Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/54—Silicon-containing compounds
  • C08K5/544—Silicon-containing compounds containing nitrogen
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
  • B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/18—Layered products comprising a layer of metal comprising iron or steel
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/42—Introducing metal atoms or metal-containing groups
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2311/00—Metals, their alloys or their compounds
  • B32B2311/24—Aluminium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2311/00—Metals, their alloys or their compounds
  • B32B2311/30—Iron, e.g. steel

Definitions

• the present invention concerns a modified polyolefine having good adhesion to metals and to polar substances.
• Polyethylene and polyolefines in general are characterized by poor adhesion to metals and to materials containing polar groups. Some- what better adhesion is obtained in certain instances by copoly- merization of unsaturated esters, such as vinyl acetate or alkyl- (meth)acrylate (methylacrylate, ethylacr late, butylacrylate, etc.), but the adhesion also of these copolymers is insufficient in most multi-layer structures.
• Endeavours have been made to improve this adhesion in a number of ways.
• unsaturated acids or acid anhydrides have been used as comonomer when poly ⁇ merizing copolymers or terpolymers of ethylene.
• Examples of com ⁇ flashal applications are: ethylene/acrylic acid copolymer containing 9% acrylic acid, and ethylene/methacrylic acid copolymer containing 9% methacrylic acid.
• a commercial terpolymer known in the art contains 4% acrylic acid and 7% butylacrylate.
• Also commercially available is a product in which the methacrylic acid has been partially neutralized to be present as a salt, so that a so-called ionomer has been obtained.
• An example of the use of maleic acid anhydride towards improving adhesion is the application in which maleic acid anhydride has been grafted to LDPE, HDPE or EVA.
• Another example is the terpolymer of ethylene, butylacrylate and maleic acid anhydride. It is also known that the adhesion of defines to metals and to substances containing polar groups can be improved by copolymerization or grafting of unsaturated silanes.
• the object of the present invention is to achieve an improvement of modified ethylene or define polymers known at present.
• the polyolefine of the invention is mainly characterized in that it consists of a polyolefine to which has been admixed or chemically adjoined 0.01-10% substances classifiable as alkoxyaminosilanes.
• the silane chemically adjoined to the polyolefine may be any alkox aminosilane suited to this purpose.
• These alkoxyaminosilanes include the following: 3-aminopropyltrimethoxysilane, 3-amino- propyltriethoxysilane, and N-aminoethyl-3-aminopropyltrimethoxy- silane, which shall be referred to as MEAM, EAM and DIAM, respec- tively, in the following.
• aminosilanes in polyolefines is not novel in itself.
• hydrolyzable alkoxysllanes were developed for improving the miscibilrty of polymers and inorganic fillers and glass and artificial fibres (for use as so-called coupling agents) .
• the alkoxy groups of the silane are hydrolyzed to become hydroxy groups, this being followed by condensation with hydroxyl groups on the surface of the fillers.
• These silanes contain, in addition to alkoxy groups, one or several groups having a chemical composition such that they mix well with the polymer (e.g. vinyl, glycidyl, amino, mercapto, isocyanate or other reactive groups).
• silanes Since the alkoxy groups of silane are hydrdyzed and condensed by effect of water and of a catalyst, for instance dibutylstannic dilaurate, silanes have also been introduced in cross-linking techniques. This is based on the principle that an unsaturated alkoxyaminosilane is copolymerized with the polymer or chemically adjoined thereto with the aid of peroxide, cross-linking only taking place after the end product has been completed, with the aid of water or steam. Hereby it becomes possible to mould the polymer at high temperatures without risk of cross-linking; in addition, the cross-linking step is less expensive in energy as well as investment cost. When silanes are used for cross-linking, a condensation catalyst must always be present.
• Silanes are also well-known as agents improving the adhesion of various glues and coatings.
• the silane has to be able to form strong bonds both to the matrix of the glue, or cement, substance and to the laminations which are being glued.
