JPS604218B2 - Mercaptoorganopolysiloxane elastomers catalyzed with metal compounds in the presence of peroxides - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to compositions containing sulfur-containing siloxane polymers and siloxane-based elastomers.

Nos. 4,039,504 and 40, issued to Homan and Lee on August 2, 1977.
No. 39505 is generally directed to compositions curable to elastomers at room temperature or by heating.

These compositions are made from mixtures of certain polymethylvinylsiloxanes and mercabutorganopolysiloxanes with organic peroxides and optional fillers. US Pat. No. 4,070, issued to Homan and Lee on January 24, 1978, discloses compositions made from mixtures of mercaptoorganopolysiloxanes and organic peroxide catalysts. No. 4,070,328, also issued to Homan and Lee, issued Jan. 24, 1979, US Pat. Discloses a composition made of

The compositions prepared according to these documents can be used as fast-curing sealants to elastomers with non-tacky surfaces. The prior art literature is extensive regarding compositions containing mercaptoorganopolysiloxanes and their mixtures with alkenyl-containing siloxanes and curing systems using electromagnetic and particle radiation. Among these documents are Van 20 May 1969;
U.S. Pat. No. 344,541 to Derlinde, U.S. Pat. No. 3,816,282 to Viventi dated June 11, 1974, U.S. Pat.
German Published Patent Application (OB) No. 2008426 of September 10, 1970 to Bazant et al., 1977
U.S. Patent No. 4064 to Gant dated January 20, 2013
No. 027, U.S. Pat.
197 against Ehrman and Kalinowski.
& Wang, Japan Patent No. 930035 dated October 7th. Reference is made to the disclosures of these patents for the purpose of illustrating the state of the prior art. A mixture of an alkenyl-containing polysiloxane and an organic peroxide with a mercaptoorganopolysiloxane, a mixture of an organic peroxide alone with a mercaptoorganopolysiloxane, or a mixture of an organic hydroperoxide and a selected nitrogen compound with a mercaptoorganopolysiloxane. Although the prior art describes elastomeric materials formed by mixing
Adding certain selected transition metal compounds into a mixture of mercaptoorganopolysiloxane and organic peroxide will substantially accelerate the rate at which the mixture cures into an elastomeric composition. Nothing predicted that.

In accordance with the present invention, novel compositions are provided by mixing mercaptoorganopolysiloxanes with selected transition metal compounds and organic peroxides. Compositions provided by the present invention include compositions that can be cured to elastomers at room temperature in the presence or absence of an oxygen-containing atmosphere such as air. The curable compositions of the present invention may optionally include fillers;
and a sealant that rapidly cures in a fraction of the time required to cure a mixture of mercaptoorganopolysiloxane and peroxide that does not contain metal compounds, resulting in an elastomeric material with a non-tacky surface. I can do it. The present invention includes: (1) dimethylsiloxane unit, trimethylsiloxane unit, hydroxydimethylsiloxane unit, unit of formula, unit of formula, unit of formula, unit of formula, unit of formula, unit of formula (in the formula, R is a carbon number -valent group selected from the group consisting of 1 to 3 alkyl groups and phenyl groups, R
I is methyl or ethyl, and n has a value from 1 to 4. , contains an average of more than two mercapto-containing siloxane units per molecule, and the content of mercapto-containing siloxane units is 10 mol % or less based on the total number of siloxane units contained in the mercaptoorganopolysiloxane. Mercaptoorganopolysiloxane; (B}
Organic peroxide in an amount equal to 0.5 to about 6 parts by weight per 100 parts by weight of organic peroxide: [C) an amount of about 0.1 to about 1 part by weight of peroxide, by reacting A transition metal compound selected from those that give oxidized metal ions in the presence of Tsukuda and give reduced metal ions in the presence of ■; and {D} from 0 to 10 parts by weight of ■. It relates to a composition consisting essentially of a material produced by admixing filler in an amount of up to 20 parts by weight.

Mercaptoorganopolysiloxanes useful in the practice of this invention include dimethylsiloxane units, trimethylsiloxane units, hydroxydimethylsiloxane units and formulas and [wherein R is an alkyl group having from 1 to 3 carbon atoms]
RI is methyl or ethyl; and n has a value from 1 to 4, preferably a value of 3. containing on average at least 2 mercapto-containing siloxane units per molecule, and having a content of mercapto-containing siloxane units of 10 mercapto-containing siloxane units based on the total units contained in the mercaptoorganopolysiloxane. This includes those in which the amount is less than or equal to mol%.

