JPS59149938A - Vulcanizable polymer compositions - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION This application is a continuation-in-part of U.S. Application No. 456,874, filed January 10, 1983.

The present invention relates to peroxide vulcanizable polymeric compositions containing a combination of zinc dimethacrylate and various fillers or mixtures of fillers.

In particular, the present invention provides copolymers of natural rubber or conjugated dienes with monoolefins, zinc dimethacrylate with a small specific surface area, various fillers or mixtures of fillers, as well as The present invention relates to vulcanizable polymer compositions containing peroxide vulcanizing agents. The invention further relates to certain vulcanizable polymeric compositions containing a combination of zinc dimethacrylate and clay to synergistically enhance the strength of the vulcanized compositions. It is something.

U.S. Pat. No. 3,823,122 relates to vulcanizable SBR or neoprene elastomer compositions containing from 1 to 15 parts by weight of substituted acrylic acid or salt per 100 tons of elastomer. It is a thing,
The preferred acid salt shown here is zinc methacrylate. The disclosed elastomeric compositions include reinforcing fillers, such as carbon blanks, but do not include peroxide vulcanizing agents.

U.S. Pat. No. 4,082,288 discloses a perfutide cross-linked 6F elastomer, 10 to about 60 parts by weight basic methacrylic F4 per 100 parts by weight of elastomer, a peroxide vulcanizing agent and optionally Discloses free radical cross-linking capable elastomer compositions containing reinforcing fillers such as litharge or zinc oxide in an amount of 2 to 10 parts by weight per 100 tons of elastomer. .

US Patent Specification 4. , L91,671 is (A) a diene elastomer, (B) an alpha, beta ethylenically unsaturated carboxylic acid, where the weight ratio of component (A) to component (B) is from 87/13 to 55/45. (c) a divalent metal compound present in an amount of 50 to 150 parts by weight per ioo parts by weight of component (B'); and (D) 100 parts by weight of the total weight of components (A) and (B). Hit 0, 3~
organic peroxide present in an amount of 5.0 parts by weight.

The compositions may also contain a non-polymerizable carboxylic acid, a carbon blank in an amount of up to 50 parts by weight per 100 parts of elastomer, and also amines and/or phenolic compounds.

U.S. Pat. No. 4,192,790 relates to elastomeric compositions having reduced Mooney viscosity in the blended state. The Mooney viscosity of elastomeric compositions is reduced by adding thereto from 0.1 to 7.0 parts by weight of basic zinc methacrylate per xoo parts by weight of elastomer. In addition to the basic zinc methacrylate, the elastomer compositions may contain various elastomers or elastomer blends, inorganic particulate fillers such as silica, calcium carbonate, clays, hydrated aluminum silicates, etc. silicates,
and optionally carbon black (100, 20 to 150 parts per L-section elastomer), as well as vulcanizing agents, such as peroxide vulcanizing agents.

U.S. Pat. )
and vulcanizing agents such as peroxide vulcanizing agents. The compositions optionally contain reinforcing fillers such as litharge or lead oxide, for example too much. It can also be contained in an amount of 2 to 10 parts per part of beam stroma.

British Patent Specification 1.091,818 discloses that alpha-fin polymers and 1 to 10% of alpha-fin polymers per 100 parts of polymer are used.
Vulcanizable compositions have been disclosed which are made of a vulcanization system consisting of a metal salt of acrylic acid or methacrylic acid and an organic peroxide in an amount of 50%. The compositions further include reinforcing agents and fillers, such as carphone blanks,
Metal oxides, clays and silica pigments can also be used.

British Patent Specification 2.042.553 discloses natural and/or synthetic rubbers, crosslinkers such as peroxides, monoadhesive metal salts such as zinc dimethacrylate, zinc diacrylate, preferably basic methacrylate. Bonded cellular elastomer compositions made from an elastomer composition comprising acid lead and a blowing agent are disclosed. The compositions may also contain fillers such as carbon black or titanium dioxide, and other known miscible additives. Although the patents listed in No. J describe compositions similar in some respects to the compositions of the present invention, they do not disclose or suggest two elements of uninvented compositions. Not yet. That is, these patents did not recognize the importance of using zinc dimethacrylate having a surface area of about 3.7 to about 5', 4 m2/g or more. Furthermore, the patents did not disclose or suggest compositions containing synergistic combinations of zinc dimethacrylate and clay.