• the silane may have a character such that it mainly forms bonds to one given material surface, not very easily to any material flowing along the surface. Properties of this kind are required, for instance, when it is desired to prevent adhesion of a resin to the reaction vessel or to a working surface. In that case the silane serves as a so-called release substance. Adhesion-promoter or release agent properties are mainly achieved by selecting silanes on the basis of suitable chemical groups.
• polyolefines are modi ⁇ fied with alkoxyaminosilanes
• the mixing of the invention may also be performed in one step, directly in the conversion machine, in the way that the alkoxyaminosilane is first dry-mixed with the polyolefine, whereupon the" mix is melted in the initial stages of the conversion extruder at low temperature, in order to ensure complete melting of the polyolefine and uniform mixing of the alkoxyaminosilane, avoiding excessive reaction of the alkoxysilane at this stage.
• the temperature is only raised in the final extruder stage in order that the emerging mixture might be maximally reactive from the viewpoints of chemical bonding as well as adhesion, when it meets the substrate surface.
• the high-content aminosilane mix of the invention may also be used by diluting it into the base plastic at the con ⁇ version stage.
• Said base plastic may be, but it must not neces ⁇ sarily be, the same plastic on which the above-mentioned high- content mixture is based.
• Alkylacrylate copolymers react with aminosilanes through the alkoxy and/or a ino groups.
• the end products may on the basis hereof differ in that the branch may be connected to the polyolefine through an amide group or through an ester group.
• the alkoxy groups are mediators to the other substrate, while in the latter both alkoxy and amino groups are present as mediators to form adhesion reactions to the other substrate.
• Fig. 3 shows how it is possible to adjoin an aminosilane compound to an ethylene/vinylacetate copolymer through an amino or alkoxy group.
• the adhesion re ⁇ actions to other substances are based on reactions of the amino and silane groups.
• EBA 17 (MI — 7, BA -- 17%) was extruded together with an alkoxy ⁇ aminosilane in a Brabender extruder ( ⁇ — 19 mm, L - 20 D, and compression ratio 3:1).
• the silane in question which was 3-amino- propyltrimethoxysilane, henceforward referred to as MEAM, was used in quantity 0.2-1%.
• a nozzle was constructed through 0 which the metal strip (20 mm x 1.0 mm) could pe pushed.
• the tem ⁇ perature profile of the extruder was maintained such that in the three steps of the screw there was 105°C, 200°C and 250°C and finally in the nozzle, 250°C.
• laminated strips were extruded (modified polyethy ⁇ lene copolymer and Al (or Fe)), which were tested for adhesion a ter 24 hrs.
• This test was carried out with an Instron tension tester (Peel test) , the pulling rate being 50 mm/min. The force was measured after establishment of equilibrium and expressed in 0 units N/cm.
• VTMO means vinyltrimethoxysilane adjoined to the polymer chain in connection with polymerizing.
• VISICO 1407 or VISICO 1442 It is also seen that the adhesion can be even further improved by admixing MEAM aminosilane to said VISICO polymers.
• EMA 17 was first admixed with a given quantity of 8 MEAM (0.01-1.0%) in a Werner-Pfleiderer ZSK 30 twin screw extruder with screw diameter 30 mm and L - 38 D.
• the temperatures in the different extruder zones were 60, 70, 160, 170, 170, 170 and 170°C, and the production rate was 15 kg/h.
• the higher MEAM contents were added periodically in a Haake Rheomix 5000 mixer. Mixing temperature was 200°C and total mixing time, about 10 min.
• the mix from the mixer was pressed together with the desired materials, using a laboratory press.
• Pressing conditions were: temperature 180°C, pressure 50 tons, and duration 60 seconds.
• An epoxy surface was produced by coating a steel plate at 200°C, prior to the pressing step, with epoxy powder blown thereon.
