DE1912671A1 - Process for making a curable organopolysiloxane composition - Google Patents

Description

LAWYERS

D ... JUR. DIPL-CHEM. WALTER BEIL

DR. JUR. DIPL ₁ -CHEM. H.-J. WOLFP
DR. JUR. HANS CHR. BEIL .

FRANKFURT AM MAIM-UOCiISf

AOElONSTiASSE M

Our no. 15 390

Stauffer Chemical Company-New York, N.Y., V.St.A.

Process for making a curable organopolysiloxane composition.

The present invention relates to the manufacture of modified ones Organopolysiloxanes with thixotropic properties that are produced in a solvent system. The new Organopolysiloxanes can also be modified to form polysiloxanes which are curable at room temperature and which are self-adhesive are.

Due to their thermal resistance, diyi-electrical properties and resistance to destruction by the atmosphere, the organopolysiloxanes have so far been used in a wide range of technical fields. In some applications it has been found desirable to improve the physical properties, for example tensile strength, elongation and tear strength. To improve these properties, various reinforcing agents and fillers have been incorporated into the organopolysiloxanes. With the fillers or reinforcing agents mentioned, however, tensile strength, tear strength and elongation could not be improved in such a way that the values approach the physical properties of other synthetic or natural rubbers _e

It is known that organopolysiloxanes with in situ, formed particle-resistant systems with advantageous properties. The particulate component can be prepared in such systems by reacting monomers with organopolysiloxanes under carefully controlled reaction conditions generated in the absence of a solvent. The reaction is exothermic, however, and due to the strong evolution of heat it becomes extremely difficult to have a larger, batch-wise operation Keeping the reactor under control. For this reason, only a limited number of modified organopolys could so far iloxanes are produced in larger-volume reactors.

It was also necessary to use jjt in as a sealant using organopolysiloxanes curable at room temperature Incorporate fillers to give a composition with the desired properties and consistency required obtain. However, since organopolysiloxanes modified by fillers do not adhere to a substrate without a primer, this had to be done Substrate must first be treated with a primer before the filler-containing organopolysiloxane can be applied was. Numerous primers are effective on some substrates, but ineffective on others, i.e. metal primers, for example, are not Always good wood primers, and steel primers are not necessary also good aluminum primers, and vice versa.

The present invention therefore provides modified organopolysiloxanes with thixotropic properties, and also the provision of a room temperature curable, modified organopolysiloxane based on Adheres substrates without primer. Furthermore, according to the invention, there are self-adhesive, modified organopolysiloxanes curable at room temperature obtained with particulate component. According to Another aspect of the present invention is a controllable process for the preparation of the organopolysiloxanes mentioned provided.

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The invention initially relates to a process for the production of thixotropic, modified organopolysiloxanes with particulate component in a solvent system. Man these organopolysiloxanes are obtained by making an organopolysiloxane with an organic monomer or mixture of I-ionomers in the presence an organic solvent and a free radical initiator in contact, thereby grafting and the formation of particles can be achieved in situ.

Modified organopolysiloxanes with improved physical properties are obtained according to the invention by controlling the amount of organic solvent during the graft polymerization.

Figure 1 shows the thixotropic properties of a modified organopolysiloxane prepared in a solvent system in comparison with an organopolysiloxane prepared in the absence of a solvent.

According to the present invention, the olefinic Monomers on the organopolysiloxanes in the presence of a free radical initiator and an organic solvent are grafted to form modified organopolysiloxanes of the following. Formula:

3-n

Z _n SiO--

3-n

-SiZ.

in which the symbol R can stand for identical or different radicals and denotes monovalent hydrocarbon radicals, Q one Siloxane radical of the formula

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denotes, where the radicals H ¹ , which can be identical or different, are monovalent hydrocarbon radicals, halogenated monovalent hydrocarbon radicals or cyanoalkyl radicals, H "is a divalent hydrocarbon radical, R"'is a P ° ¹ y ^mere _c ⁿ _ar ° _s ^r ^ _e ^a f _len nical radical which is bonded to R "by a CC bond, * 'Z is a hydrolyzable or condensable functional group such as hydrogen, a hydroxyl, amino, amido, aminooxy, oxime group, halogen, an aryloxy, azyloxy , Alkoxy or phosphato group, η is an integer from 1 to 3, χ is an integer from 0 to 20,000 and y is an integer from 1 to 500.

The organopolysiloxanes used in the grafting stage can be represented by the following formula:

3-n

SiZ _n

x + 1

in which R, R ¹ , Z, η and χ have the above meanings · In the above formulas, in which R and R ^{1 can be the} same or different, these · substituents mean organic radicals such as alkyl groups, for example methyl or ethyl -, propyl or butyl groups, or aryl groups, for example the phenyl, ToIy1 or a chlorophenyl radical.

