HK1067141A - Adhesive compositions - Google Patents

Description

Adhesive composition

Technical Field

The present invention relates to an adhesive polymer composition comprising at least one, optionally hydrogenated, nitrile rubber polymer having a Mooney viscosity (ML1+4, 100 ℃) of less than 30, optionally at least one filler and optionally at least one cross-linking agent, to a process for the preparation of said polymer composition wherein at least one, optionally hydrogenated, nitrile rubber polymer having a Mooney viscosity (ML1+4, 100 ℃) of less than 30, optionally at least one filler and optionally at least one cross-linking agent are mixed, and to a self-supporting shaped article comprising said composition optionally laminated or interposed between one or more supports. In another aspect, the invention also relates to an adhesive tape comprising said adhesive polymer composition optionally laminated or interposed between one or more supports. In yet another aspect, the invention also relates to sealant compositions containing the adhesive polymer compositions.

Background

Hydrogenated nitrile rubber (HNBR), which is prepared by selective hydrogenation of acrylonitrile-butadiene rubber (nitrile rubber; NBR, a copolymer containing at least one conjugated diene, at least one unsaturated nitrile and other optional comonomers), is a specialty rubber which has very good heat resistance, excellent ozone and chemical resistance and excellent oil resistance. Due to the excellent mechanical properties (in particular abrasion resistance) of the rubber, it is not surprising that NBR and HNBR find widespread use in the automotive industry (sealants, hoses, bushings), oil production (stators, well sealers, valve disks), electrical (cable sheathing), mechanical engineering (rollers, pulleys) and shipbuilding (pipe sealants, couplings), among other industries.

The Mooney viscosity of the commercially available HNBR is in the range from 55 to 105, the molecular weight is in the range from 200,000-500,000g/mol, the polydispersity is greater than 3.0 and the Residual Double Bond (RDB) content is in the range from 1 to 18%, determined by IR spectroscopy.

One limitation in HNBR processing is the relatively high mooney viscosity. In principle, HNBR having a lower molecular weight and a lower Mooney viscosity will have better processability. Attempts have been made to reduce the molecular weight of polymers by mastication (mechanical breakdown) and chemical methods (e.g., the use of strong acids), but such methods have the disadvantage of introducing functional groups (e.g., carboxyl and ester groups) into the polymer and altering the microstructure of the polymer. This results in deterioration of polymer properties. In addition, due to its characteristics, the molecular weight distribution of the polymer produced by the method is wide.

It is difficult to manufacture hydrogenated nitrile rubbers having the same microstructure as commercially available rubbers of this type, a low Mooney viscosity (< 55) and improved processability using current technology. Hydrogenation of NBR to produce HNBR results in an increase in the Mooney viscosity of the base polymer. The Mooney growth rate (MIR) is typically about 2, which depends on the polymer grade, the degree of hydrogenation and the properties of the feedstock. Furthermore, limitations associated with the production of NBR by itself dictate the low viscosity range of the HNBR feedstock. One of the lowest commercially available products is currently Therban  VP KA8837 (commercially available from Bayer), which has a Mooney viscosity of 55(ML1+4, 100 ℃) and an RDB of 18%.

The pending applications CA-2351961, CA-2357470, CA2350280 and CA 2357465 disclose a low Mooney NBR and HNBR and methods for making the NBR and HNBR. Although the disclosed NBR or HNBR is well suited for the present invention, the application does not disclose compositions containing the low-Mooney NBR and/or HNBR and methods of producing shaped articles from the low-Mooney NBR and/or HNBR.

An adhesive (glue) is a substance that can form and maintain an adhesive bond between two surfaces, while a sealant material (caulk) is a substance that is used to fill the gap or joint of two-part materials to prevent the passage of liquids, solids, or gases. Because a given formulation often has two functions, these two materials are often considered together.

The sealant material can be used as a single-component solvent volatilization curing product and a thermoplastic hot melt. Without a curing process, the compound acts by removing the solvent and/or lowering the temperature. When the sealant material is used, the solvent evaporates or enters the porous mass, leaving the hard, rubbery compound in place. This is in contrast to other chemically cured sealant material types.

Disclosure of Invention

In one aspect, the present invention relates to an adhesive polymer composition comprising at least one, optionally hydrogenated, nitrile rubber polymer having a Mooney viscosity (ML1+4, 100 ℃) of less than 30, optionally at least one filler and optionally at least one crosslinking agent. Preferably, the NBR is fully or partially hydrogenated ("HNBR"). In particular, the present invention relates to polymer compositions comprising at least one, optionally hydrogenated, nitrile rubber polymer having a Mooney viscosity (ML1+4, 100 ℃) of less than 20, preferably less than 10.

In another aspect, the present invention relates to a process for preparing said polymer composition, wherein at least one nitrile rubber polymer having a Mooney viscosity (ML1+4, 100 ℃) of less than 30, optionally at least one filler and optionally at least one cross-linking agent are mixed.

In another aspect, the invention relates to a self-supporting shaped article comprising said composition optionally laminated or embedded between two or more supports.

In another aspect, the invention relates to an adhesive tape comprising the adhesive polymer composition optionally laminated or embedded between two or more supports.

In yet another aspect, the present invention relates to sealant compositions comprising said adhesive polymer composition.

Detailed Description

The term "nitrile polymer" or NBR as used throughout this specification is intended to be broadly construed to mean a copolymer comprising repeat units derived from at least one conjugated diene, at least one α, β -unsaturated nitrile and optionally one or more additional copolymerizable monomers.

The conjugated diene may be any known conjugated diene, especially C₄-C₆A conjugated diene. Preferred conjugated dienes are butadiene, isoprene,1, 3-pentadiene, 2, 3-dimethylbutadiene and mixtures thereof. More preferred is C₄-C₆The conjugated diene is butadiene, isoprene or a mixture thereof. Most preferred C₄-C₆The conjugated diene is butadiene.

