an arbitrary and random distribution of the dimethylsiloxy and diphenylsiloxy units, namely because of the equilibration and cyclization that takes place out of order and arrangement imposed by the cyclic Trisiloxane should be introduced to take place.

Example 23;

Following the procedure of Example 22, an active polystyryl lithium solution was prepared by mixing 5 ml of dry, freshly distilled styrene and 2 millimoles of n-butyllithium, and 40 ml of dry cyclohexane, followed by stirring the resulting reaction mixture for 48 hours at a temperature from -20 to 30 ⁰ G. at about 3 g of these active PolyBtyryl lithium solution was then 5 g cis ^^ ^^ ö ö-trimethyl-triphenylcyclotrisiloxane in 5 ml THF (dried over CAHP) was added After 15 minutes Stirring became the solvent by applying

109830/1552

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- sheet 60 -

removed in a vacuum, leaving a residue volume of Io ml. After stirring for an additional 16 hours, were. 2o ml benzene which a few drops of glacial acetic acid contained, added and then the resultant mixture was poured in methyl alcohol, wherein a hard resin Weissee which was purified by iuo has a softening point of 60 ⁰ C. A sample of this polymer was refluxed in methyl ethyl ketone until white flocculation began. The portion insoluble in methyl ethyl ketone was analyzed by differential scanning calorimetry. The heat capacity curves indicated two crystalline transitions for the block copolymer insoluble in methyl ethyl ketone, namely T _M = 100 ^° C., T ^ ₉ * 288 ^° C.; the nuclear magnetic resonance spectra of the block copolymer showed a high isotactic content (> 60 %) of the methylphenylsiloxane block. This polynar was composed of polystyryl blocks and methylphenyleiloxane blocks, the latter being regularly spaced in accordance with the molar concentration used.

Example 24:

Isoprene was polymerized and dissolved in hexane in a closed reaction vessel, with butyllithium being used for polymerization was used. Polyisoprene was obtained, with mainly cis-1,4 bonds being present. Then cis-2,4,6-trimethyJ 2,4,6-triphenylcyclotrisiloxane, which is dissolved in tetrahydrofuran was present, added and the mixture of ingredients, similarly as described in Example 22, implemented. When the polymerization is in progress, a polymethylphenylsiloxane segment is formed added to the reactive hydrocarbon segment, where the 2/3 isotactic and 1/3 heterotactic siloxane segment with respect to the conformation of the methylphenyl loxy units.

109830/1552 _ ₆₁ _

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The polymerization proceeded in quantitative conversion as opposed to the much weaker conversion when used other systems catalyzed by strong alkali metal, for example when using potassium instead of lithium. It was no evidence of homopolymer segments was found in the system, which had a significant effect on the final properties of the block copolymer.

The following example illustrates the preparation of the block terpolymer poly-CDiphenylsiloxane-block-dimethylsiloxane-block-styrene-block-dimethylsiloxane-block-diphenylsiloxane), which corresponds to the formulation ABGGBA, where A is the diphenylsiloxy units, B is dimethylsiloxy units and C is the polystyryl unit means.

Example 25:

18 g (0.173 mol) of styrene were dissolved in 10 ml of dry benzene and polymerized with dilithiostilbene (0.02 mol) at 0 ° to 27 ° C. in one hour. Then, 20 g (0.09 moles) of hexamethylcyclotrisiloxane dissolved in 100 ml of THP was added to the polystyryl reaction mixture and polymerization was carried out with stirring for 18 hours. Then 15 g (0.1685 mol) of hexaphenyloyclotrisiloxane, which had been dissolved in 100 ml of THP, were added and the mixture was stirred vigorously for a further 2 hours to ensure that the reaction was complete. Subsequently, the solvent was removed, by introducing a stream of nitrogen, and then heated, the resulting polymer-Gemiech 4 hours to 200 ⁰ G, whereby again a security has been ensured that the reaction has gone to completion. The reaction mixture was then cooled and then worked up by extraction with η-hexane, which contained a trace of gravel. The yield of benzene-soluble blook terpolymer was more than 90% . This polymer formed

109830/1552

"• On ·"

- sheet 62 -

white, flexible, crystalline solvent-resistant sheets, when it is pressed for 15 minutes at a temperature of 25O ⁰ C and a pressure of 350 kg / cm and then quenched in cold water.

The following example shows the production of a poly (dimethylsiloxane-block-isoprene-block-dimethylsiloxane.

Example 26;

34 g (ο.5 mol) of isoprene were distilled in vacuo over fresh sodium in a flask, in which it was then polymerized with o, ooo2 mol of dilithio tubes in 2oo ml of anhydrous n-hexane for 16 hours at ordinary temperature, a viscous solution of the Polyisoprene was obtained. 14.8 g (0.067 mol) of hexamethylcyclotrisiloxane, which had been sublimed off via calcium hydride, were then added to the reaction mixture, and the reaction mixture was diluted with 100 ml of anhydrous THP with subsequent stirring for 16 hours at ordinary temperature. Then 50 ml of benzene containing 0.1 ml of acidic acetic acid was added, causing the reaction mixture to dissolve and neutralize. The polymer was obtained by pouring the solution into methanol saturated with carbon dioxide; the polymer was dried in vacuo and a yield of 48 g was obtained. This block polymer had a block purity of at least 96.5% . 5 g of this polymer were dissolved in benzene and reacted with 0.5 ml of methyltriacetoxysilane, with subsequent drying under nitrogen and exposure to (humid) atmospheric conditions for one hour; this resulted in crosslinking to form a benzene-insoluble film. This polymer, ie the product before the treatment with methyltriacetoxysilane, is a difunctional body and can advantageously be used as a composition curable at ordinary temperature.