The modified organopolysiloxanes thus consist of an organosiloxane polymer with one or more side chains from a polymer with a carbon chain ». In the preparation of of these compositions, hydrogen is split off from the organopolysiloxane by the free / radical initiator, creating an active center where the grafting starts. The term "plug" is used here to refer to production such compositions are understood in which all or part of the organic polymer is attached to the siloxane polymer

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is bound via a C-C link.

All organopolysiloxane polymers that are capable of forming free radicals or active sites can be used in the grafting process. The polymer must therefore be able to form free radicals by removing hydrogen, and it should show essentially no tendency to polymerize further under the conditions used. That is, the siloxane polymer should be essentially free of aliphatic multiple bonds, but a small degree of such multiple bonds does not preclude the desired reaction, even if a competitive reaction occurs which is usually expedient to avoid. Preferably. If the organopolysiloxane contains lower alkyl radicals on the silicon atoms, since these give off hydrogen more easily than other radicals _e

Examples of suitable organosiloxane polymers and copolymers used to form the modified polymers of the present invention can be used are liquid siloxanes with terminal hydroxyl groups such as liquid methylphenyl silicones, Copolymers of dimethylsiloxane and methylphenyl or diphenylsiloxane units.

- The organosiloxane polymers can be in the form of partially condensed or fully condensed polysiloxanes are present «. Examples of fully condensed polysiloxanes are the hexamethyldisiloxanes, cyclic siloxanes such as octamethylcyclotetrasiloxane and trimethylsiloxy end-blocked polymers of dimethylsiloxanes.

Any organic monomers with multiple aliphatic bonds can be grafted onto the organosiloxane polymer. Examples of suitable olefinic compounds are the straight chain hydrocarbons of low molecular weight such as ethylene, propylene, bubylene, vinyl halides such as vinyl fluoride and vinyl chloride, vinyl esters such as vinyl acetate, styrene, ring

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substituted styrenes and other aromatics such as vinyl pyridine and vinyl naphthalene, acrylic acid and strong derivatives including of salts, esters, amides and acrylonitrile, N-vinyl compounds such as N-vinyl carbazole, N-vinyl pyrrolidone, and N-vinyl caprolactam, and vinyl silicon compounds such as vinyl triethoxysilane.

It is also possible to use disubstituted ethylene of the formula GH ₂ = CX ₂ , including vinylidene fluoride, vinylidene chloride, vinylidenecyanide, methacrylic acid and derivatives thereof such as their salts, esters and amides and methacrolein, methacrylonitrile and the like.

As examples of disubstituted ethylene of the formula CHX = GHX, which are also used in the formation of the modified polymers vinyl carbonate and various monomers may be mentioned, which are best in the presence of other monomers such as maleic anhydride, maleic acid esters and funiaric acid esters, Polymerize stilbene, indene and coumarone.

As already mentioned, the monomers can be used individually or in Mixtures of 2, 3 or even more monomers are used. The properties of the modified product depend of course of the type of monomer material as well as the ratio Amount used for organosiloxane polymer from »Mono * -,. · ' mers that give elastomeric homopolymers generally give elastomeric modified products, while monomers that give lead to plastic homopolymers, produce modified products of., lower elasticity. Using yon mindesjtejis Modified products can be made from a monomer of any class, which can be tailored to requirements - which previously could not be satisfied.

In the production of the modified OraanopoIysiloxane in accordance with the present invention, grafting is best accomplished using free radical initiators, usually organic peroxides, although + azo compounds are used

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den can in which both nitrogen atoms of the azo bond are bonded to tertiary carbon atoms, while the remaining Valencene of the tertiary carbon atom by nitrile, carboxyl, alkyl, cycloalkylene or alkyl radicals ,. preferably with 1 to 18 carbon atoms, are saturated · Instead of the the initiators mentioned above, ionizing radiation can also be used to form the free radicals

The most suitable peroxidic initiators are compounds of the formulas ROOH, ROOR or RCOOORy in which R means an organic residue. Specific examples are the hydroperoxides such as t-butyl hydroperoxide and cumene hydroperoxide and decalyn hydroperoxide; Diacyl peroxides, such as di-t-butyl and Dicumyl peroxidj cyclic peroxides such as ascaridol and 1,5-dimethylhexane-1,5-peroxidj Peresters, such as t-butyl perbenzoate, t-butyl peroxy isopropyl carbonate and t-butyl peroctoatej ketoperoxides, like acetone peroxide and cyclohexanone peroxide called

Acyl peroxides and peracids can also be used in the implementation of the method according to the invention are used, they however, generally result in less grafting, i.e. low yields of grafted product,

The amount of initiator which forms free radicals is not critical} you can work with any amount that causes a noticeable degree of grafting reaction. In general, amounts of only 0.05% of a more active peroxide initiator, based on the monomer weight, are sufficient. However, if the reaction rate is to be increased, then up to J% or more of initiator can be used. In general, it is advisable not to exceed a concentration of about 5% , since higher concentrations result in crosslinking and an undesirable increase in the viscosity of the reaction mixture. step·

It has been found that even the most reactive monomers for the production of modified organopolysiloxanes with.