Examples of mercaptoorganopolysiloxanes include those without formula 1, and with formula N: where R, RI and n are as defined above and x is from 18 to 1000, preferably from 200 to 800. having a "terminal" mercapto group as represented by the formula V or Formula V: (where n and R are as defined above and y+z is from 18 to 1000,
preferably has a value from 200 to 800, and z
is greater than 2 and does not exceed 10 mole % of mercapto-containing units based on the total siloxane units contained in the polymer). Those having groups are included.

Mercaptoorganopolysiloxanes of Formulas 1 and V are known in the art, as evidenced by the prior art cited herein.

Mercaptosilacyclobentylpolysiloxanes of formulas m and W and their regioisomers are disclosed in U.S. Pat. No. 36,557 issued to LeGrow on April 11, 1972.
It can be manufactured by the method specified in the specification of No. 13.
Note that this specification should be referred to as a part of this specification as it describes mercaptosilacyclobentylpolysiloxane and its manufacturing method. Mercaptoorganopolysiloxanes of formula D containing endblocking units of the formula are prepared by combining a hydroxyl endblocked polydimethylsiloxane and a mercaptoalkyltrialkoxysilane having the formula in the presence of a solid potassium hydroxide or potassium silanolate catalyst. It can be produced by reaction.

Potassium silanolate catalysts are preferred for high viscosity polydimethylsiloxanes. The mercaptoalkyltrialkoxysilane is about 10 mol% less than the stoichiometric amount.
It is desirable to use excess. The resulting product is essentially a polydimethylsiloxane endblocked with units having the formula, but it also contains a small number of young units in which two SiOH groups have reacted with one molecule of mercaptoalkyltrialkoxysilane. Thousands included.

However, the amount is small, so the properties of the end-blocked polydimethylsiloxane will not change significantly.
Compounds include:

A first group of transition metal compounds useful in the practice of this invention consists of inorganic salts of copper and cobalt.

Included are ferrous and ferric compounds such as ferrous chloride, ferric oxide, and ammonium ferrous sulfate. Also included are cuprous and cupric compounds such as cuprous chloride and cupric sulfate. Preferred transition metal compounds are ferric oxide and cupric sulfate. Cobaltous chloride (
Cobalt compounds such as hexahydrate are also useful. A second group of transition metal compounds useful in the practice of this invention include carbonyls of iron, manganese, nickel and cobalt, such as Fe(CO)5, Fe2(CO)9, Fe3(CO),
2, Mn2(CO),.

, Ni(CO)4 and Co2(CO),. It is. A third group of transition metal compounds useful in the practice of this invention has the formula: Metal compounds useful in the practice of this invention participate in "redox" equilibrium reactions with peroxide-based oxidizing agents and thiol-based reducing agents. obtained, the selected transition metal [wherein Q is iron, nickel or cobalt, and R2 and R3 are the same or different groups, hydrogen, lower (C, to C3
) selected from alkyl, acetyl, carboxyl, vinyl or trimethylsilyl].

Preferred compounds include ferrocene and cobaltocene. A fourth group of transition metal compounds useful in the practice of this invention are those of the formula and [wherein M is iron, nickel or manganese and a is 2, none, or 3 depending on the oxidation state of M.
and R4 is hydrogen, lower (C, to C3) alkyl, acetyl, carboxyl, vinyl or trimethylsilyl.

Preferred compounds also include dimeric forms of the compounds described above, such as cyclobentajenyl iron dicarbonyl dimer. A sixth group of transition metal compounds useful in the practice of the present invention has the formula T(OR5)m, where T is a transition metal selected from the group consisting of iron, manganese, cobalt, copper and nickel; R5 is a monovalent acyl group; and m is
2 or 3 depending on the most stable oxidation state of T).

Suitable monovalent acyl groups include acetyl, propionyl,
Isobutyryl, stearoyl, lauroyl, 2-ethylhexanoyl (sometimes called "octanoyl")
, oleoyl, linoleoyl, benzoyl, naphthoyl, 8-penzoylpropionyl, crotonoyl, atropoyl, palmitoyl, and cinnamoyl. The 2-ethylhexanoyl ("octanoyl") group is a preferred acyl group.