109830/1552

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The reactions presented in the preceding description and the examples can be used for further applications to be used. A particularly advantageous use consists in the production of difunctional segments which are used as Intermediate compounds can be used for bodies curable at ordinary temperature. To one at ordinary temperature Producing a curable hydrocarbon system becomes a Vinyl or diolefin compound with a difunctional organolithium catalyst prepolymerized, being a macromolecular Hydrocarbon chain is formed, which has reactive sites found at both; i.e. they are at both ends of the polymer chain the lithium atoms are present. A cyclic polysiloxane is then added in the manner described above, for the purpose of obtaining a diorganosiloxane segment on both ends of the hydrocarbon polymer chain. If you have this The end of the chain with a weak acid or another source of protons becomes a macromolecular segment obtained, which consists of hydrocarbon inside and which has terminal siloxane segments, which then with suitable Crosslinking agents can be implemented, with ordinary Temperature curable hydrocarbons are formed.

The known procedures for producing such types of systems were based almost entirely on condensation techniques and are very difficult to control and have many problems in synthesis.

These disadvantages of the prior art are overcome by the present invention while achieving advantages. One such advantage of the new system according to the present invention lies in the fact that no reconditioning procedures _f eind necessary prior to addition of the crosslinking agent are. For example , one can use the system of how θβ is obtained from the reaction

109830/1552

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I72U826

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treat multifunctional crosslinkers, where one feast and flexible products.

There are many other ways of using the invention Systems such as the manufacture of block hydrocarbon siloxane fluids that are useful as lubricants are made of resins and high temperature elastomers. Through the incorporation of sterically controlled hydrocarbon and Structural control can be exercised in siloxane segments by none of the other polymerization systems with strong Alkali metals is achievable.

Sas lithium block copolymer and terpolymer, which is composed of organic segments and silozane segments, can be used according to various procedures for the purpose of obtaining a polymer devoid of lithium atoms. Thus, the lithium polymer can be treated with an acid, for example with acetic acid, whereby the lithium atom is treated a hydrogen atom is replaced and polysiloxanes or copolymers with terminal hydroxyl groups are formed.

On the other hand, if you have a Triorganosilyl group or a similar terminal organoeilicium group desires the lithium atom of the lithium polymer for example with a triorganohalosilane, such as trimethylchlorosilane or triphenylchlorosilane, with lithiurachloride and a chain-terminating triorganosilyl group arises. In this way one arrives at stable liquids which • have unusual properties, especially if isotactic structures with more than 65 isotactic Proportion are all a result of being able to maintain the high isotactic proportion that results from the Reaction of the lithium linkage with the polymer! a free monomer

ORIGINAL INSPECTED 109830/1552 _ ₆₅ _

! 72U826

- sheet 65 -

with formation of the organolithium segment originates, this Finally, there is a high proportion in the polysiloxane segment.

To ensure complete removal of the acetic acid, Washed with methanol and in particular with a 90 to 10 percent by weight mixture of methanol and water, so that the freedom of the polymer from any residual liquid acid is fully guaranteed.

The block copolymers obtained according to the invention can in particular in the crosslinked state to produce high-temperature solid Sealing materials, for example of sealing rings, for the production of tubular materials, of fuel lines, used in insulation, engine fittings, and a variety of molded and extruded products.

The polymers made according to the rules of the present invention as pointed out, possess unique and unexpected properties. You can easily be drawn from the products of the stand the technology, and indeed also from those products that have been manufactured by processes that relate to the manufacturing process target of block copolymers.

The most important fact 1st the that the inventively prepared polymers, and this applies both to the Lithiumhaltlgen and for the non-lithium-containing products at least 98 i "and praktisoh to $ 100> have a predetermined regularity of the arrangement of the Blockeegmente, unlike the much less upstream block segments which, at best, were achievable by the processes of the prior art for the production of block copolymers.

-66-109830 / 1552

I72U826

- sheet 66 -

Furthermore, the products according to the invention have unusual tensile strength properties and extensibility, even if the products are not filled when the products are in use of normal crosslinking agents, e.g. benzyl peroxide, di- (oc-cumyl) peroxide and tertiary butyl perbenzoate in the hardened Transferred state. The Krietallinität, which as a result of the regular Arrangement of the components of the polymer according to the invention is carried into this is also a unique property, which are not known from the polymers of the prior art with a comparable organosiloxane content.

