WO2004056898A2 - Adhesives - Google Patents
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- WO2004056898A2 WO2004056898A2 PCT/EP2003/014658 EP0314658W WO2004056898A2 WO 2004056898 A2 WO2004056898 A2 WO 2004056898A2 EP 0314658 W EP0314658 W EP 0314658W WO 2004056898 A2 WO2004056898 A2 WO 2004056898A2
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- acrylate
- copolymer
- polymer
- shell
- core
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- 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
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
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- 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
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
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- 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
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
Definitions
- the present invention relates to branched acrylic polymers, processes for obtaining them and to their uses for example as adhesives (e.g. such as pressure sensitive adhesives (PSA) and/or hot melt adhesives).
- adhesives e.g. such as pressure sensitive adhesives (PSA) and/or hot melt adhesives.
- PSA pressure sensitive adhesives
- Particular embodiments of the branched acrylic polymers of the invention are star shaped thermoplastic elastomeric acrylic block copolymers obtained by radical polymerization for example using a transition metal catalyst.
- Such copolymers can be highly polydisperse and can comprise an inner core of polymer chain branches with low glass transition temperatures and an outer shell of polymer chain branches with high glass transition temperatures.
- Polyacrylate adhesives emerged in the early 1960s as a valuable alternative to the rubber adhesives previously used. Polyacrylates exhibit many useful properties such as very good resistance to aging, good weather performance, and good adhesion to polar substrates. Acrylic monomers are reactive and highly versatile so can be polymerized under mild conditions to yield adhesive formulations which do not require any additional compounding.
- Hot-melt adhesives mostly comprise thermoplastic elastomers (TPE) comprising block copolymers, of typically three hydrocarbon segments (e.g. styrene-butadiene or isoprene-styrene). These tri-block copolymers are obtained by living anionic polymerization. TPEs have desirable properties such as high maximum elongation at break and high tensile strength. Radial structures of TPEs have been proposed to increase cohesive strength whilst lowering viscosity. TPEs also have various disadvantages.
- TPEs must be synthesised under highly stringent conditions which limits the range of monomers and functionality that can be used.
- the upper temperature at which TPEs can be used is low.
- the presence of an unsaturated mid block in these polymers imparts poor resistance to oxidation and/or UV and leads to poor aging. It is expensive to hydrogenate the polymer to address this.
- UV-curable acrylate polymers have been used were the polymer is irradiated to form chemical cross-links to ensure sufficient cohesive strength.
- UV-curable acrylic polymers exhibit other disadvantages. For example there can be a lack of consistency in the final adhesive due to curing. Only certain coat weights can be used. The UV curing process is slow and the raw materials are expensive. The requirement to be UV-curable limits the amount and type of other ingredients (such as tackifiers) which may be added to the formulation. Acrylic polymers adhere poorly to non-polar substrates and the scope for modifying a UV curable formulation and/or polymer to improve adhesion is also limited.
- EP 0243120 (Du Pont) describes polymers made by group transfer polymerisation (GTP). As indicated above these polymers will have a theoretical maximum polydispersity of 2.0.
- US 5,399,620 (BASF) describes a process for making block copolymer including star polymers which have a polydispersity of less than 2.
- the polymers are prepared by an uncontrolled free radical polymerisation and have a molecular weight of less than 100,000 daltons (see page 2, lines 39 to 40).
- US 6,288,173 (PPG Industries) describes polymers made by atom transfer radical polymerisation (ATRP).
- the silane transfer agent used is incompatible with functional (e.g. hydroxy) monomers and this reference also requires that one of the monomers which form the A or B blocks is an amine functional monomer.
- the copolymers of the present invention can comprise common functional groups and can made from common functional monomers.
- WO 98/40415 discloses a controlled free radical polymerization process of atom or group transfer radical polymerization in which the polymerization is made in presence of an initiator, a transition metal in its zero oxidation state which forms a first transition metal compound that participates in a reversible redox cycle with the initiator and a ligand which coordinate in a sigma- or pi-bond to the transition metal. This process leads to different forms of block copolymers than those of the present invention.