The most preferred compound is ferric octoate. Mixtures containing the above-mentioned compounds exhibit a significant increase in reaction rate, as evidenced by the significantly reduced time required to achieve cure of the elastomeric compound.

The preferred amount of metal compound used in the mixture is from about 0.1% to about 10% per 100 parts by weight of polymer. within the range of parts by weight. In the practice of this invention, the following conventional organic peroxides are used: 2,4-dichlorobenzoyl peroxide, t-butylberbenzoate, benzoyl peroxide, t-
butylberoctoate (2-ethylhexoate),
One or more of p-menthane hydroperoxide, t-butyl hydroperoxide and cumene hydroperoxide can be used. The amount of organic peroxide used in combination with the mercaptoorganopolysiloxane can vary over a wide range depending on the desired degree of reactivity of the mercapto groups contained in the mercaptoorganopolysiloxane. To optimize the physical properties of the cured elastomeric product, use an amount of peroxide such that the molar ratio of peroxide molecules to mercapto groups is at least 1:2, and the weight of the mercaptoorganic It should be in the range of about 1 to about 6 parts by weight per part by weight of polysiloxane 10. As will be clear from the Examples below, organic peroxides that include peroxyester functionality are far more preferred than peroxides that do not contain this type of group. When the mercaptoorganopolysiloxane and the organic peroxide are homogeneously mixed with the metal compound in the mixture of the present invention, the metal compound acts as a promoter to form a bond between the mercaptoalkyl group of the mercaptoorganopolysiloxane and the organic peroxide. , and the formation of one S-S- covalent bond becomes more distant.

In the practice of this invention, the formation of this type of -S-S bond is demonstrated using 3-mercaptopropylheptamethyltrisiloxane as a representative mercaptoorganopolysiloxane, ferric oxide and dibenzoyl peroxide. This can be demonstrated by nuclear magnetic resonance (NM liver) spectroscopy in a typical system in which the appropriate disulfide compound is exclusively obtained upon standing at room temperature when mixed with Mercaptoorganopolyses of formula W without formula 1 in the compositions of the present invention. When xane is used alone, linear gums are obtained; when mercaptoorganopolysiloxanes of formula V or dish are used alone or in combination with polymers of formula 1 to formula W, elastomeric materials are formed. Good morning. Fillers can be used in the compositions of the invention, but are not required ingredients.

Fillers include treated and untreated reinforcing fillers, such as fumed silica and fumed silica with triorganosiloxy groups such as trimethylsiloxy groups on the surface, carbon black or precipitated silica, and extending fillers, such as crushed or may be ground quartz, diatoms and calcium carbonate. Desirably, the curable elastomeric composition contains up to about 20 parts by weight of filler per 100 parts by weight of mercaptoorganopolysiloxane.
Compositions of the invention that cure to elastomers cure rapidly at room temperature in the presence of an oxygen-containing atmosphere, such as air.

The resulting elastomer has a dry or non-tacky surface. Unlike in the case of peroxide-cured silicone rubber compositions that do not contain mercapto according to the prior art, no air suppression is observed and also platinum-catalyzed silicone rubber compositions, including aliphatically unsaturated and SiH-containing siloxanes. Unlike the composition, there is no air suppression by various substances such as sulfur and phosphorus. Rapidly curing elastomers according to the present invention are expected to be particularly useful sealants and can be provided in two-component packaging. The examples described below are for illustrative purposes only and should not be understood as limiting the invention.

Examples 1 and 25 generally relate to the use of the first group of transition metal compounds. Example 1 A mercaptoorganopolysiloxane of the type exemplified by formula V, with a ratio of methylmercaptopropylsiloxane units to dimethylsiloxane units of about 1.0 mole %, was prepared according to the following procedure.

A mixture of 53.65 mm of hydrolyzate of methylmercaptopropyldimethoxysilane and 12.97 mm of hexamethyldisiloxane is heated in a 5,000 mm three-neck flask equipped with a reflux condenser, a thermometer, and a thermometer. did. When the temperature of the mixture reached 70 qC, 1.5 ml of trifluoromethanesulfonic acid was added and the mixture was heated to 85 qC for 30 minutes. While maintaining the temperature at 8,500 ℃, 2,933.37 g of octamethylcyclotetrasiloxane was slowly added from a pressure compensation funnel through a reflux condenser over about 2 hours. After the addition was complete, 0.18 g of water was added and the mixture was allowed to equilibrate for about 5 hours. After adding 15 ml of sodium carbonate, the mixture was allowed to stand for about 1 hour.