According to the invention, certain rubbery polymers, especially zinc dimethacrylate having a surface area of F', various fillers or mixtures of fillers, and a peroxide vulcanizing agent are included. Vulcanizable polymer compositions are provided. The compositions include (a) a rubbery polymer selected from the group consisting of natural rubber and a conjugated diene together with at least one monoolefin; Approximately 2.5 per rubbery polymer
~20 parts by weight of lead dimethacrylate having a surface area of from about 3.7 to about 5.4 m2/g or more; (c) from about 30 to about 70 parts by weight per 100 parts by weight of the rubbery polymer; a filler selected from the group consisting of carbon black, clay, silica, mixtures of carbon black and clay, as well as mixtures of clay and silica;
and (d) a vulcanizing effective amount of a peroxide vulcanizing agent.

Contains.

In a preferred embodiment of the invention, a vulcanizable polymeric composition containing a copolymer of natural rubber or a conjugated diene and a vinyl aromatic hydrocarbon and a synergistic combination of zinc dimethacrylate and clay. types are provided. It has been discovered that the combination of zinc diacrylate and clay in these compositions synergistically enhances the strength of highly vulcanized compositions.

Rubbery polymers that can be used in the compositions of the invention include:
Included are natural rubber and copolymers of conjugated dienes and at least one monoolefin.

Copolymers of functional dienes include, for example, l,3-butadiene, 2-methyl-1,3-butadiene (-(soprene), 2,3-dimethyl-1,3-butadiene, −
It can be derived from conjugated dienes such as pentadiene, 1,3-hexadiene, etc., as well as mixtures of the aforementioned dienes. A preferred conjugated diene is 1,3-butadiene.

Copolymers include vinyl aromatic monomers such as styrene, alpha methylstyrene, vinylnaphthalene, vinylpyridine, etc.; alkyl acrylic acids or methacrylates 1 such as ethyl acrylate, ethyl acrylate, butyl acrylate, methacrylate methyl acid, butyl methacrylate, etc.; unsaturated nitriles, such as acrylonitrile, methacrylonitrile, etc., and vinyl halides, such as vinyl chloride, 1! ! It can be derived from a variety of heptanoolefin monomers, including vinylidene chloride and the like, as well as mixtures of the monoolefins mentioned above. The copolymer can contain up to 50% by weight of heptanoolefin, based on the total weight of the copolymer. Suitable copolymers are copolymers of conjugated dienes, especially butadiene, with vinylenes, aromatic hydrocarbons, especially styrene. A typical styrene-butadiene rubbery copolymer that can be used is a 23.5% bound styrene-containing Zino 1,50, available from Firestone Tire & Uchiha Company under the designation 51502. (ML4 at 212″F) and a specific gravity of 0.94.
Both butadiene and E are combined.

Copolymers of conjugated dienes and methods for their preparation are well known in the rubber and polymer arts.

A large number of polymers and copolymers are commercially available.

The zinc dimethacrylate used in the composition chain is about 3.
The dimethacrylic zinc powder has a surface area of 7 to about 5.4 m2/g or more. Zinc dimethacrylate powder with the required surface area is prepared by dispersing +5 lead oxide and methacrylic acid in a liquid aliphatic hydrocarbon dispersion medium in an amount of about 0.5 to 0.6 moles of zinc oxide per mole of methacrylic acid. by reacting the particles of zinc dimethacrylate in a liquid medium under stirring in a liquid medium, recovering the particles of zinc dimethacrylate from the liquid medium, and drying the particles of zinc dimethacrylate. Can be manufactured. A detailed description of the method for manufacturing zinc dimethacrylate powder is also provided by Robert A.
Hayes and W e n dell R, Con.
Currently pending Application No. D 8.1 +) 70 filed in the name of rad and co-assigned to the assignee of this application.
No. 46, the disclosure of which is incorporated herein by reference.

A preferred zinc dimethacrylate powder has a surface area of 4.5 m27 g prepared according to the process set forth in Example 3 of the above-referenced co-pending application.

