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
  • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
  • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
• • 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
  • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
  • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
  • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
• • 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
  • C09J133/00—Adhesives based on 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
  • C09J133/04—Homopolymers or copolymers of esters
• • 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
  • C09J133/00—Adhesives based on 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
  • C09J133/04—Homopolymers or copolymers of esters
  • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C09J133/10—Homopolymers or copolymers of methacrylic acid esters
  • C09J133/12—Homopolymers or copolymers of methyl methacrylate
• • 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
  • C09J2301/00—Additional features of adhesives in the form of films or foils
  • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
  • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

Definitions

• the present invention relates to a composition suitable as (meth) acrylic adhesive composition
• a composition suitable as (meth) acrylic adhesive composition comprising a multistage polymer in form of polymeric particles and a (meth) acrylic polymer, its process of preparation, and its use.
• the present invention relates to a structural (meth) acrylic adhesive composition
• a structural (meth) acrylic adhesive composition comprising a multistage polymer in form of polymeric particles made by a multistage process and a (meth) acrylic polymer, its process of preparation and its use.
• the present invention relates to structural (meth) acrylic adhesive composition made from a two part composition comprising a multistage polymer in form of polymeric particles made by a multistage process and a (meth) acrylic polymer, its process of preparation, and its use.
• Structural adhesives are materials of high strength and performance. Their function is primary function is to hold structures together and to be capable of resisting to high loads.
• Thermosetting acrylic adhesives are rubber-toughened systems that cure rapidly at room temperature to provide a crosslinked structural adhesive suitable for bonding metals, engineering plastics, composites and many other substrates with minimal surface preparation.
• the two materials to be bonded can be of different nature .
• the core-shell polymer has to be distributed homogeneously throughout the adhesive in order to guaranty a satisfying impact performance of the adhesive. This homogenous distribution is not easily achieved with all kind of core shell impact modifiers.
• the objective of the present invention is to propose a multistage polymer composition which is rapidly and easily dispersible in liquid and/or reactive resins suitable for (meth) acrylic adhesive compositions.
• An objective of the present invention is also to propose a multistage polymer composition which is easily dispersible in liquid and/or reactive resins in form of a polymer powder suitable for
• An additional objective of the present invention is to propose structural adhesive polymer composition that has good compromise between a good tensile strength and a high elongation at break.
• An additional objective of the present invention is to propose structural adhesive polymer composition that has satisfying impact performance and a high tensile strength, while having at the same time an increased adhesion as measured by the shear strength (lap shear test) .
• Another objective of the present invention is to propose a method for structural adhesive polymer composition which comprises a multistage polymer (MP1) having a core-shell structure, that is easily dispersible in in liquid and/or reactive resins.
• MP1 multistage polymer
• Still a further objective of the present invention is the use of a liquid polymer composition comprising a multistage polymer having a core-shell structure, with a homogenous distribution of the multistage polymer for preparing structural (meth) acrylic adhesive .
• the document WO2013/126377 discloses a structural acrylic adhesive.
• the adhesive can comprise toughening agents.
• the document WO02/076620 discloses an easy to manufacture (meth) acrylic adhesive composition.
• the composition comprises core shell impact modifiers that are dispersed in order to insure a high impact resistance.
• compositions for a structural adhesive are based on acrylates and methacrylates and comprises as well elastomeric block copolymers and elastomeric polymeric particles.
• composition comprising a) a first part composition (PI) comprising
• the polymer (CI) is having a mass average molecular weight Mw between 2 OOOg/mol and 1 000 OOOg/mol, is suitable as (meth) acrylic adhesive composition.
• composition comprising a) a first part composition (PI) comprising
• the polymer (CI) is having a mass average molecular weight Mw between 2 OOOg/mol and 1 000 OOOg/mol, yields to a (meth) acrylic adhesive composition having increase elongation at break and shear strength adhesion.
• the polymer (CI) is having a mass average molecular weight Mw between 2 OOOg/mol and 1 000 OOOg/mol, yields to a (meth) acrylic adhesive composition having increase elongation at break and shear strength adhesion.
• a polymerization initiator characterized in that the polymer (CI) is having a mass average molecular weight Mw between 2 OOOg/mol and 1 000 OOOg/mol, can be used for (meth) acrylic adhesive composition having increase elongation at break and shear strength adhesion.
• the present invention relates to a composition suitable as (meth) acrylic adhesive composition
• a composition suitable as (meth) acrylic adhesive composition comprising
• the polymer (CI) is having a mass average molecular weight Mw between 2 OOOg/mol and 1 000 OOOg/mol.
• the present invention relates to a method for manufacturing the polymer composition suitable as (meth) acrylic adhesive composition comprising the steps of
• the polymer (CI) is having a mass average molecular weight Mw between 2 OOOg/mol and 1 000 OOOg/mol.
• the present invention relates to a structural adhesive polymer composition
• a structural adhesive polymer composition comprising a) a first part composition (PI) comprising
• the polymer (CI) is having a mass average molecular weight Mw between 2 OOOg/mol and 1 000 OOOg/mol.
• the present invention relates to the use of a polymer composition
• a polymer composition comprising
• polymer powder as used is denoted a polymer comprising powder grain in the range of at least ⁇ obtained by agglomeration of primary polymer comprising particles in the nanometer range.
• primary particle as used is denoted a spherical polymer comprising particle in the nanometer range.
• the primary particle has a weight average particle size between 20nm and 800nm.
• particle size as used is denoted the volume average diameter of a particle considered as spherical .
• thermoplastic polymer as used is denoted a polymer that turns to a liquid or becomes more liquid or less viscous when heated and that can take on new shapes by the application of heat and pressure.
• thermosetting polymer as used is denoted a polymer that is irreversibly into an infusible, insoluble polymer network after curing.
• copolymer as used is denoted that the polymer consists of at least two different monomers.
• multistage polymer as used is denoted a polymer formed in sequential fashion by a multi-stage polymerization process.
