Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
  • C09J151/06—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on 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
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/36—Polymerisation in solid state
• • 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
  • 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

Definitions

• the invention relates to a process for the preparation of carboxylated ethylene polymer blends composed of at least two different ethylene homopolymers and / or copolymers, in two stages and their use as adhesion promoters in plastic-metal composites.
• carboxylated olefin polymers based on polyethylenes of different density (LDPE, MDPE, HDPE), ethylene / ⁇ , ß-ethyle- nically unsaturated C 3 takes place - to C 2- olefin copolymers (LLDPE, POE) or else of propylene homo- (HPP) as well as random (random) and heterophasic propylene copolymers (RCP, HCP), ethylene / propylene copolymers (EPC) or ethylene / propylene / diene terpolymers (EPDM), the (C 150-300 0) are prepared by grafting a carboxyl-containing monomer such as acrylic acid, fumaric acid, and especially maleic anhydride, the olefmische backbone polymer in the presence of a radical generating peroxidic initiator generally by reactive extrusion at high temperatures ( WO WO
• the carboxylation of olefin polymers carried out in solid-fluid particulate polymer phase is based on an economical technology (DD 275160, below the melting or softening temperature of the graft substrate) A3, DD 275161 A3, DD 300977 A7, DE 4123972 A1, DE 4342605 A1, EP 0469693 B1).
• Especially suitable backbone polymers are partially crystalline olefin polymers which, in the amorphous phase which forms between their glass and melting point, have high diffusion rates for low molecular weight compounds such as acid groups.
• Anhydride monomers one of the prerequisites for their high Pfropfpolymerisations GmbHen allow.
• Amorphous and low-crystalline olefin elastomers having a specific morphology can also be used as the polymer backbone for the free-radical solid-state graft modification under certain polymerization conditions (EP 0642538 B1, EP 0805827 B1), but without the use as highly effective adhesion promoters, in particular for demanding metal / plastic Consortia to achieve required properties.
• adhesion promoters include not only carboxylated (maleated) poly- ethylenes with high density (HDPE) or branched low density polyethylenes (LDPE) especially carboxylated linear low density ethylene copolymers, either with a low C 3 - to C 2 olefin -Comonomeranteil below 15% by mass (LLDPE) or with higher C 3 - to C 2 -olefin comonomer content (above 15% by mass, POE), in particular ethylene / octene (C ⁇ ) copolymers (EOC), as well as predominantly Propylene units existing random-propylene / ethylene copolymers, which for the purpose of their carboxylation exclusively by melt-grafting - preferably using MSA as Pfropfagens - prepared (US 5,346,963, US 6,384,139 B1, US 6,331,592 B1, US 6,884.
• MSA as Pfropfagens - prepared
• EP 0659784 B1 can be used as adhesives for various applications (EP 0696303 B1, EP 0754731 B1, EP 0878510 B1J.
• melt-carboxylated (-maleinated) ethylene / vinyl acetate (EVA) or ethylene / (meth) acrylic acid ester copolymers (E (M) AE) are used (EP 0266994 A2, EP 0647246 B1, WO 93/01052 A1 ).
• adhesive resin compositions using graft copolymerized mixtures of a crystalline polyolefin, eg. HDPE or LLDPE, and an amorphous or low crystalline olefin copolymer, e.g. B. ethylene / propylene rubber (EPM) known EP 0501762 B1.
• the object of the present invention was - while avoiding the disadvantages described - a process for the preparation of a coupling agent (adhesive) based on the carboxylation of polyethylenes (HDPE, LDPE) and / or ethylene / ⁇ , ß-ethylenically unsaturated C 3 - to Ci 2- olefin copolymers (EPC, LLDPE, POE) to develop.
• a coupling agent adheresive
• HDPE polyethylenes
• LDPE polyethylenes
• EPC ß-ethylenically unsaturated C 3 - to Ci 2- olefin copolymers
• the present invention is a process for the preparation of carboxylated ethylene polymer blends in two stages, according to which in a first stage in a fluid mixing reactor to 100 parts by mass solid-fluid particulate ethylene polymer with MFR (190 0 C / 2.16 kg coating weight)> 20 g / 10 min, selected from ethylene homopolymers and / or linear ethylene copolymers of the composition ⁇ 80 to 98% by mass of ethylene / 2 to ⁇ 20% by mass of C 3 to C 4 olefin units, 0.05 to 15 parts by mass an ⁇ , ß-ethylenically unsaturated mono- and / or dicarboxylic acid or its anhydride (carboxyl monomer) or a monomer mixture containing at least one carboxyl monomer and 0.01 to 10 parts by weight of a free radical initiator having a 1-hour half-life temperature (THW / IIO added between 50 and 200 0 C or corresponding initiator mixture and graft polymerized at reaction
• an olefinic elastomer selected from among the elastomeric polypropylenes (ELPP) or random propylene copolymers containing from 5 to 50% by weight of ethylene and / or ⁇ , ⁇ -ethylenically unsaturated C 4 to C 8 olefin and / or diene units is most commonly used , preferably 10 to 25 mass% ethylene units (PER), or ethylene copolymers with ⁇ 20 mass% ⁇ .
• PER mass% ethylene units
• EOR ethylene copolymers with ⁇ 20 mass% ⁇ .
• ß-ethylenisch insatiated C 3 - to C 2 -Olef ⁇ n Anlagenen (EOR) preferably propylene, butene, hexene or Methylpenten- or octene units, more preferably with 25 to 50% by mass of propylene (EPR *), butene-1 (EBR *) or octene-1 units (EOR *), or an
• the addition of the olefinic elastomer can be omitted (special embodiment based on 0 parts by mass of elastomer).
• the linear high density polyethylenes are between 0.940 and 0.965 g / cm 3 (HDPE) and linear ethylene / ⁇ 15% by mass of C 3 - to C 2 olefin copolymers with low density ⁇ 0.940 g / cm 3 (LLDPE) generally by means of known technologies of the coordinative catalysis using the catalysts of the Ziegler or Ziegler-Natta - or Phillips-type generated.
• the present invention can be used ethylene copolymers having a high C 3 are - to C 2 olefin content ⁇ 15% by mass (EOP, EOR) and the composite containing predominantly propylene units, olefin, such as especially PER, as well as elastomeric polypropylenes (ELPP) known to be using made of special metallocene catalyst systems.
• blends consisting of at least two different ethylene (co) polymers, in particular for the melt-grafting stage, in the form of compounds or reactor blends, is a suitable embodiment of the process according to the invention, according to which a blend of 10-90% by weight % LDPE or LLDPE and 90-10% by mass HDPE, preferably from 20-80% by mass LLDPE and 80-20% by mass HDPE, with MFR (190 ° C / 2.16 kg) ⁇ 20 g / 10 min , the reactor, preferably a twin-screw kneader (DSK), is used.