- WO 2000/39233 (3M) describes various hot-melt adhesives comprising tackifiers mixed with linear or radial acrylic block copolymers obtained by living anionic polymerization or by controlled radical polymerization.
- the copolymers are well-defined materials having a polydispersity lower than 2.0, and they have at least two A blocks and one B block.
- the adhesive compositions have a broad formulation latitude and adequate cohesive strength, without the need for a curing step.
- WO 2000/43344 discloses branched polymers or copolymers prepared by atom transfer polymerization in the presence of an at least trifunctional alpha-halocarboxylic acid ester initiator and an oxidisable transition metal complex catalyst. When a copolymer containing two different monomers is made, it is done in two separate steps, with purification of the polymer obtained in the first step.
- the applicant has unexpectedly discovered that certain branched acrylic polymers can be prepared easily and yet have advantageous properties useful to address some or all of the problems discussed herein
- a branched polymer comprising an acrylic copolymer having one or more core arm(s) comprising one or more core polymer(s) and one or more shell arm(s) comprising one or more shell polymer(s) and where said acrylic copolymer is obtained or obtainable by (an optionally transition metal catalysed) radical polymerization and has a polydispersity of from about 3 to about 10, and where (a) the or each core polymer(s) has a polydispersity of at least about 2 and a T g of from about -65°C to about -20°C, and (b) the or each shell polymer(s) has a T g of from about 70°C to about 160°C.
- acrylic star shaped block copolymers of the present invention may exhibit improved properties compared to simple chain polymers, for example improved heat resistance, unexpectedly high cohesive strength and/or low viscosity.
- the polymers of the invention may optionally be formulated with tackifiers to provide high performance adhesives and may also act as compatibilising agents to prepare formulations of two otherwise incompatible acrylic polymers.
- reaction mixture where at least one of the polymerisation initiator and/or first acrylate polymer precursor(s) comprise at least three active functionalities capable of reacting to form polymeric core arms; (b) polymerising the polymer precursor(s) in the reaction mixture until at least about 91 % of the total weight of the polymer precursor(s) have been polymerised; to produce an acrylate polymer comprising polymeric core arms; (c) adding to the reaction mixture, without any purification thereof, one or more second acrylate polymer precursor(s) capable of forming polymeric shell arms; (d) polymerising the further polymer precursors to produce an acrylate copolymer comprising polymeric shell arms until: (i) at least about 95% of the total weight of the second polymer precursor(s) has been polymerised: and/or (ii) the M n of at least one of the arm(s) of the shell polymer reaches at least about 5 kilodaltons (preferably
- the method of the invention is performed in one reaction vessel without any intermediate purification or isolation steps.
- an adhesive composition comprising a branched polymer of the invention and optionally from about 5 to about 150 phr of a tackifier, calculated by the weight of the polymer.
- polymers of the invention may be formulated with any other suitable ingredients for use as adhesives, such as PSA.
- Adhesives of the present invention (which may be solvent based PSAs and/or hot-melt PSA without solvents) have been found to have cohesion as good as that of prior art stryene-isoprene-stryene (SIS) adhesives on stainless steel and have a good resistance to high temperature as measured by SAFT (shear adhesion failure test).
- the adhesives of the invention can also exhibit improved cohesion, adhesion and/or tack on non-polar surfaces such as polyethylene. Their elongation at break is more than 2500%. Their mechanical properties, such as a high strength at break and an high elongation at break, can easily be tuned by varying monomer nature and ratios.
- a branched polymer is a polymer the molecules of which are branched chains; that is a chain with at least one branch point intermediate between the boundary units.
- a branch point is a point on a chain at which a branch is attached.
- a branch point from which 'n' linear chains emanate may be termed an 'n'-functional branch point, e.g. five-functional branch point.
- the terms trifunctional, tetrafunctional, pentafunctional, etc. may be used, e.g. pentafunctional branch point.
- a branch point in a network may be termed a junction point.
- a branch (or side chain or pendant chain) is an oligomeric or polymeric offshoot from a macromolecular chain.
