Binding polymer with metal and compounds and compositions suitable for it. RU patent 2513018.

FIELD: chemistry.

SUBSTANCE: invention relates to compositions of adhesive, suitable for binding polymer with metal and compounds used in them. Claimed are compounds of the structures given below , in which n has values 1-2; a equals 1-3 and b equals 0-2; but if a=3, b=0; if a=2, b=1; so that, at least, one alkoxy group is present; R¹ is selected from H and C₁-C₂ alkyl, and where, when a>1, at least, one of R¹ is not hydrogen; R² is selected from C₁-C₂ alkyl; X and Y can represent O; and R³ represents residue, containing nitrobenzene, quinone dioxime or quinone oxime. Also claimed are: oligomer of said composition, compositions for binding element with natural or synthetic caoutchouc, method of binding said substrates and obtained product.

EFFECT: possibility if obtaining caoutchouc/metal compound, long-lasting at relatively high mechanical tensions and atmospheric impact.

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THE LEVEL OF TECHNOLOGY

The technical field to which the invention relates

Describes the composition of adhesives suitable for use when linking polymer with metal, such as elastomer with metal, such as rubber with metal. One aspect provides connections, suitable for use in such applications adhesive compositions when bonding rubber to metal.

Short description of related technologies

Linking polymer with metal and, in particular, rubber to metal practised for many years. There are many uses of drugs that reach binding polymer or rubber to metal. Linking rubber with metal is widely used to associate various metals with natural or synthetic rubber. Linking polymer with metal carried out for many reasons.

One aspect of bonding rubber to metal is to combine structural strength of metal with elastomeric properties of rubber.

Accordingly, metals and polymers such as rubber, often associated with each other for applications in the absorption of shocks, such as in suspension, wheels, shock absorbers, floating head hard disks, and the like. Such components can be used in a very small scale, for example, in the components of personal computers, or on a very large scale, for example, in structures such as bridges and buildings. Noise reduction can be achieved through the use of binding of metal, with rubber. It is generally accepted that great efforts may be tested by any component that contains metal and rubber, linked together. Accordingly, it is desirable that a communication metal, with rubber, which can withstand considerable efforts such as squeezing or stretching pressure, including shock, without separation of metal or rubber from each other. There are many other applications linking rubber with metal, including the production of tyres, where the inner wire reinforcement for bus bound with rubber tires.

As a rule, provides for adhesive drug to link selected rubber selected metal substrate.

Traditional linking rubber with metal uses a two-stage system, where in the first stage put a first coat, and then in the second stage put the adhesive. Primer usually consists of solutions or suspensions of chlorinated rubber and phenol resins containing chemically active groups, and pigments, such as titanium dioxide, zinc oxide, carbon black, and the like. The primer is usually applied as a thin layer on the treated (cleaned) surface of a metal component, such as a component of processed steel, for example, a component that exposes sanding or chemically treated.

Adhesive, as a rule, consists of a wide range of rubber materials and agents for the cross-linkage. These include but are not limited to, chlorinated and bromchlormethane rubbers, aromatic nitrosobenzene connections and bismaleimide as agents for the cross-linkage, xylene, perchloroethylene and ethylbenzene as solvents, and some salts of lead or zinc. Adhesive layer, as a rule, represents the relationship between primed metal and rubber.

Common agents to cross links that are used in technology of linking rubber with metal, are aromatic nitroso compounds, such as p dinitrobenzoyl.

In many areas where the use of linking rubber with metal, there are numerous possibilities for solving different types of problems, including the strength and durability of communication, sample preparation and ease of adhesive application, the comparison of the systems with one and two components coating, reducing toxicity and improved properties in relation to the environment, among others.

There are many medications for bonding rubber to metal. For example, silanes are used as corrosion inhibitors and adhesion promoters when bonding rubber to metal. The decrease of VOC (volatile organic compounds) and reducing costs, such as costs associated with salts of cobalt, which are used as adhesion promoters in certain systems is desirable, for example, as shown in the following publications of patent applications in 2007 US/0056469A1 2005 and US/0079364A1, and US 6756079B2 and patent US 6409874. Specific noted silanes are bis(trimethoxytrityl)Amin and bis(threatexplorer)tetrasulfide, as a rule, when combined in a ratio of 1:3, respectively, in the solution of ethanol/water. It is clear that silanes, thus, hydrolyzed, either individually or together, before applying on the metal.

Publication of the International patent № WO 2004/000851, Qinetiq Ltd., describes how hydrolysis of silane with a good level of control. The method is realized in solution in the presence of water and catalyst. Publication of the International patent application (PCT) no WO 2004/078867, Lord Corporation, describes the adhesive solvent-based to one-component coating, designed to link thermoplastic elastomers containing adduct alkoxysilane/urethane, and chlorinated polymer. The methods of synthesis and preparation described in the patent document. US patent # 4031120, Lord Corporation describes the composition containing organosilane with isocyanate functional groups in combination with polyisocyanate and aromatic nitroso compound. The obtained system is described as an adhesive for the single-layer coating to link different elastomeric materials with metal and other substrates.