The alpha, beta-unsaturated nitrile may be any of the known alpha, beta-unsaturated nitriles, especially C₃-C₅An α, β -unsaturated nitrile. Preferred is C₃-C₅The α, β -unsaturated nitriles are acrylonitrile, methacrylonitrile, ethacrylonitrile, and mixtures thereof. Most preferred C₃-C₅The α, β -unsaturated nitrile is acrylonitrile.

The copolymer preferably contains 40 to 85% by weight of repeating units derived from one or more conjugated dienes and 15 to 60% by weight of repeating units derived from one or more unsaturated nitriles. More preferably, the copolymer contains from 60 to 75 weight percent of repeating units derived from one or more conjugated dienes and from 25 to 40 weight percent of repeating units derived from one or more unsaturated nitriles. Most preferably, the copolymer contains from 60 to 70 weight percent of repeating units derived from one or more conjugated dienes and from 30 to 40 weight percent of repeating units derived from one or more unsaturated nitriles.

Optionally, the copolymer may further comprise repeating units derived from one or more copolymerizable monomers, such as unsaturated carboxylic acids. Non-limiting examples of suitable carboxylic acids are fumaric acid, maleic acid, acrylic acid, methacrylic acid and mixtures thereof. It will be apparent to those skilled in the art that repeating units derived from one or more copolymerizable monomers can replace the nitrile or diene portion of the nitrile rubber and that the above numbers must be adjusted to a final 100% by weight. In the case of the above-mentioned unsaturated carboxylic acids, the nitrile rubber preferably contains from 1 to 10% by weight, based on the weight of the rubber, of recurring units derived from one or more unsaturated carboxylic acids, in such an amount as to replace the corresponding amount of conjugated diene.

Other preferred optional monomers are unsaturated mono-or dicarboxylic acids or derivatives thereof (e.g., esters, amides, etc.), including mixtures thereof.

The hydrogenation according to the invention is preferably understood to mean that preferably more than 50% of the Residual Double Bonds (RDB) present in the starting nitrile polymer/NBR are hydrogenated, preferably more than 90% of the Residual Double Bonds (RDB) are hydrogenated, more preferably more than 95% of the Residual Double Bonds (RDB) are hydrogenated, most preferably more than 99% of the Residual Double Bonds (RDB) are hydrogenated.

The Mooney viscosity of the rubber was determined by ASTM test D1646.

The polymer compositions according to the invention contain at least one, optionally hydrogenated, NBR having a Mooney viscosity (ML1+4, 100 ℃) of less than 30, in particular of less than 25, preferably of less than 20, more preferably of less than 15, and more preferably of less than 10.

Preferably, the low-mooney, optionally hydrogenated NBR of the present invention has a polydispersity index of less than 3, more preferably less than 2.9, more preferably less than 2.8, more preferably less than 2.7, more preferably less than 2.6, more preferably less than 2.5, more preferably less than 2.4, more preferably less than 2.3, more preferably less than 2.2.

The invention is not restricted to a particular process for preparing the optionally hydrogenated NBR. However, the NBR/HNBR of the present invention is readily available in a two-step synthesis as disclosed in CA-2351961, CA-2357470, CA2350280 and CA 2357465, which can be carried out in the same reactor or in different reactors. CA-2351961, CA-2357470, CA2350280, and CA 2357465 are hereby incorporated by reference as if granted.

Step 1: translocation

The metathesis reaction is carried out in the presence of one or more compounds of formula I, II, III, or IV;

general formula I

Wherein:

m is osmium, ruthenium;

r and R¹Each of which isIndependently a hydrogen atom or a hydrocarbon group selected from C₂-C₂₀Alkenyl radical, C₂-C₂₀Alkynyl, C₁-C₂₀Alkyl, aryl, C₁-C₂₀Carboxylic acid ester group, C₁-C₂₀Alkoxy radical, C₂-C₂₀Alkenoxy radical, C₂-C₂₀Alkynyloxy, aryloxy, C₂-C₂₀Alkoxycarbonyl radical, C₁-C₂₀Alkylthio radical, C₁-C₂₀Alkylsulfonyl radical, C₁-C₂₀An alkyl-sulfinyl group, a phenyl-sulfinyl group,

x and X¹Each independently of the others, is any anionic ligand, and

l and L¹Each independently of the other, any neutral ligand, e.g. phosphine, amine, thioether or imidazolidine subunit or any neutral carbane, optionally L and L¹Neutral ligands that can be linked to each other to form bidentate ligands;

general formula II

Wherein:

M¹is osmium or ruthenium;

R²and R³Each independently is a hydrogen atom or a hydrocarbyl group selected from C₂-C₂₀Alkenyl radical, C₂-C₂₀Alkynyl C₁-C₂₀Alkyl, aryl C₁-C₂₀Carboxylic acid ester group C₁-C₂₀Alkoxy radical, C₂-C₂₀Alkenoxy radical, C₂-C₂₀Alkynyloxy, aryloxy, C₂-C₂₀Alkoxycarbonyl radical, C₁-C₂₀Alkylthio radical, C₁-C₂₀Alkylsulfonyl radical, C₁-C₂₀An alkyl-sulfinyl group, a phenyl-sulfinyl group,

X²is an anionic ligand, and

L²are neutral pi-bonded ligands, independently of whether they are mono-or polycyclic

L³Is a ligand selected from the group consisting of phosphines, sulfonated phosphines, fluorinated phosphines, functionalized phosphines, phosphines having up to 3 aminoalkyl, ammonioalkyl, alkoxyalkyl, alkoxycarbonylalkyl, hydroxycarbonylalkyl, hydroxyalkyl or ketoalkyl groups, phosphites, phosphinites, phosphonites, phosphinimines, arsines, stibines, ethers, amines, amides, imides, sulfoxides, thioethers and pyridines,

Y^-is a non-coordinating anion, and is,

n is an integer of 0 to 5.