The amount of zinc dimethacrylate that can be used in the composition chain depends on the type of rubbery polymer, the type and amount of filler or mixture of fillers, and the properties desired in the vulcanized composition. are doing. Generally, zinc dimethacrylate can be used in an amount of about 2.5 to about 20 parts by weight per 100 parts of rubbery polymer.

Fillers or mixtures of fillers that can be used in the composition chain include carbon black, clay.

・Mixtures of glue, sword-bon blanks and clay,
Also included are mixtures of clay and silica.

The amount of such fillers or mixtures of fillers that can be used in the composition chain depends on the type of rubbery polymer, the amount of zinc dimethacrylate, and what is desired in the vulcanized composition. Depends on nature. Generally, the filler or mixture of fillers is about 30% filler per 100 parts rubbery polymer.
It can be used in amounts of up to about 70 parts by weight.

Peroxide vulcanizing agents that can be used in the compositions include organic peroxides such as dicumyl peroxide, bis-(L-butylperoxy)diisopropylbenzene, t-perbenzoate,
Butyl, di-t-butyl peroxide, 2,5-dimethyl-2
, 5-di-5-bunalberoxy-hexane, and the like.

Suitable peroxide vulcanizing agents are bis-(t-butylperoxy)diisopropylbenzene and dicumyl peroxide.

The amount of peroxide vulcanizing agents that can be used in the compositions is dependent on the type of rubbery polymer used and can be broadly referred to as the vulcanization disintegration amount.

On the other hand, such amounts can be from about 0.2 to about 2.00 parts per 100 parts by weight of rubbery polymer. The compositions may also optionally contain other additives commonly used in rubbery compositions, such as processing and extending oils, antioxidants, waxes, and the like.

In a preferred embodiment of the compositions of the present invention, a rubbery polymer selected from natural rubber or a copolymer of a conjugated diene and a vinyl aromatic hydrocarbon is combined with zinc dimethacrylate and clay. Vulcanizable tq-capable polymer compositions containing in combination are provided. A surprising and unexpected aspect of such compositions is the discovery that the combination of clay and zinc dimethacrylate synergistically enhances the strength of the vulcanized compositions. That is, as shown in Examples 7-17 below, these vulcanized E
The effect of the combination of zinc dimethacrylate and clay on the strength of mIllt objects is not just the separate effects of zinc dimethacrylate alone and clay alone, but is in fact much greater than that. This is particularly surprising since clay itself provides little if any reinforcing effect on rubbery compounds.

The following examples are provided for the purpose of further illustrating the nature of the invention and are not intended to limit the scope thereof. Unless otherwise specified, the values are based on the weight tt'.

In these examples, vulcanizable TJ-capable polymer compositions of the present invention containing styrene-butadiene, zinc dimethacrylate, HAF carbon black, and a peroxide vulcanizing agent. was manufactured. Group J&' products containing the same components other than the zinc dimethacrylate component were also prepared for control purposes. The compositions were mixed in an electric mill without applying external heat. d1', the combined compositions were vulcanized and then tested for stress-strain properties. The composition, vulcanization conditions, and stress-strain properties of the composition are shown in Table 3.

MPa means megapascal.

(a) The Firestone Tire and Rubber
Viscosity of 50 (M at 2126F) containing 23.5% combined sutyrene available from
(b) Bis-(t-butylperoxy) diisopropyl peneylbenzene (2j These Examples Vulcanizable polymer compositions of the present invention containing styrene-butadiene rubber, zinc dimethacrylate, silica, an antioxidant agent, and a peroxide vulcanizing agent were prepared. Compositions containing the same ingredients other than the zinc methacrylate component were also prepared for control purposes.

- The above compositions were thoroughly mixed on an electric mill by applying external heat. The mixed compositions were vulcanized and then tested for stress-strain properties. The composition, vulcanization conditions and stress-strain properties of the composition are shown in Table II.

(a) Precipitated hydrated silica ('+) having a specific gravity of 2.0 available from PPG Inc., Inc. and having a specific gravity of 0.99 available from 22 Royal. Tri(nonylated phenyl)phosphite antioxidant Examples 7-17 of the present invention contain a synergistic combination of natural rubber and styrene-butadiene rubber and zinc dimethacrylate and clay. There are descriptions of polymer compositions capable of zero sulfurization.