As a rule, it is desirable that the binding was achieved during step of vulcanization, similar to direct to pressing, injection pressing, casting under pressure and heat in the autoclave, for example, with the help of steam or hot air. For example, semi-solid rubber could be ejected in the form. Then semi-solid rubber cross sewn into a fully cured rubber and at the same time formed a relationship with the substrate.

Desirable are certain requirements to system hardening. These include easy handling, stability (for example, the exception sedimentation), easy application, fast drying (to make possible manipulation without pollution), good wetting properties and good durability during curing. Curing should be achieved regardless of the type of elastomer (rubber), and regardless of the type of substrate. It will be clear that some resins are mixed materials and, accordingly, are desirable in order for such mix of materials was achieved good cure. The appropriate cure is achieved at different parameters of the process. Durability is also desirable. For example, the connection rubber/metal must be durable, with a relatively high mechanical stresses, for example, at high pressure, and even when exposed to aggressive atmospheres, e.g. hot fluids, such as oil.

Despite the state of technology, it would be desirable to create a connection and compositions for associating polymer substrates with metal substrates that eliminate some or all of the known weaknesses of and/or creates an alternative to existing technologies, so that consumers have more choices.

Summary of the invention

Provides connection, suitable for use when linking rubber with metal.

In the first aspect is foreseen compound containing:

a) at least one alkoxysilanes balances; and

b) at least one remnant, chosen from aromatic nitroso or predecessor aromatic nitroso and their combinations.

The connection can contain:

a) at least one alkoxysilanes balances; and

b) at least one remnant, chosen from nitrosobenzene or predecessor of nitrosobenzene and their combinations.

In the context of this description, the term "balance of aromatic nitroso" refers to the aromatic balance with at least one nitroso group. Similarly, the term "precursor balance aromatic nitroso" refers to any connection that can be converted into balance aromatic nitroso at least one nitroso group. The term "aromatic" includes both condensed and unfused aromatic ring. For example, a non-limiting choice condensed and unfused aromatic residues nitroso covered by the present invention, is shown below:

As will be clear to the experts in this field, structure nitroso described above may not necessarily be replaced by one or more times, for example, at least one rest of the C 1-C 20 alkyl, C 1-C 20 cicloalchil, C 1-C 20 alkoxy, 6 C-C 20 Uralkali, 6 C-C 20 alcaria, 6 C-C 20 arylamine, 6 C-C 20 amilnitrit, cyano, amino, hydroxy, halogen and their combinations. Such substitution is possible, provided that they do not affect the binding or effective cure songs.

These connections help in the formation of relations rubber with metal. They can easily be applied to the boundary between the rubber and metal, and assisting in the development of durable and long-lasting relations during the curing process.

In contrast to conventional systems, adhesives under the present invention can be applied to devulcanizing rubber (unlike metal) before vulcanization and bond formation, and the subsequent vulcanization is the connection. This means that the system adhesives can be applied either rubber or metal substrate. Basic form of communication, if applied in such a way.

The predecessor of the balance of aromatic nitroso can include any aromatic oxime, aromatic dioxin and their combinations. For example, the predecessor of the balance aromatic nitroso can be a mono - or dioxin connection, selected from the group consisting of:

As will be clear to the experts in this field, diatomovye patterns described above may not necessarily be replaced by one or more times, for example, at least one rest of the C 1-C 20 alkyl, C 1-C 20 cicloalchil, C 1-C 20 alkoxy, 6 C-C 20 Uralkali, 6 C-C 20 alcaria, 6 C-C 20 arylamine, 6 C-C 20 amilnitrit, cyano, amino, hydroxy, halogen and their combinations. Such substitution is possible, provided that there is no impact on the effective linking or cure songs, for example, by generating aromatic nitroso compounds in situ .

The remainder of aromatic nitroso compounds according to the present invention may contain nitrosobenzene the rest. Nitrosobenzene the rest can be mononitrotoluenes, dinitrobenzoyl or their combinations. Similarly, the predecessor of the balance aromatic nitroso compositions of the present invention may contain predecessor nitrosobenzene balance. The predecessor of nitrosobenzene can be a predecessor of mononitrotoluene, the predecessor of dinitrobenzene or their combinations. It will be clear that the predecessor of nitrosobenzene can form the structure of nitrosobenzene in situ . The predecessor of nitrosobenzene can at least be a one connection from chinondiimine or chinaexim. Found that these structures help in the formation of the desired links.

As will be clear to the experts in this field, links to nitrosobenzene residues and predecessors nitrosobenzene residues include nitrosobenzene residues and predecessors nitrosobenzene residues that may not necessarily be replaced by one or more times, at least one rest of the C 1-C 20 alkyl, C 1-C 20 cicloalchil, C 1-C 20 alkoxy, 6 C-C 20 Uralkali, 6 C-C 20 alcaria, 6 C-C 20 arylamine, 6 C-C 20 amilnitrit, cyano, amino, hydroxy, halogen and their combinations. Such substitution is possible, provided that there is no impact on the effective linking or cure songs. For example, assuming that it has no influence on the generation nitrosobenzene balance in situ.