• Preferred is a multi-stage emulsion polymerization process in which the first polymer is a first-stage polymer and the second polymer is a second-stage polymer, i.e., the second polymer is formed by emulsion polymerization in the presence of the first emulsion polymer, with at least two stages that are different in composition.
• (meth) acrylic as used is denoted all kind of acrylic and methacrylic monomers.
• (meth) acrylic polymer as used is denoted that the (meth) acrylic polymer comprises essentially polymers comprising (meth) acrylic monomers that make up 50wt% or more of the (meth) acrylic polymer.
• dry as used is denoted that the ratio of residual water is less than 1.5 wt% and preferably less than 1 wt% .
• the polymeric composition according to the invention is a two part acrylic adhesive composition that comprises a first part composition (PI) and a second part composition (P2) .
• the first part (PI) comprises at least the following components: al) at least one (meth) acrylic monomer (Ml), a2 ) a multistage polymer (MP1) having a core-shell structure and a3) a polymer (CI ) .
• the (meth) acrylic monomer (s) (Ml) may represent at least 20wt% of the sum of all components of the first part composition (PI) .
• the (meth) acrylic monomer (s) (Ml) may represent at most 75 t% of the sum of all components of the first part composition (PI) .
• the multistage polymer (MP1) may represent at least 5 t% of the sum of all components of the first part composition (PI) .
• the multistage polymer (MP1) may represent at most 75 t% of the sum of all components of the first part composition (PI) .
• the multistage polymer (s) (MP1) represent (s) from 10wt% to 20wt%, preferably from 12 t% to 20 wtl, more preferably from 13 t% to 18 t%, advantageously from 15 t% to 18 t% of the sum of all components of the first part composition (PI) ⁇
• the polymer (CI) may represent at least l t% of the sum of all components of the first part composition (PI) .
• first part composition (PI) may optionally comprisesone or more additional compounds, in particular selected from the group consisting of:
• the second part composition (P2) comprises at least bl) a polymerization initiator.
• the second part composition (P2) may optionally comprise one or more additional compounds, in particular selected from the group consisting of:
• a diluent non-reactive diluent or reactive diluent
• a plasticizer an adhesion promoter
• (meth) acrylic monomer (Ml) may be chosen from a methacrylic monomer or an acrylic monomer or a mixture thereof.
• the (meth) acrylic monomer (Ml) is preferably chosen from acrylic acid, methacrylic acid, acrylic ester monomers, methacrylic ester monomers and mixtures thereof.
• (meth) acrylic monomer (Ml) is chosen from acrylic acid, methacrylic acid , alkyl acrylic monomers, alkyl methacrylic monomers and mixtures thereof, the alkyl group having from 1 to 22 carbons, either linear, branched or cyclic; preferably the alkyl group having from 1 to 12 carbons, either linear, branched or cyclic.
• the (meth) acrylic monomer (Ml) is chosen from methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, methacrylic acid, acrylic acid, n-butyl acrylate, iso- butyl acrylate, n-butyl methacrylate, iso-butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, allyl acrylate, allyl methacrylate, n-propyl acrylate, n-propyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, n- octyl acrylate, n-octyl methacrylate, n
• At least 50 t%, preferably at least 60 t% of the (meth) acrylic monomer (Ml) is methyl methacrylate.
• the (meth) acrylic monomer (s) (M2) is (are) different from the (meth) acrylic monomer (Ml) .
• the (meth) acrylic monomer (M2) may be chosen from acrylic ester monomers or methacrylic ester monomers that have at least one atom that is not a carbon or hydrogen in the group of the alcohol part of the ester (not taking into account the atoms of the ester group itself) .
• the atom is oxygen.
• An example is hydroxyl ethyl methacrylate or polyether chains comprising acrylic momoners.
• (Meth) acrylic monomer (M2) are for example chosen from the group consisting of: 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2- and 3-hydroxypropyl acrylate, 2- and 3- hydroxypropyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl acrylate, 2-ethoxyethyl methacrylate, 2- or 3-ethoxypropyl acrylate, 2- or 3-ethoxypropyl methacrylate, 2 ( 2-ethoxyethoxy) ethyl acrylate, methoxy polyethylene glycol methacrylate (preferably comprising 2 to 8 repeating (EO) units), methoxy polyethylene glycol acrylate preferably comprising 2 to 8 repeating (EO) units), polyethylene glycol methacrylate preferably comprising 2 to 8 repeating (EO) units) , polyethylene glycol acrylate preferably comprising 2 to 8
• the (meth) acrylic monomer (M3) can be the same as the (meth) acrylic monomer (Ml) .
• the (meth) acrylic monomer (M3) is methyl methacrylate .
• the flexibilizer may be chosen from block copolymer, for example chosen from styrene block copolymer (SBC) and styrene-isoprene-styrene (SIS) .
• SBC styrene block copolymer
• SIS styrene-isoprene-styrene
• the flexibilizer can also be chosen from a liquid elastomer.
• the liquid elastomer may have a weight average molecular weight Mw in the range of lOOOg/mol to 100 000 g/mol, preferably of 1000 g/mol to 15 000 g/mol, more preferably of 1000 g/mol to 9000g/mol and may functionalized with ethylenically unsaturated groups.
• the liquid elastomer is chosen from urethanes oligomers.
• the urethane oligomers comprise at least two double bonds, preferably from 2 to 9 two double bonds.
• the double bonds are part of an acryl group, a methacryl group or an allyl group.
• the flexibilizer is chosen from the urethane (meth) acrylate oligomer and mixture thereof.
• a urethane (meth) acrylate oligomer may be any of the type familiar to the skilled person in either the coatings or the adhesives industries.
• urethane (meth) acrylate oligomers are usually the reaction products of an isocyanate component containing at least two isocyanate functional groups with a (meth) acrylate component containing at least one (meth) acrylate functional group and at least one group (such as for example hydroxyl or amino) reactive with the isocyanate functional group.