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particulate component can be produced if one the graft in the presence of a critical amount of an organic Solvent carries out.

The amount of solvent should range zwischen.etwa • 2 and about 50, preferably about 5 to 30 wt -.% Of the total mixture, ie, solvent and reactants are. If more than about 50% of the total weight of the organic solvent is used, the modified siloxanes have properties after curing which are closer to the organic phase than to the siloxane phase, from which it can be seen that an inversion of the phase relationship has occurred it has a detrimental effect on the strength of the system »

The organic solvent also provides an agent for Control of the temperature during the grafting, so that the possibility of faulty batches is reduced a sufficiently volatile solvent, the boiling point of which is essentially the same as the temperature used for grafting is, the exothermic reaction can be effectively controlled. It is now possible to establish connections that were previously in were not available on an industrial scale. The presence of the solvent also creates a liquid phase system, with which, especially when using volatile or gaseous monomers, a significant reduction in the Grafting time and substantial increase in the yield of modified Organopolysiloxane polymer is achieved.

All organic solvents with boiling points between about 50 and 160 ° C and with relatively low chain transfer ^ - Constants can be used in grafting. Suitable solvents are, for example, aromatic hydrocarbons such as Benzene, toluene, xylene} chlorinated aromatic hydrocarbons such as chlorobenzene, aliphatic hydrocarbons such as pentane, Hexane, octane, cycloaliphatic hydrocarbons such as 1,1-dimethylcyclopentane, Cyclohexane, 1,1-dimethylcynlohexane, cyclo-

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heptane, cyclpoctane and the like. Furthermore, esters such as methyl, ·. Ethyl, propyl, butyl, amyl and isoamyl acetate, methyl propionate, Methyl and ethyl butyrate, methyl valerate, methyl trimethyl acetate, methyl caproate, ethyl valerate, ethyl trimethyl acetate are used will.

The proportion of organosiloxane used in grafting can vary within wide limits. However, it has been found that optimum physical properties are obtained when the siloxane makes up 25 to 60 # of the reactants, without a solvent. You can also work with a higher proportion, but the properties of the resulting siloxane then deteriorate. If the siloxane content is below about 25% _t , the organic polymer becomes a continuous phase and a semi-solid product can be obtained. Although the level of organosiloxane polymer can be below about 25% by weight based on the weight of the reactants, levels of about 25 % to $ 0% are preferably provided.

The viscosity of the organosiloxane polymer used as the starting material has a lasting influence on the physical properties of the end product. Although the viscosity of the liquid organopolysiloxanes can vary within a wide range, is preferably carried out with starting materials having viscosities from about 1.00 to 20000 cSt at 25 ⁰ C, and preferably between about 250 and 10,000 cSt at 25 ⁰ G.

An advantage of using the solvent system rather than the solventless methods is that a product with thixotropic properties is obtained. This property shows up at a solvent concentration of about $ 2 to $ 50 based on total weight. It has also been found that the thixotropic properties are a function of the solvent concentration in the system. In other words, when the solvent concentration is increased, the thixotropy is increased . . .- ■: -: -. ': ■' ·

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The thixotropic organopoly-,. Siloxanes are particularly suitable in the field of sealants, because this property makes it possible to produce amount of filler required for a non-seeping sealant can reduce. ■

The organopolysiloxanes obtainable according to the invention can also be used as elastomers curable at room temperature. In a one-component system, for example, a polymer can be used which is end-blocked by groups that hydrolyze at atmospheric humidity. sate. To oganopolysiloxanes with terminal hydroxyl groups, for example, silanes of the general formula X ^ _m SiY _{m are} added, in which X is a relatively inert group such as an alkyl, alkoxy or aryl radical, Y is an acyloxy, oxime, alkoxy, aryloxy group, halogen , an aminooxy or phosphato group, and m represent an integer from 3 to k , as end-blocking -_-. Agents added which functionally the hydroxyl group. Groups of the formula OSiXu Y -, replace. Examples of such silanes are methyltriacetoxysilane, isopropyltriacetoxysilane, isopropoxytriacetoxysilane, methyltriacetoxime silane, methyl-tris-diethylaminooxysilane, methyl-tris- (diethylphosphato) silane and the like. *

In general, the end-blocking agent is added to the modified organopolysiloxane immediately after it has been formed, while it is still hot or at least slightly. Under these conditions the terminal hydroxyl groups of the modified organopolysiloxane are replaced by functional groups which can be hydrolyzed by atmospheric moisture. The compositions can be cured by simply exposing them to the atmosphere, optionally with the addition of water vapor. ^; Under the influence of moisture, the compositions are cured for a few minutes to several hours or days.

