WO1985003512A1 - Procedure for improving the adhesion properties of polyolefins - Google Patents

Procedure for improving the adhesion properties of polyolefins Download PDF

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Publication number
WO1985003512A1
WO1985003512A1 PCT/FI1984/000014 FI8400014W WO8503512A1 WO 1985003512 A1 WO1985003512 A1 WO 1985003512A1 FI 8400014 W FI8400014 W FI 8400014W WO 8503512 A1 WO8503512 A1 WO 8503512A1
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Prior art keywords
polyolefin
adhesion
anhydride
procedure according
copolymer
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PCT/FI1984/000014
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French (fr)
Inventor
Salme Koskimies
Jouko Huttunen
Christer BERGSTRÖM
Johan Brenner
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Neste Oy
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Application filed by Neste Oy filed Critical Neste Oy
Priority to NL8420025A priority Critical patent/NL8420025A/en
Priority to PCT/FI1984/000014 priority patent/WO1985003512A1/en
Priority to GB08521523A priority patent/GB2163171B/en
Priority to DE19843490657 priority patent/DE3490657T1/en
Publication of WO1985003512A1 publication Critical patent/WO1985003512A1/en
Priority to NO853642A priority patent/NO853642L/en
Priority to DK448585A priority patent/DK448585A/en
Priority to SE8504543A priority patent/SE8504543D0/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0853—Vinylacetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L35/06—Copolymers with vinyl aromatic monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the present invention concerns a procedure for modifying polyolefins so that their adhesion to polar polymers and/or metals improves, by admixing to the polyolefin in molten state polymeric compounds improving the adhesion and, possibly, a small amount of organic peroxide for grafting the polymer partly to the polyolefin.
  • the invention concerns a procedure for improving the adhesion characteristics of polyolefins by adding such substances improving the adhesion properties which cause no health detriments.
  • the adhesion-improving agent is either a copolymer or a polymer containing unsaturated polyester groups of olefins and anhydrides containing double bonds or a mixture of said polymeric compounds.
  • the modifying agents used are high-molecular or polymer-type substances.
  • the procedure of the invention is exceedingly simple because the adhesion-improving substances are simply admixed to the polyolefin in molten state. For this reason, the modifying agents added in this way have no harmful effect on the tensile strength properties or the melt index values of the procedure.
  • the adhesion may be further improved by means of partial grafting, by which is understood the adding of a small peroxide quantity along with the adhesion-improving substances.
  • partial grafting such small peroxide quantities are used that they have no detrimental effects on the ultimate products.
  • the invention concerns especially those procedures in which the modifying agent is added to the polyolefins by heating the initial substances past the melting point of the polyolefin that is used and by performing the mixing either in a Brabender, in a Banbury mixer, an extruder, a twin-roll mixer or a Buss cokneader.
  • Polyolefins are understood to be polymers or copolymers of ethylene, propylene, butylene or other aliphatic unsaturated hydro carbons. It is especially recommendable to use homopolymers which have been made either by the high or low pressure method (linear, branched, high or low density polyethylene) and such copolymers in which the contribution of ethylene is over 40 %. Among other polyolefins the following are recommendable: polypropylene, poly1-butylene, and poly-1-hexylene and poly-4-methyl-1-pentene. It is occasionally also recommendable to use blends made by mixing together two or several of the homopolymers, copolymers or terpolymers of the olefins mentioned.
  • a first group of adhesion-improving agents used in the procedure of the invention comprises polymer-type modifying agents which have been made by copolymerising various olefins with anhydrides containing double bonds.
  • Olefins to be recommended are ethylene, other aliphatic olefins, dienes and styrene.
  • For anhydrides may be used maleic acid anhydride and cyclic anhydrides obtained therefrom by Diels-Alder addition reaction.
  • the structure of these polymers may be generally represented by means of formulae (1) to (3).