Silane the remainder may have a structure:

where 'a' can be a 1-3 and 'b' can be a 0-2, but if a=3, b=0; or if a=2, b=1; so that there is at least one alkoxy group;

R 1 can be selected from the group consisting of H, C 1-C 24 alkyl, C 3-C 24 acyl, preferably, from the C 1-C 4 alkyl;

where, when a & GE; 1, at least one of the R 1 is not a hydrogen; and

R 2 can get out of C 1-C 24 alkyl and C 3-C 24 acyl, preferably, from the C 1-C 4 alkyl.

In one of the variants of implementation, a is 3 and R 1 is a C 1-C 24 alkyl. R 1 can be a C 1-C 4 alkyl and a can be equal to 3.

Connections can be a reaction products obtained from isocyanate or isothiocyanate and active compounds of hydrogen, such as-NH x (where x=1 or 2), -SH or-OH. Thus, the described connections must contain at least one connection is described as:

where X can be a S or O, and Y includes-NH x (where x=1 or 2), -S, or-O.

The General structure of these compounds are shown below:

where 'a' can be a 1-3 and 'b' can be a 0-2; but if a=3, b=0; or if a=2, b=1; so that there is at least one alkoxy group;

R 1 can be selected from the group consisting of H, C 1-C 24 alkyl, C 3-C 24 acyl, preferably, from the C 1-C 4 alkyl, and where, when a & GE; 1, at least one of the R 1 is not a hydrogen; and

R 2 can get out of C 1-C 24 alkyl and C 3-C 24 acyl, preferably, from the C 1-C 4 alkyl;

n can be a 1-5;

X can be a O or S;

Y can be a-O-S, or-NH x (where x=1 or 2); and

R 3 represents the balance that contains nitrobenzol, kinondoni or chinaexim.

R 3 can be a residue containing nitrosoanabasine balance or predecessor nitrosoamines balance, as defined in this document.

Patterns R 3 , showing us through 'Y'may include:

where Z shows that rings the above structures, may not necessarily be mono-, di-, tri -, or Tetra-substituted by a group of alkyl, cicloalchil, alkoxy, Uralkali, alcaria, arylamine, amilnitrit, amino, hydroxy, halogen and their combinations, and, in addition, where deputies on each carbon atom in the ring can be either equal or different. Such substitution may be possible, provided that there is no impact on the effective linking or cure songs. For example, assuming that it has no influence on the generation nitrosobenzene connection in situ .

The connection of the present invention may have a common structure:

where n can be a 1-5;

'a' can be a 1-3 and 'b' can be a 0-2; 'a' can be a 1-3 and 'b' can be a 0-2; but if a=3, b=0; or if a=2, b=1; so that there is at least one alkoxy group;

R 1 can be selected from the group consisting of H, C 1-C 24 alkyl, C 3-C 24 acyl, preferably, from the C 1-C 4 alkyl, and where, when a & GE; 1 at least one of the R 1 is not a hydrogen; and

R 2 can get out of C 1-C 24 alkyl and C 3-C 24 acyl, preferably, from the C 1-C 4 alkyl.

X can be a O or S;

Y can be a-O-S, or-NH x (where x=1 or 2).

R 1 can be selected from the group consisting of C 1-C 24 alkyl, C 3-C 24 acyl. R 1 can be selected from the group consisting of C 1-C 24 alkyl, C 3-C 24 acyl, and 'a' can be equal to 3. X can represent O. Y can be an O or-NH x (where x=1). R 1 can get out of C 1-C 4 alkyl, X can be a O and 'a' is equal to 3. R 1 can get out of C 1-C 4 alkyl, X can be a O Y can be an O and 'a' can be equal to 3. R 1 can get out of C 1-C 4 alkyl, X can be a O Y can be a-NH x (where x=1) and 'a' can be equal to 3. R 1 can get out of C 1-C 4 alkyl, X can be a O Y may constitute O n can be equal to 3 and 'a' can be equal to 3.

In another aspect of the present invention provides oligomeric and cooligomers compounds consisting of monomers containing:

a) at least one alkoxysilanes balances; and

b) at least one remnant, chosen from aromatic nitroso or predecessor aromatic nitroso and their combinations, where cooligomers connection consists of various monomers.

Oligomeric and cooligomers connection can be made up of monomers, including:

a) at least one alkoxysilanes balances; and

b) at least one remnant, chosen from nitrosobenzene or predecessor of nitrosobenzene and their combinations.