- An oligomeric branch may be termed a short-chain branch.
- a polymeric branch may be termed a long-chain branch.
- a polymer chain denotes the whole or part of a macromolecule, an oligomer molecule or a block, comprising a linear or branched sequence of constitutional units between two boundary constitutional units, each of which may be either an end group, a branch point or an otherwise-designated characteristic feature of the macromolecule.
- a cyclic macromolecule has no end groups but may nevertheless be regarded as a chain. Any number of branch points may be present between the boundary units.
- Preferred branched polymers of the invention comprises dendritic polymers and/or star copolymers, more preferably star copolymers.
- a dendritic polymer denotes a polymer with a crystalline morphology produced by skeletal growth, leading to a 'treelike' appearance.
- a star copolymer denotes a copolymer where chains having different constitutional or configurational features are linked through a central moiety.
- Either dendritic polymers or star-shaped copolymer may be obtained from an initiator and/or polymer precursor which has at least a functionality of three, and preferably four or more.
- the branched polymers of the present invention are star-shaped thermoplastic elastomeric acrylic block copolymers. It is desired that copolymers of the present invention comprise an inner core of polymer arms of low T g and an outer shell of polymer arms of high T g .
- a multi-functional polymerisation initiator of a star-shape may be used. Without wishing to be bound by any mechanism it is believed that due to coupling of radicals, the arms of the star may become branched when polymerisation proceeds.
- star-shaped structures can be obtained using a monofunctional initiator with a mixture of multifunctional (meth)acrylates such as tri- or tetra-acrylates.
- the large elastomer and/or copolymer chain(s) of the invention may comprise distinct regions therein for example A / B type blocks in a block copolymer and/or distinct regions of core or shell arms in a star polymer.
- T g of such sub-sections or portions of a larger polymer may be incapable of being measured separately from the T g of the whole polymer.
- the T g of such sub-sections described herein refers to the T g of the corresponding homopolymer or co polymer which can be obtained or is obtainable from polymerising those polymer percursor(s) and/or mixture(s) of polymer percursor(s) which can form the repeat unit(s) for that sub section of the polymer.
- the core polymer has a T g from about -50 to about -30°C
- the shell polymer has a T g from about 100 to about 150°C
- Polymers of the present invention may be prepared by one or more suitable polymer precursor(s) which may be organic and/or inorganic and comprise any suitable (co)monomer(s), (co)polymer(s) [including homopolymer(s)] and mixtures thereof which comprise moieties which are capable of forming a bond with the or each polymer precursor(s) to provide chain extension and/or cross-linking with another of the or each polymer precursor(s) via direct bond(s) as indicated herein.
- suitable polymer precursor(s) may be organic and/or inorganic and comprise any suitable (co)monomer(s), (co)polymer(s) [including homopolymer(s)] and mixtures thereof which comprise moieties which are capable of forming a bond with the or each polymer precursor(s) to provide chain extension and/or cross-linking with another of the or each polymer precursor(s) via direct bond(s) as indicated herein.
- Polymer precursors of the invention may comprise one or more monomer(s), oligomer(s), polymer(s); mixtures thereof and/or combinations thereof which have suitable polymerisable functionality.
- a monomer is a substantially monodisperse compound of a low molecular weight (for example less than one thousand daltons) which is capable of being polymerised.
- a polymer is a polydisperse mixture of macromolecules of large molecular weight (for example many thousands of daltons) prepared by a polymerisation method, where the macromolecules comprises the multiple repetition of smaller units (which may themselves be monomers, oligomers and/or polymers) and where (unless properties are critically dependent on fine details of the molecular structure) the addition or removal one or a few of the units has a negligible effect on the properties of the macromolecule.
- a oligomer is a polydisperse mixture of molecules having an intermediate molecular weight between a monomer and polymer, the molecules comprising a small plurality of monomer units the removal of one or a few of which would significantly vary the properties of the molecule.
- polymer may or may not encompass oligomer.
