DE1902086C - Stabilization of the shelf life of thermosetting molding compounds based on organosilicon compounds - Google Patents

Description

I 902086

Many of the commercially available molding compounds ίΐιιΓ (>rgano-I> 111 ysi I n χ i »n μ tu η VI I u yc k Γι ι mc 11 easily brought into the desired shape odor mil'cine gewihschle Obcrlladie applied iiiul then ίΐιιΓ simply unler For example, organopolysiloxanes are supplied as mouldable paints for fusions, and thin-liquid materials can be produced, straight-line products. These products are made into the desired shape by pre-pressing oiler threads Ι-Ίιπη gebraehl and then transferred by curing in the elastoiiieren state, a process that in /.iisainmenluiiig with Flastomereii liäuiig · as "vulcanization" bezeichnel is. the molding beliiill its given shape in oiler i ^r, attempts at Dcrormieniiig in its by Vulcanization or hardening retracts a given form oducts, fusible solids or solutions are ■ · '> available, deformed or applied and then hardened.

The hardening processes that can be used for organosilicon hydrogenation can be classified into two groups. The first group is those in which hardening occurs spontaneously at room temperature. The second group, on the other hand, consists of crosslinking agents such as organic peroxides or sulfur compounds and heat to initiate the hardening reaction Since the systems that cure at room temperature generally only have a very short pot life, which is the time available to the consumer for processing, further systems have been developed in the meantime that only work at slightly higher temperatures This group includes, for example, the systems described in German patent I 066 7.17 made of alkenyl lipids and polysiloxanes containing Si 1 I-Hindiingcn, which are crosslinked in the presence of Plntinkalysaloren diiich Fri. | <> warm to 50 to S1) C. Although such systems only harden at weakly low temperatures, hardening naturally begins at room temperature, which is reflected in an increase in viscosity. In other words, it is also dysfunctional in terms of use when the consumer is struggling with a product that is becoming more and more persistent during processing. The system used in accordance with the invention is that in Canadian patent specification 6 ⁵ St) ..! 11 is almost comparable, but differs from this because) at room temperature an increase in the molecular weight is prevented - The constituents of the air are not inhibited, they are activated by heat, and the healings l'nnlukie, especially .stable.

The use of '. ■ n Π I Iu. MM) ¹ ! · '»DrHauosiliconvcrhindum / .cu ί Ι) Λ · ί ι !!: · -'» ■ nieinen l'nrniel

| (ΊΙ, ( ¹ II) ₁ Si

W ») '!' U, which is based on the total profit of (lMimi (2), OigaiiosiliciiiiiiveibiiHluugenl ^ l., You almost always have one to three monovalent hydrogen sulfide residues, monovalent halogenated hydrocarbons without aliph'alisehe Meigeioächbiiulimu eulhallen, where there are two single hydrocarbon radicals with aliphalic multiple bonds per molecule, and the remaining valences of the Si atoms with oxygen atoms, divalent hydrocarbon, colileuwa-ismloflälher or llalogeiiarylene radicals are each unsaturated with one more valence Si-Aloiu are bound, as organosilicon compoundseii (A) with monovalent, aliphatically unsaturated residues for slabilizing the positional wedge in heat-activatable oil ^; (II) Organosilicon compounds with Si-iu · biuuleneii Wa Sserslolfaloinen, which in addition by sehnilllicii contain up to two single carbohydrates the Si atoms with oxygen atoms, two wavy hydrocarbons, hydrocarbons · stollalherreslen. in each case without aliphatic multiple groups or halogenarylene radicals, which are bonded with their second valence to a further Si-aloin, but in such a way that the sum of the linear number of monovalent, aliphatic unsaturated radicals per molecule of (A) and the average number of Si-formed hydrogen atoms per molecule of (1!) is at least \ and of component (I) 0.5 to ¹ W, ¹ ) parts by weight, of component (2) I) to 99.45 parts by weight and of component (H ) 0.5 to ')'), ') 5 parts by weight are present, and (') platinum analyzers in an amount of at least 0.1 ppm platinum, based on the total weight of (A) and (11), optionally fillers and other common additives claimed.

