The catalyst accelerated vulcanization

 

(57) Abstract:

Use: in the manufacture of catalysts for the synthesis of organosilicon compounds and synthetic rubber. The inventive catalyst accelerated vulcanization is a reaction product sulfoxide of platinum complexes with unilateraily the siloxanes. As the use of platinum complexes of the compounds of General f - crystals: {Pt(L2X2} and {Pt(L1L2Cl2} , L L1, L2(CH3)2SO ; (C2H5)2SO ; (C3H7)2SO ; (i-C3H7)2SO ; (C6H5CH2)2SO ; (p-C4H9)2SO ; (p-CH3C6H4)(CH3)SO ; X Is Cl, Br. The concentration of platinum complexes in minilateral the siloxane is 510-8-110-5Mr. al/ml. table 1.

The invention relates to chemical technology, namely catalytic processes cured polysiloxane compositions by polyaddition reaction. This invention can be used in manufacturing silicon - organic compounds and synthetic rubber, and the products produced by the curing reaction, can find application in newly developing areas is Noah technique.

Known use as a catalyst vulcanization [U.S. Pat. USA. N 3775452] product processing mixture haloesters complex of platinum (H2tCl6TO2tCl4, L2tCl2with vinylsilanes solutions foundations with the subsequent separation of the phases and vacuum.

The catalyst is a mixture of an uncertain, unstable composition with a lower content of halogen and its preparation involves considerable difficulties and inevitable losses of platinum.

This patent has the following disadvantages.

Catalysis in some cases takes place in heterogeneous conditions because of the formation of insoluble products of interaction of the catalyst components of the mixture.

Obtained catalysts, the composition and activity of which is difficult to standardize, resulting in poor reproducibility and controllability of the process, especially high-speed thermal reactions of the type.

There is a lack of viability of the compositions at room temperature.

To stabilize compositions using various additives to hexachloroplatinic acid, which inhibi-

The closest analogue is the prototype of the claimed invention is the use as catalyst of platinum-containing compounds, mainly of N2tCl6with additions of organic sulfoxidov in the number of 200-2000 mol per mol of the platinum complex (3). These supplements sulfoxidov allow to inhibit the curing process system based on vinyl - and heritagebased kremniyorganika - ical oligomers up to the required temperature. However, the uncertainty of the complex formed in situ, it is difficult for the regulation of the catalytic properties of systems, and large excess sulfoxide in the polymer composition is undesired hair - tion of low-molecular-weight impurity, impairing its properties. At the same time when the ratio of the additive to the complex, close to equimolecular not achieve the desired inhibition of the rate of curing. In addition, extremely high hygroscopicity of hexachloroplatinic acid (initially applied in the form of uranyl), as well as most of the sulfoxidov complicates prevent secondary process dehydrocondensation N groups of the oligomer with water molecules, which is accompanied by emission (H2and, as a consequence, the violation of ognore the years the proposed curing catalyst.

The technical effect is to increase the rate of vulcanization, and reducing consumption of platinum.

The technical effect is achieved by the fact that as a catalyst for accelerated vulcanization use the products of interaction sulfoxide of platinum complexes with unilateraily the siloxanes, and as complexes according to the invention it contains platinum compounds of General formula

[Pt(L)2X2] and [PtL1L2Cl2] , where L, L1, L2- (CH3)2S = 0,

(C2H5)2S = 0, (C3H7)2S = 0, (i-C3H7)2S = 0, (C6H5CH2)2S = 0,

(n-C4H9)2S = 0, (p-CH3C6H4)(CH3S = 0; X-Cl, Br and the concentration of platinum complexes in minilateral the siloxane is 5 x 10-8-1 x 10-5g-at/ml.