In your two-component systems, the modified Organopolysiloxanes with terminal hydroxyl groups with

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mixed wetting agents, e.g. polyalkoxysilanes of the formula fc ^a 0) SiR ¹³ I ₁ or with polyalkoxysiloxanes in which the silicon atoms are linked to one another by Si ~ O-Si bonds,

while their remaining valencene are saturated by R 0 and R. In the above formula, the groups R denote monovalent hydrocarbon radicals with fewer than 8 carbon atoms, and the groups R denote monovalent hydrocarbon radicals or halogenated monovalent hydrocarbon radicals with fewer than 8 carbon atoms, while ζ denotes the number 3 or K. Examples of monovalent hydrocarbon ^{radicals R a} are the methyl, ethyl, propyl, butyl, hexyl, octyl, phenyl, vinyl, allyl, ethylallyl, butadienyl radical and the like. The radicals R are the same as for R ^{a in} question, also the corresponding halogenated radicals such as chloromethyl, 2-BrOm- ^ ₁ 6-diiodophenyl, 1,2-difluorovinyl, 3, ^ - difluorocyclopentyl, 2-bromo-cyclopenten-2,3 ~ yl and 6-chloro-hexyl radical. Such polyalkoxysilanes include, for example, the monoorgano-trihydrocarbonoxysilanes, tetrahydrocarbonoxysilanes, alkyl silicates and partial hydrolyses of such silanes. The polyalkoxy compounds, for example ethyl orthosilicate or partially hydrolyzed ethyl silicates such as ethyl silicate ¹¹ ^ O ", which mainly consists of decaethyl tetrasilicate, are mentioned as examples of these compounds. Examples of further usable alkyl silicates are, for example, ethyltrimethoxysilane, methylanethosilicate, methyl anodoxylethosilicate, methyl anodoxyethosylethoxylethoxylethoxylethoxylethoxylethoxylethoxylethoxylethoxylethosilicate, methylanethosylethoxylethoxylethoxylethoxylethoxylethoxylethoxylethoxylethoxylethoxylethoxylethoxylethoxylethoxylethoxylethoxylethoxylathoxylethylsilicate, methylanethosilethoxylethoxylethoxylethoxylethoxylethoxylethoxylathoxylethoxylethoxylathoxylethoxylathoxylethylsilicate, methylanethosiloxylethoxane Examples of alkyl polysilicates include ethyl polysilicate, isopropyl polysilicate, butyl polysilicate, dimethyl tetraethoxydisiloxane, trimethylpentabutoxytrisiloxane and the like.

The polyalkoxysilanes and polyalkoxysiloxanes can be used alone or in admixture. They should be used in a ratio of about 0.5 to 20, preferably about 1 to 10% by weight , based on the weight of the organopolysiloxane. If the total weight of polyalkoxysilanes or polyalkoxysiloxanes is below about 0.5 $, based on the weight of the modified organopolysiloxanes, there is only very little crosslinking. On the other hand, if one works with a total weight of polyalkoxysilanes or polyalkoxyεiloxanes of more than 10 $,

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based on the weight of the organopolysiloxane, the curing time is significantly reduced «,

The modified organopolysiloxane compositions are cured by the organopolysiloxanes having terminal hydroxyl groups with the polyalkoxysilanes or Polyalkoxysiloxa- one nen in the presence of a catalyst, preferably a metal salt or a metal compound mixed. The metallic component of the catalyst preferably consists of tin, but lead, chromium, antimony, iron, cadmium, barium, calcium, titanium, bismuth or magnesium are also possible. Examples of suitable salts are tin naphthenate, lead octoate, tin octoate, iron stearate, tin oleate, antimony octoate, tin butyrate and the like. Others