• the combinations listed below consisted of two components VISICO 1441 and Hoechst PVA brand MOWIOL 4-88, which are chemically bonded end result copolymers of said materials. The results are presented In Table III.
• the purpose was in this case to institute a comparison of the adhesion of certain homopolymers and copolymers of ethylene to epoxy by detaching perpendicularly an epoxy layer coated on a steel plate, from an ethylene polymer layer coated thereupon. A steel nut fused into the ethylene polymer layer served as the other fixed point.
• the specimen was prepared by spraying epoxy powder (Bitumes-Speci- aux Eurokote 714,13) on a sand-blasted steel plate heated to 200°C. After a delay of 5 seconds, powdery ethylene polymer was further ⁇ more sprayed on the epoxy, thus producing a steel plate with two plastic coatings (steel/epoxy/PE) .
• the steel nut mentioned above was fused at 200°C into the surface layer consisting of PE homo- polymer or copolymer.
• the PE polymers that were tested were the polymers described before: VISICO 1407 (see Example 2), EBA 17 (see Example 1), EVA 19 (see Example 5) , and B 7518 (see Example 8) . They were tested in the manner described, either as such or admixing 1% MEAM to them. The results are presented in Table IV.
• the results are based on a pulling test in which the measured values were obtained by detaching a PE/epoxy intermediate layer by perpendicular pull.
• the abbreviation "EVA 19" is here, and subsequently, used to refer to the experimental brand NTR 223 by the company Neste Oy.
• the above- defined silanes, MEAM, EAM and DIAM, were used in quantities from 0,25% to 2%.
• the temperature profile in the extruder was 105°C, 250°C and 300°C in the different parts of the cylinder, and 300°C in the nozzle.
• the output was conducted into contact with the 12 aluminium side of a paper/Al lamination affixed to a belt web.
• the paper/Al lamination had 60 um thickness.
• the speed of travel of the web was 5 m/min,
• the speed of rotation of the extruder screw was 41 min .
• the molten plastic became immediately subjected to pressure between a press roller weighing 5 kg and the web.
• lamination strips modified polymer and aluminium
• Example 5 In this case testing was done as in Example 5, except that instead of EVA was used the above-mentioned ethylene/butylacrylate copoly ⁇ mer, EBA 17 (MI - 7, BA - 17%).
• EVA 9 Alkoxyaminosilanes MEAM and DIAM were ad ⁇ mixed at 0.5% and at 2%. 17
• Example 10 The aim was in this case similar to that in Example 10, differing only in that, instead of EVA, EBA materials with various BA con ⁇ tents were used.
• the 8.5% EBA occurring in the table is a mix made by mixing in equal quantities polyethylene homopolymer LDPE (MI — 7.5) and EBA 17 (MI - 7, BA - 17%).
• Table XIII reveals how said modified polymers and their basic polymers adhere to various materials.
• Table XIV shows the manner in which MEAM-modified EBA, EVA and EMA adhere to various materials, compared with commercial adhesion plastics.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Laminated Bodies (AREA)
• Adhesives Or Adhesive Processes (AREA)

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• 1987
  • 1987-01-15 FI FI870161A patent/FI870161A/fi not_active Application Discontinuation
• 1988
  • 1988-01-12 EP EP88901048A patent/EP0302906A1/en not_active Withdrawn
  • 1988-01-12 BR BR8804824A patent/BR8804824A/pt unknown
  • 1988-01-12 WO PCT/FI1988/000004 patent/WO1988005449A1/en not_active Application Discontinuation
  • 1988-01-12 JP JP63501296A patent/JPH01501949A/ja active Pending
  • 1988-01-12 AU AU11822/88A patent/AU1182288A/en not_active Abandoned
  • 1988-03-22 CN CN88101487A patent/CN1036018A/zh active Pending
  • 1988-09-05 NO NO883946A patent/NO883946D0/no unknown
  • 1988-09-15 DK DK514288A patent/DK514288D0/da not_active Application Discontinuation

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