Such oligomeric and cooligomers connection can have the General formula:

where m can be a 1-100; n can be a 1-5; p can be a 1-5; q can be a 0-50; and if q=0, m & GE; 2;

R 1 can be selected from the group consisting of H, C 1-C 24 alkyl, C 3-C 24 acyl, and preferably, from the C 1-C 4 alkyl;

R 2 can be selected from the group consisting of OR 1 , C 1-C 24 alkyl and C 3-C 24 acyl, and where, when R 2 =OR 1 , at least one of the R 1 is not a hydrogen;

R 4 can be selected from the group consisting of acrylate, aldehyde, amino, anhydride, azide, maleimide, carboxylate, sulfonate, epoxide, ester functional group, halogen, hydroxyl, isocyanate or blocked isocyanate functional groups sulfur, vinyl and olefinic functional group or polymeric structures;

X can be a O or S;

Y can be a-O-S, or-NH x (where x=1 or 2); and

R 3 represents the balance that contains nitrobenzol, kinondoni or chinaexim.

R 3 can be a residue containing nitrosoanabasine balance or predecessor nitrosoamines balance, as defined in this document.

R 1 can be selected from the group consisting of C 1-C 24 alkyl, C 3-C 24 acyl. R 1 can be selected from the group consisting of C 1-C 24 alkyl, C 3-C 24 acyl and R 2 may constitute OR 1 . X can represent O. Y can be an O or-NH x (where x=1). R 1 can get out of C 1-C 4 alkyl, X can be a O R 2 may constitute OR 1 . R 1 can get out of C 1-C 4 alkyl, X can be a O Y can be a O R 2 may constitute OR 1 . R 1 can get out of C 1-C 4 alkyl, X can be a O Y can be a-NH x (where x=1 and R 2 may constitute OR 1 . R 1 can get out of C 1-C 4 alkyl, X can be a O Y may constitute O n can be equal to 3, R 2 may constitute OR 1 and 3 can be a remnant, containing nitrobenzol. R 1 can get out of C 1-C 4 alkyl, X can be a O Y may constitute O n can be equal to 3, R 2 may constitute OR 1 , R 3 can be a residue containing nitrobenzol, q can be 0, and m can be > 2. R 1 can get out of C 1-C 4 alkyl, X can be a O Y may constitute O n can be equal to 3, R 2 may constitute OR 1 , R 3 can be a residue containing nitrobenzol, q can be 0, m can be > 2, and R 4 can be a vinyl or ester.

Specific examples of the compounds according to the present invention comprise the following:

The reaction scheme for the synthesis of (A) below (all connections get a similar way).

It will be clear that the composition suitable for bonding of metal, with rubber, can be prepared with appropriate quantities of one or more of these so compounds.

Accordingly, it is also envisaged composition to tie together substrates, where the composition contains:

(i) at least one compound containing;

a) at least one alkoxysilanes balances; and

b) at least one remnant, chosen from aromatic nitroso or predecessor aromatic nitroso and their combinations; and

(ii) the appropriate media for the connection. Be clear, that can be used by any usable media. Is desirable that the media has been good for the environment. Such compositions are suitable for use when binding of the substrate, such as a metal substrate, with natural or synthetic rubber.

Composition for binding of the substrate together can contain

(i) at least one compound containing;

a) at least one alkoxysilanes balances; and

b) at least one remnant, chosen from nitrosobenzene or predecessor of nitrosobenzene and their combinations; and

(ii) the appropriate media for the connection.

Compound containing at least one alkoxysilanes balance and at least one remnant, chosen from aromatic nitroso or predecessor aromatic nitroso, there could be a number from 1 to 20% of the mass/mass from the composition as a whole. Accordingly, at least one predecessor aromatic nitroso compounds may be present in quantities ranging from 1 to 15% of the mass/mass, for example, from 4 to 12% of the mass/mass. At least one predecessor aromatic nitroso compounds may be present in 6% of the mass/mass from the composition as a whole.

The compositions of the present invention may be useful in all applications where it is desirable formation of aromatic nitroso balance in situ . Similarly, the compositions of the present invention can be useful in any application where is desirable formation of the balance of aromatic dinitroso in situ . It will be clear that in these compositions connection can interact in situ with the formation nitrosobenzene balance. It is also assumed that the connection can interact in situ with the formation dinitrobenzene balance. For example, for especially good link may be desirable that the connection is engaged in situ with the formation of vapor-nitrosophenol balance.

The compositions of the present invention can be a composition consisting of a single part. The compositions of the present invention can be a composition of two parts.

Also provides a way to link the two substrates together, including the application described thus compositions on the surface binding, at least one of the substrates and surfaces bind substrates together. For example, the first substrate may consist of natural or synthetic rubber, which must contact another substrate. Another of the substrate can be a metal substrate. As a rule, alkoxysilanes the remainder of the connection is fixed on a metal surface. A remnant, chosen from aromatic nitroso or predecessor aromatic nitroso will, as a rule, to gain a foothold on the rubber. Similarly, a remnant, chosen from nitrosobenzene or predecessor of nitrosobenzene, as a rule, it will be fixed on the rubber. Accordingly, each of the ends of the molecule is functionalized and helps with binding materials with the help of strong and durable connection.

Thus, metal, covered with adhesive composition, such as described, can stick to the polymer material, for example in the composition of the rubber, through the application of a polymeric material uncured able to metal coated with adhesive composition, and curing polymer material on it to link it with the metal. In the case of rubber polymer material uncured rubber can vulcanized using heat and pressure for some period of time for curing rubber, which leads to the binding of rubber with metal.