"Suitable catalysts are, for example," bis (dibutylphenyltin) oxide, bis (acetoxydibutyltin) oxide, bis (tributyltinri) oxide, dibutoxyditutyltin, tri-t-butylzirium hydroxide, triethyltin hydroxide, diamyldipropoxytin, dioctyltin , Diphenyloctylzinn acetate, Dodecyldiäthylzinn-Gcetat, trioctyltin acetate, Triphenvlzinn acetate, triphenyltin laurate, triphenyltin methacrylate, dibutyltin butoxychloride and the like _e These catalysts can be dispersed in the solvent and then the modified organopolysiloxanes having terminal hydroxyl groups is added, or in a suitable filler or additive and then ground with the modified polymer. Examples of suitable hydrocarbon solvents are benzene, toluene, xylene and the like. Halogenated hydrocarbons such as tetrachlorethylene or chlorobenzenes, organic ethers such as dietary ethers, dibutyl ethers and the like, or liquid are also suitable , polysiloxanes free of hydroxyl groups If the same solvent is used to disperse the catalyst as for the preparation of the modified organopolysiloxane, / or at least one solvent which is miscible therewith. The solvent: should be volatile enough to evaporate at tree temperature.

The organopolysiloxanes can be prepared in a customary manner conventional siloxane elastomers with additives will. Shall the products be stored before use

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-j 13 -

- 13 -

then the catalyst or crosslinking agent, such as a polyalkoxysilane or polyalkoxysiloxane, must be applied separately. This means that the modified organopolysiloxanes with terminal hydroxyl groups, crosslinking agents and optionally filler can be mixed together while the catalyst is only is added directly before use. According to another method, the organopolysiloxane, catalyst and optionally filler are first mixed, while the crosslinking agent is only added shortly before use. A filler can either be added to the modified organopolysiloxane or the crosslinking agent before the addition of the catalyst, or directly after combination the reaction part be participants added. the thus obtained compositions cure spontaneously at room temperature after mixing of its components. the amount of catalyst in these systems may range from about 0.05 to about 2 wt .- ^, preferably from about 0.1 to about 1 t Gew «- $, related en on the weight of the composition, vary. If appropriate, it is also possible to work with a mixture of two or more catalysts of the type mentioned above. The amount of catalyst depends on the respective use, in particular the pot life BEZW. the required working time. For example, a working time of one to two hours is required for sealing, ie so much catalyst is added that the sealant does not stiffen within a shorter period of time. Usually the composition is tack-free within two to four hours after sealing and is largely cured after about 2b hours and completely cured after about 7 days. The curing time can vary slightly depending on the humidity and temperature.

Fillers can, if desired, be incorporated into the organopolysiloxane compositions. Examples of suitable ones Fillers are: fumed silica, precipitated silica with large surface area, and silica aerogels, both as Coarse-grained silicas such as diatomaceous earth, crushed quartz and the like. Other suitable fillers are, for example, metal oxides such as titanium oxide, iron oxide, zinc oxide, Päsermateflalien such as asbestos, fiberglass and the like. Other additives such as

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Pigments, antioxidants, UV absorbers and the like. Added.

The modified orenopolysiloxanes curable at room temperature according to the present invention can be used in various ways as sealants. While one in general must work with a primer in the case of such sealants before use, the organopolysiloxane compositions according to the invention adhere Surprisingly, even in order to achieve good adhesion, it is no longer necessary to use a primer will. This is of great economic importance, since it reduces both the cost of the primer itself and for it Application can be saved.

In the following examples, "parts" each mean »Rioht parts, unless otherwise stated.

example 1

62.5 parts of styrene, 179.4 parts were placed in a reaction vessel Butyl acrylate, 162.1 parts of a polydimethylsiloxane with terminal hydroxyl groups, 1.2 parts of di-t-butyl peroxide and 21.3 Parts of toluene introduced. The reaction vessel was purged with nitrogen and then the contents were stirred for 4 hours heated to 130i2 ° C.

The above example was repeated using different amounts of toluene. The monomer conversion was at least $ 90 in each case. The reaction products were removed from the reactor and the viscosity of all products was measured with a Brookfield Viscometer (Model LVT, Spindle # k). As can be seen from the change in viscosity according to the stirring speed, the products are clearly thixotropic.

FIG. 1 shows the thixotropic properties of the organopolysiloxane compositions prepared in a solvent compared to the properties of an organopolysiloxane prepared in the absence of a solvent.

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Example 2

(a) 62.5 parts of styrene oil, 179.4 parts of butyl acrylate, 162.1 parts of a polydimethylsiloxane having terminal hydroxyl groups, 1.2 parts of di-t-butyl peroxide and 21.3 parts of toluene were introduced into a reaction vessel. The Renktionsgefäß was flushed with nitrogen IMD, the contents were heated with stirring for 4 hours at 130 + 2 ⁰ C "

(Td) For comparison, the above example is repeated, but with 40.5 parts of toluene were used.