In these examples, vulcanizable polymers of the invention containing styrene-butadiene comb, zinc dimethacrylate, clay, a peroxide vulcanizing agent, and an antioxidant. Compositions were prepared as in Examples 1-6, tempered, cured, and tested for stress-strain. For comparison purposes, A containing only zinc dimethacrylate (A) and only clay (13) using substantially the same process.
Control compositions designated as B and B were prepared, mixed, vulcanized, and tested for stress-hardness properties. The composition, vulcanization conditions, and stress-hardness properties of the composition are shown below.
Shown below.

As shown by Man-Yu in Part 1-1, the combination of lead in dimethacrylic acid and 1/- in dimethacrylic acid has the effect of the separate components alone on the strength of the vulcanized compositions of the present invention. It has been shown that the combination produced a synergistic effect on such properties, thereby enhancing the properties beyond the merely added criteria. Thus, for example, a composition containing 10 parts zinc dimethacrylate and 60 parts clay would have a vulcanization of about 6.8 MPa, if the effect of the combination was merely adding to the effect of the separate components. tensile strength (i.e.
Example At-3Jl: Combined tensile strength of B)
? It would have been predicted to show.

[7] As seen from Example 1O, this combination actually yields a vulcanized tensile strength of 16.2 MPa, whereby the combination synergistically increases the strength of the vulcanized composition. Compositions containing up to 9.10 parts of zinc dimethacrylate and 60 parts of clay were predicted to have a vulcanized tensile strength of up to 6.8 MPa. Will. However, as shown in Examples 7-9, compositions containing 2, 5,560 and 7.5 parts of zinc dimethacrylate in combination with 60 parts of clay were 1O17 and 1O17, respectively.
12,9 and 16,7MP a'cy) vulcanized tensile strength, thereby indicating that these combinations are also synergistic.

In these examples, vulcanizable rubbers of the present invention containing styrene-butadiene rubber, various standards of zinc dimethacrylate and clay, peroxide vulcanizing agents, and antioxidants are used. Polymer compositions were prepared as in Examples 1-6, mixed, vulcanized, and tested for stress-strain properties. For comparison purposes, controls, designated Examples C, D and E, containing only zinc dimethacrylate (C and D) and only clay (E) using substantially the same process. Compositions were prepared, mixed, vulcanized, and tested for stress-hardness properties. The composition, vulcanization conditions, and stress-hardness properties of the composition are shown in Table 1. As can be seen from the above data, dimethacrylic acid 111C
When the ship and clay are combined on a basis of 10 parts or more of zinc dimethacrylate and 60 parts or less of clay, the strength of the vulcanized compositions of the present invention is determined by simply adding the combined effects of the separate components alone. It has been shown that the combination produced a synergistic effect on such properties.

In these examples, vulcanizable polymeric compositions containing natural rubber (NR), zinc dimethacrylate, clay, and a peroxide vulcanizing agent are used. They were prepared, conditioned, vulcanized, and tested for stress-hardness as in Examples 1-6. For comparison [1] Control compositions, designated Examples F and G, containing only zinc dimethacrylate (F) and only clay (G) using substantially the same process. manufacturing, mixing, vulcanizing, and
Tested for stress-strain properties. The composition, vulcanization conditions and stress-strain properties of the composition are shown in Table V.

As can be seen from a comparison of Examples F and G with Example 16, the combination of 10 parts zinc dimethacrylate and 60 parts clay improves the strength of the vulcanized compositions of the invention as separate components. It has been shown that the effect of the combination alone was stronger than the merely added criteria, thereby indicating that the combination produced a synergistic effect on such properties. That is,
If the result is additive to Φ, then about 8 M P a
Although it would have been expected that only the pull of Example 16 would be obtained.
The tensile strength result was 12.8 MPa.