Two portions of toluene were added and heated through a charcoal filter. The volatile materials were stripped off at 150°C (pressure below 667 Pa) to yield a polymer with a viscosity of about 0.0052 mm/sec at 280°C.

This polymer has the general formula:

Analysis of the polymer by iodometric titration revealed approximately 0.49% by weight of -SH (or 0.0148 mol-SH/10
0 tabolimer) was found to be included. Example 2 A mercaptoorga/polysiloxane exemplified by formula V, with a ratio of methylmercaptopropylsiloxane units to dimethylsiloxane units of about 1.0 mole %, was prepared by the same procedure as in Example 1.

The viscosity of the polymer is 0.022 m/sec at 2 o and can be expressed by the formula:

When the polymer was analyzed by iodometric titration, it was found that approximately 0.44
Weight percent -SH was observed. Example 3 Polymer 10 of Example 2
A mixture of 1 part by weight of Daiichi Steel Chloride was prepared using a three-roll kneader.

A sample of this mixture was placed in a 15,000 oven. The surface of the heated mixture was hardened after one powder, and was completely hardened within 24 hours. snap time
The composition has a recovery property.
ies). Hereinafter, when the term "snap cure" is used, it refers to the point during the curing process when the composition exhibits recovery properties. The sample left at room temperature cured in a snap within 4 hours, and after 4 days it was quite well crosslinked but the surface was sticky, and after 2 weeks the surface was slightly sticky but completely cured. This example is for comparison purposes. Example 4 10 parts of the polymer/cuprous chloride mixture of Example 3 mixed with 0.5 parts t-butyl hydroperoxide cures snap within 39 seconds at room temperature and becomes non-tacky within about 5 minutes. A mixture was obtained.

EXAMPLE 5 10 days of the polymer/cuprous chloride mixture of Example 3 was mixed with 0.1 day of t-butyl hydroperoxide at room temperature for 69°C.
A mixture was obtained which hardened snap within seconds and became completely non-tacky within less than 4 glue hours.

EXAMPLE 6 One hundred grams of the polymer from Example 2 was mixed with three millimeters of ferric oxide on a three-roll mill.

Samples of the red mixture showed no signs of hardening after being left at room temperature for over 6 months. This example is for comparison. Example 7 Two samples of the mixture of Example 6, each containing 10 ml of 0.
Mixed with 5 and 0.1 nights of t-butyl hydroperoxide.

The mixtures cured at room temperature into elastomers with snap times of 5 minutes and 5 minutes, respectively. Both mixtures were still slightly sticky after 3 days at room temperature. Example 8 Parts by weight of Polymer 10 of Example 2 and 1 part by weight of cuprous chloride tetrahydrate were mixed on a three-roll mill.

A sample of the translucent, pale yellow mixture was placed in a 150-hole open tube. The mixture surface cured in 3 minutes and fully cured in less than 1 hour to form a black, highly crosslinked elastomer. Samples kept at room temperature showed a skin layer after about two weeks, but showed no evidence of hardening below the skin layer. This example is for comparison. Example 9 10 parts of the polymeric Daiichi Steel chloride mixture of Example 8 and 0.5 parts of t-butyl hydroperoxide were mixed.

When mixed, the color changed from pale yellow to light yellow, resulting in a material that hardened to a snap at room temperature in 12 to 2 minutes. This material had a dry surface in about 30 minutes and was fully cured in about 2 hours at room temperature. Example 10 A mixture of parts by weight of Polymer 10 of Example 2 and 1 part by weight of ammonium ferrous sulfate hexahydrate was prepared in a three-roll mill.

When the sample was placed in an oven at 150° C., no evidence of hardening was observed even after two weeks. This example is for comparison. Example 11 10 parts of the mixture of Example 10 were mixed with 0.5 parts of t-butyl hydroperoxide.

