NO853642L - PROCEDURE FOR IMPROVING THE ADHESION PROPERTIES OF POLYOLEFINES. - Google Patents
PROCEDURE FOR IMPROVING THE ADHESION PROPERTIES OF POLYOLEFINES.Info
- Publication number
- NO853642L NO853642L NO853642A NO853642A NO853642L NO 853642 L NO853642 L NO 853642L NO 853642 A NO853642 A NO 853642A NO 853642 A NO853642 A NO 853642A NO 853642 L NO853642 L NO 853642L
- Authority
- NO
- Norway
- Prior art keywords
- polyolefin
- weight
- polymer
- adhesion
- ethylene
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 25
- 229920000098 polyolefin Polymers 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 20
- 229920000642 polymer Polymers 0.000 claims description 17
- 229920001577 copolymer Polymers 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 12
- -1 aliphatic olefin Chemical class 0.000 claims description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 9
- 150000001336 alkenes Chemical class 0.000 claims description 8
- 150000008064 anhydrides Chemical class 0.000 claims description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000005977 Ethylene Substances 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 150000002739 metals Chemical class 0.000 claims description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 5
- 229920006305 unsaturated polyester Polymers 0.000 claims description 5
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 4
- 150000001451 organic peroxides Chemical class 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 229920001400 block copolymer Polymers 0.000 claims description 3
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 3
- 150000001993 dienes Chemical class 0.000 claims description 3
- 229920001519 homopolymer Polymers 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- 229920006112 polar polymer Polymers 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 238000005698 Diels-Alder reaction Methods 0.000 claims description 2
- 238000007259 addition reaction Methods 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 230000000996 additive effect Effects 0.000 claims 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 description 10
- 239000000945 filler Substances 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 229920001684 low density polyethylene Polymers 0.000 description 5
- 239000004702 low-density polyethylene Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000004677 Nylon Substances 0.000 description 4
- WOLATMHLPFJRGC-UHFFFAOYSA-N furan-2,5-dione;styrene Chemical compound O=C1OC(=O)C=C1.C=CC1=CC=CC=C1 WOLATMHLPFJRGC-UHFFFAOYSA-N 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229920001778 nylon Polymers 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- YYXLGGIKSIZHSF-UHFFFAOYSA-N ethene;furan-2,5-dione Chemical compound C=C.O=C1OC(=O)C=C1 YYXLGGIKSIZHSF-UHFFFAOYSA-N 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- 239000004129 EU approved improving agent Substances 0.000 description 2
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- 101100257127 Caenorhabditis elegans sma-2 gene Proteins 0.000 description 1
- 101100257133 Caenorhabditis elegans sma-3 gene Proteins 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000001268 conjugating effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 231100000206 health hazard Toxicity 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- 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
Landscapes
- 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)
Description
Foreliggende oppfinnelse vedrører en fremgangsmåte til modifisering av polyolefiner, slik at adhesjonen til polare polymerer og/eller metaller forbedres, ved at det til polyolefinen i smeltet tilstand tilsettes polymerforbindelser som forbedrer adhesjonen og, eventuelt, en liten mengde organisk peroksyd for delvis poding av polymeren til polyolefinen. The present invention relates to a method for modifying polyolefins, so that the adhesion to polar polymers and/or metals is improved, by adding to the polyolefin in a molten state polymer compounds that improve adhesion and, optionally, a small amount of organic peroxide for partial grafting of the polymer to the polyolefin.