General formula III

Wherein M is²Is a mixture of molybdenum or tungsten, and is,

R⁴and R⁵Each independently is a hydrogen atom or a hydrocarbyl group selected from C₂-C₂₀Alkenyl radical, C₂-C₂₀Alkynyl, C₁-C₂₀Alkyl, aryl, C₁-C₂₀Carboxylic acid ester group, C₁-C₂₀Alkoxy radical, C₂-C₂₀Alkenoxy radical, C₂-C₂₀Alkynyloxy, aryloxy, C₂-C₂₀Alkoxycarbonyl radical, C₁-C₂₀Alkylthio radical, C₁-C₂₀Alkylsulfonyl radical, C₁-C₂₀An alkylsulfinyl group which is a substituent of a fatty acid,

R⁶and R⁷Each independently selected from optionally unsubstituted or halogenated alkyl, aryl, aralkyl and silicon-containing analogs thereof.

General formula IV

Wherein M is osmium or ruthenium,

r and R¹Each independently selected from a hydrogen atom, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted alkyl group,

x and X¹Each independently of the others, is any anionic ligand, and

l and L¹Each independently of the other, is any neutral ligand, such as a phosphine, amine, thioether or imidazolidine subunit or any neutral carbane, optionally L and L¹Neutral ligands that can be linked to each other to form bidentate ligands;

preference is given to compounds of the formula I. More preferably in the compounds of formula I L and L¹Is a trialkylphosphine, X and X¹Is chloride and M is ruthenium.

The amount of the compound used depends on the nature and catalytic activity of the compound. Typically, the ratio of compound to NBR is in the range of 0.005 to 5, preferably in the range of 0.025 to 1, more preferably in the range of 0.1 to 0.5.

The metathesis is carried out in the presence of a copolyolefin (co-olefin), preferably C₂-C₁₆Linear or branched olefins such as ethylene, isobutylene, styrene or 1-hexene. If the co-olefin is a liquid (e.g.1-hexene), the amount of co-olefin used is preferably in the range of from 1 to 200% by weight. If the co-olefin is a gas (e.g. ethylene), the co-olefin is used in an amount such that the pressure in the reaction vessel is 1 x 10⁵ Pa-1*10⁷Pa, preferably 5.2 x 10⁵ Pa-4*10⁶In the Pa range.

The metathesis reaction may be carried out in any solvent which is inert to the catalyst or otherwise does not interfere with the reaction. Preferred solvents include, but are not limited to, methylene chloride, benzene, toluene, tetrahydrofuran, cyclohexane, and the like. The most preferred solvent is Monochlorobenzene (MCB). In certain cases, the co-olefin itself acts as a solvent (e.g., 1-hexene), in which case no other solvent is required.

The concentration of Nitrile Butadiene Rubber (NBR) in the reaction mixture is not critical and obviously should be such that the reaction is not hindered, for example if the mixture is too viscous to stir effectively. The NBR concentration is preferably in the range of 1 to 20% by weight, most preferably in the range of 6 to 15% by weight.

The metathesis reaction is carried out at the temperature of 20-140 ℃; preferably in the range of 60-120 ℃.

The reaction time depends on many factors including the cement concentration, the amount of catalyst used and the temperature at which the reaction is carried out. Metathesis is usually complete within the first 2 hours under normal conditions. The progress of the metathesis reaction is monitored by standard analytical means, such as using GPC or solution viscosity. The polymer molecular weight distribution referred to anywhere in the specification was determined by Gel Permeation Chromatography (GPC) using a Waters 2690 separation module and a Waters 410 differential refractometer running Waters Millenium version 3.05.01 software. The samples were dissolved in Tetrahydrofuran (THF) stabilized with 0.025% BHT. The column used for the measurements was a three-sequence mixed-B gel column from Polymer laboratories. The reference standard used was a polystyrene standard supplied by American Polymer standards corp.

Step 2: hydrogenation

After metathesis, the nitrile rubber must be hydrogenated to produce a partially or fully hydrogenated nitrile polymer (HNBR). HNBR is preferred in the present invention. Reduction of the metathesis reaction product may be accomplished using reduction techniques known in the art. For example, homogeneous hydrogenation catalysts known to those skilled in the art, such as Wilkinson's catalyst { (PPh) can be used₃)₃RhCl, and the like.

The hydrogenation can be carried out in situ in the same reactor in which the metathesis step is carried out without first isolating the metathesis products. The hydrogenation catalyst was added directly to the vessel and then treated with hydrogen to produce HNBR.

Conversion of Grubb's catalyst to a dihydride complex (PR) in the presence of hydrogen₃)₂RuCl₂H₂Which is itself an olefin catalyst. Thus, in an ideal one-pot reaction, Grubb's catalyst is used to reduce the molecular weight of NBR in the presence of co-olefins. The reaction mixture is then treated with hydrogen to convert the Grubb's complex to the dihydride type and then the metathesis product is hydrogenated to give the HNBR of the invention. The hydrogenation rate in this case is slower than in the case of Wilkinson's catalyst used in the hydrogenation step, but it is clear that the above procedure is really feasible.

The low-Mooney NBR and the low-Mooney HNBR used in the preferred components of the polymer compositions of the present invention are likewise characterized by standard techniques known in the art. For example, the molecular weight distribution of the polymer is determined by Gel Permeation Chromatography (GPC) using a Waters 2690 separation module and a Waters 410 differential refractometer running Waters millenium3.05.01 version of the software. The samples were dissolved in Tetrahydrofuran (THF) stabilized with 0.025% BHT. The column used for the determination was a three-sequence mixed-B gel column from Polymer laboratories. The reference standard used was a polystyrene standard supplied by American Polymer Standards corp.