The resulting mixture showed only a slight thickening phenomenon after 3 days at room temperature. EXAMPLE 12 10 parts of the polymer/ferric oxide mixture of Example 6 were mixed with 0.5 parts of tert-butylberbenzoate and cured to a snap in 65°C at room temperature and completely cured in less than 3 minutes. A mixture was obtained which became non-sticky.

EXAMPLE 13 10 parts of the polymer/ferric oxide mixture of Example 6 were mixed with 0.1 parts of t-butylbenzoate and cured to snap in 5.25 minutes at room temperature and was very slightly tacky in 13 minutes. , and a mixture was obtained which became non-stick in about 16 minutes.

EXAMPLE 14 10 parts of the polymer/ferric oxide mixture of Example 6 were mixed with 0.05 parts of t-butylberbenzoate to give a snap cure in one powder at room temperature, leaving a non-tacky surface after 48 minutes. The mixture shown was obtained.

Example 15 10 parts of the polymer/ferric oxide mixture of Example 6 were mixed with 0.01 part of t-butylberbenzoate.

When the sample was placed in a 150 qo open, it snapped after 3 minutes of heat treatment. As a result of continued heat treatment, after one month, although it was substantially hardened, it became stringy.
ngy) elastomer. This example is for comparison. Example 16 Polymer/ferric oxide mixture prepared according to Example 6 10
To the mixture, 5 t-butylberbenzoate was added.

The resulting material snaps at room temperature for 65 seconds and
It completely hardened within a few months. EXAMPLE 17 Ten samples of the polymer/ferric oxide mixture of Example 6 were mixed with 1.0 parts of 2,4-dichlorobenzoyl peroxide (50% solution in low molecular weight polydimethylsiloxane).

Samples placed in a 15,000° oven cured in less than 3 minutes to a non-tacky, glossy surface.

Another sample left at room temperature had a snap time of about 1 hour and was still tacky after about 3 hours. This sample became non-stick after being left at room temperature for 3 days. Example 18 100 parts of the polymer of Example 2 were combined with 3 parts of cupric sulfate.

For each 10 night sample of this mixture, t of 0.5 night, 0.1 night, 0.05 night and 0.02 night, respectively.
-Butylberbenzoate was added. The first sample is
The snap time was 1.5 minutes at room temperature and was fully cured with a dry surface in 2.5 minutes. The second sample is
It had a snap time of 7.2 degrees at room temperature and was fully cured with a dry surface in 14 minutes. The third sample is
The snap time was about 18 minutes at room temperature, slightly tacky after 3 hours, and substantially hardened after 1 hour to a low modulus material. The fourth sample did not snap hard even after being left at room temperature for 18 hours. The fourth sample is for comparison. example
19 A mercaptoorganopolysiloxane having a ratio of dimethylmercaptatopropylsiloxane units to dimethylsiloxane units of about 1.5 mol % and of the type exemplified by Formula 1 was prepared by the following procedure.

In a flask equipped with a condenser, a thermometer, and a nitrogen gas purge tube, a mixture of 74.85 mm of tetramethyldimercaptopropyldisiloxane and 3305.45 mm of a cyclic tetramer of dimethylsiloxane was added. Heated. After purging the system with nitrogen gas while heating the mixture to 6,000 ℃ under water, 1.77 μl of trifluoromethanesulfonic acid solution (1.696 μl/ml) was added. The polymerization reaction was allowed to proceed for 4 hours. Sodium bicarbonate 3
The mixture was neutralized over 3 hours with cooling. The polymer was filtered to remove volatile substances at 150°C (under a pressure of about 20 mA) and heated at 25°C.
The viscosity at about 0.467 Pa. Approximately 3,000 units of polymer were obtained. The polymer was analyzed by iodometric titration and the content of -SH was found to be approximately 0.6% by weight (0.0191 mol-SH/100 tapolymer). Example 20 A mercaptoorganopolysiloxane of the type exemplified by formula V, in which the ratio of methylmercaptopropylsiloxane units to dimethylsiloxane units is about 5.0 mole %, was prepared according to the procedure described in Example 1.

This polymer can be represented by the general formula: The polymer was analyzed by iodometric titration and the amount of -SH was found to be about 2.3% by weight. Example 21 On a three-roll mill, parts by weight of polymer 10 of Example 19 kneaded with 1 part by weight of magnesium oxide, 3 parts by weight of cupric sulfate.
A mixture was prepared using 1 part by weight of GD2417 and 0.5 parts by weight of GD2417 (violet) captan masking compound.