The heat-activatable I'oninnassen are of extraordinary inspiration, since geniuses from organosilicon units with aliphatically unsaturated, monovalent Kohlcuwasscrslolfresten, Organo'.iliciuinveibindimgen with Si-bundles Wa-.sei ■ stol'fatonien and laline catalysts, the more common Reaeieien wisely by increasing the molecular weights at room temperature, through which Presence of the iris - (iriorganosilyl) - amiuveibindlhdei deliiiierlen kind this Ue.iklion at space temperature either completely prevented or Ix: - irädillii.'h veilamisanil is.

li-i, |) iele fi'ii I ri ·; (irioi jiano-.ilvl) amin; · ni.l Ί'.Ικ · the I πι nu-ln

IH'II,

I (Cl I, (ΊΙ) Ι (Ή,), ^ν ; ί |, ι ^χ ί
I'll), It'll,) ·, ί |.,; Ί
ί II) ₁ (Cl I ₁ ) Si |, Μ ·; κ (H ₁ I ₁

where R denotes methyl and, or vinyhee> U: and \ I or 1 is. i'eui'hciienlalls im Cienusch with bi. to

or 1 (CII, CHl (CH ₁ ),:, ι |, HSi (ClI ₁ ) ICH (IL),

The most successfully used Tris-ttiiorganosilyD-nmiue .are of particular interest in this respect, because they fulfill two functions: On the one hand, they prevent the plalinkalysierlc reaction between aliphatically unsaturated Orgiinosijiciiimverbindungen and Sigebundcnen Hydrogen automeii at Kaumlempcriilur and on the other hand they react with the Si-bound ones Wnsserslolfalomen and thus become part of the lindpnuhiklcs.

The tris (lriorgaiiosilyl) amines retard the reaction rate of the plalin-catalyzing reaction even in amounts as small as 0.1%, based on the weight of (A) and (H). If, however, the concentration is between 0.1 to 10 "/ I ₁ , based on the weight of (A) and (Ii), the reaction is not stopped at room temperature, but only considerably slowly, so that the molding compositions are in front of theirs Optimal molecular weight, which is practically infinite, can be processed well in all practical applications of the process, if the tris- (triorganosilyl) -amines are present in amounts greater than 10%, based on the weight of (A) and (I)) are, the platinum-catalyzed reaction between aliphatically unsaturated organosilicate compounds and Si-building hydrogen atoms is completely prevented in all practical applications.

The oligo-silicon compounds (2) can be monomers or resinous, liquid or practically no longer flowable high polymers, which are usually for the production of organopolysiloxane elastomers Use linden. They can be any monovalent hydrocarbon radicals, halogenated hydrocarbon radicals or contain bound cyanoalkyl radicals.

According to delineation, in component (2) an average of at least two aliphatically unsaturated radicals should be present per molecule. These leftovers play a decisive role in the hardening reaction Role, which will be discussed below. There may also be more of these residues, but the minimum of at least two (average per molecule) is for curing under formation a polymeric product is absolutely necessary. If the average number of aliphatic unsaturated radicals per molecule is greater than two. becomes a correspondingly more networked product receive.

The remaining valences of the Si atoms in the organosilicon bond (2) can be finitioiisgcby by oxygen atoms, divalent hydrocarbon, Hydrocarbon, ether or ilalogenarylene radicals are saturated, with any one or more these residues may be present.

Examples of divalent hydrocarbon radicals are:

CIL

ClI ₁
CILClI

CII ₁
CILC
CILCII CHClL

CII ClI ■ -

Vi Leu / ⁷

CJI ₁ or

CILCJI ..
for hydrocarbon resins:

Cl LCI LOCI LCl L or

CJI _t OCJI,
and for llalogenarylene resol;

CJl ₁ CI-

C ,, 1'4 or

( ¹ Jl ₁ I) IClLCJI ₁ Hr

If, however, more than. "! Si-AtOiDO are present on average per molecule, it is advantageous if at least 50% of the divalent radicals are oxygen atoms, especially if the finished Product is designed to withstand extremely high as well as extremely low temperatures. However, it is not absolutely necessary, especially if component (2) is an eyclic product.

The production of organosilicon compounds which are used as component (2) can take place according to known methods. The monovalent radicals can, for example, after the so-called "Direct procedure" can be introduced or by means of. Reactions according to Grig η a r d or in some cases also through a pseudo Friedel-Crafls reaction. Of course, the organic residues can also be introduced in any other way. Sig-bonded oxygen atoms are formed by hydrolysis introduced a hydrolyzable group on the Si atom (such as halogen atoms, alkoxy or acyloxy groups). The divalent organic radicals can, for example, be synthesized according to Wnrtz, Grignard or also by the direct method to be introduced. These modes of manufacture are known, so that their description in detail unnecessary here.

The presence of the Oiganosilieiumveibindungen (2) in the molding compounds activated by heat is delinilionsgeinäü not absolutely necessary. If the reaction is to be completely hindered at room temperature, it is advantageous if (2) is present in amounts of 0 to ()%, based on the weight of (1) and (2). Conversely, if the Reaklionsgeschwiiidiüki'il is to be slowed to the desired extent, it is advantageous if (. ') In amounts of ¹ M) until') ')')% is present.