The polymer composition of the present invention further optionally comprises at least one filler. The filler may be a reactive or non-reactive filler and mixtures thereof. The fillers may be in particular:

highly dispersed silicas, e.g. precipitated from silicate solutions or prepared by flame hydrolysis of silicon halides, with specific surface areas of 5-1000m²(ii)/g, primary particle size in the range of 10-400 nm; the silica may also optionally be present as a mixed oxide with other metal oxides such as oxides of aluminum, magnesium, calcium, barium, zinc, zirconium and titanium;

synthetic silicates, such as aluminum silicate and alkaline earth metal silicates, such as magnesium silicate or calcium silicate, having BET specific surface areas of from 20 to 400m²In the range of/g, the primary particle size is in the range of 10-400 nm;

natural silicates, such as kaolin and other naturally occurring silicas;

glass fibers and glass fiber products (woven, extruded) or glass microbeads;

metal oxides, such as zinc oxide, calcium oxide, magnesium oxide and aluminum oxide;

metal carbonates, such as magnesium carbonate, calcium carbonate and zinc carbonate;

metal hydroxides, such as aluminum hydroxide; and magnesium hydroxide;

-carbon black; the carbon blacks used here are prepared by the lamp black, furnace black or gas black process and have BET (DIN 66131) specific surface areas of 20 to 200m²Between/g, such as SAF, ISAF, HAF FEF or GPF carbon black;

rubber gels, especially those based on polybutadiene, butadiene/styrene copolymers, butadiene/acrylonitrile copolymers and polychloroprene;

or mixtures thereof.

Examples of preferred mineral fillers include silica, silicates, clays such as bentonite, gypsum, alumina, titanium dioxide, talc, mixtures thereof and the like. The surface of these particles has hydroxyl groups, which make them hydrophilic and oleophobic. This increases the difficulty of achieving good interaction between the filler particles and the rubber. For this reason, the more preferred mineral is silica, especially silica obtained by carbon dioxide precipitation of sodium silicate. Suitable dried amorphous silica particles according to the present invention have an average agglomerate particle size of from 1 to 100 microns, preferably from 10 to 50 microns and most preferably from 10 to 25 microns. Preferably less than 10 volume percent of the agglomerated particles have a size of less than 5 microns or greater than 50 microns. Furthermore, suitable amorphous dry silicas generally have BET specific surface areas, measured in accordance with DIN (German industry Standard) 66131, in the range from 50 to 450 square meters per gram, dibutyl phthalate absorption, measured in accordance with DIN 53601, in the range from 150 to 400 grams per 100 grams of silica, and a loss on drying, measured in accordance with DIN ISO 787/11, in the range from 0 to 10% by weight. Suitable fillers are available from PPG Industries co under the trade marks HiSil  210, HiSil  233 and HiSil  243. Also suitable are Vulkasil  S, Vulkasil  N from Bayer AG.

It is generally advantageous to use carbon black as filler. Generally, the amount of carbon black in the composition is from 20 to 200 parts by weight, preferably from 30 to 150 parts by weight, more preferably from 40 to 100 parts by weight. Furthermore, it is advantageous to use carbon black and mineral fillers in combination in the compositions of the invention. The mixing ratio of the mineral filler to the carbon black is usually 0.05 to 20, preferably 0.1 to 10.

The polymer composition may further preferably contain other natural or synthetic rubbers such as BR (polybutadiene), ABR (butadiene/acrylic acid-C)₁-C₄Alkyl ester copolymers), CR (polychloroprene), IR (polyisoprene), SBR (styrene/butadiene-copolymers) having a styrene content of 1 to 60% by weight, NBR (butadiene/acrylonitrile copolymers) having an acrylonitrile content of 5 to 60% by weight, HNBR (partially or fully hydrogenated NBR rubber) having a mooney viscosity (ML1+4, 100 ℃ according to ASTM test D1646) of at least 30, EPDM (ethylene/propylene/diene-copolymers), FKM (fluoropolymers or fluororubbers), and mixtures of the polymers listed. Careful blending with conventional HNBR often reduces the cost of the polymer while not sacrificing processability. The amount of conventional HNBR and/or other natural or synthetic rubbers used depends on the process conditions applied in the manufacture of the shaped article and can be obtained by some preliminary tests.

The polymer composition further optionally contains one or more crosslinking agents or curing systems. The present invention is not limited to a particular curing system, but peroxide curing systems are preferred. Furthermore, the present invention is not limited to a particular peroxide cure system. For example, inorganic or organic peroxides are suitable. Organic peroxides such as dialkyl peroxides, ketal peroxides, aralkyl peroxides, peroxy ethers, peroxy esters, such as di-tert-butyl peroxide, bis- (tert-butylperoxyisopropyl) benzene, dicumyl peroxide, 2, 5-dimethyl-2, 5-di (tert-butylperoxy) -hexane, 2, 5-dimethyl-2, 5-di (tert-butylperoxy) -hexene- (3), 1, 1-bis- (tert-butylperoxy) -3, 3, 5-trimethylcyclohexane, benzoyl peroxide, tert-butylcumyl peroxide and tert-butyl perbenzoate are preferred. The peroxide is generally used in the polymer composition in an amount in the range of from 1 to 10phr (for each 100 parts of rubber), preferably from 4 to 8 phr. The postcuring is generally carried out in the range from 100 to 200 ℃ and preferably at 130 ℃ and 180 ℃. The peroxide is preferably applied in polymer bound form. Suitable systems are commercially available, such as Polydispersion T (VC) D-40P from Rhein CPCHemie Rheinau GmbH, D (di-T-butylperoxy-cumene complexed with polymer).

The composition further optionally comprises at least one diluent. The diluent serves to reduce the viscosity of the composition and preferably volatilizes after the composition has entered its final position. The term "diluent" includes solvents for the polymer components or the entire composition. The present invention is not limited to a specific solvent. For example, aromatic or cyclic hydrocarbons such as toluene and cyclohexane or aliphatic hydrocarbons (e.g. hexane) are suitable. Preferred diluents for the polymer component are aliphatic or cyclic hydrocarbons. The diluent is generally used in the composition in an amount in the range of from 0 to 200phr (per 100 parts of rubber), preferably from 0 to 150 phr.