To 20 mg of the mixture thus prepared, 0.5 mm of t-butylberbenzoate and 0.5 mm of the polymer of Example 20 were added. A sample of this mixture fully cured in about 45 minutes at room temperature. Another sample was fully cured in 2 minutes when heated to 15,000°C. Example 22 A mixture of 100 parts of the polymer of Example 2 and 1 part of cobaltous chloride (hexahydrate) was prepared on a three-roll mill.

To this mixture was added 0.5 hours of t-butyl hydroperoxide. The resulting material gelled slightly after 4 hours at room temperature and cured to a low durometer rubber after 1 week at room temperature. From the above examples, ferrous, ferric, cuprous and cupric compounds are combined with mercaptoorganopolysiloxanes having terminal and internal mercapto functional groups and peroxyester-type organic peroxides and hydroperoxides. , for example t-butylberbenzoate, 2.4
-dichlorobenzoyl peroxide and t-butyl hydroperoxide to give useful elastomers.

Such mixtures may be provided in the form of conventional two-component packaging in which one component consists of, for example, a polymer containing terminal mercapto groups, a polymer containing internal mercapto groups, and a metal compound, and the other component consists of a peroxide. can be done. If it is desired to include an acid acceptor material, such as magnesium oxide, in the mixture, ternary packaging can be used. The following examples demonstrate that magnesium compounds are generally ineffective as catalysts in the cosmetics of this invention and that alkyl peroxides are generally ineffective for rapid room temperature curing purposes.

Example 23 A mixture of 100 parts of the polymer of Example 2 and 1 part of magnesium sulfate was prepared in a three-roll mill.

A sample of this mixture showed no evidence of curing after 24 hours at 150 oo. Another 10 samples of the mixture were mixed with 0.5 parts of t-butyl hydroperoxide. After 3 days at room temperature, no evidence of curing was seen on this sample. This example is for comparison. Example 24 Polymer 10 of Example 1 was mixed with 2,5-dimethyl-2,5-di(t-butylberoxy)hexane (Lupe ol).
lol) o. Mixed with 5 nights.

Samples left at room temperature for one month were still fluid. Another sample was placed in a 150oO oven and cured to a non-stick material in about an hour. This example is for comparison. Example 25 In this example, the effects of formulation variables on the physical property profile of elastomers made in accordance with the present invention [i.e., '1' polymer molecular weight, [2] 'crosslinking agent' (internal mercaptope).

The effects of pyru group-containing polymer), '3' peroxide, '4' filler and {5-amount of metal compound promoter used] will be explained. One type of polymer was used: a mercaptopropyl endblocked linear polymer of the type exemplified by Formula 1 and a "crosslinker" polymer as defined in Example 20.

The latter was prepared as described in Example 1. Five polymers of the type represented by Formula 1 were prepared by the method described in Example 19. The viscosities and number average molecular weights of these polymers determined by gel permeation chromatography (GPC) analysis were as follows. A Effect of Polymer Molecular Weight Each of Polymers A to E was mixed with the same compounding base, namely: Polymer 10 Anchor treated silica (fumed silica having triorganosiloxy groups) 3 Sides ferric oxide (promoter) 3 Part oxidation Magnesium (acid acceptor) was included in 2 parts.

To 100 parts of the formulation base, 2.5 parts of t-butylberbenzoate (curing agent) and varying parts of the crosslinker polymer as prepared in Example 20 were added. The results of observing the influence of polymer molecular weight on the outline of physical properties are shown in Tables 1 to 5.

Generally, as the polymer molecular weight decreases, the ultimate elongation rate also decreases, but the durometer value increases. B. Effect of Crosslinker Amount Used To demonstrate the effect of crosslinker usage on physical properties and cure rate, the amount of crosslinker (polymer of Example 20) was varied from 0 to 25 parts per 100 parts of base. Polymer DIO Boto of Example 25, treated filler 30, varying within the range of
A base consisting of 2033 parts Fe, 02 parts Mg and 2.5 parts t-butylberbenzoate was cured at room temperature.

The results observed were as summarized in Table 6.