- the polymer precursor of and/or used in the invention may be prepared by direct synthesis or (if the polymeric precursor is itself polymeric) by polymerisation. If a polymerisable polymer is itself used as a polymer precursor of and/or used in the invention it is preferred that such a polymer precursor has a low polydispersity, more preferably is substantially monodisperse, to minimise the side reactions, number of by-products and/or polydispersity in any polymeric material formed from this polymer precursor.
- the polymer precursor(s) may be substantially un-reactive at normal temperatures and pressures.
- the substituents on the repeating unit of a polymer and/or oligomer may be selected to improve the compatibility of the materials with the polymers and/or resins in which they may be formulated and/or incorporated for the uses described herein.
- the size and length of the substituents may be selected to optimise the physical entanglement or interlocation with the resin or they may or may not comprise other reactive entities capable of chemically reacting and/or cross-linking with such other resins as appropriate.
- the polymer precursors used in the method of the present invention to obtain copolymers of the invention comprise one or more multifunctional (meth)acrylates, especially if a mono-functional initiator is used.
- Suitable multifunctional (meth)acrylates may be selected from: trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythrytol triacrylate, ethoxylated and propoxylated trimethylolpropane triacrylate, glyceryl propoxylated triacrylate, pentaerythritol tetra-acrylate, ditrimethylolpropane tetra-acrylate, alkoxylated tetra-acrylates, dipentaerythritol penta-acrylate or dipentaerythritol hexa-acrylate.
- Preferred star shaped acrylic copolymer of the invention comprise a shell polymer having at least three shell arms, and preferably four or more arms.
- the core polymers (comprising one or plurality of core arms) have a preferred theoretical average number molecular weight (M n ) from about 60 to about 250 kilodaltons, more preferably from about 120 to about 200 kilodaltons.
- the shell polymers (preferably comprising at least three shell arms) have a preferred M n from about 20 to about 80 kilo-daltons, more preferably from about 30 to about 60 kilodaltons.
- M n kilo-daltons
- the mass percentage of the copolymer of the invention which consists of shell polymer is from about 10% to about 50%, more preferably from about 15% to about 30%.
- the polymer(s) which form the core arm(s) have a low T g and preferably comprise suitable polymeric moieties obtained and/or obtainable from one or more monomers (optionally substituted by one or more hydroxy and epoxy groups): C ⁇ - ⁇ 0 alkyl acrylates, amyl acrylates, stearyl acrylate, lauryl acrylates and/or mixtures and/or derivatives thereof.
- the core arm monomers are selected from methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, tert.-butyl acrylate, sec-butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, nonyl acrylate, decyl acrylate, stearyl acrylate, lauryl acrylate and/or mixtures thereof.
- the polymers which form the shell arm(s) have a high T g and preferably comprise suitable polymeric moieties obtained and/or obtainable from one or more monomers selected from (optionally substituted by one or more hydroxy and epoxy groups): d-ioalkyl acrylates, amyl acrylates, stearyl acrylate, lauryl acrylates and/or mixtures and/or derivatives thereof:
- the shell arm monomers are selected from methyl methacrylate, ethyl methacrylate, tert.-butyl acrylate, cyclohexyl methacrylate, isobornyl methacrylate and/or mixtures thereof.
- any other types of monomers such as glycidyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, hydroxy (meth)acrylates, styrene derivatives can be readily incorporated in the polymers which form the core and/or shell arm(s).
- Monomers used in the present invention may comprise latent functional monomers such as t-butyl acrylate
- copolymers of the invention comprise core arms and shell arms which form two or more phases of a multi-phase copolymer system and optionally also comprise a gradient zone at the interface between at least two of said phases.
- the respective ratio between amount of polymer inhabiting the core phase(s) and shell phase(s) may be measured quantitatively using atomic force microscopy (AFM), for example by visual inspection or other analysis of micro-phase images of copolymer films of the invention observed with tapping AFM.
- AFM atomic force microscopy
- the core to shell phase ratio of polymers of the invention is optionally from about 1 to about 10, preferably about 2 to about 6.
- the copolymer is derived from acrylic monomers only i.e. is full acrylic polymer.