The organo.-iilieiiiinverbinhiugen (H) can delinitiongemälA two-oiler more Si-covered water-loafalome contain a few radicals per Si atom per molecule and an additional average of up to two. This includes, for example, alkyl radicals such as methyl, ethyl, isopropyl, lert. Amyl, octadecyloil Myrieyl residues; ('ycloalk \ lrcste. such as Cyelolientyl- or cyclohexyl radicals; Aralkylte.ste, like Hen-

/ yl-, / (- Phenyliilhyl- or Xylylrcslc; Arylresle, such as Phenyl-, 'I'olyl-, Xenyl-, Niiphlhyl- or Anthrncylitjsk ^1. Furthermore monovalent, halid te hydrocarbon residues such as Chlormulhyl-, .WVTnlluorpropyl-, ", (Mi-Trilluoilolyl-, Hiomphenyl- or 2,3-DihiOin · s eyclopenlylicslo, as well as Cyanoalkylrcsle, like Cyanoiilhylodei Cyanobiitylreste, In addition, the organic KeMe can be the same or different. Component (II) can be honey polymers, copolymers. Monomers or mixtures | _O and two or more of these products exist, as long as they are free of aliphatically unsaturated bonds and contain an average of at least 2 sig-bonded H atoms per molecule.

The remaining valences of the Si alomes in (Ii) can Delinilion according to oxygen atoms, divalent hydrocarbon, hydrocarbon radicals, the are in each case free from aliphatic multiple bonds or be ilalogenarylene radicals, with any one or more of these residues may be present. If per molecule an average of more than 3Si-AtOiIiC are present, it is for component (H) just as advantageous for component (2) if at least 50% of the divalent radicals are oxygen atoms are. However, this is not absolutely necessary, especially if component (B) is an eyclisehes Product is.

The manufacture of products that fall under the definition given for component (H) is known, and many of these products are commercially available so there is no need to describe them here.

The selection of components (A) and (13) depends to a small extent on one another. If the average number of aliphatically unsaturated groups per molecule in component (A) is, for example, 2.0, a product should be selected as component (B) whose average number of Si-bonded H-alomes per molecule is at least 2.0, so that the total of these quantities just defined is at least A. The analogous case is given when the selected component (H) contains an average of 2 Si-bonded II atoms per molecule. However, if one of the two components has more than 2.0 of the named groups, the selection of the other aiii on this basis does not apply. It goes without saying that the larger this sum is, the stronger the networking of the end product will be, as already mentioned.

The molar V''liäl:, üs the aliphatically unsaturated Cj groups in (A) to the Si-bonded H-alomes in (H) can be of particular importance in some cases. Then the relationship between these two (kuppen preferably between O. (i7 and 1.5. Fs gibi however, there are many cases in which the balance between these two groups does not play a decisive role. For example, if component (A) is divided six aliphatically unsaturated gilippen each Molecule has, kaiM dei liinsal / of same small amounts of Si-able I! -atoms increase eiiii'i to staiken networking of the desired F.nd- f «> lead product. In this all it is necessary. littleei odei much weiiigi'i than ä (| uimolaie sets of To use Si-gebiiiidenen H-Almnen. wrapped around ilen llärtungsgiad / ti reach. But when a maximum of stability is managed, isl it before- e.f. leilhafl. the molaicn sets of Si-bound II atoms in (H) the aliphatically unsaturated lipids in Ά).

The PliUinkomponoiile (C) can be in one of the following known forms are used, which are made of metallic platinum per se or platinum on carrier substances, such as silica gel or powdered charcoal, up to pliitinchloid, plalmalt or hexachloroplalin pass. All of these forms are useful in the chasing system in question; llexachloroplatinic acid however, is in the form of the commonly used iloxahydral or in anhydrous form preferred because they are easily dispersed in organosilicon precursors and do not discolour Mixture causes.

Dofmitionsgomiiß should be at least 0.1 weight lcile Platinum used on 1 million parts by weight of (A) and (H). However, since impurities in The system can easily poison such small amounts of catalyst, preferably I to 20 ppm platinum used. Larger amounts of platinum do not affect the reaction, but do the same larger amounts of component (I) are required and are also uneconomical.

If the component (I) is present in sufficient amounts, it prevents the platinum catalyzed Reaction between the Si-H groups in (H) and the aliphatically unsaturated radicals in (A) Room temperature (and up to about 60 C) completely.

Regardless of the overall composition the molding compound can contain the minimum amount of tris (iriorganosilyl) amine (1) required for effective neutralization the Kalalylischcn effective wedge of platinum Ordinary temperature, causing the reaction between Si-I! groups and aliphatically unsaturated Residues is triggered, is necessary, easily determined by the person skilled in the art within the given framework graze. It brings neither advantages nor disadvantages, more than the required minimum amount Tiis- (tnoiganosilyl) -amine use, although it is out For reasons of safety for complete prevention can be beneficial, about a 50% Use excess over the determined minimum amount.