It can be concluded that lowering the concentration of crosslinker improves the general property profile, including cure speed. It is interesting to note that some crosslinking occurs even in the absence of a crosslinking agent.

This phenomenon was observed in the presence and absence of triorganosiloxy-treated silica fillers.
This behavior is due to the low level of branching in Polymer D. C. Influence of fillers The influence of the type of filler and its amount added on the physical properties and curing speed of the resulting elastomer is demonstrated by various fillers.

The data shown in Table 7 is for crushed (5A) quartz, calcium carbonate, diatomite and treated silica, with the base (polymer BIOO parts, 3 parts ferric oxide, 2 parts M and fillers as indicated) 10 parts), 2.5 parts of crosslinker polymer as defined in Example 20 and 2.5 parts of t-butylberbenzoate. D Effects of the amount of peroxide used Table 8 shows the effects of the amount of peroxide used.

The formulation consists of 100 parts of base (polymer AIOO, 3 parts of treated silica, 3 parts of Fe, and 0 parts of Mg), a crosslinker polymer as defined in Example 20, x
and t-butylberbenzoate as indicated.
It was constructed using the following sections. The overall physical properties obtained using 1.25 pph peroxide were slightly better than with 2.5 pph peroxide.

However, when the amount of peroxide was small, the curing rate decreased abnormally as seen from the table. Peroxide pair -SH
As long as the molar ratio of peroxide was maintained at at least 1:2, the physical properties were not drastically affected by changing the peroxide concentration. E Effect of Accelerator Usage It has been demonstrated that by lowering the peroxide usage, the cure rate can be reduced without sacrificing the physical properties of the cured elastomer.

Another way to control the cure rate is to vary the amount of accelerator (Fe203) in the formulation. This is shown in Table 9. Polymer C was used and 1 part of the crosslinker polymer defined in Example 20 was added to the formulation base along with Polymer C. When the concentration of Fe203 was increased, the curing rate increased abnormally. A full cure time of 50 minutes was obtained using 5 pph Fe203 with 2.5 pph peroxide, but doubling the amount of peroxide used would reduce the full cure time to 2 to 30 minutes. It was possible.

Ferric oxide has been used effectively to control cure rate without sacrificing physical properties.

Therefore, by adjusting the amounts of peroxide and accelerator used, as long as the peroxide to -SH molar ratio is at least 1/2. It was possible to obtain complete curing times ranging from 1 hour to 24 hours. example
26 A mercaptoorganopolysiloxane of the type exemplified by formula V, with a ratio of methylmercaptopropylsiloxane units to dimethylsiloxane units of 0.75 mol %, was prepared according to the procedure described in Example 1.

This polymer can be represented by the general formula:

According to iodometric titration, the -SH content of the polymer is approximately 0.4
It was 1% by weight. The viscosity of the polymer was 0.03893/sec. For comparison, this polymer 100 m and t
-butylberbenzoate was prepared.
An increase in the viscosity of the mixture was clearly observed after standing at room temperature for two days. Even if it takes many days,
Complete curing of the mixture did not occur. The following examples illustrate that the second group of transition metal compounds according to the above classification are useful in the practice of this invention.

Example 27 A solution of 100% of the polymer of Example 26, 1.0% of t-butylberbenzoate and 1.0% of iron pentacarbonyl in mineral oil.
0%) 0.5% mixture was prepared.

This mixture hardened into a snap in about 2 hours at room temperature and was completely cured after being left for 2 hours. Example 2 below
Examples 8 and 29 relate to the utility of the third group of transition metal compounds in the practice of the present invention.

Example 28 20 parts of the polymer of Example 26, 10 parts of t-butylberbenzoate and 0.5 parts of an 8% by weight solution of ferrocene in toluene.
A mixture was prepared using the following ingredients.

This mixture hardens to a snap at room temperature in about 110 minutes;
It was completely cured in about 168 minutes. Example 29 The procedure of Example 28 was repeated using an 8% by weight solution of cobaltocene in toluene instead of the ferrocene solution.

The mixture was snap cured in 1 minute at room temperature and fully cured in 10 minutes. The following examples relate to the utility of Group 4 transition metal compounds in the practice of the present invention.

Example 30 In a polymer having the general formula prepared according to the procedure of Example 1, cumene hydroperoxide
．． A mixture was prepared using 1 mol. and 0.1 mol.