  • a second group of adhesion agents comprises modifying agents containing an unsaturated polyester group and which have preferentially been made by condensing phthalic acid, fumaric acid, maleic acid and/or their anhydride with ethylene glycol, propylene glycol, diethylene glycol and/or dipropylene glycol.
  • a third group of adhesion-improving agents to be used in the procedure of the invention comprises the mixtures of the abovementioned types of adhesion agent.
  • olefin/maleic acid anhydride copolymer as well as polyester-type adhesion agent, one achieves a remarkable additional improvement of adhesivity, in particular to aluminium and steel, compared with the effect of each type of adhesion agent alone by itself.
  • the modifying is carried out at a temperature higher than 130°C, preferably at 150-300°C.
  • the mixing time is 2-30 minutes, preferably 5-15 minutes.
  • the share of the modifier agent of the polyolefin quantity is 0.1-15 % by weight, preferably 0.5-10 % by weight.
  • the recommended peroxide quantity is 0.01-1 %, preferably 0.02-0.2 % by weight.
  • the product may be diluted by mixing it with unmodified polyolefin.
  • both in the modifying and the diluting step may be used e.g. ethylene/vinylacetate (EVA)-copolymer or styrene/butadiene (SBS)-block copolymers.
  • EVA ethylene/vinylacetate
  • SBS styrene/butadiene
  • the modified polyolefin of the invention may be used in many different ways in applications in which is implied the adhesion of the polyolefin to materials containing polar groups such as polyamide, polyvinylalcohol, EVAL (ethylenevinylalcoholcopolymer), polyurethanes, wood, paper and metals, and by facilitating the combining with polyolefins of various fillers such as talc, chalk, glass, mica, etc.
  • polar groups such as polyamide, polyvinylalcohol, EVAL (ethylenevinylalcoholcopolymer), polyurethanes, wood, paper and metals
  • polar groups such as polyamide, polyvinylalcohol, EVAL (ethylenevinylalcoholcopolymer), polyurethanes, wood, paper and metals
  • various fillers such as talc, chalk, glass, mica, etc.
  • talc talc
  • chalk chalk
  • glass glass
  • mica e.g. the coating of metallic or nylon tubes
  • polyolefin according to the invention as film which adheres to nylon and/or aluminium and other polar surfaces, and to the polyolefin itself.
  • polyolefin may also contemplate multi-ply films, such as combination of unmodified polyethylene with nylon. It is thus understood that the polyolefin of the invention may be applied as such or as coating on other films or tubes or interposed between them, depending on the intended use.
  • Polyethylene with low density (density 0.92 g/cm 3 , melt index 4.5 g/10 min.) was modified by mixing thereto, in a twin-roll mixer, various styrene/maleic acid anhydride (SMA) copolymers.
  • SMA styrene/maleic acid anhydride
  • Low density (0.92 g/cm 3 , melt index 4,5 g/10 min.) polyethylene was modified by admixing thereto, in a twin-roll mixer, 0.5-5 % by weight unsaturated polyester A or B, either alone or together with styrene/maleic acid anhydride copolymer or with ethylene- /maleic acid anhydride polymer.
  • the mixing temperature varied in the range from 150 to 190oC and the mixing time in the range 10-15 min.
  • Polyester A had been made by condensing phthalic acid and maleic acid with ethyleneglycol and diethyleneglycol.
  • Polyester B had been made by condensing the carbonic acids mentioned with propyleneglycol and dipropyleneglycol. Table 3 below states the compositions and characteristics of the mixtures.
  • Low density (0.92 g/cm 3 ) polyethylene with melt index 4.0 g/10 min. was modified by admixing thereto in a Brabender Plasticord, 0.5-10 % by weight diene/maleic acid anhydride copolymer (DIEN-MHA) and 0.05-0.2 % by weight organic peroxide, and (mixtures 27 and 28) 5-20 % ethylene/vinylacetate (EVA)-copolymer or styrene/butadiene block copolymer (SBS) .
  • the mixing temperature was 130-300oC and the mixing time, 5-10 min. The results are stated In Table 4.
  • Low density (0.92 g/cm 3 ) polyethylene was modified by admixing thereto in a Brabender Plasticord mixer, 1-2 % by weight unsaturated polyester and 0.05-0.2 % by weight organic peroxide, and to the mixture a small quantity of styrene/maleic acid anhydride copolymer (SMA 3).
  • SMA 3 styrene/maleic acid anhydride copolymer
  • Mixtures equivalent to mixtures 8 and 14 were prepared in a Buss cokneader-type apparatus, and with the mixtures were run films of 0.04 mm thickness, using a Brabender Plasticorder PLE 651 and its ancillary equipment. The characteristics of the films were as shown in Table 6.