- the copolymer can be heated (for example at about 200°C under vacuum) to liberate the tert.-butyl groups and leave carboxylic acrylic acid groups along the copolymer chains.
- the preferred process used for synthesising the copolymers of the invention is radical polymerisation optionally transition metal catalysed, and more preferably atom transfer radical polymerization (ATRP), for example as described in Chemical Reviews, 2001 , 101 , 2921-2990, Matyjaszewski & Xia.
- ATRP atom transfer radical polymerization
- Trifunctional or polyfunctional initiators may be used in ATRP, such as the complete condensation product of pentaerythritol and 2-bromoisobutyryl bromide, of pentaerythritol and 2-bromopropanoyl bromide. These initiators are tetrafunctional.
- Halogenated alkanes, benzylic halides, alpha-haloesters, alpha-haloketones, alpha-halonitriles and/or sulfonyl halides may also be used as ATRP initiators.
- Preferred catalysts (and/or catalyst precursors) which may be used in the method of the present invention comprise metals, salts and/or complexes thereof; more preferably transitional metals, salts and/or complexes thereof, most preferably Cu(0), Cu(l)Br, Cu(l)CI, Fe(ll)Br, Fe(ll)CI, salts and/or complexes of Ru[ll], salts and/or complexes of Ni[ll] and/or suitable mixtures thereof.
- transitional metal includes all metals in Groups 3 to 12 of the Periodic Table (including for example the noble metals, copper and zinc) and in any suitable oxidation state.
- the metallic catalysts may be combined with one or more of: mono-, bi- or multi-dentate nitrogen-based ligands, polyamine ligands (preferably 2,2'-bipyridine derivatives such as N,N,N',N',N" pentamethyldiethylenetriamine) and/or phosphorous-based ligands (preferably triphenyl phosphine and/or tricyclohexyl phosphine).
- polyamine ligands preferably 2,2'-bipyridine derivatives such as N,N,N',N',N" pentamethyldiethylenetriamine
- phosphorous-based ligands preferably triphenyl phosphine and/or tricyclohexyl phosphine
- the unpurified monomers which will form the low T g core arms are placed together with solvent (typically toluene) and reactants in a reactor.
- solvent typically toluene
- the reaction mixture is degassed by continuously bubbling nitrogen through the mixture for about 45 minutes.
- Polymerisation of the low T g monomers is then initiated at a typical concentration of 60% solids in the solvent.
- the reaction temperature is from about 90°C to about 110°C and the reaction is continued for 8 to 16 hours until the percentage monomer converted to polymer is at least from about 91 % to 95%, preferably higher than 95%.
- All the monomers for the high T g shell polymers are then added at the same time to the reaction mixture containing the unpurified core polymer.
- the second polymerization is stopped after 12 to 16 hours once the percentage conversion of the final monomers is higher than 95%.
- a non-solvent for the copolymer such as an alcohol is then added to the reaction mixture.
- super-critical fluid extraction can be employed to remove residual monomer(s), solvent(s) and transition-metal catalyst.
- Dense phase CO 2 can be used to purify the ATRP polymers prepared using the method of the invention. Extraction of reactive component residues (acrylated / methacrylated monomers), residual solvent (toluene), extraction of transition-metal catalyst (with co-solvent present) is compatible with CO 2 extraction techniques.
- the ratio between the initiator and the monomers used to make the low and high T g polymers determines the various block lengths, and therefore also the ratio between the low T g core block polymers and high T g shell block polymers.
- the mole ratio between monomers and initiator is preferably from about 300 to about 1800, more preferably from about 600 to about 1200.
- the theoretical mole ratio between the initiator and the copper catalyst is 1 :4 for a tetrafunctional initiator, although a reduced amount of copper salt may be used to give a lower mole ratio from about 1.2 to about 1.3..
- the theoretical mole ratio of ligand to copper is 1.
- the copolymer according to the invention may be used as such, but it can also be mixed with additives such as tackifiers to form for example an adhesive formulation.
- Preferred amounts of tackifier, calculated on the weight of the copolymer are from about 5 to about 150 phr, more preferably from about 25 to about 150 phr.