Furthermore, the insolubility of the manufactured according to the invention makes Polymers that exist even in the uncured state, in contrast to these uniquely suited to uses to the polymers of the prior art, which are generally soluble, for example in benzene and toluene. This insolubility of the products produced according to the invention also a greatly increased swelling resistance to hydrocarbon solvents when these polymers are converted into the infusible and insoluble state by means of peroxide hardeners or by means of high energy irradiation, for example electron beams high energy.

The ability to create or carry out an unambiguous synthesis of block copolymers of the organocyclosiloxanes brings the possibility of obtaining both crystalline and amorphous blook segments in the polymer chain, where the crystalline segments cause the solvent resistance, the high temperature stability and the tensile strength properties, while the amorphous segments cause the low-temperature flexibility or ductility. These common properties can be changed by a previous thermal or solvent treatment.

OfHGINAL WSPECTED

109830/1552

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172U826

- sheet 67 -

This is achieved through the hot-dip treatment of an ABBA polymer and shown by precipitation with, for example, methanol. Under the hot-dissolving conditions, the diphenylsiloxane blocks extended and the dimethylsiloxane blocks due to their weak Solvation ability compressed or restricted.

The practical result is that when the polymer precipitates from this state, the diphenylsiloxane segments exert a greater influence on the blocking properties. These results are an apparent demonstration of switching the polymer from a rubbery polymer into a resinous product as detailed above. This change is accompanied by the networked state an increase in tensile strength and a decrease in flexibility, whereby the swelling resistance to the usual aromatic solvents is significantly increased.

The products of the present invention, especially those Qn, b < which the lithium atom is removed and, for example, by hydrogen, by a triorganosilyl radical or by another Organosilicon radical is replaced, have numerous applications. They can be mixed with various fillers, e.g. with finely divided silica and carbon black, and then either by means of organic peroxides with those generally organopolysiloxane elastomers cured or by applying high energy radiation as described in U.S. Patent 2,763,609 is to be transferred to the networked state. In the cured state, these polymers can be used in all sorts of ways Used for insulation purposes, for example for the insulation of electrical conductors, they can also be used as encapsulation means, for example in capacitors and as coating materials for surfaces where there is a

109830/1552 -68-

- sheet 68 -

Resistance to moisture and heat matters. Due to the exact choice of the organosiloxane units forming the polymers It is possible to produce fluids that can be used both as dielectric fluids and as lubricants can be used advantageously.

On the other hand, one can these polymers, especially those that contain no lithium atoms, use to control the foam or foaming liquids, the normal "as echaumbildungs SENS borrowed are. The organopolysiloxanes, which contain terminal silicon-bonded hydroxyl groups, can furthermore be condensed by the use of dehydrating agents or by the use of organometallic compounds, for example of beenoctoate, chain lengthening being achieved via the medium of the silanol group. In this case, the hydroxy-1-endblocked polysiloxane can be used as a reactant for the production of compositions which can be hardened at ordinary temperatures.

^ he block copolymers obtained with dienes, ie copolymers composed of polydiene segments and polyeiloxane segments, can be hardened or vulcanized by the usual methods of hardening hydrocarbon rubbers, for example by using sulfur and other suitable materials. Other vulcanization or hardening accelerators that can be used instead of sulfur are, for example, disulfides, alkylphenol sulfides, p-dinitrobenzene, sulfur dichloride, tetramethylthiuram disulfide and tetraethylthiuram disulfide. In general, one can perform this Vulkanisation- or curing daduroh that is ground Blook the copolymer with or without filler, and then together with the Vulkanieiermittel

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Heated for 5 to 30 minutes to a vulcanization temperature in the large-scale arrangement of 125 to 175 ⁰ G, pressure preferably being applied; this gives the desired heat-cured vulcanization products. The use of vulcanization accelerators, for example phenyl-beta-naphthylamine and triphenyl phosphite, and also those of the usual fillers, for example silica, clay or titanium dioxide, is not excluded here.

/ Claims:

109830/1552

Claims (3)

Claims 1.) Process for the preparation of block-block organosiloxane copolymers by polymerizing an organotriailoxane in the presence of an alkali metal, characterized in that that you can do the reaction in an aprotic solvent between (A) (1) an organic lithium compound that is at least contains a lithium atom that is bonded to a silicon atom via an oxygen atom, (2) an organic lithium compound of the formula (KV- ¹ * - ⁴ * '- ° * ^Li) 3-m or (3) a macromolecular organic segment terminated with lithium and (B) a cyclic polyeiloxane of the formula R ^M Si ( performs, where R is a monovalent hydrocarbon ^{radical, R 1 is} an alkylene radical with 1 to 10 carbon atoms, R "is an organic radical which has no aliphatically substituted halogen, namely a hydrocarbon radical, cyanoalkyl radical or halogenated aryl radical, and m is O, 1 or 2. 2.) The method according to claim 1, characterized in that one reacting the reaction product with a cyolotrieiloxane as defined in claim 1. ORIGINAL INSPECTED 109830/1552 - patent claims - 3.) The method according to claim 1 or 2, characterized in that the lithium atom in the block-block organopolysiloxar is replaced by a segment arranged at the chain end, namely by hydrogen, an organosilyl or an acyloxy radical . 109830/1552