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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)
  • Graft Or Block Polymers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
  • Silicon Polymers (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

A procedure for modifying polyolefins so that their adhesion to polar polymers and/or metals improves, by admixing to the polyolefin in molten state adhesion-improving compounds and possibly a small quantity of organic peroxide for partial grafting of the polymer to the polyolefin. The adhesion-improving polymeric compound is a copolymer of olefins and anhydrides containing double bonds, a copolymer containing unsaturated polyester groups, or a mixture of the polymeric compounds mentioned. The anhydride is maleic acid anhydride or cyclic anhydride obtained therefrom by Diels-Alder addition reaction. The polymer containing a polystyrene part has been made by condensing phthalic acid, fumaric acid, maleic acid and/or their anhydride with ethyleneglycol, propyleneglycol, diethyleneglycol and/or dipropyleneglycol.

Description

Procedure for improving the adhesion properties of polyolefins
The present invention concerns a procedure for modifying polyolefins so that their adhesion to polar polymers and/or metals improves, by admixing to the polyolefin in molten state polymeric compounds improving the adhesion and, possibly, a small amount of organic peroxide for grafting the polymer partly to the polyolefin.
It is well known that combining polyolefin with other polymers and with metals is difficult. The use of many fillers also usually implies modification either of the polyolefins or of the filler. Towards modifying fillers, usually methods are applied in which the surface characteristics of the filler are changed by treating them with reagents which either react with the polyolefin or otherwise, again, may be modified e.g. by grafting to them carboxylic acid anhydrides or esters containing double bonds. The modifying may be accomplished either in dilute solutions or as a molten state reaction. The first of these methods is usually expensive because the losses both of solvent and of monomer are high. The drawback of the latter method is often a drop of the melt index so far down that the processibility of the product will be poor.
It is known, however, that grafting of a variety of polar and/or chemically reactive vinyl compounds to polyolefins improves their miscibility with common fillers such as talc, chalk, glass, titanium oxide and equivalent. Likewise, the adhesion to polar polymers such as nylon, polyvinylalcohol or polyurethane, and to wood, paper and metals, also improves.
In case polyolefin modified by grafting is used as packaging material for foodstuffs, on the inner surfaces of drinking water pipes, etc., attention must be paid to the monomer residues. This is because most commonly known monomers are dangerous to health at very low concentrations already. This circumstance restricts the use of some already commercially available modified polyolefins, although recently greater attention has been paid to the efficiency of the grafting procedures.
The invention concerns a procedure for improving the adhesion characteristics of polyolefins by adding such substances improving the adhesion properties which cause no health detriments. In the procedure of the invention, the adhesion-improving agent is either a copolymer or a polymer containing unsaturated polyester groups of olefins and anhydrides containing double bonds or a mixture of said polymeric compounds.
One avoids in the procedure of the invention the detriments introduced by monomer residues because the modifying agents used are high-molecular or polymer-type substances. The procedure of the invention is exceedingly simple because the adhesion-improving substances are simply admixed to the polyolefin in molten state. For this reason, the modifying agents added in this way have no harmful effect on the tensile strength properties or the melt index values of the procedure.