In these examples, a rubbery nitrile polymer (T
copolymer of butadiene and 7-crylonitrile as defined below), zinc dimethacrylate, clay, peroxide vulcanizing agent and antioxidant 1! Vulcanizable polymer compositions containing the agent were prepared as in Examples 1-6, mixed, vulcanized, and tested for stress-hardness properties. For comparison purposes, clay alone (H) and zinc methacrylate alone (H) were prepared using substantially the same formula.
Control compositions designated as H, J and K were prepared, mixed, vulcanized and tested for stress-hardness properties. The Ml composition, vulcanization conditions, and stress-hardness properties of the composition are shown in Table 1.

('a) Butadiene-acrylonitrile copolymer with acrylonitrile content of 32%, ratio Φ of 0.98 and ML4Q at 2127 of 50-60.

In the evaluation in Section 1-, the combination of zinc dimethacrylate and clay in a composition containing a butadiene-acrylonitrile copolymer did not appear to synergistically enhance the strength of the vulcanized composition. be.

In these examples, a vulcanizable polymer composition containing natural rubber, zinc dimethacrylate, clay, carbon black, a peroxide vulcanizing agent, and an antioxidant. The compositions, vulcanization conditions, and stress-strain properties of nine compositions prepared as in Examples 1-6, mixed, vulcanized, and tested for stress-strain properties are shown in Table 1.

(a) N-(1,3-dimethylbutyl)-N'-phenyl-para-phenylenediamine.

Examples 26-28 In these examples, vulcanizable polymer compositions containing styrene-butagenocom, zinc dimethacrylate, clay, silica, an oxide vulcanizing agent, and an oxidizing inhibitor. were prepared as in Examples 1-6A, kneaded, vulcanized, and tested for stress-hardness properties. Kerr strain properties are shown in Table ■.

Tororo Q Rororo's Nψ oo c3c3B6cm56 eJ
t4fflo.

Prisoner Low ω's To - ■ - One To Call 0 Rororo 0 Mute's Ro ■ To d Mouth c'cidL: i ml - 11 Prisoner Low V Prisoner To - ■ - Kuza 0 To Ro Sho 8 To - Ro
−Last p ζ 0 ≧ Φ.

Claims (1)

[Scope of Claims] 1. (a) A rubber-like polymer selected from the group consisting of natural rubber and a copolymer of a conjugated diene and at least one mo-olefin; (b) a '100 polymer; Approximately 2.5 coagulated parts per rubbery polymer
~20 parts by weight of zinc dimethacrylate having a surface area of from about 3.7 to about 5.4 m2/g or more; (c) from about 30 to about 70 parts by weight per 100 parts by weight of the rubbery polymer; , carbon black, clay, silica, mixtures of carbon black and clay, and mixtures of clay and silica;
and (d) a vulcanizable peroxide vulcanizing agent. 2. The copolymer contains up to 50% by weight of the monoolefin, based on the total weight of the copolymer. A composition according to claim 1. 3. The copolymer is a copolymer with a conjugated diene or vinyl aromatic hydrocarbon. A composition according to claim 1. 4. The composition according to claim 3, wherein the copolymer is a copolymer of butadiene and styrene. 5. The composition according to claim 1, wherein the copolymer is a copolymer of butadiene and 7-crylonitrile. 6. The composition of claim 1, wherein the zinc dimethacrylate has a surface area of 4.5 m2/g. 7. About 0°2 to 100 parts by weight of the rubbery polymer
Contains about 2.0 parts by weight of peroxide vulcanizing agent. A composition according to claim 1. 8. The peroxide vulcanizing agent is dicumyl peroxide or bis(
t-butylperoxy)diisobrobylbenzene, wherein the rubbery polymer is natural rubber and the copolymer has a combined content of 23.5%. The composition according to claim 1, which is a copolymer of styrene and butadiene containing styrene. 10. The composition of claim 1, wherein the copolymer is a copolymer of butadiene and acrylonitrile containing 32% by weight of acrylonitrile. 11, the rubbery polymer is natural rubber or a styrene-butadiene copolymer containing 23.5% bound styrene, the filler is clay, and where zinc dimethacrylate The composition of claim 1, wherein the combination of and clay synergistically increases the strength of the composition upon vulcanization. 12. The composition according to claim 11, wherein the peroxide vulcanizing agent is bis-(t-butylperoxy)diisopropylbenzene.