(c) Example 2 (a) was further made using 61 parts Toluene repeated

(d) Example 2 (a) was further repeated using 81 parts of toluene,

(e) For further comparison, Example 2 (a) above was repeated, but without solvents »

About 100 parts of that obtained according to the above procedures modified organopolysiloxane compositions were given with 5 Parts of methyltriacetoxysilane mixed and poured into a mold and stored at room temperature and relative humidity of 30 to 70 ^ 7 days l ^ ug hardened As from the following facts I can be seen, the products according to the invention showed an improved Strain.

Table I.

toluene ν, υ.βΐ e? ti g- " Physical properties Tear-resistant hardness Example No. speed kg / cm strain speed kg / cm 5 3.8 % 2.15 13th 2 (a) 10 4.2 ij-71 2.68 16 (b) 1.5 3.0 485 1.96 27 (c) - 20th 3.5 348 1.96- 11th (d) 0 429 2.86 19th (β) 230

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Example 3

Each of the according to the provisions of Example 2 (a) to (e) Organopolysiloxane obtained was with 5 parts of methyltriacetoxysilane mixed and applied to previously cleaned and degreased substrates and then at room temperature and one cured relative humidity of $ 30 to $ 70 for 7 days. The improved adhesion of the prodxicts according to the invention is off Table II can be seen.

Table II ;

liability

(3) 5 (b) 10 (c) 35 (d) 20th

Ex. No. Toluene glass plastic alumi- not rusting ^ tile nium der '.steel

w 3 (a) 5 excellent bad good fairly good

"pretty good good" " " good Good

¹¹ good and bad

E.g.

Example 4

(a) About 100 parts of the organopolysiloxane composition prepared according to the procedure of Example 2 (d) were mixed with about 5 parts of methyltriacetoxysilane and applied to substrates that had been cleaned and degreased beforehand. Then, at room temperature and a relative humidity of 3: 0 to Cured for 7 days, after which the bodies produced in this way were immersed in distilled water for 7 days and then according to Federal Specification TT-S-23 ^: 0a, 4.3.9. tested. .

(b) The organopolysiloxane prepared according to Example 2 (d) with about 5 parts of methyltriacetoxysilane and about 10 parts of HI-SIL 233 mixture * was applied in a similar manner to cleaned and degreased substrates. It was then cured and tested in the manner described above ,

(c) In a similar manner, 100 parts of the

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game 2 (e) produced organopolysiloxane with about 5 parts Methyltriacetoxysilane mixed and cleaned on and degreased Applied substrates. Then it was at a relative humidity hardened from 30 to 70 ^ 7 days, then the Samples immersed in distilled water for 7 days and prepared as described above according to Federal Specification TT-S-230a, 4.3.9. tested.

The results of these tests are summarized in Table III, from which the improved adhesion of the invention Products on aluminum.

toluene Table III liability when peeling i Glass ₂ Aluminum ^ 20th
20th
0 kg / cm kg / cm " Example no. filler 0.80
0.91
0.80 0.84
0.98
0.48 Kind of parts Ma)
(b)
(c) HI-SIL 233 10

HI-SIL 233 = precipitated silica

Example 5

(a) Into a reaction vessel were charged about 208 parts of styrene, about 800 parts of ethyl acrylate, about 6-1 parts of a hydroxyl-terminated polydimethylsiloxane, 20.1 parts of t-butyl peroctoate, and 721 parts of toluene. The Beaktionsgefäß was purged with nitrogen and the contents were heated for 2 hours with stirring to about 80 ⁰ C.

(b) The above procedure was repeated, but in the absence of toluene. In addition, the t-butyl peroctoate was replaced with 2.08 g (parts) of 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane in dibutyl phthalate. The reaction was difficult to control and the temperature rose to about 100 ^° C.

(c) Part of the product prepared according to Example 5 (b)

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was then dissolved in toluene to form a 30% solution solution β

About 100 parts of the above oreranopolysiloxane compositions were each mixed with about 5 parts of methyltriacetoxysilane and applied to cleaned and degreased substrates, Dana was cured for ^{7 days at a relative humidity of up to 7½} %. The results are summarized in Table IV below.

toluene Tabel IV liability excellent
quite. Well
Il 30th
0
30th Example no. Glass aluminum 5 (a)
(>.)
(c) lu ^ ge ^ ei ^ hn
Well
Well et good
pretty much
It non-rusting concrete
The Steel s: ut
good ^r iut
bad

About 100 parts of the organopolysiloxanes according to Example 5 (a and (b) like vmrden each with 5 parts of methyltrxaoetoxysilane Iseht and poured into a mold and at room temperature and cured at a relative humidity of 30 to 70 $ 2 for 7 days. After that, the physical properties of the Specimens determined. The results are shown in Table V.