Det er kjent at kombinering av polyolefiner med andre polymerer og med metaller er vanskelige. Anvendelsen av mange fyllstoffer krever også ofte modifikasjon, enten av polyolefinene eller av fyllstoffet. Når det gjelder modifikasjon av fyllstoffer anvendes vanligvis femgangsmåter hvor overflate-egenskapene for fyllstoffet forandres ved at det behandles med reagenser som enten reatgerer med polyolefinen eller på annen måte kan modifiseres, f.eks. ved at det til disse podes karboksylsyre-anhydrider eller estere som inneholder dobbeltbindinger. Modifikasjonen kan enten utføres i fortynnede oppløsninger eller som en reaksjon i smeltet tilstand. Den første av disse fremgangsmåtene er vanligvis dyr fordi tapene, både av oppløsningsmiddel og monomer, er høye. Ulempen ved den sistnevnte fremgangsmåten er ofte fall i smelteindeksen til en så lav verdi at bearbeidbarheten av produktet vil være dårlig. It is known that combining polyolefins with other polymers and with metals is difficult. The use of many fillers also often requires modification, either of the polyolefins or of the filler. When it comes to modifying fillers, five-step methods are usually used where the surface properties of the filler are changed by treating it with reagents that either react with the polyolefin or can be modified in some other way, e.g. in that carboxylic acid anhydrides or esters containing double bonds are grafted to these. The modification can either be carried out in dilute solutions or as a reaction in the molten state. The first of these processes is usually expensive because the losses, both of solvent and monomer, are high. The disadvantage of the latter method is often a drop in the melt index to such a low value that the workability of the product will be poor.
Det er imidlertid kjent at poding av en rekke polare og/eller kjemisk reaktive vinylforbindelser til polyolefiner forbedrer blandbarheten med vanlige fyllmidler som f.eks. talg, kalk, glass, titandioksyd o.l. På tilsvarende måte forbedres adhesjonen til polare polymerer som f.eks. nylon, polyvinylalkohol eller polyuretan, og til tre, papir og metaller. However, it is known that grafting a number of polar and/or chemically reactive vinyl compounds to polyolefins improves miscibility with common fillers such as e.g. tallow, lime, glass, titanium dioxide etc. In a similar way, the adhesion to polar polymers such as e.g. nylon, polyvinyl alcohol or polyurethane, and to wood, paper and metals.
I tilfeller hvor polyolefiner modifisert ved poding benyttes som forpakningsmaterialer for matvarer, på den indre overflaten av drikkevanns-rør, osv., må man være oppmerksom på monomer-restene. Dette fordi de flåeste vanlig kjente monomerene er helseskadelige allerede ved svært lave konsentrajsoner. Denne omstendigheten begrenser anvendelsen av noen allerede kommersielt tilgjengelige modifiserte polyolefiner, slev om man i den senere tid har lagt større vekt på efektiviteten av podefremgangsmåtene. In cases where polyolefins modified by grafting are used as packaging materials for foodstuffs, on the inner surface of drinking water pipes, etc., attention must be paid to the monomer residues. This is because the lowest commonly known monomers are harmful to health already at very low concentration zones. This circumstance limits the use of some already commercially available modified polyolefins, even if more emphasis has recently been placed on the effectiveness of the grafting methods.
Oppfinnelsen vedrører en fremgangsmåte for forbedring av adhesjonsegenskapene for polyolefiner ved tilsats av stoffer som forbedrer adhesjonsegenskapene uten å forårsake noen helsefare. Ved fremgangsmåten ifølge oppfinnelsen er det adhesjons-forbedrende middelet enten en kopolymer eller en polymer som inneholder umettede polyestergrupper av olefiner og anhydrider som inneholder dobbeltbindinger, eller en blanding av disse polymerforbindelsene. The invention relates to a method for improving the adhesion properties of polyolefins by adding substances that improve the adhesion properties without causing any health hazards. In the method according to 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 these polymer compounds.