In the case of compositions intended for application in hot melt adhesives, little or preferably no diluent is present in the composition.

The rubber composition of the present invention may further contain rubber auxiliary products such as reaction accelerators, vulcanization accelerators, antioxidants, foaming agents, anti-aging agents, heat stabilizers, light stabilizers, ozone stabilizers, processing aids, plasticizers, tackifiers, foaming agents, colorants, pigments, waxes, extenders, organic acids, polymerization inhibitors, metal oxides, activators such as triethanolamine, polyethylene glycol, hexanetriol, etc., which are known to the rubber industry. The rubber auxiliaries are used in conventional amounts, which vary according to the application. Conventional amounts are, for example, from 0.1 to 50% by weight, based on the rubber. Preferably, the composition comprises in the range of from 0.1 to 20phr of an organic fatty acid as an adjunct product, preferably an unsaturated fatty acid having one, two or more carbon double bonds in the molecule, more preferably comprising 10% by weight or more of a conjugated diene acid having at least one conjugated carbon-carbon double bond in the molecule. Preferred are those fatty acids having from 8 to 22 carbon atoms, more preferably from 12 to 18 carbon atoms. Examples include stearic acid, palmitic acid and oleic acid and their calcium-, zinc-, magnesium-, potassium-or ammonium salts. Preferably the composition comprises from 5 to 50phr of an acrylate salt as an adjuvant product. Suitable acrylates are disclosed in EP-A1-0319320 (especially in p.3, 1.16-35), U.S. Pat. No. 4,520829 (especially in Col.2, 1.25-40), U.S. Pat. No. 4983678 (especially in Col.2, 1.45-62). Of particular interest are zinc acrylate, zinc diacrylate or zinc dimethacrylate or liquid acrylates such as trimethylolpropane Trimethacrylate (TRIM), Butylene Dimethacrylate (BDMA), and Ethylene Dimethacrylate (EDMA). It is advantageous to use the above-mentioned acrylates and/or metal salts thereof in combination. It is particularly advantageous to use metal acrylates in combination with sterically hindered phenols such as ScorpCCH-retarder (e.g.methyl-substituted aminoalkylphenols, in particular 2, 6-di-tert. -butyl-4-dimethylaminomethylphenol).

The ingredients of the final polymer composition are mixed together, suitably warmed to 25-200 ℃. Usually the mixing time does not exceed 1 hour and usually 2-30 minutes are sufficient. The mixing is suitably carried out in an internal mixer such as a Banbury mixer, or a Haake or Brabender miniature internal mixer. The two-roll mill also provides good dispersion of the additives in the elastomer. The extruder also provides good mixing and allows for shorter mixing times. The mixing can be carried out in two or more stages, and the mixing can be carried out in different equipment, for example one stage on an internal mixer and the other on an extruder. However, undesired pre-crosslinking (═ scorch) should be prevented from occurring during the mixing stage. Mixing and vulcanization are described in: encyclopedia of Polymer science engineering, Vol.4, p.66 or less (mixed) and Vol.17, p.666 or less (vulcanized).

Due to the low viscosity of the polymer composition, the polymer composition is ideally suited for, but not limited to, mold injection processes. The polymer composition may also be used for compression molding, liquid injection molding. The polymer composition comprising the crosslinking system is typically introduced into a conventional injection molding and injected into a hot (approximately 160-230 ℃) mold cavity, the crosslinking vulcanization taking place depending on the temperature of the polymer composition and the mold.

Generally, the self-adhesive rubber compositions of the invention do not contain tackifiers. However, for certain applications it may be advantageous to use a tackifier. Petroleum resins are commonly used for this purpose. These resins are often polymerized from distillate mixtures obtained from petroleum cracking, usually with a boiling point of 25 ℃ to 80 ℃, and monovinyl aromatic monomers having 8 to 9 carbon atoms forming resins containing 5 to 15% by weight of monovinyl aromatic compounds (obtained by nuclear magnetic resonance analysis (NMR)).

The distillates obtained from petroleum cracking contain mixtures of saturated and unsaturated monomers, the unsaturated monomers being monoolefins and diolefins, and there being some feedstock of higher or lower number of carbon atoms, e.g. C₆Olefins and dienes, although the unsaturated material is predominantly C₅An olefin. The distillate may also contain saturated or aromatic feedstocks as polymerization solvents.

The tackifying resin further comprises a terpene resin and a blend of unsaturated C₅-C₉A resin formed by the polymerization of a hydrocarbon monomer. Commercially available base C₅An example of such a resin for olefin fractions is the tackifying resin Wingtack^TM95 and 115(Goodyear Tire and Rubber co., Akron, Ohio). Other hydrocarbon resins include Regalrez^TM1078 and 1126(Hercules CPCHEMICAL Co. Inc., Wilmington, Delaware), Arkon^TMResins such as Arkon^TMP115(Arakawa Forest CPCHEMICAL Industries, CPCHicago, Illinois) and Escorez^TMResin (Exxon cpcheimcial co., Houston, Texas). Suitable terpene resins include terpene polymers such as polymeric resins comprising materials obtained by polymerization and/or copolymerization of terpene hydrocarbons such as alicyclic, monocyclic and bicyclic monoterpenes and mixtures thereof. Commercially available terpene resins include the B series and 7000 series (Arizona cpcheimul. Wayne, new jersey) Zonarezm terpene resins. The tackifying resin may be unsaturated vinyl, although oxidation resistance is important, and saturated tackifying resins are more preferred. Also suitable are sold under the trademark Rhenosin CPCHEMIE by Rhein, Germany^(Rhenosin^Type (2): coumarone-indene resin of C10, C30, C90, C100, C110, C120, C150), hydrocarbon resin (Rhenosin)^Type (B): TP100, TT10, TT30, TT90, TT100, TD90, TD100, TD110), phenolic resin (Rhenosin)^Type (2): P9447K, P7443K, P6204K)) and pitch resins (Rhenosin)^Type (2): 145 and 260).