The adhesion may be further improved by means of partial grafting, by which is understood the adding of a small peroxide quantity along with the adhesion-improving substances. In partial grafting such small peroxide quantities are used that they have no detrimental effects on the ultimate products.
The invention concerns especially those procedures in which the modifying agent is added to the polyolefins by heating the initial substances past the melting point of the polyolefin that is used and by performing the mixing either in a Brabender, in a Banbury mixer, an extruder, a twin-roll mixer or a Buss cokneader.
Polyolefins are understood to be polymers or copolymers of ethylene, propylene, butylene or other aliphatic unsaturated hydro carbons. It is especially recommendable to use homopolymers which have been made either by the high or low pressure method (linear, branched, high or low density polyethylene) and such copolymers in which the contribution of ethylene is over 40 %. Among other polyolefins the following are recommendable: polypropylene, poly1-butylene, and poly-1-hexylene and poly-4-methyl-1-pentene. It is occasionally also recommendable to use blends made by mixing together two or several of the homopolymers, copolymers or terpolymers of the olefins mentioned.
A first group of adhesion-improving agents used in the procedure of the invention comprises polymer-type modifying agents which have been made by copolymerising various olefins with anhydrides containing double bonds.
Olefins to be recommended are ethylene, other aliphatic olefins, dienes and styrene. For anhydrides may be used maleic acid anhydride and cyclic anhydrides obtained therefrom by Diels-Alder addition reaction. The structure of these polymers may be generally represented by means of formulae (1) to (3).
Figure imgf000005_0001
In the procedure of the invention, a second group of adhesion agents comprises modifying agents containing an unsaturated polyester group and which have preferentially been made by condensing phthalic acid, fumaric acid, maleic acid and/or their anhydride with ethylene glycol, propylene glycol, diethylene glycol and/or dipropylene glycol.
A third group of adhesion-improving agents to be used in the procedure of the invention comprises the mixtures of the abovementioned types of adhesion agent. When adding olefin/maleic acid anhydride copolymer as well as polyester-type adhesion agent, one achieves a remarkable additional improvement of adhesivity, in particular to aluminium and steel, compared with the effect of each type of adhesion agent alone by itself.
It is to be recommended that the modifying is carried out at a temperature higher than 130°C, preferably at 150-300°C. The mixing time is 2-30 minutes, preferably 5-15 minutes. It is to be recommended that the share of the modifier agent of the polyolefin quantity is 0.1-15 % by weight, preferably 0.5-10 % by weight. In case the modifying is performed so that partial grafting also takes place at the mixing step, the recommended peroxide quantity is 0.01-1 %, preferably 0.02-0.2 % by weight.
If the modifying is carried out using large amounts of modifying agent, the product may be diluted by mixing it with unmodified polyolefin. For additives both in the modifying and the diluting step may be used e.g. ethylene/vinylacetate (EVA)-copolymer or styrene/butadiene (SBS)-block copolymers.