Ved fremgangsmåten ifølge oppfinnelsen unngår man farene som er forbundet med monomerrestene, fordi de modifiserende midlene som benyttes er høymolekylære eller stoffer av polymertypen. Fremgangsmåten ifølge oppfinnelsen er uhyre enkel, idet de adhesjons-forbedrende stoffene enkelt blandes med polyolefinen i smeltet tilstend. Av denne grunn har de modifiserende midlene som tilsettes på denne måten ingen negativ virkning på strekkstyrke-egenskapene eller på smelte-indeksverdiene ved fremgangsmåten. With the method according to the invention, the dangers associated with the monomer residues are avoided, because the modifying agents used are high molecular or polymer-type substances. The method according to the invention is extremely simple, as the adhesion-improving substances are simply mixed with the polyolefin in a molten state. For this reason, the modifying agents added in this way have no negative effect on the tensile strength properties or on the melt index values of the process.
Adhesjonen kan videre forbedres ved hjelp av delvis poding, herunder forstås tilsats av en liten mengde peroksyd sammen med de adhesjons-forbedrende stoffene. Ved delvis poding anvendes så små mengder peroksyd at det ikke har noen nedbrytende virkning på sluttproduktene. Adhesion can be further improved by means of partial grafting, which means the addition of a small amount of peroxide together with the adhesion-improving substances. In partial grafting, such small amounts of peroxide are used that it has no degrading effect on the final products.
Oppfinnelsen vedrører spesielt de fremgangsmåtene hvor modifiseringsmiddelet tilsettes til polyolefinene ved å oppvarme førstnevnte stoff over smeltepunktet for polyolefinen som benyttes og ved å utføre blandingen enten i en "Brabender"-, i en "Bandbury"-blander, en ekstruder, en to-rulls blander eller en "Buss" elte-innretning. The invention relates in particular to the processes where the modifier is added to the polyolefins by heating the first-mentioned substance above the melting point of the polyolefin used and by carrying out the mixing either in a "Brabender", in a "Bandbury" mixer, an extruder, a two-roll mixer or a "Buss" kneading device.
Polyolefiner skal forstås som polymerer eller kopolymerer av etylen, propylen, butylen eller andre alifatiske umettede hydrokarboner. Det anbefales spesielt å anvende homo-polymerer som er fremstilt enten ved høy- eller lavtrykks-fremgangsmåter (liniært, forgrenet, polyetylen med høy eller lav tetthet) og kopolymerer hvor andelen etylen er over 40%. Bl.a. kan følgende polyolefiner anbefales: polypropylen, poly-1-butylen og poly-1-heksylen og poly-4-metyl-1-penten. Det kan enkelte ganger også anbefales å benytte blandinger som er fremstilt ved å blande sammen to eller flere av homopolymerene, kopolymerene eller terpolymerene av de nevnte olefinene. Polyolefins are to be understood as polymers or copolymers of ethylene, propylene, butylene or other aliphatic unsaturated hydrocarbons. It is particularly recommended to use homopolymers that have been produced either by high or low pressure methods (linear, branched, high or low density polyethylene) and copolymers where the proportion of ethylene is over 40%. Blue. the following polyolefins can be recommended: polypropylene, poly-1-butylene and poly-1-hexylene and poly-4-methyl-1-pentene. It can sometimes also be recommended to use mixtures which have been prepared by mixing together two or more of the homopolymers, copolymers or terpolymers of the mentioned olefins.
En første gruppe adhesjons-forbedrende midler som benyttes ved fremgangsmåten ifølge oppfinnelsen innbefatter modifiserende midler av polymertypen som er fremstilt ved ko-polymerisasjon av foskjellige olefiner med anhydrider som inneholder dobbeltbindinger. A first group of adhesion-improving agents used in the method according to the invention includes modifying agents of the polymer type which are produced by copolymerization of various olefins with anhydrides containing double bonds.
Foretrukne olefiner er etylen, andre alifatiske olefiner, diener og styren. Som anhydrider kan man benytte malein-syreanhydrid og cykliske anhydrider som oppnås derav ved Diels-Alder addisjonsreaksjoner. Strukturen av disse polymerene kan generelt angis ved hjelp av formlene (1) til (3) . Preferred olefins are ethylene, other aliphatic olefins, dienes and styrene. Maleic anhydride and cyclic anhydrides obtained from it by Diels-Alder addition reactions can be used as anhydrides. The structure of these polymers can generally be indicated using the formulas (1) to (3).