These resins are generally used in amounts of from 0.1 to 150 parts by weight per 100 parts of nitrile polymer.

Since the adhesive composition of the invention shows excellent adhesion at high temperatures, especially above 80 ℃ and more preferably above 100 ℃, the invention is clearly applicable to an adhesive polymer composition comprising at least one, optionally hydrogenated, nitrile rubber polymer having a Mooney viscosity (ML1+4, 100 ℃) of less than 30, optionally at least one filler and optionally at least one cross-linking agent, which shows a decrease in adhesion at temperatures of 80-150 ℃, especially 100-.

Furthermore, the present invention provides a self-supporting shaped article comprising the above-described binder polymer composition comprising at least one, preferably hydrogenated, nitrile rubber polymer having a Mooney viscosity (ML1+4, 100 ℃) of less than 30, optionally laminated or interposed between one or more supports.

The unsupported, self-supporting shaped articles are three-dimensional articles such as sheets, pellets, rods, films or beads.

Yet another aspect of the present invention is an adhesive tape comprising the above adhesive polymer composition comprising at least one, preferably hydrogenated, nitrile rubber polymer having a Mooney viscosity (ML1+4, 100 ℃) of less than 30 laminated or interposed between one or more supports.

For this application, the self-adhesive rubber composition of the invention is preferably used for the pretreatment of the surface of a suitable support, such as a substrate. The layer of rubber mixture is generally 6 to 250 μm, in particular 10 to 100. mu.m, thick. Preferred substrates are polyolefins such as LDPE, HDPE, PP, BOPP, polyurethane, polyethylene terephthalate, PVC, ABS, polycarbonate, polyamide and polyester.

The primer material is for example neutral hydrogenated rosin. By pretreating the substrate with this composition, the primer remains strongly bonded to the substrate even after the substrate composition has been applied to a surface. The primer composition of the invention creates a highly polar surface to which the self-adhesive composition can adhere.

Suitable types of rosin for the primer composition include polar rosins containing acidic groups. Preferably an at least partially hydrogenated rosin. Commercially available rosins include Foral^TMAX hydrogenated rosin, Dresinol^TM205 rosin and Staybelite^TMHydrogenated rosin (all from Hercules CPCHEMICal Co.) and Hypale^TMRosin (Arakawa). Acid-containing rosins are highly polar and can also be used as surfactants and/or tackifiers in the self-adhesive compositions of the invention.

However, such rosins are used as primers to improve the adhesion of the rubber composition to a substrate.

To neutralize the acid-containing rosin, for example, the rosin is reacted with a solution of a basic compound to form a metal salt. Suitable bases include alkali metal hydroxides (e.g., LiOH, NaOH, KOH) and alkaline earth metal hydroxides (e.g., Ca (OH))₂，Mg(OH)₂). Alkali metal hydroxides are preferred due to their solubility, particularly KOH and NaOH. The above-mentioned hydroxide may be dissolved in a polar solvent such as water.

In order to react the rosin with the basic compound, both substances are usually dissolved in a solvent, preferably a polar solvent (since these compounds tend to show polarity), most preferably water. This material is then allowed to undergo an acid-base reaction. The above reaction usually occurs spontaneously, so no special measures (e.g. temperature or pressure increase) are required, but can be used if desired. Usually, stoichiometric amounts of rosin and base (or a slight excess of base) are used.

The neutralized rosin may optionally be mixed with an elastomeric compound prior to coating the substrate. Elastomeric compounds that are highly compatible with the organic portion of the rosin and saturants used in adhesive tape substrates are preferred. The elastomer may also preferably be dispersed in water. Since many available substrates contain creped paper impregnated with acrylate polymers or Styrene Butadiene Rubber (SBR), and since acrylate and styrene butadiene rubber are compatible with the organic portion of rosin, they are the preferred type of elastomer.

Styrene butadiene rubber is known in the art and is available from various suppliers. Common examples include Butofan^TMNS209, NS222, NS155, and NS248 rubbers (BASF Co., Parsippany, New Jersey, available from Polymer Latex GmbH)&Kg, perbuman (tm) emulsion from germany). Other suitable polymers include nitrile rubbers such as HycarTM polymers series (b.f. goodricpch co., Akron, Ohio) and (meth) acrylate polymers. Suitable elastomers may also be of the carboxyl NBR, HNBR and liquid NBR type, for example Therban^VBKA8889，Krynac^K.x.7.40, k.x.7.50, k.x.90 and k.e.34.38 from bayer ag.

U.S. Pat. No.5,385,965(Bernard et al) discloses a blend of a rubber-based emulsion polymer, a rosin-based surfactant, and a pine-based fragrance tackifier.

A list of suitable rubber-based polymers includes carboxylated statistical styrene-butadiene copolymers. Oral^TMThe AX rosin compounds fall within the list of suitable tackifying resins.

If an elastomeric component and a neutral rosin are used in the primer, the two components are mixed in any ratio in the range of 0.01: 99.99 to 75: 25, preferably 50: 50 (by weight). (other ranges may also be appropriate depending on the coating process used). Mixing is simply achieved by adding the elastomer to the neutral aqueous rosin mixture. The mixture is then diluted to the desired concentration for coating. The preferred concentration is 5-25 wt.%, more preferably 10-20 wt.%.

At high temperature (e.g., 88 deg.C), in water, by neutralizing the Foral with about a stoichiometric amount of a strong base (e.g., aqueous KOH)^TMAX rosin production for SPreferred primer compositions for BR-impregnated tape substrates. After the neutralized rosin mixture was removed from the heat source, it was combined with an approximate amount (by weight) of Butofan^TMThe NS209 SBR was mixed and the resulting mixture was diluted in water to a solids content of about 15%. Also preferred are primer compositions having a low amount of double-stranded, such as ethylene-vinyl acetate copolymers, ethylene-alpha-olefin copolymers or ethylene-alpha-olefin-diene terpolymers having a vinyl acetate content of less than 40% by weight.