The modified polyolefin of the invention may be used in many different ways in applications in which is implied the adhesion of the polyolefin to materials containing polar groups such as polyamide, polyvinylalcohol, EVAL (ethylenevinylalcoholcopolymer), polyurethanes, wood, paper and metals, and by facilitating the combining with polyolefins of various fillers such as talc, chalk, glass, mica, etc. Among the practical applications in the combining of various plastics or metals may be mentioned e.g. the coating of metallic or nylon tubes or flasks with modified polyolefin. Furthermore may be mentioned the use of polyolefin according to the invention as film which adheres to nylon and/or aluminium and other polar surfaces, and to the polyolefin itself. One may also contemplate multi-ply films, such as combination of unmodified polyethylene with nylon. It is thus understood that the polyolefin of the invention may be applied as such or as coating on other films or tubes or interposed between them, depending on the intended use.
The procedure disclosed in this invention is more closely described In the examples now following.
Example I
Polyethylene with low density (density 0.92 g/cm3, melt index 4.5 g/10 min.) was modified by mixing thereto, in a twin-roll mixer, various styrene/maleic acid anhydride (SMA) copolymers. The mixing temperature was 150-190ºC and the mixing time, 10-15 min. The results are stated in Table 1.
Figure imgf000007_0001
MI = melt index in g/10 min., ASTM D 1238, adhesion: ASTM D 903-49 and ASTM D 1876-72, pressing temperature 200°C, pressure 40 kp/cm, preheating time/heating time 3 min./3 min., SMA 1 = DYLARK 240 (high MW), SMA 2 = DYLARK 250 (high MW) , SMA 3,4 MP = 1500-3000 (Arco Polymers Inc.).
Example II
Low density (0.92 g/cm3) polyethylene, melt index 4,5 g/10 min., was modified by admixing thereto, in a twin-roll mixer, 1-2 % by weight of different ethylene/maleic acid anhydride (EMA) copolymers. The mixing temperature was 180-190ºC and the mixing time, 10-15 min. The results are stated in Table 2.
Figure imgf000008_0001
Example III
Low density (0.92 g/cm3, melt index 4,5 g/10 min.) polyethylene was modified by admixing thereto, in a twin-roll mixer, 0.5-5 % by weight unsaturated polyester A or B, either alone or together with styrene/maleic acid anhydride copolymer or with ethylene- /maleic acid anhydride polymer. The mixing temperature varied in the range from 150 to 190ºC and the mixing time in the range 10-15 min.
Polyester A had been made by condensing phthalic acid and maleic acid with ethyleneglycol and diethyleneglycol. Polyester B had been made by condensing the carbonic acids mentioned with propyleneglycol and dipropyleneglycol. Table 3 below states the compositions and characteristics of the mixtures.
Figure imgf000009_0001
MK = non-separable bonding
(in parentheses : adhesion to steel)
Example IV
Low density (0.92 g/cm3) polyethylene with melt index 4.0 g/10 min. was modified by admixing thereto in a Brabender Plasticord, 0.5-10 % by weight diene/maleic acid anhydride copolymer (DIEN-MHA) and 0.05-0.2 % by weight organic peroxide, and (mixtures 27 and 28) 5-20 % ethylene/vinylacetate (EVA)-copolymer or styrene/butadiene block copolymer (SBS) . The mixing temperature was 130-300ºC and the mixing time, 5-10 min. The results are stated In Table 4.
Figure imgf000010_0001
Example V
Low density (0.92 g/cm3) polyethylene was modified by admixing thereto in a Brabender Plasticord mixer, 1-2 % by weight unsaturated polyester and 0.05-0.2 % by weight organic peroxide, and to the mixture a small quantity of styrene/maleic acid anhydride copolymer (SMA 3). The mixing temperature was 130-300ºC and the mixing time, 5-10 min. The results are stated in Table 5 below.
Ta
Figure imgf000011_0001
Example VI
Mixtures equivalent to mixtures 8 and 14 were prepared in a Buss cokneader-type apparatus, and with the mixtures were run films of 0.04 mm thickness, using a Brabender Plasticorder PLE 651 and its ancillary equipment. The characteristics of the films were as shown in Table 6.
Figure imgf000012_0001