The use of tris- (irioiganosilyl) -amine to the full However, preventing the molding compound from hardening at room temperature is only one use same. The Ί ris- (triorganosilyl) -amine can also be used in smaller amounts than for the whole It is necessary to prevent the reaction at room temperature In this case, the reaction rate of the system at Raumtenipeialiii according to the added amount of Tiis- (iiiorganosilyl) -amine slowed down. This is for example in such cases extraordinarily Weilvoll, in which a molding compound in 4 hours at Raumlempeiatui would harden, the same combination but the addition of the same amount of tris- (Irioiganosihl | -amin a lapse time of 24 hours ciIomIciI. Daihiich suits the needs! one lenghts · Veiaibcilungszeit fiii HeschichUings-, Tauchoilei Driving available. The consecration de; Attitude can at any time clinch Fihit / cn dei ι oimmassen uu / ugswcisi · on iibci 70 C graze lifted, which then accelerates the keeping wild.

The Ί IIS (tiiorganosil \ l) -amine (1) therefore l.ann as Migcnaniiie "Sehliissclsuhslanz" dei invention, both / in Wi / öj'cruni ¹ and zui Vcrhiiulciung. wdiiiniii a ·· / eiilkh iiiihejuenzlc delay to u'iMehcn is. \ on I oi leave with Raiimlcmpcialui

used by a pkitinkatiilysicrlc Reaction between Si-bonded water aliphatic atoms and Si-bonded unsaturated aliphatic groups are hardenable.

The amount of tris (triorganosilyl) amine required to delay the reaction is also as in the case of preventing the reaction from the amount and kind of the platinum catalyst and the others Components of the molding compound to be hardened dependent. In addition, if you use more Tris- (triorganosilyl) -amine a stronger delay, but if less is added, a smaller delay achieved. The amount of tris (triorganosilyl) amine (1) required in a given system to achieve a A certain delay is necessary can easily be determined by a person skilled in the art. By definition components (1), (2) and (B) are 0 to 99.45 parts by weight (2), 0.05 to 50 parts by weight (1) and 0.5 to 99.95 parts by weight of (B) and preferably

Use 0 to 98 parts by weight (2), 0.05 to 40 parts by weight (1) and 0.75 to 95 parts by weight (B). If the Reaction between the silicon bonded hydrogen atoms and the aliphatically unsaturated groups should be completely prevented, 0 to 95 parts by weight (2), K) to 40 parts by weight (1) and

1 to 95 parts by weight (B) are used.

The individual components in molding compositions which can be activated by heat can be used in any order are mixed together. Although the addition of platinum without tris (lriorganosilyl) amine (1) the reaction between components (2) and (B) is triggered, this reaction can last from a few minutes, which is usually required for the incorporation of the tris (triorganosilyl) amine (I) is to be neglected. For systems that have already been damaged by this minor reaction the tris (triorganosilyl) amine (I) can be incorporated before the platinum. Compliance with a However, the specific order of addition is not essential for the functioning of this hardening system crucial.

The molding compounds can be mixed shortly before use (intended curing) or stored in mixed form for later use. The mixtures can also be stored separately, but if the components (2). (B) and (C) are present, component (I) must also be present. However, the storage of mixtures of (B) and (C) alone is not very advantageous, since undesirable intermediate reactions can occur if moisture is added.

As already explained in detail, the molding compounds with sufficient amounts of tris- (triorganosilyO-amine (1) are stable, ie no hardening is initiated at room temperature sufficient amount of tris ((riorganosilyl) amine (I) • no change in viscosity even at 49 "C after 4 days. At 70" C, however, the same mixture is bonded to an elastomer within 24 hours and at ISO C within . it follows from IO Minulcii that this molding compound completely stable <\ s at temperatures of about 50 to WC, which because above normal l.agertemperaturen.

In addition to the components mentioned, other constituents can also be used in such auxiliary systems be included, which are usually used in the field of organopolysiloxanes, for example Fillers (carbon black, carbonic acid aerogels, pyrogenic recovered silicas, surface-treated silicas, alumina, clays, Metal oxides, carbonates, silicates) or pigments, additives for elastomers, such as agents for preventing the permanent set or plasticizers based on organosilicon compounds or purely organic compounds. Materials known to be known to be platinum catalyst poisoning. are of course to be excluded.