Ved fremgangsmåten ifølge oppfinnelsen innbefatter en andre gruppe adhesjonsmidler modifiserende midler som inneholder en umettet polyestergruppe og som fortrinnsvis er fremstilt ved kondensasjon av ftalsyre, fumarsyre, maleinsyre og/eller anhydrider derav med etylenglykol, propylenglykol, dietylenglykol og/eller dipropylenglykol. In the method according to the invention, a second group of adhesion agents includes modifying agents which contain an unsaturated polyester group and which are preferably produced by condensation of phthalic acid, fumaric acid, maleic acid and/or anhydrides thereof with ethylene glycol, propylene glycol, diethylene glycol and/or dipropylene glycol.
En tredje gruppe adhesjons-forbedrende midler som kan benyttes i fremgangsmåten ifølge oppfinnelsen innbefatter blandinger av de ovenfor nevnte typene adhesjonsmidler. Når det tilsettes olefin/maleinsyreanhydridkopolymer såvel som adhesjonsraiddel av polyestertypen oppnås en bemerkelses-verdig ekstra forbedring av adhesjonen, spesielt til aluminium og stål, sammenlignet med virkningen av den enkelte type adhesjonsmiddel alene. A third group of adhesion-improving agents which can be used in the method according to the invention includes mixtures of the above-mentioned types of adhesion agents. When olefin/maleic anhydride copolymer as well as polyester-type adhesion promoter are added, a remarkable additional improvement in adhesion is achieved, especially to aluminum and steel, compared to the effect of the individual type of adhesion agent alone.
Modifikasjonen utføres fortrinnsvis ved en temperatur over 130°C, fortrinnsvis ved 150-300°C. blandtiden er 2-30 minutter, fortrinnsvis 5-15 minutter. Det foretrekkes at mengden av det modifiserende middelet utgjør 0,1-15 vekt-%, fortrinnsvis 0,5-10 vekt-% av polyolefinmengden. Dersom modifikasjonen utføres slik at delvis poding også finner sted i bland-trinnet er den foretrukne peroksydmengden 0,01-1 vekt-%, fortrinnsvis 0,02-0,2 vekt-%. The modification is preferably carried out at a temperature above 130°C, preferably at 150-300°C. the intermediate time is 2-30 minutes, preferably 5-15 minutes. It is preferred that the amount of the modifying agent constitutes 0.1-15% by weight, preferably 0.5-10% by weight of the amount of polyolefin. If the modification is carried out so that partial grafting also takes place in the mixing step, the preferred amount of peroxide is 0.01-1% by weight, preferably 0.02-0.2% by weight.
Dersom modifikasjonen utføres ved å benyte store mengder av det modifiserende middelet kan produktet fortynnes ved at det blandes med umodifisert polyolefin. Som additiver både i modifiserings- og fortynningstrinnet, kan man benytte f.eks. etylen/vinylacetat (EVA)-kopolymer eller styren/- butadien (SBS)-blokk kopolymerer. If the modification is carried out by using large quantities of the modifying agent, the product can be diluted by mixing it with unmodified polyolefin. As additives both in the modification and dilution step, you can use e.g. ethylene/vinyl acetate (EVA) copolymer or styrene/butadiene (SBS) block copolymers.
Den modifiserte polyolefinen ifølge oppfinnelsen kan benyttes på mange forskjellige måter i anvendelser hvor det kreves adhesjon av polyolefinen til materialer som inneholder polare grupper som f.eks. polyamid, polyvinylalkohol, EVAL (etylenvinylalkoholkopolymer), polyuretaner, tre, papir og metaller, og for å lette sammensetningen av polyolefiner med forskjelligefyllstoffer, som f.eks. talk, kalk, glass, glimmer osv. The modified polyolefin according to the invention can be used in many different ways in applications where adhesion of the polyolefin to materials containing polar groups such as e.g. polyamide, polyvinyl alcohol, EVAL (ethylene vinyl alcohol copolymer), polyurethanes, wood, paper and metals, and to facilitate the composition of polyolefins with various fillers, such as e.g. talc, lime, glass, mica, etc.