This material gels immediately at room temperature, with a surface area of approximately 30
It became dry after a few minutes. The examples described below illustrate the utility of Group 5 transition metal compounds in the practice of this invention.

Example 31 20% of the polymer of Example 26, 1.0% of t-butylberbenzoate and manganese octoate (50% solution in mineral oil)
A mixture was made containing 0.1 min.

The mixture snapped to room temperature cure in 1 minute and fully cured in about 3 minutes. EXAMPLE 31 Example 31 was repeated using 0.1 ml of nickel octoate solution (20% in key oil) in place of the manganese octoate solution.

The resulting mixture is roasted in sardines at room temperature for about 80 minutes,
It completely cured in about 2 steps. EXAMPLE 33 Example 31 was repeated using a 0.1 hour naphthoate solution (50% in mineral oil) as a substitute for the manganese octoate solution.

The mixture was snap cured with room temperature 2 sand and fully cured with 4 stone sand. Example 34 Example 31 was repeated using a 0.19 ferric octoate solution (50% in tin oil) instead of the manganese octoate solution.

This mixture hardens to a snap in 5 minutes at room temperature and approximately 11 minutes.
Fully hardened with powder. Example 35 100% of the polymer of Example 26, 1.0% of t-butylberbenzoate and a solution of cobalt octoate (20% of the polymer in mineral oil)
%) was prepared containing 0.25%.

The mixture was snap cured in 65 minutes and fully cured in 120 minutes. It will be apparent from the foregoing description that numerous modifications and variations in the practice of this invention are possible to those skilled in the art of silicone technology, but they are limited only by the scope of the appended claims. Should be limited.

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Claims (1)

[Scope of Claims] 1 (A) Dimethylsiloxane unit, trimethylsiloxane unit, hydroxydimethylsiloxane unit, unit of the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Units of the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ , Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Units, Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Units, Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. There are tables etc. ▼ units (wherein R is an alkyl group having from 1 to 3 carbon atoms or a phenyl group; R^1 is methyl or ethyl; and n is from 1 to mercaptoorganopolysiloxane consisting essentially of a combination of units selected from (B) 100 parts by weight of (A
) an organic peroxide in an amount of from 0.5 to about 6 parts by weight per 100 parts of (A); The reaction gives oxidized metal ions in the presence of (B), and (A
); and (D) 100
A composition, characterized in that it consists essentially of a material prepared by admixing with parts by weight of (A) a filler in an amount of from 0 to 200 parts by weight. 2. The composition according to 1 above, wherein the transition metal compound is selected from the group consisting of inorganic salts of iron, copper and cobalt. 3. 1 above, wherein the transition metal compound is selected from the group consisting of iron, nickel, manganese, and cobalt carbonyl.
The composition described in . 4. The transition metal compound has the formula ▲ mathematical formula, chemical formula, table, etc. ▼ [wherein Q is iron, nickel or cobalt, and R^2 and R^3 are the same or different groups,
The composition according to 1 above, which is a metallocene having hydrogen, lower (C_1 to C_3) alkyl, acetyl, carboxyl, vinyl or trimethylsilyl. 5. The transition metal compound has the formula ▲ mathematical formula, chemical formula, table, etc. ▼ or [wherein M is iron, nickel or manganese, a is 2 to 3 depending on the oxidation state of M, and R 4 is a cyclopentadienylcarbonyl compound having hydrogen, lower (C_1 to C_3) alkyl, acetyl, carboxyl, vinyl, or trimethylsilyl. 6 The transition metal compound has the formula T(OR^5)_m (where T is iron, manganese, cobalt, copper or nickel, R^5 is a monovalent acyl group, and m is T 2 or 3 depending on its most stable oxidation state). 7 (A) is a formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, z > 2 and y + z has a value from about 18 to 1000) consisting essentially of one or more mercaptoorganopolysiloxanes, and (B) in an amount sufficient to provide a molar ratio of peroxide molecules to mercapto groups in the mercaptoorganopolysiloxane of at least 1:2. A composition as described in item 1 above, which can be cured into an elastomer. 8. Further contains one or more mercaptoorganopolysiloxanes selected from the group consisting of formula ▲ mathematical formula, chemical formula, table, etc. ▼ (in the formula, x has a value from 18 to 1000) 7. The composition described in 7 above.