The molding compounds, which can be activated by heat, are suitable for all types of application on the elastomer or Suitable for resin areas where heat-activated curing is possible. The molding compounds can be in closed or open systems, in thin or thick layers under pressure or under atmospheric pressure can be activated with equal ease by heating to above about 70 "C, thereby there is no unwanted sponge formation, which is often the case with other molding compounds when they are not used associated with pressure, there are still unhardened surfaces, especially those with organic peroxides can be observed when the molding compounds are cured in the open with access to air. Further advantages of these molding compounds are excellent curing, even in deep layers, and that Absence of disruptive effects of air, so that the finished moldings are uniformly cured. In addition, if desired, the curing rate can be increased at room temperature in the molding compositions controlled (slowed down).

Preparation of a compound to be used according to the invention

A mixture of 185.4 g of [(CH ₂ = CHKCHj) ₂ Si] ₂ NH and 40.96 g of sodium amide in 2 (X) ml of toluene was placed in a 500 ml flask equipped with a stirrer, reflux condenser and gas inlet tube. heated for 24 hours at 70 'C under reflux and under ¹ Durchleitcn of nitrogen. The unreacted sodium amide was removed from the toluene solution by vacuum filtration with exclusion of air, and the unreacted di- (vinyldimethylsilyl) amine was distilled off. The residue was dissolved in hexane and 114.0 g of trimethylchlorosilane were added to the solution. The solution was then heated to 50 ° C. under nitrogen for 5 hours. Distillation gave 107.3 g (yield 41%) of the product of the formula

[(CH ₂ = CH) (CHj) ₂ Si] ₂ NSi (CH ₃ ).,

receive. Melting point: 66 "C; the value of the energy analysis agreed with the given formula:

Found:

C 51.4, Si 32.9, H 10.8, N 5.4%;
theoretically:

C 51.3, Si 32.7, H 10.6. N 5.4%.

Example I.
From the previously made

T (CII, CH) (CIUSiI, NSi (CH.,).,
and a polymer of the formula

IUni, l, SiO 1 (Cl U-SiOl _x Si (CI I,). H

109674/260

where χ has an average value of 15.2, various mixtures were prepared, each catalyzed with 0.014 g of chloroplatinic acid (12 parts by weight per million platinum). For each of the following H (CHj) ₂ SiOrJCHj) ₂ SiO] _x Si - (CHj) ₂ H
used while the amount of

[(CH ₂ = CH) (CHj), - Si] ₂ Si (CHj) J

Jemiscne were j, uiwg 5 varied. CH, - CHSiUSi Mixtures [(CH, = CH) (CI l,), Si], NSi (CH,)., 1.067 A. 0.654 g 1.025 B. 0.623 g 0.916 C. 0.561 g 0.971 D. 0.595 g 0.882 E. 0.5420 g 0.903 F. 0.5544 g 0.916 G 0.5606 g 0.924 H 0.5669 g 0.945 I. 0.5793 g

Containers with Mixtures A, B, C and D were placed in an oven heated to 90 ° C overnight. The viscosity of the mixtures increased, indicating that polymerization had taken place.

Containers with mixtures E, F, G, H and I were left to stand overnight at room temperature. The mixtures remained unchanged. These mixtures were then placed in an oven heated to 50 ° C. for 24 hours. The mixtures remained unchanged. The mixtures were then placed in an oven heated to 90 ° C. for 8 hours. The viscosity of the mixtures increased, indicating that polymerization had taken place. The viscosity of the products was measured using a "Hoake Rotovisiometer". The viscosity measured in cP had the following values:

40

product viscosity
(cP) H (CH,) ₂ SiO [(CH3 \ ₂ SiO] _{J (} Si (CH,) ₂ H 9 A. 76 B. 191 C. 4099 D. 856 ; e 185 SF 1287 O 2930 H 9979 I. 568

The products are copolymers made from the following general formula units;

Himself,),

(CH,) ₂

B e i s ρ i c I 2

The following mixture can be echoed for longer than 1 month at room temperature, but cured to one coherent solid when heated to 70 "C.

Parts by weight of one with phenylmethylhydrogensiloxy groups end-blocking dimethylpolysiloxane with a viscosity of 100,000 cSt / 25 "C,

Parts by weight of a liquid copolymer of average formcl

Si

CH ₃ \
OSi-CH ₃

CH = CH,

10

45 0.002 parts by weight of platinum in the form of a solution

of platinum sulfate in ethanol and
Parts by weight

[(CH ₂ = CHMCH ₃ J ₂ Si] ₂ NSi (CH.,),

55

60

SiO [(CH. »> ISiO], Si

B c i s ρ i e I 3

Two siloxane mixtures were made from the following components:

Mixture A

Parts by weight of a dimethylvinylsiloxy end-blocked methylpolysiloxane with a viscosity of 25OOcSt / 25 ° C, Parts by weight of calcined Diathomecnerde, Parts by weight of a finely divided zirconium silicate, Part by weight of butyl curbitol acetate with a platinum content of 0.19% in the form of chloroplatinum acid.