Blant de praktiske anvendelsene ved kombinasjon av forskjellige plaster eller metaller kan f.eks. nevnes beleg-gingen av metall- eller nylonrør eller -flasker med modifisert polyolefin. Vider kean man nevne anvendelsen av polyolefin ifølge oppfinnelsen som film som kleber til nylon og/eller aluminium og andre polare overflater, og til polyolefinen selv. Det er også vurdert flerlagsfilmer, som f.eks. en kombinasjon av umodifisert polyetylen og nylon. Det skal følgelig understrekes at polyolefinen ifølge foreliggende oppfinnelsekan anvendes som sådan, eller som belegg på andre filmer eller rør, eller plassert mellom disse, avhengig av den planlagte anvendelsen. Among the practical applications when combining different plastics or metals can e.g. mention is made of the coating of metal or nylon tubes or bottles with modified polyolefin. Furthermore, mention should be made of the use of polyolefin according to the invention as a film which adheres to nylon and/or aluminum and other polar surfaces, and to the polyolefin itself. Multi-layer films, such as e.g. a combination of unmodified polyethylene and nylon. It must therefore be emphasized that the polyolefin according to the present invention can be used as such, or as a coating on other films or pipes, or placed between these, depending on the intended application.
Fremgangsmåten ifølge oppfinnelsen er nærmere beskrevet i eksemplene som følger. The method according to the invention is described in more detail in the examples that follow.
Eksempel IExample I
Polyetylen med lav tetthet (tetthet 0,92 g/cm 3, smelteindeks 4,5 g/10 min.) ble modifisert ved at den, i en to-rulls-blander, ble blandet med forskjellige styren/maleinsyre-anhydrid (SMA) kopolymerer. Blandtemperaturen var 150-190°C og blandtiden 10-15 min. Resultatene er gjengitt i tabell 1 . Low density polyethylene (density 0.92 g/cm 3 , melt index 4.5 g/10 min.) was modified by mixing it, in a two-roll mixer, with different styrene/maleic anhydride (SMA) copolymers. The mixing temperature was 150-190°C and the mixing time 10-15 min. The results are reproduced in table 1.
MI = smelteindeks i g/10 min., ASTM D 1238, adhesjon: ASTM D 903-49 og ASTM D 1876-72, pressetemepratur 200°C, trykk 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, forvarmingstid/oppvarmingstid 3 min./3 min.,40 kp/cm, preheating time/heating time 3 min./3 min.,
SMA 1 = "DYLARK 240" (høymolekylvekt), SMA 2 = "DYLARK 250" SMA 1 = "DYLARK 240" (high molecular weight), SMA 2 = "DYLARK 250"
(høymolekylvekt), SMA 3,4 MP = 1500-3000 (Arco Polymers Inc.). (high molecular weight), SMA 3.4 MP = 1500-3000 (Arco Polymers Inc.).
Eksempel IIExample II
Polyetylen med lav tetthet (0,92 g/cm 3) og smelteindeksPolyethylene with low density (0.92 g/cm 3) and melt index
4,5 g/10 min., ble modifisert ved at den, i en to-rulls-blander, ble blandet med 1-2 vekt-% av forskjellige etylen/- maleinsyreanhydrid (EMA) kopolymerer. Blandtemperaturen var 180-190°C og blandtiden 10-15 min. Resultatene er gjengitt i tabell 2. 4.5 g/10 min., was modified by mixing it, in a two-roll mixer, with 1-2% by weight of various ethylene/maleic anhydride (EMA) copolymers. The mixing temperature was 180-190°C and the mixing time 10-15 min. The results are reproduced in table 2.