- Preferred tackifiers are selectively compatible, more preferably compatible with the soft block copolymers in the low T g core but incompatible with the hard block copolymers in the high T g shell..
- Suitable tackifiers may comprise any of the following and/or mixtures thereof: hydrogenated rosin esters - such as the commercial products: Foral ® 85 E (based on glycerol, mixture of di- and triesters) and Foral ® 105 E (based on pentaerythritol, tri- and tetraesters), phtalate esters of hydroabietyl alcohol - such as the commercial product Cellolyn ® 21 E; and/or terpene phenolics, polyterpenes, and/or hydrogenated or non-hydrogenated hydrocarbon resins - such as the commercial products Escorez ® 1310, 2420 and/or 5380; Regalrez ® 1018; Regalite ® 1010; Piccotac ® 95, 212 and/or 6095-; and/or Norsolene ® S115.
- Plasticizer can also be added to formulations of the present invention in an amount calculated on the weight of the copolymer, from about 5 to about
- Suitable plasticizers may comprise any of the following and/or mixtures thereof: hydrocarbon oils (aromatic, paraffinic, or naphtenic) such as the commercial products Edelex ® 945 & 956 and/or OH8777, hydrocarbon resins, phtalates, and/or combinations thereof.
- hydrocarbon oils aromatic, paraffinic, or naphtenic
- copolymers of the invention can be used in a variety of applications in the automotive, construction, medical, personal care, food and beverage, electrical (wire and cable), appliance, sports and leisure fields. They are also usable as (pressure sensitive) adhesives for tapes and labels, as sealants, coatings, sound deadening compounds, in pipeline protection, in bitumen modification, in footwear applications, in food packaging.
- Cupric bromide (CuBr) was added to a dry glass tube.
- Degassed syringes were used to add to the tube the ligand N,N,N ⁇ N',N"-pentamethyldiethylenetriamine (PMDETA, 0.1 M in toluene) and degassed monomers for the core polymer, solvent (toluene and/or dodecane) and the initiator 2-bromoisobutyrate of pentaerythritol (PEEiBr).
- the tube was sealed with a rubber septum and three freeze-pump-thaw cycles were performed. The tube was then immersed in an oil bath held at 90°C by a thermostat.
- the degassed monomers for the shell polymer were added at the same time.
- the reaction was left at 90°C until sufficiently high conversion of shell monomers was attained.
- the copolymer was then diluted with toluene, precipitated in methanol, collected by filtration and dried under vacuum at 80°C for a few hours.
- the impure copolymer prepared as described above contained CuBr PMDETA catalyst, aromatic solvent (toluene) and (meth)acrylate monomer.
- the impure copolymer was added to a Soxhlet extraction thimble and loaded into an extraction cell.
- a polar extraction co-solvent (methanol or water) was then added to the extraction cell by adsorption on to an inert solid.
- the extraction cell was placed into a conventional device for supercritical extraction which was pressurized to 300 bar with CO 2 and heated to 65°C. The CO 2 pressure was reduced continuously in a controlled manner for several hours and the cell contents were extracted by passing the depressurised
- nBuA n-butyl acrylate
- tBuA tert.-butyl acrylate
- 2-EHA 2-ethylhexyl acrylate
- HBA hydroxy functionalized acrylate
- IBMA isobornyl methacrylate
- MA methyl acrylate
- MMA methyl methacrylate
- PEEiBr 2-bromoisobutyrate of pentaerythritol
- PMDETA N,N,N',N',N"-pentamethyl diethylene triamine.
- the block lengths are the theoretical molecular weight.
- copolymer 1 The data in the following tables can be used to prepare copolymers of the invention (Copolymers 1 to 10 respectively) in combination with the method previously described. Copolymer 1
- T g Thermal transition temperatures
- the adhesive properties of the copolymers were tested on samples prepared by coating a polyester substrate (of 23 ⁇ m thickness) with a thin film of the copolymers formulated with toluene as solvent
- After application the coating was dried for 5 minutes at room temperature and then a further 3 minutes at 110°C.