Such linking with metals is achieved by nitroso groups that can interact with polymers, in particular, polymer with alkanova/allneu functional group in the polymer chain. For example, with diene or allneu functional group in the polymer chain. This reaction produces various cross-linking, for example, between nitrosgroup and material rubber. The materials of the present invention, considered to restore available nitrosgroup when nitroso the group is in the molecular structure. When interacting nitroso and silane, nitroso interacts with alkanova functional group in natural rubber, while silane forms a bond with the metal.

Dinitrobenzoyl, as you know, is a very effective agent for the cross-linkage in adhesive products, and often leads to links which are of high standing durability and high resistance to aggressive media. However, unreacted free nitrozomocevina, such as dinitrobenzoyl, can cause the continuation of vulcanization in the case of composition after the heat treatment, which leads to undesirable increase the fragility of communication. For those cases in the implementation of the present invention which do not provide for the release of dinitrobenzene, the latter problem can be facilitated by the fact that the reaction product nitroso and silane should not contain free nitrozomocevina, such as dinitrobenzoyl and thus should not be subject to additional vulcanization. Reducing the hazards associated with conventional systems is also important.

Combination silanes can be used in the present invention. For example, one or more additional silanes can be included in the composition of the present invention. These silanes, as a rule, have the formula:

where: n is either 1 or 2;

each R 1 can get out of C 1-C 24 alkyl or 2 C-24 C acyl;

each R 2 can get out of C 1-C 30 aliphatic groups, substituted C 3-C 30 aromatic groups or unsubstituted C 3-C 30 aromatic groups;

R 5 may get out of hydrogen, C 1-C 10 alkylene,

C 1-C 10 alkylene, substituted by one or more amino groups, C 2-C 10 Alcanena, substituted by one or more amino groups, 6 C-C 10 ariline or 7 C-C 20 alkylsilane;

X is optional and is either:

where each R 3 can get out of hydrogen, C 1-C 30 aliphatic groups or 6 C-30 C aromatic groups; and

R 4 can get out of C 1-C 30 aliphatic groups or 6 C-30 C aromatic groups; and where, when n=1, at least one balance of R 3 and R 5 is not hydrogen.

In one of the options for the implementation of X is present. As will be clear, when X is missing, silane can have the General formula:

Preferred silanes include bis-silisili, such as those that have two trizamyescyennykh silyl groups. These deputies can be individually get out of C 1-C 20 alkoxy, 6 C-C 30 aryloxy and 2 C-30 C, acyloxy. Appropriate bis-Silesian for use in the present invention comprise:

each R 1 can get out of C 1-C 24 alkyl or 2 C-24 C acyl;

each R 2 can be selected from the group consisting of C 1-C 20 aliphatic groups or 6 C-30 C aromatic groups;

X is optional and is either:

where each R 3 can get out of hydrogen, C 1-C 20 aliphatic groups or 6 C-30 C aromatic groups; and

R 4 can get out of C 1-C 20 aliphatic groups or 6 C-30 C aromatic groups.

In one of the options for the implementation of X is present. As will be clear, when X is missing, bis-silane can have the General formula:

Some examples bis-selyaninova covered by the present invention, includes: bis(trimethoxysilyl)Amin, bis(triethoxysilane)Amin, bis(triethoxysilane)ethylene diamine, N-[2-(vinylbenzene)ethyl]-3-aminopropyltrimethoxysilane, and aminoatil-aminopropyltrimethoxysilane. Such additional silanes can be entered in the range from 1:3 to 3:1 in relation to the compounds according to the present invention. Such a mix can lead to the formation of excellent bonding rubber to metal.

In particular, the introduction of amino bis(propyltrimethoxysilane) in addition to nitrosoaniline significantly improves the durability of connection of rubber with metal. It is believed that amino bis(propyltrimethoxysilane) has many features in the product. These include the facilitation of crust and "wetting" metal surface.

Silane may be present in quantities of 1 to 10% of the mass/mass from the composition as a whole. Accordingly, silane may be present in quantities of 1 to 5% of the mass/mass, for example, from 1 to 3% of the mass/mass. Silane may be present at 3% of the mass/mass from the composition as a whole.

The significant difference between the present invention and the prior art is that in the present invention silanes can be "sufficiently non-hydrolyzed", which means that they are used in non-hydrolyzed condition. It occurs because the materials can be applied in themselves and/or without any presence of water.

Aminosilan(s) and nitrosation(s) can be independently either hydrolyzed and/or mixed and either hydrolyzed with the formation of the final solution of silane. 5% aqueous solutions are generally sufficient to ensure that the hydrolysis of silanes. Alternative silanes can be added to the pure solvent, used as received, without adding water intended to facilitate hydrolysis.