Eksempel III Example III
Polyetylen med lav tetthet (0,92 g/cm 3, smelteindeksLow density polyethylene (0.92 g/cm 3, melt index
4,5 g/10 min.) ble modifisert ved at den, i en to-rulls-blander, ble blandet med 0,5-5 vekt-% umettet polyester A eller B, enten alene eller sammen med styren/maleinsyre-anhydridkopolymer eller med etylen/maleinsyreanhydrid-polymer. Blandtemperaturen varierte i området fra 150-190°C og blandtiden i området 10-15 min. 4.5 g/10 min.) was modified by mixing it, in a two-roll mixer, with 0.5-5% by weight of unsaturated polyester A or B, either alone or together with styrene/maleic anhydride copolymer or with ethylene/maleic anhydride polymer. The mixing temperature varied in the range from 150-190°C and the mixing time in the range 10-15 min.
Polyester A var fremstilt ved kondensasjon av ftalsyre og maleinsyre med etylenglykol og dietylenglykol. Polyester B var fremstilt ved kondensasjon av de nevnte karbonsyrene med propylenglykol og dipropylenglykol. Tabell 3 nedenfor angir propylenglykol og dipropylenglykol. Tabell 3 nedenfor angir sammensetningene og egenskapene for blandingene. Polyester A was produced by condensation of phthalic acid and maleic acid with ethylene glycol and diethylene glycol. Polyester B was produced by condensation of the mentioned carboxylic acids with propylene glycol and dipropylene glycol. Table 3 below indicates propylene glycol and dipropylene glycol. Table 3 below indicates the compositions and properties of the mixtures.
Eksempel IV Example IV
Polyetylen av lav tetthet (0,92 g/cn<r>) med smelteindeksPolyethylene of low density (0.92 g/cn<r>) with melt index
4,0 g/10 min. ble modifisert ved at den i en "Brabender Plasticord" ble blandet med 0,5-10 vekt-% dien/maleinsyre-anhydridkopolymer (DIEN-MHA) og 0,05-0,2 vekt-% organisk perokdyd, og (blandingene 27 og 28) 5-20% etylen/vinylacetat (EVA)-kopolymer eller styren/butadienblokk-kopolyraer (SBS). 4.0 g/10 min. was modified by mixing it in a "Brabender Plasticord" with 0.5-10 wt% diene/maleic anhydride copolymer (DIEN-MHA) and 0.05-0.2 wt% organic peroxide, and (the mixtures 27 and 28) 5-20% ethylene/vinyl acetate (EVA) copolymer or styrene/butadiene block copolymers (SBS).
Blandtemepraturn var 130-300°C og blandtiden 5-10 min. Resultatene er gjengitt i tabell 4. The mixing temperature was 130-300°C and the mixing time 5-10 min. The results are reproduced in table 4.
Olefinen i DIEN-MHA kopolymeren er en blanding av konjungerende alifatiske og cykliske diener The olefin in the DIEN-MHA copolymer is a mixture of conjugating aliphatic and cyclic dienes
EVA, vinylacetatinnhold 20 vekt-%EVA, vinyl acetate content 20% by weight
SBS, styreninnhold 30 vekt-%SBS, styrene content 30% by weight
Eksempel VExample V
Polyetylen av lav tetthet (0,92 g/cm 3) ble modifisert ved at den, i en "Brabender Plasticord" blander, ble blandet med 1-2 vekt-% umettet polyester og 0,05-0,2 vekt-% organsik peroksyd, og til blandingen ble det satt en liten mengde styren/maleinsyreanhydridkopolymer (SMA 3). Blandtemperaturen var 130-300°C og blandtiden 5-10 min. Resultatene er gjengitt i tabell 5 nedenfor. Low density polyethylene (0.92 g/cm 3 ) was modified by mixing it, in a "Brabender Plasticord" mixer, with 1-2% by weight of unsaturated polyester and 0.05-0.2% by weight of organic silica peroxide, and to the mixture was added a small amount of styrene/maleic anhydride copolymer (SMA 3). The mixing temperature was 130-300°C and the mixing time 5-10 min. The results are reproduced in table 5 below.