• urethane (meth) acrylate oligomer can be found for example in US2012/0302695.Mention may be made for example of CN 965, CN 981, CN 9400, CN966H90 commercialized by SARTOMER. [066] With regard to the polymerization accelerator according to the invention, it may be chosen from those well known by the skilled person in either the coatings or the adhesives industries. Mention may be made for example of tertiary amines such as N, N-dimethyl-p- toluidine (DMPT) , N, -dihydroxyethyl-p-toluidine (DHEPT) , organic- soluble transition metal catalysts or mixtures thereof.
• DMPT N-dimethyl-p- toluidine
• DHEPT -dihydroxyethyl-p-toluidine
• adhesion promoter it may be chosen from those well known by the skilled person in either the coatings or the adhesives industries. Mention may be made for example of aminosilane, metacryloyl silane, phosphates, methacrylated phosphate ester, epoxidized silane.
• the rheology modifier it may be chosen from those well known by the skilled person in either the coatings or the adhesives industries . Mention may be made for example of silica (in particular fumed silica) , micronized amide wax (such as for example CRAYVALLAC series available from Arkema) .
• the initiator may be chosen from those well known by the skilled person in either the coatings or the adhesives industries. Mention may be made for example of peroxides or hydroperoxides (such as for example diacyl peroxides, dialkyl peroxides), peroxy esters, peroxyacetals , azo compounds, and mixtures thereof.
• peroxides or hydroperoxides such as for example diacyl peroxides, dialkyl peroxides
• peroxy esters such as for example diacyl peroxides, dialkyl peroxides
• peroxyacetals peroxyacetals
• azo compounds azo compounds
• the initiator for starting the polymerization may be chosen from isopropyl carbonate, benzoyl peroxide, lauroyl peroxide, caproyl peroxide, dicumyl peroxide, tert-butyl perbenzoate, tert- butyl per ( 2-ethylhexanoate ) , cumyl hydroperoxide, l,l-di(tert- butylperoxy) -3,3, 5-trimethylcyclohexane, tert-butyl peroxyisobutyrate, tert-butyl peracetate, tert-butyl perpivalate, amyl perpivalate, tert-butyl peroctoate, azobisisobutyronitrile (AIBN) , azobisisobutyramide, 2,2' -azobis (2, 4-dimethylvaleronitrile) or 4 , 4 ' -azobis (4-cyanopentanoic) .
• the initiator is benzoyl peroxide or a dibenzoyl peroxide.
• diluent may be chosen from liquid epoxy resins.
• plasticizer it may be chosen from those well known by the skilled person in either the coatings or the adhesives industries. Mention may be made for example of phthalate based plasticizers , of polyol ester (such as for example pentaerythritol tetravalenate, available from Perstop, of epoxidized oil, and mixtures thereof.
• polyol ester such as for example pentaerythritol tetravalenate, available from Perstop, of epoxidized oil, and mixtures thereof.
• the multistage polymer (MPl) of the composition according to the invention may have at least two stages that are different in its polymer composition.
• the multistage polymer is preferably in form of polymer particles considered as spherical particles. These particles are also called core shell particles. The first stage forms the core, the second or all following stages the respective shells. Such a multistage polymer which is also called core/shell particle is preferred .
• the particles according to the invention which is the primary particle, it may have a weight average particle size between 15nm and 900nm.
• the weight average particle size of the polymer is between 20nm and 800nm, more preferably between, more preferably between 25nm and 600nm, still more preferably between 30nm and 550nm, again still more preferably between 35nm and 500nm, advantageously between 40nm and 400nm, even more advantageously between 75nm and 350nm and advantageously between 80nm and 300nm.
• the primary polymer particles can be agglomerated giving a polymer powder.
• the primary polymer particle according to a first preferred embodiment of the invention has a multilayer structure comprising in particular at least one stage (A) comprising a polymer (Al) having a glass transition temperature below 10°C, at least one stage (B) comprising a polymer (Bl) having a glass transition temperature over 60°C and at least one stage (C) comprising a polymer (CI) having a glass transition temperature over 30°C.
• the primary polymer particle comprises the components a2 ) and a3) of the composition according to the invention.
• (A) comprising a polymer (Al) having a glass transition temperature below 10°C, at least one stage (B) comprising a polymer (Bl) having a glass transition temperature over 60 °C and the component a3) the polymer (CI) as additional stage (C) .
• stage (A) is the first stage of the at least two stages and the stage (B) comprising polymer (Bl) is grafted on stage (A) comprising polymer (Al) or another intermediate layer.
• stage (A) There could also be another stage before stage (A) , so that stage (A) would also be a shell.
• the polymer (Al) having a glass transition temperature below 10°C comprises at least 50wt% of polymeric units coming from alkyl acrylate and the stage (A) is the most inner layer of the polymer particle having the multilayer structure. I n other words the stage (A) comprising the polymer (Al) is the core of the polymer particle.
• the polymer (Al) of the first preferred embodiment is a (meth) acrylic polymer comprising at least 50wt% of polymeric units coming from acrylic monomers. Preferably 60wt% and more preferably 70wt% of the polymer (Al) are acrylic monomers.
• the acrylic momonomer in polymer (Al) may comprise monomers chosen from CI to C18 alkyl acrylates or mixtures thereof. More preferably acrylic monomer in polymer (Al) comprises monomers of C2 to C12 alkyl acrylic monomers or mixtures thereof Still more preferably acrylic monomer in polymer (Al) comprises monomers of C2 to C8 alkyl acrylic monomers or mixtures thereof.
• the polymer (Al) can comprise a comonomer or comonomers which are copolymerizable with the acrylic monomer, as long as polymer (Al) is having a glass transition temperature of less than 10°C.
• the comonomer or comonomers in polymer (Al) are preferably chosen from (meth) acrylic monomers and/or vinyl monomers. [086] Most preferably the acrylic or methacrylic comonomers of the polymer (Al) are chosen from methyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, tert-butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and mixtures thereof, as long as polymer (Al) is having a glass transition temperature of less than 10°C.