Mixture B

KX) parts by weight of the same dimethylpolysiloxane as in mixture A,

Parts by weight of calcined diethome clay, Weight of a finely divided zirconium silicate, (weight of a mixture of iron oxide

in a hydroxyl-containing dimethylpolysiloxane with low viscosity, the mixture having 10 percent by weight iron,

59.5 parts by weight of one having trimethylsiloxy groups end-blocked methyl hydrogen polysiloxane with an average of 10 1 atoms each Molecule.

When 100 parts by weight of the mixture A and 4 parts by weight of the mixture B were mixed, it cured the sample at room temperature in 24 hours and at 150 C in 15 minutes to an elastomer.

If 100 parts by weight of the mixture A, 4 parts by weight of mixture B and 2.0 parts by weight

[(CH ₂ = CH) (CH,), Si] ₂ NSi (CH _{3) 3}

mixed, the mixture remained unchanged for more than 2 weeks, but hardened on heating to 150 ^° C. in 15 minutes to form an elastomer.

Example 4

A mixture was made from the following ingredients:

Mixture C

KX) parts by weight of a dimethylpolysiloxane end-blocked with vinyldimelhylsiloxy groups and having a viscosity of 25OO cSt / 25 "C,
80 parts by weight of quartz powder with an average particle size of 5 microns, 1 part by weight of butyl carbitol acetate with a Pl ".tine content of 19% in the form of chloroplitic acid.

If 100 parts by weight of mixture C and 4 parts by weight of mixture B according to Example 3 mixed, the mixture hardened into an elastomer after mixing. The full Cure at room temperature required less than

2 hours. If 97 parts by weight of mixture C,

3 parts by weight of a paste made of 50 percent by weight dimethylpolysiloxane with a viscosity of 100 cSt / 25 "C and 50 percent by weight zinc oxide, 4 parts by weight of mixture B and 0.15 part by weight

[(CH ₂ = CHKCHj) ₂ Si] ₂ NSi (CH ₃₎ J

mixed, the mixture cured to an elastomer after 24 hours at room temperature.

Example p

Practically the same results were obtained when, instead of the butyl carbitol acetate of chloroplatinic acid from Example 3, equivalent amounts of powdered platinum metal on γ-aluminum oxide or (CHjCH ₂ CH ₂ CH ₂ P] ₂ PtCli were used.

Example 6

If one of the following polysiloxanes a) to e) was used instead of the dimethylpolysiloxane in mixture A used and with 100 parts by weight of mixture A, 4 parts by weight of mixture B and 20 pieces

Mixtures more stable at room temperature than the mixtures without

[(CH ₂ = CH) (CH ₃ ^ Si] ₂ NSi (CH ₃ ).,

a) A methyl-3,3,3-trifluoropropylpolysiloxane end-blocked with methylphenylallylsiloxy groups with a viscosity of 50000 cSt / 25 "C;

b) a copolymer end-blocked with dimethylcyclopcntenylsiloxy groups with about 50 mol percent Ethylmethylsiloxane units, 5 mole percent octadecylmethylsüoxane units, 20 mole percent 2-phenylethylmethylsiloxane units and 25 mol percent of units of the formula

CH ₃

-Si

CH ₃

CH ₃

Si-O-

CH ₃

with a viscosity of 250,000 cSty25 ° C;

c) a mixture of (1) 10 parts by weight of a 2-butynyldimethylsiloxy end-blocked, liquid / f-cyanoethyl methylsiloxane with a viscosity of 700 cSt / 25 "C and (2) 90 parts by weight of a copolymer composed of W mol percent chlorophenoxane units and methylene chloride in the terminal units 2 mole percent vinyllinhylsiloxane units with a viscosity of 55OcSt / 25 "C;

d) one end-blocked with vinyldimethylsiloxy groups Copolymer of 70 mol percent dimethylsiloxane units, 10 mol percent dimethylsiloxane units, 10 mole percent diphenylsiloxane units, 5 mole percent benzylmethyltilosane units and 15 mole percent units of the formet,

as described in Example 3, mixed, were the

ss with a »Will [ams-PI» stiiiWHi of 2.5 mm (0.1 in) ..

Example 7

Were equal amounts of the following oninoleic compounds a) to f) used instead of the methyl hydrogen polysiloxane in mixture B. and 4 parts by weight of the obtained GemiMdeit with Parts by weight of “Mixtures” Λ and fcO Ot * parts by weight

[(CH ₁ - CHXCHj) ₁ Si] ₁ NSi (CHj) ₁

mixed, productively the same results were obtained

receive:

with a viscosity of 25000000cSt / 25 ° C; c) a copolymer of 89.86 mole percent dimethylsilosane units, 0.14 mole percent methylvinylsiloxane units and 10 mole percent units of the formula

CH,

HSi-O

I.