The primer composition and/or the self-adhesive composition is applied to a substrate (e.g., a tape substrate) by a number of different methods, including solvent coating, solvent spraying, emulsion coating, low pressure coating, or other methods known to those skilled in the art. Suitable substrates include polyolefin films (e.g., polyethylene and polypropylene films), particularly corona treated polyolefin films, and elastomer impregnated papers. The appropriate coating weight is 0.1-5mg/cm²Preferably 0.2 to 1.0mg/cm²More preferably 0.3 to 0.5mg/cm². Drying is preferably performed after the primer layer is applied to the substrate. Drying is preferably carried out at elevated temperature, reduced pressure, or both.

A further preferred method for producing coated substrates is coextrusion coating, which is usually carried out on a coating apparatus using a molten film of a self-adhesive composition which is melted in an extruder and applied to a substrate consisting of one or more polymer layers by means of a flat sheet-like die. The composition thus formed is then cooled and pressed flat in a cooling/rolling unit. The strip-like material of the composition is then wound on a respective winder.

In a further preferred lamination process, the coating composition can be applied to a carrier tape, smoothed and cooled, peeled and coiled in a similar manner to the coating process. In the actual extrusion lamination, a pre-manufactured carrier tape is fed into a calender roll with 4 rollers. In this case, the carrier strip is coated with a melt film melted by an extruder before the first nip and passed through a flat sheet die. The second premade tape is added prior to the second roll seam. The resulting composition is flattened through a second nip, then cooled and stripped and coiled on a take-up device. So-called cast films can be pretreated to improve the composite adhesion range (carrier film/self-adhesive composition). Polyolefin carrier films are typically subjected to corona oxidation or surface coating with a silicone layer.

According to the more preferred blown/flat die extrusion process, the compositions of the present invention are generally first melted in anhydrous form and the various polymers in different extruders and under suitable conditions and then formed as a melt stream in an extrusion apparatus into a multilayer melt stream. The composition is then coiled by discharging, peeling and cooling a plurality of layers of molten, self-adhesive tape containing the self-adhesive composition. Thereby obtaining a composite film. In this connection, the flat die extrusion method is preferably applied.

Suitable polymers for use in the process include, inter alia, thermoplastic resins, for example, polyamides, polystyrenes, polyesters, polycarbonates or polyolefins. Preferably, polyolefins are used, such as ethylene homopolymers, propylene homopolymers or statistical propylene ethylene copolymers. The above polyolefins can generally be produced by polymerization reactions known to the person skilled in the art, for example by Ziegler-Natta polymerization, polymerization by means of Phillips catalysts, by high-pressure polymerization or polymerization by means of metallocene-containing catalysts.

The coating/extrusion process is typically carried out at a temperature of 170 ℃ to 300 ℃ and a pressure of 250 to 400 bar for an average of 5 to 20 minutes. Because of the high tendency of melt copolymers and film copolymers to stick to all contact surfaces, it is advantageous for the rolls used to produce the composition and the stripper rolls to be coated with a material that prevents blocking of the copolymer, such as polytetrafluoroethylene. For example, this allows for maintaining a proper tape tension for good coiling of the composite.

The films of the compositions coated with a binder polymer, i.e.comprising at least one, preferably hydrogenated, nitrile rubber polymer, having a Mooney viscosity (ML1+4, 100 ℃) of less than 30, are preferably used for the production of glass, wood, porcelain, floor coverings or for the coating of various painted articles, such as metals, alloys and plastics, such as polycarbonates, polyamide polyesters and ABS. Generally the above applications are intended to protect high quality surfaces for a certain period of time.

Yet another aspect of the present invention is an adhesive polymer composition comprising said adhesive polymer composition, wherein the adhesive polymer composition comprises at least one, preferably hydrogenated, nitrile rubber polymer having a Mooney viscosity (ML1+4, 100) of less than 30, in particular a hot melt adhesive system.

Still another aspect of the present invention is a sealant composition comprising said adhesive polymer composition wherein the adhesive polymer composition comprises at least one nitrile rubber polymer, preferably hydrogenated, having a Mooney viscosity (ML1+4, 100) of less than 30, especially a hot melt adhesive system.

This hot melt system is preferably a 100% solids system, wherein the composition is typically provided in the form of small particles, such as pellets or another shaped article, such as a stick. The shaped article is heated to a softening temperature, preferably 200 ℃ and 215 ℃, and applied to or between the sealant or bonding materials by a suitable method. It is advantageous to coat the shaped articles with a powder material, such as a polyolefin powder, in order to reduce the tackiness of the shaped articles and to ensure that the articles do not stick together after shipment to the customer.

Self-supporting shaped articles, such as tapes, are particularly suitable for use in building engineering and insulating glass sealants. The hot melt systems containing the compositions of the present invention are particularly useful as insulating sealant for glazing and doors. Other fields of application include: the automotive industry, especially in the areas of hood and/or higher ambient temperatures, construction/construction, bridges, roads, transportation, woodworking and wood bonding, bookbinding, printing industry, packaging industry, personal care products, laminates, shoe manufacturing, adhesives for end-user applications, and sealant and insulation.

The compositions of the invention are permanently tacky, remain flexible, and are particularly recommended for use at elevated temperatures.

Examples

Example 1

Ruthenium, [1, 3-bis- (2, 4, 6-trimethylphenyl) -2-imidazolidinylidene ] dichloro (benzylidene) (tricyclohexylphosphine) (Grubb's 2nd generation metathesis catalyst), ethylene and Monochlorobenzene (MCB) were purchased from Materia, Praxair and PPG, respectively, and used as they were. Perbunan is supplied by byater corporation.