• polymer (Al) is a homopolymer of butyl acrylate .
• the glass transition temperature Tg of the polymer (Al) comprising at least 70wt% of polymeric units coming from C2 to C8 alkyl acrylate is between -100°C and 10°C, even more preferably between -80°C and 0°C and advantageously between -80°C and -20°C and more advantageously between -70°C and -20°C.
• the polymer (Al) having a glass transition temperature below 10°C comprises at least 50wt% of polymeric units coming from isoprene or butadiene and the stage (A) is the most inner layer of the polymer particle having the multilayer structure. In other words the stage (A) comprising the polymer (Al) is the core of the polymer particle.
• the polymer (Al) of the core of the second embodiment mention may be made of isoprene homopolymers or butadiene homopolymers, isoprene-butadiene copolymers, copolymers of isoprene with at most 98 wt% of a vinyl monomer and copolymers of butadiene with at most 98 wt% of a vinyl monomer.
• the vinyl monomer may be styrene, an alkylstyrene, acrylonitrile, an alkyl (meth) acrylate, or butadiene or isoprene.
• the core is a butadiene homopolymer.
• the glass transition temperature Tg of the polymer (Al) comprising at least 50wt% of polymeric units coming from isoprene or butadiene is between -100°C and 10°C, even more preferably between -90°C and 0°C, advantageously between -80°C and 0°C and most advantageously between -70°C and -20°C.
• the polymer (Al) is a silicone rubber based polymer.
• the silicone rubber for example is polydimethyl siloxane.
• the glass transition temperature Tg of the polymer (Al) of the second embodiment is between -150°C and 0°C, even more preferably between -145°C and - 5°C, advantageously between -140°C and -15°C and more advantageously between -135°C and -25°C.
• polymer (Bl) With regard to the polymer (Bl) , mention may be made for example of homopolymers and copolymers comprising monomers with double bonds and/or vinyl monomers.
• the polymer (Bl) is a (meth) acrylic polymer.
• the polymer (Bl) comprises at least 70wt% monomers chosen from CI to C12 alkyl (meth) acrylates . Still more preferably the polymer (Bl) comprises at least 80 wt% of monomers CI to C4 alkyl methacrylate and/or CI to C8 alkyl acrylate monomers.
• the acrylic or methacrylic monomers of the polymer (Bl) are chosen from methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and mixtures thereof, as long as polymer (Bl) is having a glass transition temperature of at least 60 °C.
• the polymer (Bl) comprises at least 70wt% of monomer units coming from methyl methacrylate.
• the glass transition temperature Tg of the polymer (Bl) is between 60°C and 150°C.
• the glass transition temperature of the polymer (Bl) is more preferably between 80°C and 150°C, advantageously between 90°C and 150°C and more advantageously between 100°C and 150°C.
• the polymer (Bl) is grafted on the polymer made in the previous stage.
• the polymer (Bl) is crosslinked.
• the polymer (Bl) comprises a functional comonomer.
• the functional copolymer is chosen from acrylic or methacrylic acid, the amides derived from this acids, such as for example dimethylacrylamide, 2-methoxy-ethyl acrylate or methacrylate, 2- aminoethyl acrylate or methacrylate which are optionally quaternized, polyethylene glycol (meth) acrylates, water soluble vinyl monomers such as N-vinyl pyrrolidone or mixtures thereof.
• the polyethylene glycol group of polyethylene glycol (meth) acrylates has a molecular weight ranging from 400g/mol to 10 000 g/mol.
• the polymer (CI) may be a copolymer comprising (meth) acrylic monomers. More preferably the polymer (CI) is a (meth) acrylic polymer. Still more preferably the polymer (CI) comprises at least 70wt% monomers chosen from CI to C12 alkyl (meth) acrylates . Advantageously preferably the polymer (CI) comprises at least 80 wt% of monomers from CI to C4 alkyl methacrylate and/or CI to C8 alkyl acrylate monomers.
• the glass transition temperature Tg of the polymer (CI) is between 30°C and 150°C.
• the glass transition temperature of the polymer (CI) is more preferably between 40°C and 150°C, advantageously between 45°C and 150°C and more advantageously between 50°C and 150°C.
• the polymer (CI) is not crosslinked.
• the polymer (CI) is not grafted on any of the polymers (Al) or (Bl) .
• the polymer (CI) comprises also a functional comonomer.
• the functional comonomer has the formula (1)
• wherin Ri is chosen from H or CH3 and R2 is H or an aliphatic oraromatic radical having at least one atom that is not C or H.
• the functional monomer is chosen from glycidyl (meth) acrylate, acrylic or methacrylic acid, the amides derived from these acids, such as, for example, dimethylacrylamide, 2- methoxyethyl acrylate or methacrylate, 2-aminoethyl acrylates or methacrylates are optionally quaternized, polyethylene glycol (meth) acrylates.
• the polyethylene glycol group of polyethylene glycol (meth) acrylates has a molecular weight ranging from 400g/mol to 10 000 g/mol.
• the polymer (CI) comprises from 80wt% to 100wt% methyl methacrylate, preferably from 80wt% to 99.9 t% methyl methacrylate and from 0. l t% to 20wt% of a CI to C8 alkyl acrylate monomer.
• the CI to C8 alkyl acrylate monomer is chosen from methyl acrylate, ethyl acrylate or butyl acrylate .
• the polymer (CI) comprises between 0wt% and 50wt% of a functional monomer.
• the meth) acrylic polymer (PI) comprises between 0wt% and 30wt% of the functional monomer, more preferably between lwt% and 30wt%, still more preferably between 2wt% and 30wt%, advantageously between 3wt% and 30wt%, more advantageously between 5wt% and 30wt% and most advantageously between 5wt% and 30wt%.
• the functional monomer of the second preferred embodiment is a (meth) acrylic monomer.