Excellent adhesion between the polymer materials such as compositions of rubbers, and metals with minimum loss of silane solution can be implemented through the use of compounds and compositions as described. At the mention of their use in adhesive applications, the compositions of the present invention, as a rule, have thinner than the songs that are present in traditional systems, adhesives for bonding rubber with metal, without any loss of performance. The thickness of the composition can be determined by the concentration of the reaction product nitroso and silane, and she is in the range from 0.1 to 12 microns, and more preferably, in the range from 0.5 to 10 microns.

Many different metals can be processed using the compositions described in the present invention, and can communicate with the polymer materials. These metals include, but are not limited to, zinc and zinc alloys such as zinc alloys, Nickel and zinc, cobalt, metal substrate with a zinc coating, steel and, in particular, and cold-rolled carbon steel, aluminum and aluminum alloys, copper and copper alloys such as brass, and tin, and alloys of tin, including metal substrate with coating containing tin.

Detailed description

The composition of the rubber involved in linking rubber to metal with the use of these methods on the present invention may additionally include additives known, usual for the compositions of rubbers. They include reinforcing carbon soot; inactive fillers such as carbonates of calcium, chalk, talc or metal oxides; system of accelerators; moderators vulcanization; promoters, such as zinc oxide or stearic acid; plasticizers such as aromatic, paraffin, naphthenic mineral and synthetic oils; sostarivayut, black sonataside, protivopolozhnye tinted and technological auxiliary substances and sulfur. Usually these additives may be present in quantities ranging from about 0.1 to about 80 parts per 100 parts of the mass of the composition of the rubber.

Hydrolysis, education silanol groups, i.e. SiOH, as a rule, is carried out effectively in the pH range of 3 to 7. At pH below or above this range, condensation may form on silane through a process where silanol combined with caffeine semicondensed with the formation of siloxane. During this process of hydroxyl molecules neighboring molecules interact with each other with elimination of water molecules and with the formation of cross stitched siloxane structures containing functional group-Si-O-Si-O-Si.

To accelerate the hydrolysis of silane and inhibition of condensation of silane during the stage of hydrolysis, the pH of the solution of silane can be maintained below approximately 7 and, preferably, in a moderately acidic range from about 4 to 6.5 (especially during the hydrolysis bis-silyl of aminosilanes). This can be accomplished by adding one or more compatible acids. For example, organic acids such as acetic acid, oxalic acid, formic acid, propionic acid, can be added to gidroliznaya solution for establishing pH. Sodium hydroxide or other compatible bases can also be used, if necessary, to increase the pH of the solution of silane. Some silanes give a solution with moderately acidic pH, when mixed with water, and may not require pH adjustment to accelerate the hydrolysis. Don't confuse the pH ranges discussed in connection with the preparation gidroliznaya silane solutions with a pH of the final solution of silane, which is applied on metal substrate.

Gidrolizuemye solutions silane can optionally contain one or more compatible solvents. To solubilize and hydrolysis silanes, as a rule, use alcohol. The corresponding alcohols include, without limitation, methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol and aliphatic alcohols with a longer chain. The ratio of water to the solvent in the solution hydrolyzed silane (as applied on metal substrate, by volume) can be in the range between about 1:99 and about 99:1, and preferably between 1:1 and 1:20.

Before solution drawing silane, the metal surface, which must be applied coating, can be purified to allow better adhesion. For example, cleaned with a solvent or alkaline materials. Then may be applying through various means, including immersion, spray, brush or cloth solution for the metal. It is suggested that to improve the adhesion of rubber coating remained partially cross stitched up vulcanization. For this reason, the cover is usually air-dried at room temperature because the heat drying can cause a higher degree of cross-linking, which will lead to poor adhesion between the rubber and the metal surface.

The connection of the present invention are given as below.

Examples

Connections A, B, C and D (above) synthesize, in accordance with the following experimental procedure, and as illustrated in the diagram of the reaction, above.

Reaction (2) : g-Isocyanatopropyltrimethoxysilane (GE Bayer Silicones A-1310) (2,35 g, 9,5 mmol) solvation in 10 ml of anhydrous THF in a 50 ml round-bottom flask. The reaction vessel is washed with nitrogen and load N,N-bis(2-hydroxyethyl)-4-nitroso-aniline (2 g, 9.5 mm), and then catalytic number dibutilsul of dilaurate (1.5 mmol). The reaction mixture was heated under reflux for an additional 2 hours in an atmosphere of nitrogen. Spending isocyanate (2275 cm-1 ) monitor using infrared spectroscopy. The solvent is removed under reduced pressure, with the obtaining of a product with a quantitative yield.

Response 3: g-Isocyanatopropyltrimethoxysilane (ABCR GmbH) (1.5 grams of 7.3 mmol) solvation in 8 ml of anhydrous THF in a 50 ml round-bottom flask. The reaction vessel is washed with nitrogen and load N,N-bis(2-hydroxyethyl)-4-nitroso-aniline (1,53 g 7,3 mmol), and then catalytic number dibutilsul of dilaurate (1 Microm). The reaction mixture was heated under reflux for an additional 2 hours in an atmosphere of nitrogen. Spending isocyanate (2275 cm-1 ) monitor using infrared spectroscopy. The solvent is removed under reduced pressure, with the obtaining of a product with a quantitative yield.