The metathesis reaction was carried out in a test vessel under the following conditions:

the concentration of the glue solution is 15 percent

Copolymerized olefins ethylene

Coolefin concentration 500psi

Stirring speed 600rpm

The reactor temperature was 80 deg.C

Catalyst addition 0.05phr

Monochlorobenzene as solvent

A statistical butadiene-acrylonitrile copolymer having a substrate acrylonitrile content of 33% by weight, an acrylic acid content of 5% and a Mooney viscosity (ML1+4, 100 ℃) of 30.

The polymer (490g) was dissolved in monochlorobenzene (2.8 kg). The reactor was heated to the desired temperature and 40ml of a monochlorobenzene solution containing Grubb's catalyst was added to the reactor. The reactor was pressurized with ethylene to 500 psi. The temperature was kept constant to continue the reaction. Cooling coils connected to the temperature controller and the heat sensitive element are used to regulate the temperature.

The hydrogenation reaction was carried out in the same vessel as the metathesis reaction under the following conditions:

the solid content of the glue solution is 15 percent

H₂(g) Pressure 1200psi

Stirring speed 600rpm

Reactor temperature 138 deg.C

Catalyst addition (Wilkinson's) 0.075phr

1phr of triphenylphosphine

Monochlorobenzene as solvent

H for obtaining glue solution by metathesis reaction₂(100psi) degassing 3 times with full speed stirring. The reactor temperature was raised to 130 ℃ and 40ml of a monochlorobenzene solution containing Wilkison's catalyst and triphenylphosphine was added to the reactor. The temperature was increased to 138 ℃ and kept constant to continue the reaction. The hydrogenation reaction was monitored by measuring the amount of residual double bonds at various times using infrared spectroscopy.

Alternatively, ruthenium metathesis catalysts can be used to hydrogenate the polymer.

Examples 2 to 3: mixing and physical Property testing

The polymer composition was mixed on an open mill. In a separate mixing step, the curatives were added to a cold open mill. The formulations used for the evaluation were based on the simplified peroxide formulation 1 described in table 1.

Carbon Black N660 Sterling-V available from Cabot fire Blacks

Maglite  D, magnesium oxide available from c.p.

Naugard  445, diphenylamine available from Uniroyal CPCHEMICal.

Plasthall TOTM, trioctyl trimellitate from C.P.Hall.

Vulkanox  ZMB-2/C5 zinc salt of 4-and 5-methyl-mercaptobenzimidazole from Bayer AG

DIAK #7 Triallylisocyanurate available from DuPont Dow Elastomers

Vulcup 40KE from Harwick Standard 2, 2' -bis (tert-butylperoxydiisopropylbenzene).

TABLE 1 composition formula

Examples	2 (comparison)	3
			Therban  A3407 HNBR carbon black of example 1, N326Maglite  DNaugard  445Plasthall TOTMVulkanox  ZMB-2/C5 (ZMBI) Zinc oxide (Kadox  920) grade PC216 vulcanizing agent Spider SulfurStrukol ZP 1014DIAK #7Vulcup 40KE	100302150.530.31.57.5	1003010.371.57.5

Polymer Properties

Table 2 shows the properties of the base polymers in brief. The polymer molecular weight (Mw) of example 1 was 1/4 of the standard Therban  a3407 molecular weight, while the narrow polydispersity was 2.0 compared to standard grade 3.2.

Table 2 summary of base polymer properties

	Mn	Mw	PDI	ML1+4，100℃
					Polymer of example 1	25000	50700	2.0	1.5
TherbanA3407	97000	314000	3.2	70.5

Properties of the Polymer composition

Table 3 shows the properties of the polymer compositions of examples 2-3. Example 2 is for comparison.

TABLE 3 summary of Polymer composition Properties

Examples	2	3
			Self-adhesive (unvulcanized)	98	＞100a
Adhesion to steel(unvulcanized)	8	29
			Adhesive agent
For brass (N)m)	Is not provided with	112

^aNo cracking of the sample

Adhesion was measured by separating the unvulcanized rubber from the steel material by applying a 90 ° pull. As shown in Table 3, the rubber-to-rubber bond of example 3 was stronger than the unvulcanized sample. The adhesion to steel was 3.5 times better than that of comparative example.

Adhesion to brass was measured on an Instron 4501 instrument ID.

This method measures the tensile force required to delaminate a cured specimen. In table 3, it is apparent that example 3 significantly improves adhesion to brass. Coupled with the high degree of flowability associated with new products, makes them ideal for adhesive applications.

Claims (9)

1. An adhesive polymer composition comprising at least one, optionally hydrogenated, nitrile rubber having a Mooney viscosity (ML1+4, 100 ℃) of less than 30, optionally at least one filler and optionally at least one cross-linking agent.

2. The composition of claim 1, wherein the Mooney viscosity (ML1+4, 100 ℃) of the base polymer is less than 20.

3. The composition of claim 1, wherein the Mooney viscosity (ML1+4, 100 ℃) of the base polymer is less than 10.

4. The composition of any of claims 1-3, wherein the polymer composition comprises a peroxide, resin, or sulfur curing system.

5. Process for the preparation of a polymer composition according to any one of claims 1 to 4, wherein at least one, optionally hydrogenated, nitrile rubber polymer having a Mooney viscosity (ML1+4, 100 ℃) of less than 30, optionally at least one filler and optionally at least one cross-linking agent are mixed.

6. A self-supporting shaped article comprising a binder composition, wherein the binder composition comprises at least one, optionally hydrogenated, nitrile rubber polymer having a mooney viscosity (ML1+4, 100 ℃) of less than 30.

7. The article of claim 6, wherein the article further comprises at least one support having the composition laminated thereon.

8. An adhesive tape comprising the composition of any one of claims 1-4 and optionally one or more supports.

9. A sealant or adhesive composition comprising the composition of any one of claims 1 to 4.