• the functional monomer has the formula (2) or (3
• Y is N and R4 and/or R3 is H or an aliphatic or aromatic radical.
• the functional monomer (2) or (3) is chosen from glycidyl (meth) acrylate, acrylic or methacrylic acid, the amides derived from these acids, such as, for example, dimethylacrylamide , 2-methoxyethyl acrylate or methacrylate, 2-aminoethyl acrylates or methacrylates are optionally quaternized, acrylate or methacrylate monomers comprising a phosphonate or phosphate group, alkyl imidazolidinone (meth) acrylates, polyethylene glycol (meth) acrylates.
• the polyethylene glycol group of polyethylene glycol (meth) acrylates has a molecular weight ranging from 400g/mol to 10 000 g/mol.
• the polymer (CI) has a mass average molecular weight Mw between 2 OOOg/mol and 1 000 OOOg/mol.
• the polymer (CI) has a mass average molecular weight Mw of at least 100 OOOg/mol, preferably more than 100 OOOg/mol, more preferably more than 105 OOOg/mol, still more preferably more than 110 OOOg/mol, advantageously more than 120 000 g/mol, more advantageously more than 130 000 g/mol and still more advantageously more than 140 000 g/mol .
• the polymer (CI) may have a mass average molecular weight Mw below 1 000 OOOg/mol, preferably below 900 OOOg/mol, more preferably below 800 OOOg/mol, still more preferably below 700 OOOg/mol, advantageously below 600 000 g/mol, more advantageously below 550 000 g/mol and still more advantageously below 500 000 g/mol and most advantageously below 450 000 g/mol.
• the mass average molecular weight Mw of polymer (CI) is preferably between 100 OOOg/mol and 1 000 OOOg/mol, preferably between 105 000 g/mol and 900 000 g/mol and more preferably between 110 OOOg/mol and 800 OOOg/mol advantageously between 120 OOOg/mol and 700 OOOg/mol, more advantageously between 130 OOOg/mol and 600 OOOg/mol and most advantageously between 140 OOOg/mol and 500 OOOg/mol.
• the polymer (CI) has a mass average molecular weight Mw of less than 100 OOOg/mol, preferably less than 90 OOOg/mol, more preferably less than 80 OOOg/mol, still more preferably less than 70 OOOg/mol, advantageously less than 60 000 g/mol, more advantageously less than 50 000 g/mol and still more advantageously less than 40 000 g/mol.
• the polymer (CI) has preferably a mass average molecular weight Mw above 2 OOOg/mol, preferably above 3000g/mol, more preferably above 4000g/mol, still more preferably above 5 OOOg/mol, advantageously above 6 000 g/mol, more advantageously above 6 500 g/mol and even more advantageously above 7 000 g/mol, still more advantageously above 10 000 g/mol and most advantageously above 12 000 g/mol.
• the mass average molecular weight Mw of the polymer (CI) is preferably between 2 OOOg/mol and 100 OOOg/mol, preferably between 3 000 g/mol and 90 000 g/mol and more preferably between 4 OOOg/mol and 80 OOOg/mol advantageously between 5000g/mol and 70 OOOg/mol, more advantageously between 6 OOOg/mol and 50 OOOg/mol, even more advantageously between 10 OOOg/mol and 50 000 g/mol and most advantageously between 10 OOOg/mol and 40 OOOg/mol.
• the mass average molecular weight Mw of the polymer (CI) is chosen according to the first more preferred embodiment or the second more preferred embodiment on function of the acquired viscosity of the composition. If the viscosity has to be low or an additional rheology modifier is present the second more preferred embodiment is preferred. If the viscosity has to be higher or no additional rheology modifier is present the first more preferred embodiment is preferred.
• the primary polymer particle according to the invention may be obtained by a multistage process comprising at least two stages. At least the component a) and the component b) are in particular part of a multistage polymer (MP1) .
• the polymer (Al) having a glass transition temperature below 10°C made during the stage (A), is made before stage (B) or is the first stage of the multistage process.
• the polymer (Bl) having a glass transition temperature over 60 °C made during the stage (B) is made after the stage (A) of the multistage process.
• the polymer (Bl) having a glass transition temperature of at least 30 °C is an intermediate layer of the polymer particle having the multilayer structure.
• the polymer (CI) having a glass transition temperature over 30 °C made during the stage (C) is made after the stage (B) of the multistage process.
• the polymer (CI) having a glass transition temperature over 30°C made during the stage (C) is the external layer of the primary polymer particle having the multilayer structure. In this case the components a2) and a3) are together as part of the composition (PI) .
• stage (A) and stage (B) There could be additional intermediate stages, either between stage (A) and stage (B) and/or between stage (B) and stage (C) .
• the polymer (CI) and the polymer (Bl) are not the same polymer, even if their composition could be very close and some of their characteristics are overlapping.
• the essential difference is that the polymer (Bl) is always part of the multistage polymer (MP1) .
• the weight ratio r of the polymer (CI) of the external layer comprised in stage (C) in relation to the complete polymer particle comprising multistage polymer (MP1) having a core-shell structure and a polymer (CI) (components a2 ) + a3) ) may be at least 5wt% , more preferably at least 7wt% and still more preferably at least 10wt%.
• (C) comprising polymer (CI) in relation to the complete polymer particle comprising multistage polymer (MP1) having a core-shell structure and a polymer (CI) (components a2) + a3)) is preferably at most 30w%.
• the ratio r of polymer (CI) in view of the primary polymer particle comprising multistage polymer (MP1) having a core- shell structure and a polymer (CI) (components a2) + a3) ) is between 5wt% and 30wt% and preferably between 5wt% and 20wt%.
• the polymer (Bl) having a glass transition temperature of at least 30°C is the external layer of the primary polymer particle having the multilayer structure in other words the multistage polymer (MP1) .
• At least a part of the polymer (Bl) of layer (B) is grafted on the polymer made in the previous layer. If there are only two stages (A) and (B) comprising polymer (Al) and (Bl) respectively, a part of polymer (Bl) is grafted on polymer (Al) . More preferably at least 50wt% of polymer (Bl) is grafted.