The invention consists in the application of individual sulfoxide complexes of platinum (II), General formula

[Pt(L)2X2] , [PtL1L2X2] , where L, L1, L2< / BR>
- (CH3)2S = 0, (C2H5)2S = 0, (C3H7)2S = 0,

(i-C3H7)2S = 0, (n-C4H9)2S = 0, (Care stable, hygroscopic substance in the crystalline state, are well soluble components of the reaction mixture. As a result of interaction sulfoxide complexes with vinylsilanes formed stable homogeneous catalytic solution with precisely controlled content of platinum. As vinylsilane used hexaphenyldisilane (GUDS), tetramethyldisiloxane (TMDS) or oligomerisation mol. wt. 5-6 thousand received by polyarizatsiei cyclic trimer [CH3(CH2= = CH)SiO]3. If the consumption of platinum is greater than 10-5the curing process does not significantly improved, but increased consumption of platinum, if the consumption of platinum in less than 10-8then there is no consistency in reproducing the results of experiments on solidification. Depending on the structure sulfoxide ligand and selected vinylsilane can be regulated temperature range curing from 100 to 400aboutAnd the cure time from 6 min to 2-3 (see table).

A comparison of the proposed technical solutions with the prototype showed that the claimed solution is characterized by the fact that as complexes of platinum is used as a compound of General formula [Pt(L)2X2] , [Pt(LS = 0, (C3H7)2S = 0,

(i-C3H2)S = 0, (C6H5CH2)2S = 0, where X Is Cl, Br, and the concentration of platinum in minilateral the siloxane is 5 x 10-8-1x x 10-5g-al Pt/ml and, therefore, meets the criteria of the invention of "novelty."

The study of other known technical solutions in this field of technology has shown that the present invention stems from them in subtle ways and, therefore, meets the criterion of "inventive step".

Description of the process.

A portion of the complex weight of 0.03 g was dissolved in 5 ml of vinylcyclohexane at 20-50aboutWith received homogeneous catalytic solution with a certain amount of platinum. The catalytic activity of the solution remains 6-12 months. under conditions of storage at 20aboutC.

Thus obtained catalysts used in the preparation of siloxane compositions used for the primary coating of an optical fiber. The process of making siloxane polymer compositions is as follows:

to a mixture of liquid silicon rubber with vinyl groups CH2= CH--O O O i CH= CH2where R = CH2
n = 10m when R = C6H5n = 3-3,5 m n = 1000-1500 added texturing agent with gramnegative groups H O O O H where R = CP3CH2CH2; n = 7m; l = 3-5 = 5000-7000 when R = C6H5; n = 2-3m ; l = 3-5 then the solution sulfoxidation catalyst.

The composition is thoroughly mixed and brought the viscosity to the desired operating level. Resilience in the composition at 8-10aboutWith about 30 days.

The invention allows to standardize the catalyst, as all the components are stable at normal temperatures and does not lose its properties during storage. Sulfoxide complex catalysts represent individual compounds that are resistant under normal conditions, non-hygroscopic crystalline substances, soluble components of the reaction mixture. Unlike the used catalysts on the basis of H2PtCl6these complexes do not contain active functional groups and do not cause side processes associated with the presence of acid or other functions.

In addition, the catalyst allows you to keep the stability at room temperature for 6-12 months without loss of activity and to ensure the viability of Konoe few seconds. (56) U.S. Patent N 3775452, CL 08 G 31/26, publ. 1970.

U.S. patent N 3453234, CL 08 G 31/26, publ. 1968.

The CATALYST ACCELERATED VULCANIZATION based on the product of the interaction sulfoxide complexes of platinum (II) with unilateraily the siloxanes, characterized in that as complexes of platinum catalyst provides compounds of General formula

[Pt (L)2X2] and [Pt L1L2X2] ,

where L1and L2for example, (CH3)2S = 0, (C2H9)2S = 0, (C3H7)2S = 0, (i - C3H7)2S = 0, (C6H5CH2)2S = 0, (n = C4H9)2S = 0, (p = CH3C6H4) (CH3S = 0; where X Is Cl, Br,

the concentration of platinum in minilateral the siloxane is 5 10-8- 1 10-5mol Pt/ml

 

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