• a twin-screw kneader a twin-screw kneader
• the carboxyl monomer preferably maleic anhydride (MSA) and / or acrylic acid (AS), can also be used as a mixture with a comonomer from the group of vinylaromatics, preferably styrene, and / or the C 1 to C 12 alkyl esters of the acrylic or Methacrylic acid, preferably methyl methacrylate (MMA) or methyl (MA) or Ethyl (EA) or butyl acrylate (BA), corresponding compositions 99-20% by mass of carboxyl and 1-80% by mass of comonomer, preferably 90-50% by mass of MSA and / or AS and 10-50% by mass of styrene , be used in the solid phase stage.
• MMA methyl methacrylate
• MA methyl
• EA Ethyl
• BA butyl acrylate
• the free-radically initiated two-stage grafting is advantageously carried out using a free-radical generator or preferably a mixture consisting of at least two different free-radical initiators using organic peroxides having half-life temperatures after one hour T H w / h between 50 and 200 0 C in order to achieve sufficient degrees of carboxylation and a uniform grafting and after one minute T ⁇ w / imine 85-250 0 C (measured in 0.1 molar monochlorobenzene solution), in the entire ethylene polymer Pfropfsub- stratmenge related concentration between 0.001 and 5% by weight, preferably between 0, 02 and 2% by mass.
• Suitable radical initiators are Dialkylperoxidicarbonate with a 1 -hour half-life temperature (T ⁇ w / i h) between 55 and 66 0 C, preferably Dibutylperoxidicarbonat (DBPOC) and dicetyl (DCPOC) with T ⁇ w / ih of 65 0 C, dilauroyl peroxide (DLPO) with T ⁇ w / i h of 80 0 C, dibenzoyl peroxide (DBPO) with T H w / i h of 91 0 C, tert-butyl peroxy-2-ethylhexanoate (TBPEH) with T H w / ih of 91 0 C, tert.
• DBPC Dibutylperoxidicarbonat
• DCPOC dicetyl
• DLPO dilauroyl peroxide
• DBPO dibenzoyl peroxide
• TBPIB Butylperoxy-isobutyrate
• DTBPC 1, 1-di- (tert-butylperoxy) -cyclohexane
• DCP dicumyl peroxide
• a preferred embodiment of the process for producing carboxylated ethylene copolymers or ethylene copolymer blends is that in the first stage to 100 parts by weight of particulate ethylene polymer with MFR (190 ° C / 2.16 kg) between 20 and 1000 g / 10 min, selected from a Ethylene homopolymer (HDPE-NMw, LDPE-NM W ) and / or linear ethylene copolymer of composition> 90 to 98% by mass of ethylene / 2 to ⁇ 10% by mass of C 3 to C 8 olefin units (LLDPE * -NM W ) , 0.2 to 12 parts by weight of MSA, alone or as a monomer mixture with 0.02 to 6 parts by weight of styrene, with the addition of 0.05 to 5 parts by weight of at least two radical-forming denden initiators with different 1-hour half-life temperatures ( ⁇ Hw / i h ) between 50 and 120 0 C and between 120 and 180 0 C existing mixture at reaction temperatures between
• the olefinic elastomer is used to supply the stabilizer / antioxidant required for the entire carboxylated ethylene polymer blend, in or on which it has been dispersed by means of a separate mixing technology.
• Stabilizing agents and / or antioxidants are the substances known for olefinic polymers and elastomers, in particular primary antioxidants based on sterically hindered phenol compounds, in an amount of from 0.01 to 5 parts by weight, preferably from 0.1 to 2, based on 100 parts by weight of olefin elastomer Mass parts, usable. Also, combinations of at least one primary and one secondary antioxidant, such as. B. systems of a sterically hindered phenol and a phosphite compound can be used.
• the graft-modified ethylene polymer blends having a degree of carboxylation between 0.05 and 1% by mass, preferably between 0.1 and 0.6% by mass, may be used as adhesion promoters and / or adhesives for various substrates, preferably on and between metallic surfaces , be used.
• reaction mixture is dispersed in a nitrogen atmosphere at a stirring speed of 400 min '1 with simultaneous increase in temperature at a heating rate of 1, 2 ° C / min and upon reaching the final reaction temperature TRI of 70 0 C over a time tm of 60 min to TRI held.
• the solid phase reaction is terminated by discharging the reaction product into the cooling mixer having a temperature of 20 ° C, from which it is later removed for the second melt-grafting step (Example 13).
• Table 1 contains the process parameters important for the 1st stage: - Example number (column 1) Ethylene polymer (grafting substrate) used, in% by mass (Ma .-%) (column 2)
• MMIh 1.16 parts by mass per hour
• the following ethylene polymer graft substrates are:
• Table 2 lists: Column 1: Example number Column 2: Concentration of solid phase graft product used with specification of the corresponding Bspl.-Nr./Table 1, in parts by weight per hour [MT / h] Column 3: Type and concentration of LLDPE used -HM W , HDPE-HM W or
• the grafted MSA or AS content CS ex ie the degree of grafting (also referred to as carboxylation or in the MSA grafting as Malein michsgrad) is by means of back-titration of not hydrolyzed by the proportion of carboxylic acid (MSA or AS) potassium hydroxide as follows determined:
• melt flow rates MFR (190 ° C / 5 kg application weight) have been determined according to ISO 1133.
• Table 2 lists the melt-grafting parameters as well as the MFR and CSex values obtained for the carboxylated ethylene (co) polymer systems consisting of the abovementioned components.
• the adhesive strength characteristic is that in a material testing machine TC-FR010TH. A5V from Zwick GmbH & Co. has been used on clamped samples of aluminum sheet strips / 0.3 mm bonding agent film / aluminum sheet strip composites (AI / HV / AI) with a tensile strength of 100 mm / min determined peel strength.
• the granules obtained by means of UWG are extruded into 0.3 mm thick films, cut into strips 80 mm in length and 40 mm in width and placed between two Al strips of the same dimension.
• a tempering of AI / HV / AI composites which are then measured after different storage times in the oven without additional weight and pressure. The measurement is carried out after a storage time of 8 minutes on each of three cut (13.3 x 80) mm AI / HV / AI test strip.
• the peel strengths given in Table 2 are the average values obtained from in each case four Al / HV / Al composites (and thus from a total of 12 sample individual values) for a tested adhesive.
• the carboxylated ethylene polymer blends produced according to the invention are characterized by high adhesive strengths (peel strengths) while at the same time being good for use suitable melt viscosities corresponding to MFR (190 ° C / 5 kg) - values between 1 and 7 g / 10 min.
• peel strengths corresponding to MFR (190 ° C / 5 kg) - values between 1 and 7 g / 10 min.
• MFR 190 ° C / 5 kg