CH ₃

d) HSi-

OSi

^v CH ₃ "OSiH

\ C ₈ H ₁₇ J

π CH,

CH ₃

e) a copolymer of 40 mol% C ₆ H ₅ SiO _{3 / r} inclusion: n, 40 mol% cyclohexylmethylsiloxane cinlicite, 18 mol% 2-phenylpropytmethylsiloxane quinitcn and 2 mol% Mctliylhydrogensilo1 / 2: 50 ° C;

a mixture of 10 parts by weight

CH ₃ HSi CH ₃

85 parts by weight

HSi

CH ₃ OSi CH ₂ CH ₁ CF ₃

CH ₃

OSiH

CH ₃

OSiH

CH ₃

and S parts by weight

40

⁵ CI Cl

Example 8

By mixing 50 g of a mixture of 35 percent by weight of a resinous vinylsiloxane made of CH, = CH) (CH,) ₂ Si0 _{0 5} units. (CHj)., SiO ₍₁₅ units and SiO ₂ units, 65 percent by weight of one with methylphynylvinylsiloxy groups End-blocked dimethylpolysiloxane with 0.5 mol percent of methylphenylvinylisiloxy units and 8 ppm of platinum, based on the total weight of the mixture in the form of chloroplatinic acid at 0.169 g

[(CH ₂ = CH) (CHj) ₂ Si] ₂ Si (CHj) J

a mixture was prepared which was heated gently to

[(CU ₂ = CH) (CHj) ₂ Si] ₂ NSi (CHj) J
to be solved and easy to work in. This mixture was cooled to room temperature, then were

5 g of a mixture of 60 parts by weight of a copolymer of 20 mole percent trimethylsiloxycin units, 49 mole percent dimethylsiloxycin units and 31 mole percent methylhydrogen siloxane units, 40 parts by weight of the above-mentioned resinous

like vinylsiloxane and 2 parts by weight of cyclic Mcthylvinylsiloxan added and mixed. That so obtained mixture was allowed to stand at room temperature. After 16 hours the mixture was always still liquid. After 40 hours the viscosity decreased

to. After 64 hours the mixture was viscous and after 88 hours the mixture was no longer flowable. Another molding compound was produced from the same components, with the exception that instead of 0.169 g

65 [(CU ₂ CH) (CHj) -StL ₁ NSi (CH,)., Only 0.065 μ / ugefilgi were.

After the mixture is 16 sliewden at room temperature had been left standing, it was very zlih-Il (issig, and after 40 hours it had hardened to a solid.

The same molding compound was produced for comparison with the exception that)

Example 9

Was performed [(CH ₂ = CH) (CH.0 ₂ Si] ₂ NSi (CH ₃ ) _{3 from} Example 8

[(CH ₂ = (CH ₂ = CH) ₂ (CH _- Osin [Si (CHO ₂ (CH = CH ₂₎ L

[(CH ₂ -CH) (CiLO ₂ SiLNSi (CIlO ₃

was omitted, this mixture was replaced after 16 hours or [(CH ₂ = CH) ₂ (CH ₃ ) Si] NSi (CH ₃ )., were already solidified at room temperature. which get practically the same results.

Example IO
If the following mixtures were prepared, the reaction was delayed at room temperature, but at 9 (FC

easy.

= CH) (CH ₃ ) ₂ Si] ₂ NSi (CH ₃ ) ₃ and

(Λ) 0.05 g [(CH ₂ = CH) (CH ₃ ) ₂ SiLNSi (CH ₃ ) ₃ and 99.95 g

(B) 10 g
90 g

(C) 5 g
95 g

1 g

= CHXCH ₃ I ₂ Si] ₂ NSi (CH ₃ )! ,, = CH (CH ₃ ) ₂ SiO [(CH ₃ ) ₂ SiOLo Si (CH ₃ ) i ₂ CH = (CHO ₃ SiO [H (CH ₃ ) SiO ] ₂₇ Si (CH ₃ ) ₃ ; = CH ₂ and

(D) 0.05 g [(CH ₂ = CH) (CH ₃ ) ₂ Si] ₂ NSi (CH ₃ ) ₃ ,

0.5 g (CH ₃ ) ₃ SiO [H (CH ₃ ) SiO] ₂₅ Si (CH ₃ ) ₃ and 99.45 g CH ₂ = CH (CH ₃ ) ₂ SiO [(CH ₃ ) 2SiO] _I62 Si ( CH3) ₂ CH == CH ₂