Response 4: g-Isocyanatopropyltrimethoxysilane (GE Bayer Silicones A-1310) (2,35 g, 9,5 mmol) solvation in 10 ml of anhydrous THF in a 50 ml round-bottom flask. The reaction vessel is washed with nitrogen and load N,N-bis(2-hydroxyethyl)-4-nitroso-aniline (1 year, 4,75 mm), and then catalytic number dibutilsul of dilaurate (1.5 mmol). The reaction mixture was heated under reflux for an additional 5 hours in an atmosphere of nitrogen. Spending isocyanate (2275 cm-1 ) monitor using infrared spectroscopy. The solvent is removed under reduced pressure, with the obtaining of a product with a quantitative yield.

Reaction 5: g-Isocyanatopropyltrimethoxysilane (GE Bayer Silicones A-1310) (for 10.68 g, 43,18 mmol) solvation 30 ml anhydrous THF in 100-ml round-bottom flask. The reaction vessel is washed with nitrogen and download p-benzochinonomonoimino (Sigma-Aldrich) (3 g, 21,72 mmol), and then catalytic number dibutilsul of dilaurate. The reaction mixture was heated under reflux for an additional 5 hours in an atmosphere of nitrogen. Spending isocyanate (2275 cm-1 ) monitor using infrared spectroscopy. The solvent is removed under reduced pressure, with the obtaining of a product with a quantitative yield.

Preparations containing compounds of the present invention, prepare, as defined below, where connections A-C are compounds according to the present invention, as set out above under the essence of the invention. Connection E is a bis(trimethoxysilyl)Amin is commercially available from Sigma Aldrich. Connection E is a formula:

Composition of natural rubber

Research carried out with the use of natural rubber is the next song:

Ingredient

Part of the mass

Natural rubber (a)

Zinc oxide

Stearic acid

Carbon black (b)

Naphthenic oils (low viscosity) (c)

l,2-dihydro-2,2,4-trimethylquinoline (d)

N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (e)

Hydrocarbon waxes (f)

(a) NR SMR CV 60; (b) SRF N762 black; (c) Oil Strukthene 410; (d) Flectol H; (e) Santoflex 13 (HPPD); (f) Sunproof Improved Wax; (g) the vulcanization Accelerator, N-cyclohexyl-2-benzothiazole.

The composition of EPDM rubber

Research is conducted by using rubber EPDM of the next song:

Ingredient

Part of the mass

Ethylene-propylene-ethylidene norbornene (7,8% Dien) (a)

Ethylene-propylene-ethylidene norbornene (9,0% Dien) (b)

Ethylene-propylene-Dicyclopentadiene (10.5% of Dien) (c)

Carbon black

Calcium oxide

Stearic acid

Zinc oxide

Dicumyl peroxide (d)

Polyethylene (e)

(a) Buna EP G 3850; (b) Buna EP G 3963; (c) Trilene 65; (d) Dicup 40C; (e) Carbowax 400

Songs used when linking natural rubber to metal

Composition

Part of the drug, % mass

are 5.36

VINYLTRIMETHOXYSILANE

Hypalon 40s (b)

Pergut (c)

Xylene (d)

Isopropanol (d)

shed 15.37

Ethanol:water (e)

Acetic acid

% gaps rubber

a) Bis(trimethoxysilyl)Amin; (b) Chlorsulfonated polyethylene (DuPont Performance Elastomers); (c) Chlorinated rubber (Bayer MaterialScience); (d) Use as obtained; (e) Ethanol:water (95:5) adjusted to pH 4-5 using acetic acid

Songs used when linking EPDM rubber with metal

Composition

Part of the drug, % mass

Hypalon 40S (a)

Xylene (b)

Aerosil 200 (c)

Heucophos ZPA (d)

are 5.36

GP205 (e)

of 14.28

Elaztobond A250 (f)

% gaps rubber

(a) Chlorsulfonated polyethylene (DuPont Performance Elastomers); (b) Use as received; (c) Hydrophilic colloid silicon oxide; (d) Zinc - aluminium phosphate hydrate; (e) N,N'-4,4'-difenilmetana bismaleimide; (f) Rezol resin.

Research

To assess the effectiveness of the system adhesives under the present invention when linking rubbers with surfaces of metals, carry out a number of studies in accordance with ASTM 429-B when the angle of 45 degrees. Metal substrate (panel or plate width 2.54 cm (1 inch)in length 10.16 cm (4 inches) covered with adhesive and stick together with natural rubber vulcanization method. Compositions of natural rubber are cured with the help of sulfur composition, as shown in tables cooking.

Metal substrate clean ultrasound in automatic cleaning device in aqueous alkaline solution, washed with deionized water and dried with blowing hot air. The substrate can also be sandblasted using the appropriate abrasive agent.