toluene 6th Tabel V Shore-Α- To ^ fe-
Hardness
kg / cm ^ 9.5:
3 ^, 5 30th
0 32
38 Example no. strain 5 (a)
(b) 6lh example * hs r.hvFi thimble properties Heat-setting
speed kg / cm 3.95
9.8

(a) In a reaction vessel, 100 parts of styrene, 185 parts

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Butyl acrylate, 122 parts of a polydimethylsiloxane with terminal hydroxyl groups (400 cSt), 2.85 parts of tert-butyl peroctoate and 102.5 parts of benzene were added. The reaction vessel was purged with nitrogen and the contents were heated for about 4 hours with stirring lan _'3 to about 8O ⁰ C.

(Id) The above procedure was repeated in the absence of benzene.

(c) The procedure of Example "6 (a) was repeated under Use of 125 parts of styrene, 15 ^ parts of butyl acrylate, 2.79 Parts of t-butyl peroctoate and 100.2 parts of Bensol, these Components to about 119 parts of a Polydirnethylsilcxans with terminal hydroxyl groups (4000 cSt) ■ were added,

(d) Example 6 (c) was repeated in the absence of benzene.

About 100 parts of the organopolysiloxane compositions thus obtained were each mixed with about 5 parts of liethyltrlacetoxysilane and applied to cleaned and degreased substrates, then cured at room temperature and a relative humidity of 30 to 70% . The results can be seen from the following table VI:

No, S ^x : ba ^xx Table VI Well liability not ro-concrete
εtender
stole excellent 40 : 60 ßclilecht aluminum Well bad E.g, 40 : 6o Well Well no Well 6 (a) 50 : 50 Benzene glass
% bad Schlec.ii-i Well bad (b) 50 : 50 20th p; ut no (c) Styrene 0 bad (d) Butyl acrylate 20th χ _ ⁴ 0

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-, 20 -

Example 7

In an analogous manner, 62.5 parts of styrene and 166.6 parts Butyl acrylate, about 10.5 parts of Λ-vinylpyridine, and 2.4 parts of dit-butyl peroxide placed in a reaction vessel containing 159 »8 parts of a polydimethylsiloxane with terminal hydroxyl groups . Contained in 100.4 parts of toluene. The reaction vessel was with Purged with nitrogen, then the contents were refluxed with stirring for 4 hours.

About 100 parts of the reaction mass thus obtained were with About 5 parts of methyltriacetoxysilane mixed and poured into a mold, then was "at room temperature and a relative Moisture cured from $ 30 to $ 70 for 14 days. Afterward ™ have the physical properties of the sample been determined?

Tensile strength kg / cm ² 12.0 '

Elongation % 535

Tensile strength ker / cm 5.10

Shore A hardness 35

Example 8

1093 g of styrene, 24-99 g of butyl acrylate, 2418 g of a polydimethylsiloxane with terminal hydroxyl groups, 35.9 g of di-t-butyl peroxide and 1511 g of toluene were placed in a 12 liter reaction vessel provided with a reflux condenser. Then) was flushed through the reaction vessel with nitrogen and heated in an oil bath at 132 ⁰ C. By externally supplied heat and the heat of reaction the temperature of the reactants rose to 128 ⁰ C, and the toluene began to reflux. Despite the evolution of heat, the reaction temperature could be kept at 128 ° C. for 3 hours, without external cooling, apart from the reflux condenser.

In carrying out a similar experiment in the absence of toluene, the reaction rate was so high that even with continued external cooling, a rapid rise in temperature to about 200 ⁰ C and a monomer loss from the system

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enter} the conversion was extremely slow, '·

Example 9

Into a 22 liter reflux condenser The reaction vessel was 1820 g of styrene, 4160 g of butyl acrylate, 3987 g of a polydimethylsiloxane with terminal hydroxyl groups, 59.8 g of di-t-butyl peroxide and 2 ^, 92 g of toluene were added. The reaction vessel was flushed through with nitrogen and, as in Example, heated for 8.5 hours with stirring. When the toluene is boiling under reflux, the reaction temperature remained constant between 125 and 129.5 ° C, without the need for further cooling.