(E) 50 g [(CH ₂ = CHXCH ₃ ) ZSi] ₂ NSi (CH ₃ ) I ,,

0.75 g H (CH.0 ₂ SiO [(CH ₃ ) ₂ SiO] _{() 0} Si (CH ₃ ) _z H and 60 g (CH ₃ ) ₃ SiO [(CH ₃ ) ₂ SiOL "[(CH ₂ = CHXCH ₃ ) SiO] ₅ Si (CH ₃ ) ₃ ;

(F) 65 g [(CH ₂ = CHXCH ₃ J ₂ Si] ₂ NSi (CH ₃ )! ,,

95 g of H (CH ₃ ^ SiO [H (CH ₃ ) SiO] ₇ Si (CH-O ₂ H and

35 g (CH ₂ = CHCH.XCH ^ SiOaCH ^ SiOlooSiiCH ^ - (CH ₂ CH = CH ₂ );

(G) 15 g [(CH ₂ = CH) (CHj) ₂ SiLNSi (CH ₃ ) ,,

37 g CH ₂ = CHiCH-OiSiOKCH-OiSiOL.SHCH ^ CH = CH ₂ and

0.7Sg (CH _{3 I 2} SiH ₂ .

Example 11 Was a mixture of 10g

= CH) (CHO ₂ SiLNSi (CHj) ₃

Patent claims:

1. Use of 0.1 to 100% organosilicon compounds (1) of the general formula

50 g of a dimethylpolysiloxane end-blocked with methylphynylvinylsiloxy groups and having a viscosity of 100 cSt / 25 ^1J C and 25 g [H (CH ₃ ) SiO] ₅ stored at room temperature, the molding compound did not harden, but after heating to 125 ° C it was closed after 15 minutes cured an elastomeric solid. When the process was carried out using a 3,3,3-trifluoropropylmethylpolysiloxane endblocked with dimethylvinylsiloxy groups and having a viscosity of 200 cSt / 25 "C in place of the methylphenylvinylsiloxy group-blocked dimethylpolysiloxane, practically the same results were obtained when the mixture was used for 1 hour over 80 ° C C was heated.

(CH ₂ = CH) _x Si

(CH ₃ ) _{3- X}

NSiR ₃

where R denotes methyl and / or vinyl radicals and χ is 1 or 2, optionally in a mixture of up to 99.9%, based in each case on the total weight of (1) and (2), of organosilicon compounds (2) which have an average of one to contain three monovalent hydrocarbon radicals, monovalent halogenated hydrocarbon radicals without aliphatic multiple bonds or cyanoalkyl radicals per Si atom, with an average of min-

109 624/260

at least two monovalent hydrocarbon radicals with aliphatic multiple bonds are present and the remaining valences of the Si atoms with Oxygen atoms, divalent hydrocarbons, hydrocarbons, or alogonarylene radicals are saturated, each of which is bound to a further Si atom with its wide valence are, as Organosilieiumverbindungen (A) with monovalent, aliphatically unsaturated radicals for Stabilizing the shelf life in heat-activatable, curable molding compounds from (A) Organosilicon compounds with monovalent, aliphatically unsaturated radicals, (B) organosilicon compounds with Si-bonded hydrogen atoms, which additionally average up to two monovalent hydrocarbon radicals without aliphatic multiple bonds, monovalent halocarbon radicals contain no aliphatic multiple bonds or cyanoalkyl radicals per Si atom, with an average of at least two Si-bonded hydrogen atoms are present and the remaining valences of the Si atoms with oxygen atoms, divalent hydrocarbon, hydrocarbon ether residues, respectively without aliphalic multiple bonds or haloarylene radicals that are saturated with their second valence are each bonded to a further Si atom, but in such a way that the sum of the average number of monovalent, ali-

phatically unsaturated chains per molecule of (A) and the average number of Si-bonded Hydrogen atoms per molecule of (H) is at least 4 and of component (I) 0.5 to 99.95 parts by weight, of component (2) 0 to 99.45 parts by weight and of component (H) 0.5 to 90.95 parts by weight are present, and (C) platinum catalysts in an amount of at least 0.1 ppm platinum, based on the total weight, of (A) and (H), optionally fillers and other usual / usages,

2. Use of component (I) in an amount of at least 10%, based on the Weight of (A) and (H), for the in claim 1 stated purpose.

.1 Use of component (I) in an amount of 100%, based aiii the weight of (I) and (2), door has the purpose stated in claim I.

4. Use of the compound of the formula

CII3
CII ₂ -CHSi

CH,

NSi (CH ₃

as component (1) the door specified in claim 3 Purpose.