Landscapes

• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Graft Or Block Polymers (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Laminated Bodies (AREA)
• Processes Of Treating Macromolecular Substances (AREA)
• Adhesives Or Adhesive Processes (AREA)

Priority Applications (6)

Applications Claiming Priority (2)

Publications (2)

Family

ID=40256865

Family Applications (1)

Country Status (9)

Cited By (2)

Families Citing this family (7)

Family Cites Families (42)

• 2007
  • 2007-09-11 DE DE102007043972A patent/DE102007043972B4/de active Active
• 2008
  • 2008-09-09 RU RU2010114263/04A patent/RU2010114263A/ru not_active Application Discontinuation
  • 2008-09-09 WO PCT/DE2008/001506 patent/WO2009033465A2/de not_active Ceased
  • 2008-09-09 AT AT08801310T patent/ATE512167T1/de active
  • 2008-09-09 US US12/677,344 patent/US8742016B2/en active Active
  • 2008-09-09 EP EP08801310A patent/EP2190885B1/de active Active
  • 2008-09-09 CN CN2008801155638A patent/CN101939340B/zh active Active
  • 2008-09-09 CA CA2704736A patent/CA2704736C/en active Active
  • 2008-09-09 JP JP2010524348A patent/JP5690140B2/ja active Active

Also Published As

Similar Documents

Legal Events