• the ratio of grafting can be determined by extraction with a solvent for the polymer (Bl) and gravimetric measurement before and after extraction to determine the non-grafted quantity.
• the glass transition temperature Tg of the respective polymers can be estimated for example by dynamic methods as thermo mechanical analysis .
• the polymer composition of the invention comprises no solvents.
• no solvents is meant that eventually present solvent make up less than lwt% of the composition.
• the monomers of the synthesis of the respective polymers are not considered as solvents.
• the residual monomers in the composition present less than 2wt% of the composition.
• the polymer composition according to the invention is dry.
• dry is meant that the polymer composition according to the present invention comprises less than 3wt% humidity and preferably less than 1.5wt% humidity and more preferably less than 1.2wt% humidity.
• the humidity can be measured by a thermo balance that heats the polymer composition and measures the weight loss.
• composition according to the invention preferably does not comprise any voluntary added solvent. Eventually residual monomer from the polymerization of the respective monomers and water are not considered as solvents
• the two components a2 ) the multistage polymer (MP1) having a core-shell structure and a3) the polymer (CI) of the first part composition (PI) form together a polymer composition (PCI), which comprises a) the polymer (Al) having a glass transition temperature of less than 10°C, b) the polymer (Bl) having a glass transition temperature of at least 60°C and c) and the polymer (CI) having a glass transition temperature of at least 30°C.
• a) and b) together correspond to component a2) and c) corresponds to a3) .
• the component c) represents preferably at most 40wt% of the composition based on a) b) and c) .
• the component c) represents at most 35 t% of the composition based on a) , b) and c) ; more preferably at most 30wt%, still more preferably less than 30wt%, advantageously less than 25 t%, more advantageously less than 24 t% and even more advantageously less than 20 t%.
• the ratio r of the polymer (CI) in a composition comprising only the multistage polymer (MP1) and the polymer (CI) is at most 40 t%, preferably at most 35wt%; more preferably at most 30 t%, still more preferably less than 30 t%, advantageously less than 25 t%, more advantageously less than 24wt% and even more advantageously less than 20 t%.
• the component c) represents preferably more than 4wt% of the composition based on a) , b) and c) .
• the component c) represents more than 5wt% of the composition based on a) , b) and c) ; more preferably more than 6 t%, still more preferably more than 7 t%, advantageously more than 8 t% and more advantageously more than 10wt%.
• the ratio r of the polymer (CI) in a composition comprising only the multistage polymer (MP1) and the polymer (CI) is more than 5wt%; more preferably more than 6wt%, still more preferably more than 7wt%, advantageously more than 8wt% and more advantageously more than 10wt%.
• the component c) represents preferably between 4wt% and 40wt% of the composition based on a) b) and c) .
• the component c) represents between 5wt% and 35wt% of the composition based on a) , b) and c) ; more preferably between 6wt% and 30wt%, still more preferably between 7wt% and less than 30wt%, advantageously between 7wt% and less than 25wt%, more advantageously between 7wt% and less than 24wt% and even more advantageously between 10wt% and less than 20wt%.
• the ratio r of the polymer (CI) in a composition comprising only the multistage polymer (MP1) and the polymer (CI) is between 5wt% and 35wt%; more preferably between 6wt% and 30wt%, still more preferably between 7wt% and less than 30wt%, advantageously between 7 t% and less than 25 t%, more advantageously between 7wt% and less than 24wt% and even more advantageously between 10wt% and less than 20wt%.
• At least the component a) and the component b) of composition (PCI) are preferably part of a multistage polymer (MP1) .
• At least the component a) and the component b) are preferably obtained by a multistage process comprising at least two stages; and these two polymer (Al) and polymer (Bl) form a multistage polymer
• PCI polymer composition
• the polymer (CI) has a mass average molecular weight Mw of at least 100 OOOg/mol and that the component c) represents at most 30wt% of the composition based on a) b) and c) .
• step a) is made before step b) .
• step b) is performed in presence of the polymer (Al) obtained in step a) .
• the first preferred method for manufacturing the polymer composition (PCI) according to the invention is a multistep process comprises the steps one after the other of
• the polymer (CI) has a mass average molecular weight Mw of at least 100 OOOg/mol.
• the respective monomers or monomer mixtures (A m ) , (B m ) and (Cm) for forming the layers (A) , (B) and (C) respectively comprising the polymers (Al), (Bl) and (CI) respectively, are the same as defined before.
• the characteristics of the polymers (Al), (Bl) and (CI) respectively, are the same as defined before.
• the first preferred method for manufacturing the polymer composition according to the invention comprises the additional step d) of recovering of the polymer composition.
• recovering is meant partial or separation between the aqueous and solid phase, latter comprises the polymer composition.
• the recovering of the polymer composition is made by coagulation or by spray-drying.
• Spray drying is the preferred method for the recovering and/or drying for the manufacturing method for a polymer powder composition according to the present invention if the polymer (Al) having a glass transition temperature below 10°C comprises at least 50wt% of polymeric units coming from alkyl acrylate and the stage (A) is the most inner layer of the polymer particle having the multilayer structure.
• Coagulation is the preferred method for the recovering and/or drying for the manufacturing method for a polymer powder composition according to the present invention if the polymer (Al) having a glass transition temperature below 10°C comprises at least 50wt% of polymeric units coming from isoprene or butadiene and the stage (A) is the most inner layer of the polymer particle having the multilayer structure .
• the method for manufacturing the polymer composition according to the invention can comprise optionally the additional step e) of drying of the polymer composition.
• drying step e) is made if the step d) of recovering of the polymer composition is made by coagulation.
• the polymer composition comprises less than 3 t%, more preferably less than 1.5 t% advantageously less than 1% of humidity or water.
• the humidity of a polymer composition can be measure with a thermo balance.