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Claims (1)

Claims. , / l. / Process for the production of a hardenable, modifiableWn Organopolysiloxane composition, characterized in that that you can use an organopolysiloxane with functional End group ex-n with an olefin in the presence of a free radical converting initiator in an inert organic solvent " 2. The method according to claim 1, characterized in that that the composition is about 20 to 60 wt .- ^ organopolysiloxane, based on the weight of the starting materials, 3. The method according to claim 1, characterized in that that the reaction mixture is kept at reflux temperature. Λ. Method according to claim 1, characterized in that that one makes a product of the formula. f3-n Z _n SiO- -Q- iZ. in which R is a monovalent hydrocarbon radical and Q is a siloxane radical of the formula R « -SiO R " RlU represent, in which R ¹ a monovalent hydrocarbon radical, halogenated monovalent hydrocarbon radical: or cyanoalkyl radical, R "a divalent hydrocarbon radical, R" · a polymeric organic radical, which with R ^lf by a CC- 90 98 4 1/1514 Bond, Z is a functional group, η is a whole Number from 1 Ms 3, χ an integer from 0 to 20,000 and y a are an integer from 1 to 500. 5. The method according to claim 1, characterized in that ma-η is an organopolysiloxane of the formula as the starting material SiZ _n x + 1 used in which H is a monovalent hydrocarbon ^{radical, R 1 is} a monovalent hydrocarbon radical, halogenated monovalent hydrocarbon radical or cyanoalkyl radical, Z is a functional group, η is an integer from 1 to 3 and χ is an integer from 0 to 20,000 « 6. The method according to claim 5 »characterized in that that the functional group of hydrogen, a hydroxyl, amino, aminooxy or oxime group, halogen, aryloxy, acyloxy or alkoxy group. 7. The method according to claim 5 »characterized in that Z is a hydroxyl group. 8. The method according to claim 1, characterized in that the solvent is present in an amount of about $ 2 to $ 50. 9. The method according to claim 1, characterized in that the solvent used is aromatic hydrocarbons, chlorinated aromatic hydrocarbons, aliphatic hydrocarbons, cycloaliphatic hydrocarbons or Ester used. 10. The method according to claim I _9, characterized in 909841 / 15U that the olefin is an unsaturated aliphatic hydrocarbon, unsaturated halogenated hydrocarbon, a vinyl aromatic compound, unsaturated acid, unsaturated Esters, unsaturated amide, unsaturated nitrile or mixtures thereof are used «. - 11. A modified Örgänöpolysiloxari containing composition, characterized by an organopolysiloxane with end groups hydrolyzable by atmospheric moisture, which has at least one organic polymer side chain which is linked to the organopolysiloxane via a C-C bond and an inert organic solvent. 12. The composition according to claim 11, characterized in that the solvent in an amount of 2 to 50 wt. based on the total weight of organopolysiloxane and solvent, is present. 13 * Composition according to claim il ^ dättircngeken ^^ net that it contains particulate iiaterital $; , 1 ^. Composition according to Claim il _r characterized in that the modified orainopbiysilqxaii. fplgetidV formula in R a monovalent Kohleiwa | s # rsj6 © fffest; ₄ Ö a- 'siloxane residue: Formula. ■■ ^; - ^^ ;. ^; ? \ "- L - ^ - v.'vl /..^ ⁱ :?; '' - Vv.:^*Äv;** ^v 'r' .Λ ' * SiO E ¹ 10 1? in the. > R. ^f a monovalent. _; Hydrogen residue, halogenated monovalent. Hydrocarbon radical. Or cyanoalkyl radical,., B "a divalent, hydrocarbon radical,: and., R"'a._; polymeric organic components, which are linked to B "by a CC bond, ... mean, Z a functional group, n" an integer from 1 to 3, χ an integer from 0 up to 20,000 and y an integer from X to £ 00- divide *. ... 1.5., · Composition according to = claim, 1 Jf ,. characterized by ^, that, .Z, a-hydroxy 1- ^ acyloxy-, aminooxy- ,. Oxime or phosphato group represents. . . .. ....., ..-. , \ -. . 16. "Composition according to claim 1 ^, characterized in, that Z, represents hydroxyl groups. 1.7 * _: A composition according to claim _t. 16 / ,. .dadiirch marked-. net that it is curable at tree temperature and contains a crosslinking agent and a catalyst. 18. Composition .according to. Claims 1.7, dadurch.gekennzeich -, .. net that the crosslinking agent from a polyalkoxysilane or polyalkox _; ysi.loxan exists. , -. . ., ·.,. · .- 19 · Composition suitable as a sealant according to ..- .. ", -.-_ Claim 11, characterized / that the hydrolyzable groups are acyloxy, aminooxy, oxime or phosphate groups. 20. Composition according to claim 19, characterized marked. net that the organic polymer side chain of ^{vinylpyridine:} is formed, For Stauffer Cehmlcäl Company Lawyer" 9098417 1 5U. INSPECTED 1e he's eite INSPECTED ' ¹