Claims

Claims
1. Procedure for modifying polyolefins so that their adhesion to polar polymers and/or metals Improves, by admixing to the polyolefin in molten state adhesion-improving polymeric compounds and possibly a small quantity of organic peroxide for partially grafting the polymer to the polyolefin, characterized in that the adhesion-improving polymeric compound is a copolymer of olefins and anhydrides containing double bonds, a polymer containing unsaturated polyester groups or a mixture of said polymeric compounds.
2. Procedure according to claim 1, characterized in that the olefin is ethylene, another aliphatic olefin, diene or styrene.
3. Procedure according to claim 1 or 2, characterized in that the anhydride is maleic acid anhydride or a cyclic anhydride therefrom derived by Diels-Alder addition reaction.
4. Procedure according to any one of claims 1-3, characterized in that said polyolefin is a homopolymer or copolymer of ethylene, propylene, butylene or other aliphatic unsaturated hydrocarbons.
5. Procedure according to claim 1, characterized in that the polymer containing a polyester part has been made by condensing phthalic acid, fumaric acid, maleic acid and/or their anhydride with ethyleneglycol, propyleneglycol, diethyleneglycol and/or dipropyleneglycol.
6. Procedure according to claim 1, characterized in that the amount of modifying polymer is 0.1-15 % by weight referred to the polyolefin quantity.
7. Procedure according to claim 1, characterized in that the amount of organic peroxide is 0.01-1 % by weight referred to the polyolefin quantity.
8. Procedure according to any one of claims 1-7, characterized in that as additive is used 5-18 % by weight of ethylene/vinylacetate copolymer having vinyl acetate content 5-50 % by weight, or 5-20 % by weight of styrene/butadiene block copolymer.
PCT/FI1984/000014 1984-02-03 1984-02-03 Procedure for improving the adhesion properties of polyolefins WO1985003512A1 (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
NL8420025A NL8420025A (en) 1984-02-03 1984-02-03 PROCESS FOR IMPROVING THE ADHESION PROPERTIES OF POLYOLEFINS.
PCT/FI1984/000014 WO1985003512A1 (en) 1984-02-03 1984-02-03 Procedure for improving the adhesion properties of polyolefins
GB08521523A GB2163171B (en) 1984-02-03 1984-02-03 Procedure for improving the adhesion properties of polyolefins
DE19843490657 DE3490657T1 (en) 1984-02-03 1984-02-03 Process for improving the adhesive properties of polyolefins
NO853642A NO853642L (en) 1984-02-03 1985-09-17 PROCEDURE FOR IMPROVING THE ADHESION PROPERTIES OF POLYOLEFINES.
DK448585A DK448585A (en) 1984-02-03 1985-10-02 PROCEDURE FOR IMPROVING THE ADHESION FEATURES OF POLYOLEFINES
SE8504543A SE8504543D0 (en) 1984-02-03 1985-10-02 PROCEDURE FOR IMPROVING POLYOLEFIN'S ADHESIVE PROPERTIES

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PCT/FI1984/000014 WO1985003512A1 (en) 1984-02-03 1984-02-03 Procedure for improving the adhesion properties of polyolefins

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DK (1) DK448585A (en)
GB (1) GB2163171B (en)
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NO (1) NO853642L (en)
SE (1) SE8504543D0 (en)
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5296554A (en) * 1991-10-28 1994-03-22 Showa Denko K.K. Adhesive resin composition
US5593764A (en) * 1985-04-24 1997-01-14 Societe Chimique Des Charbonnages S.A. Thermoplastic composition comprising a copolymer based on ethylene and maleic anhydride, and industrial articles obtained from such a composition
KR100598240B1 (en) * 2000-10-09 2006-07-07 에스케이 주식회사 Formulation of polyolefin based adhesive resin

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3497574A (en) * 1961-04-04 1970-02-24 Jack J Press Adhesive compositions

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5593764A (en) * 1985-04-24 1997-01-14 Societe Chimique Des Charbonnages S.A. Thermoplastic composition comprising a copolymer based on ethylene and maleic anhydride, and industrial articles obtained from such a composition
US5296554A (en) * 1991-10-28 1994-03-22 Showa Denko K.K. Adhesive resin composition
KR100598240B1 (en) * 2000-10-09 2006-07-07 에스케이 주식회사 Formulation of polyolefin based adhesive resin

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SE8504543L (en) 1985-10-02
GB2163171B (en) 1987-12-02
GB8521523D0 (en) 1985-10-02
NL8420025A (en) 1985-12-02
GB2163171A (en) 1986-02-19
NO853642L (en) 1985-09-17
DK448585D0 (en) 1985-10-02
DE3490657T1 (en) 1986-02-06
SE8504543D0 (en) 1985-10-02
DK448585A (en) 1985-10-02

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