A er den samme som i eksempel III A is the same as in Example III
EVA er den samme som i eksempel IVEVA is the same as in Example IV
MK = ikke-brytbar bindingMK = unbreakable bond
(i parenteser: adhesjon til stål)(in brackets: adhesion to steel)
Eksempel VIExample VI
Blandinger svarende til blandingene 8 og 14 ble fremstilt i en "Buss" elte-innretning, og med blandingene ble det fremstilt filmer av 0,04 mm tykkelse under anvendelse av en "Brabender Plasticorder PLE 651" og dertil hørende utstyr. Egenskapene for filmene var som angitt i tabell 6. Mixtures corresponding to mixtures 8 and 14 were prepared in a "Buss" kneader, and with the mixtures films of 0.04 mm thickness were produced using a "Brabender Plasticorder PLE 651" and associated equipment. The properties of the films were as indicated in Table 6.
Turbiditet ASTM D 1003 Turbidity ASTM D 1003
Glans ASTM D 523Gloss ASTM D 523
Strekkstyrke-egenskaper ASTM D 882-75b MD = bearbeidelsesretningen på filmen Tensile strength properties ASTM D 882-75b MD = the processing direction of the film
CD = på tvers av bearbeidelsesretningen for filmen LDPE, tetthet 0,92 g/cm 3, smelteindeks 4,5 g/10 min. CD = across the processing direction of the film LDPE, density 0.92 g/cm 3, melt index 4.5 g/10 min.
Claims (8)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/FI1984/000014 WO1985003512A1 (en) | 1984-02-03 | 1984-02-03 | Procedure for improving the adhesion properties of polyolefins |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| NO853642L true NO853642L (en) | 1985-09-17 |
Family
ID=8556352
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO853642A NO853642L (en) | 1984-02-03 | 1985-09-17 | PROCEDURE FOR IMPROVING THE ADHESION PROPERTIES OF POLYOLEFINES. |
Country Status (7)
| Country | Link |
|---|---|
| DE (1) | DE3490657T1 (en) |
| DK (1) | DK448585A (en) |
| GB (1) | GB2163171B (en) |
| NL (1) | NL8420025A (en) |
| NO (1) | NO853642L (en) |
| SE (1) | SE8504543L (en) |
| WO (1) | WO1985003512A1 (en) |
Families Citing this family (3)
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3497574A (en) * | 1961-04-04 | 1970-02-24 | Jack J Press | Adhesive compositions |
-
1984
- 1984-02-03 NL NL8420025A patent/NL8420025A/en not_active Application Discontinuation
- 1984-02-03 GB GB08521523A patent/GB2163171B/en not_active Expired
- 1984-02-03 DE DE19843490657 patent/DE3490657T1/en not_active Ceased
- 1984-02-03 WO PCT/FI1984/000014 patent/WO1985003512A1/en active Application Filing
-
1985
- 1985-09-17 NO NO853642A patent/NO853642L/en unknown
- 1985-10-02 DK DK448585A patent/DK448585A/en not_active Application Discontinuation
- 1985-10-02 SE SE8504543A patent/SE8504543L/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DK448585D0 (en) | 1985-10-02 |
| GB2163171A (en) | 1986-02-19 |
| NL8420025A (en) | 1985-12-02 |
| DE3490657T1 (en) | 1986-02-06 |
| SE8504543D0 (en) | 1985-10-02 |
| GB8521523D0 (en) | 1985-10-02 |
| WO1985003512A1 (en) | 1985-08-15 |
| SE8504543L (en) | 1985-10-02 |
| DK448585A (en) | 1985-10-02 |
| GB2163171B (en) | 1987-12-02 |
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