Before applying the adhesive, areas long 2.54 cm (1 inch) wide and 2.54 cm (1 inch) on both edges of the metal plates mask to exclude the availability of this site to link with rubber, leaving the Central section of width 2.54 cm (1 inch) and a length of 5.08 cm (2 inches) available for linking with rubber.

If the bind operation of the present invention, compositions are applied on metal substrates using either way immersion, spray or brush application, to provide uniform coverage, preferably after the substrate to be cleaned.

Drying can be done with environmental conditions, that is at room temperature. The rate of evaporation of the solvent can be increased by using heat, air injection or as the one and the other.

Then layer uncured rubber is placed on each plate and utverjdayut in the standard hydraulic vulcanizing press, within the time period specified in the profile curing rubber. In the case of natural rubber is used in a way to link the present invention, rubber utverjdayut for 20 minutes at 150 C at a pressure of 20-30 tons, to ensure firm contact surfaces that contact, and adhesive.

After curing related samples sostarivayut within 24 hours at room temperature before they are subjected to investigation and note the structure of the gap. Each sample shall be examined in accordance with modified ASTM 429-B with a 45-degree angle using the research equipment Instron (Instron tester, Model No. 5500R) when stationary load speed of 50 mm per minute to complete the separation.

"Floor rubber" represents the percentage of rubber, remaining on the associated metal substrate after research of exfoliation. 100% gaps rubber means that the rubber is completely torn without damage any part of rubber from the metal surface (and equivalent to 100% of the gap rubber).

As a rule, it is desirable that the rubber underlay torn to disconnect metal to rubber. The result of reach for some drugs, as above.

The words "contains/containing" and the words "having/including"when used here with links to the present invention, are used to indicate the presence of these features, integers, stages or components, but not to exclude the presence or adding one or more other signs, integers, stages, component or their groups.

It is clear that certain features of the present invention, which for clarity are described in the context of individual variants of implementation may also be prescribed in combination, in one embodiment. On the contrary, the various signs of the present invention, which, for clarity, are described in the context of one variant of implementation, can also be provided separately or in any usable podrozetniki.

1. The connection is covered by the General structure:

where n can be a 1-2; 'a' can be equal to 1-3 and 'b' can be equal 0-2; but if a=3, b=0; or if a=2, b=1; so that there is at least one alkoxy group; R 1 can be selected from the group consisting of N and C 1-2 of alkyl, and where, when and > 1 at least one of the R 1 is not a hydrogen; R 2 can be selected from C 1-C 2 alkyl; X can represent About; Y can represent About; and R 3 represents the balance that contains nitrobenzol, kinondoni or chinaexim.

2. Compound according to claim 1, where R 3 choose from the group consisting of (showing the link through Y):

where Z shows that ring the above patterns may not necessarily be mono-, di-, tri -, or Tetra-substituted by a group of alkyl, cicloalchil, alkoxy, Uralkali, alcaria, arylamine, amilnitrit, amino, hydroxy, halogen and their combinations, and, in addition, where deputies on each carbon atom in the ring can be either equal or different.

3. Oligomer or cooligomers compound according to claim 1.

4. Oligomer or cooligomers according to the item 3, which has a total structural formula:

where m can be a 1-100; n can be a 1-2; p can be a 1-5; q can be a 0-50; and if q=0, m & GE; 2 R 1 can be selected from the group consisting of N and C 1-C 2 alkyl; R 2 can be selected from a C 1-2 of alkyl; R 4 can be selected from the group consisting of acrylate, aldehyde, amino, anhydride, azide, maleimide, carboxylate, sulfonate, epoxide, ester functional group, halogen, hydroxyl, isocyanate or blocked isocyanate functional groups sulfur, vinyl and olefinic functional group or polymeric structures; X can represent About; Y can represent About; and R 3 represents the balance that contains nitrobenzol, kinondoni or chinaexim.

5. Composition for use when linking metal with natural or synthetic rubber, containing: (i) at least one connection indicated in paragraph 1; and (ii) the appropriate media for the specified connection.

6. The composition according to claim 5, in which the specified connection can interact in situ with the formation of nitrosobenzene balance, dinitrobenzene balance or para-nitrosophenol balance.

7. The composition according to claim 5, additionally contains a silane.

8. The composition according to claim 7, in which silane is aminosilan.

9. A way to link the two substrates together, including the application of the composition according to claim 5; at least one of the substrates and information substrates together, where the first liner contains natural or synthetic rubber, which must get in touch with the second substrate, and the second is a metal substrate the substrate.

10. The method of claim 9, in which the rubber underlay cured, or is subject to cross-linking of before binding to the surface of the metal.

11. The method of claim 9, where rubber is cured, or is subject to cross-linking simultaneously with the binding to the surface of the metal.

12. The combination of at least two substrates are connected together using adhesive composition according to claim 5, where the first liner contains natural or synthetic rubber, which must get in touch with the second substrate, and the second is a metal substrate the substrate.

13. Product curing containing substrate and the composition according to claim 5, where the first liner contains natural or synthetic rubber, which must get in touch with the second substrate, and the second is a metal substrate the substrate.