• the drying of the polymer can be made in an oven or vacuum oven with heating of the composition for 48hours at 50°C.
• PCI polymeric composition
• MP1 multi stage polymer
• step a) wherein the polymer (CI) and the multi stage polymer (MP1) in step a) are in form of a dispersion in aqueous phase.
• the multi stage polymer (MP1) of the second preferred method for manufacturing the polymeric composition (PCI) is made according the first preferred method without performing step c) of the said first preferred method.
• the quantities of the aqueous dispersion of the polymer (CI) and the aqueous dispersion of the multi stage polymer (MP1) are preferably chosen in a way that the weight ratio of the multi stage polymer based on solid part only in the obtained mixture is at least 5wt%, preferably at least 10wt%, more preferably at least 20wt% and advantageously at least 50wt%.
• the quantities of the aqueous dispersion of the polymer (CI) and the aqueous dispersion of the multi stage polymer (MP1) are preferably chosen in a way that the weight ratio of the multi stage polymer based on solid part only in the obtained mixture is at most 99wt%, preferably at most 95wt% and more preferably at most 90wt%.
• the quantities of the aqueous dispersion of the polymer (CI) and the aqueous dispersion of the multi stage polymer are preferably chosen in a way that the weight ratio of the multi stage polymer based on solid part only in the obtained mixture is between 5wt% and 99wt%, preferably between 10wt% and 95wt% and more preferably between 20wt% and 90wt%.
• the polymer composition (PCI) is obtained as an aqueous dispersion of the polymer particles, if recovering step b) takes not place.
• the solid content of the dispersion is preferably between 10wt% and 65wt%.
• the recovering step b) of the process for manufacturing the polymer composition comprising the polymer (CI) and the multi stage polymer (MP1) is not optional and is preferably made by coagulation or by spray drying.
• the process of the second preferred method for manufacturing the polymer composition (PCI) comprising the polymer (CI) and the multi stage polymer can optionally comprise the additional step c) for drying the polymer composition.
• dry is meant that the polymer composition according to the present invention comprises less than 3wt% humidity and preferably less than 1.5wt% humidity and more preferably less than 1.2wt% humidity.
• the humidity can be measured by a thermo balance that heats the polymer composition and measures the weight loss.
• the second preferred method for manufacturing the polymer composition comprising the polymer (CI) and the multi stage polymer yields preferably to a polymer powder.
• the polymer powder of the invention is in form of particles.
• a polymer powder particle comprises agglomerated primary polymer particles made by multistage process and the polymer (CI) .
• the polymer composition (PCI) according to the invention can also be in form of larger polymer particles: a polymer powder.
• the polymer powder particle comprises agglomerated primary polymer particles made by the multistage process according the first preferred method or agglomerated primary polymer particles made by blending the multistage polymer (MP1) obtained multistage process with polymer particles made of polymer (CI) according the second preferred method.
• the polymer powder of the invention may have a volume median particle size D50 between ⁇ and 500 ⁇ .
• the volume median particle size of the polymer powder is between ⁇ and 400 ⁇ , more preferably between 15 ⁇ and 350 ⁇ and advantageously between 20 ⁇ and 300 ⁇ .
• the D10 of the particle size distribution in volume is preferably at least 7 ⁇ and preferably ⁇ .
• the D90 of the particle size distribution in volume is preferably at most 500 ⁇ and preferably 400 ⁇ , more preferably at most 250 ⁇ .
• composition suitable as (meth) acrylic adhesive composition comprises:
• a) a first part composition comprising: al) at least one (meth) acrylic monomer (Ml), at least one of said monomer (Ml) being methyl methacrylate ;
• a2) a multistage polymer (MP1) having a core-shell structure as defined above;
• the content of the multistage polymer (MP1) in the first part composition being preferably comprised from llwt% to 20 wt% , more preferably from 13 wt% to 18 wt%, advantageously from 15 wt% to 18 wt%;
• the composition suitable as (meth) acrylic adhesive composition comprises: a) a first part composition (PI) comprising: al) a mixture of (meth) acrylic monomers (Ml), at least one of said monomers (Ml) being methyl methacrylate, preferably the mixture comprising methyl methacrylate and tridecyl acrylate; a2) a multistage polymer (MP1) having a core-shell structure as defined above;
• the content of the multistage polymer (MP1) in the first part composition being preferably comprised from ll t% to 20 t% , more preferably from 13 t% to 18 t%, advantageously from 15 t% to 18 t%;
• a second part composition comprising: bl) at least one polymerization initiator.
• composition suitable as (meth) acrylic adhesive composition comprises:
• a) a first part composition (PI) comprising:
• a2) a multistage polymer (MP1) having a core-shell structure as defined above;
• At least one monomer (M2) selected from the group consisting of 2 ( 2-ethoxyethoxy) ethyl acrylate and methoxy polyethylene glycol methacrylate;
• the content of the multistage polymer (MP1) in the first part composition being preferably comprised from ll t% to 20 wt% , more preferably from 13 wt% to 18 wt%, advantageously from 15 wt% to 18 wt%;
• a second part composition comprising: bl) at least one polymerization initiator.
• the glass transitions (Tg) of the polymers (of the multistage polymer) are measured with equipment able to realize a thermo mechanical analysis.
• a RDAII "RHEOMETRICS DYNAMIC ANALYSER” proposed by the Rheometrics Company has been used.
• the thermo mechanical analysis measures precisely the visco-elastics changes of a sample in function of the temperature, the strain or the deformation applied.
• the apparatus records continuously, the sample deformation, keeping the stain fixed, during a controlled program of temperature variation.
• the results are obtained by drawing, in function of the temperature, the elastic modulus (G' ) , the loss modulus and the tan delta.
• the Tg is higher temperature value read in the tan delta curve, when the derived of tan delta is equal to zero.
• the mass average molecular weight (Mw) of the polymers is measured with by size exclusion chromatography (SEC) .
• the particle size of the primary particles after the multistage polymerization is measured with a Zetasizer.
• the particle size of the polymer powder after recovering is measured with Malvern Mastersizer 3000 from MALVERN.
• the tensile specimens were tested with a cross-head speed of 10 mm/min at 23°C. The samples were held using mechanical jaws. The tensile Modulus (E) , tensile stress and strain were measured at break and at yield point according to the ISO 527-2 standard requirements, using dog bone specimens.
• E tensile Modulus
• the composition comprising the multistage polymer is tested for dispersion easiness in the neat methyl methacrylate . This was evaluated by visual inspection as the time requested to reach a homogeneous dispersion state for the core/shell when added to methacrylate part (first stage of the part A methacrylate composition preparation) . In particular, attention was paid to the total disappearance of any core/shell powder agglomerates. A poor result regarding this test was qualified as difficult and long whereas a good result was qualified as easy and fast .
• PTFE molds were used for directly prepare tensile test and charpy impact strength specimens .
• a Heidolph RZR 2051 stirring motor used at a speed rotation of 200 rpm and fitted with a dispersive blade was used for the blending process of the different ingredients of the two parts methacrylate adhesive formulation at room temperature.
• Instron tensile testing machine fitted respectively with a 50 kN and 5 kN force sensor. An extensometer was used for the initial stage of the tensile test to assess the tensile modulus (E) with higher accuracy.
• the aluminum plates used as substrate to prepare the lap shear specimens were made of a 6061 alloy. A constant thickness of the adhesive layer was ensured by the use of PTFE film spacer around the bounding area. The PTFE films were 250 ⁇ thick and were purchased from Multi-Labo . Once bonded, the plates were held together with 40 mm bulldog clips to maintain the bounded plates during the curing step.
• the lap-shear sample are made from two aluminum plates, an adhesive layer with a standardized thickness (200 microns) and a clamping device.
• the surface preparation protocol of the plates used for the Lap shear test is key for the reliability of the test results.
• the different preparation steps used were the following: (i) water cleaning, (ii) acetone cleaning and finally (iii) surface abrasion .
• the water cleaning consisted of rubbing with a damp while acetone cleaning was done by rubbing with an impregnated rag.
• a fine surface abrasion process as described in the EN13887 standard was performed using R222 Emery clothe sheet grit 180 from Norton Saint Gobain: the surface was abraded along the main plate axis until it became totally bright. Then, it was abraded perpendicularly until the first abrasion marks became invisible. Finally, the plates were abraded circularly until the first two steps marks became invisible. The dust was removed by compressed dry air.
• a Teflon film was used as a spacer between the 2 plates to ensure a regular thickness for the adhesive layer.
• the overlapping adhesion surface was 12.5 mm x 25 mm x 2 mm.
• a small quantity of adhesive composition is deposited and leveled using a spatula at the surface of the extremity of one of the two aluminum plates. During this step, the Teflon spacer is held manually, to avoid movement. The second aluminum plate is pressed against the first one to ensure the right overlapping bounding area. The two plates are clamped together using 2 bulldog clips. Clips are removed when the curing process is finished.
• the curing protocol used for the lap-shear samples is the same as for the curing of the methacrylate specimens described hereafter.
• polybutadiene rubber latex Rl .
• the resultant polybutadiene rubber latex (Al) contained 38% solids and had a weight average particle size of about 160 nm.
• Second stage B - Polymerization of polymer type Bl into a
• the stabilization emulsion was prepared by mixing 3.2 parts de-ionized water (based on graft copolymer mass), 0.1 parts oleic acid, 0.1 parts potassium hydroxyde, and 0.9 parts octadecyl-3- (3 , 5-di-tertbutyl-4-hydroxyphenyl ) propionate .
• the resultant core shell polymer (A+B) had a weight average particle size of about 180 nm.
• Synthesis of the polymer CI semi continuous process : charged into a reactor, with stirring, were 10 OOOg of core shell polymer (A+B) in de-ionized water, O.Olg of FeS04 and 0.032g of ethylenediaminetetraacetic acid, sodium salt (dissolved in lOg of de- ionized water), 3.15g of sodium formaldehydesulfoxylate dissolved if llOg of de-ionized water and 21.33 g of emulsifier potassium salt of beef tallow fatty acid (dissolved in 139.44g of water), and the mixture was stirred until complete dissolution of added raw materials exept core-shell polymer.
• the reaction mixture was heated at a temperature of 80°C and the polymerization was then left to completion for 60 minutes after the end of the monomers addition.
• the reactor was cooled down to 30°C.
• MMA methyl methacrylate
• the resulting homogeneous part A composition was kept in a sealed container .
• the methacrylate part A composition and the polymerization initiator part B composition were mixed together in a 10:1 ratio (10 parts of part A per 1 part of part B) under 1200 rpm stirring during 1 min.
• the resulting homogeneous methacrylate adhesive mixture was poured into the above-described PTFE molds to be cured at room temperature during 24 hours.
• the same adhesive mixture was used to prepare the Lap-Shear specimens using the same curing conditions.
• the resulting core/shell content of this adhesive formulation is 18.2 wt%.
• the measurement consists in stretching in a test machine having a movable jaw moving with a constant speed of 100 mm/min, a standard test specimen made of the cured composition and to register, at the moment of the break of said specimen, its elongation (in %) .
• the standard specimen is in form of dumbbell, as illustrated in the international norm ISO 37 of 2011.
• the narrow part of the dumbbell has 20 mm in length, 4 mm in width, and a thickness of 500 ⁇ .
• the reference is a formulation similar to formulations Fl , F2 and F3, but without any core/shell 2.
• inventive formulations Fl, F2 and F3 advantageously exhibit a good comprise between a good tensile strength and a high elongation at break.
• a cartridge 10/1 (10 part of A and 1 part of B, 10/1 in volume) has been prepared according to a similar process than disclosed above:
• the cartridge comprises a static mixer which allows the mixing of part A and part B by the end user.

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