- the coating was applied to silicon coated paper by passing the coated polyester and the paper between 2 cylinders at the same pressure for each sample.
- the dry adhesive coatings were preconditioned for 24 hours in a conditioned room and then tested at 23 °C and 50% relative humidity.
- a comparative adhesive formulation was prepared from a known copolymer and the following ingredients
- SIS block copolymer styrene-isoprene-styrene
- D1161 block copolymer styrene-isoprene-styrene
- D1161 block copolymer styrene-isoprene-styrene
- hydrocarbon resin tackifier available commercially from Eastman under the trade mark Piccotac ® 212
- Comp B denotes the prior art PSA formulation described as Example 7F on page 37 of WO/00/39233 (3M).
- This comprises an all-acrylic triblock copolymer produced by living anionic polymerization and of the type MMA / IOA / MMA, (IOA denotes polymer blocks formed from iso-octyl acrylate monomer).
- the formulation of Example 7F comprises the MMA/IOA/MMA copolymer (50% w/w) with a mixture of two tackifiers: the rosin ester available from Eastman Chemicals under the trade mark Foral® 105 (86 phr); and the hydrogenated hydrocarbon resin available from Eastman Chemicals under the trade mark Regalrez ® 1018 (46 phr).
- the hydrogenated rosin ester tackifier comprising a mixture of di- and triesters of glycerol and available commercially from Eastman Chemicals under the trademark Foral ® 85 E; the phtalate ester of hydroabietyl alcohol, available commercially from Eastman Chemicals under the trademark Cellolyn ® 21 E; the hydrocarbon oil plasticiser available commercially from Shell under the trademark Edelex ® 945; and /or the additive available commercially from Bayer under the trademark Desmodur ® T81
- Test (i) Shear on steel, 1 inch 2 , 1 kg, aluminium face, tested according to FTM 8; data in minutes.
- Test (ii) Shear on steel, 0.25 inch 2 , 1 kg, PET face, tested according to FTM 8; data in minutes.
- Test (iii) Adhesion on stainless steel tested after 20 minutes according to FTM 1 , data in N(25 ⁇ mm) "1 .
- Test (iv) Adhesion on stainless steel tested after 24 hours according to FTM 1 , data in N(25 mm) "1 .
- Test (v) Adhesion on polyethylene (PE) film after 20 minutes according to FTM 1 , data in N(25 mm) '1 .
- Test (vi) Adhesion on PE film tested after 24 hours according to FTM 1 , data in N(25 mm) "1 .
- Test (vii) Loop on stainless steel according to FTM 9, data in N(25 mm) '1 .
- Test (viii) Loop on PE film according to FTM 9, data in N(25 mm) "1 .
- Test (ix-a) Shear adhesion failure test (SAFT) at 0.5°C according to FTM 5, data in
- Test (ix-b) Shear adhesion failure test' (SAFT) at 0.5°C according to FTM 5, data in minutes.
- Examples 1, 2, 3 and 4a have identical monomer components and Table 4 demonstrates the effect on the shear strength of the formulated material of the percentage of monomer conversion (polymerisation) during each step of the method of the present invention. High shear is observed with Ex 4a > Ex 3 > Ex 2 > Ex 1.
- the final conversion n-butyl acrylate monomer in the final product is greater than 99%.
- end blocks of a block co-polymer are believed to be responsible for the internal strength of the material due to the presence of a gradient zone between soft and hard blocks resulting from the copolymerization between unreacted nBuA and freshly added MMA and IBMA monomers.
- the conversion of the monomers which form the high T g block copolymer for shell arms is less than about 91% (and/or the molecular weight of at least one of the arm(s) of the high T g shell polymer is less than that at which chain entanglements become significant - which for example for PMMA is typically > 7 kilodaltons) it is believed that the lengths of the end-blocks in the shell arms are too short to form a gradient zone sufficient to reinforce the material to the desired extent.
- overall T g of the thermoplastic domains is significantly reduced due to copolymerization between residual nBuA with MMA and IBMA added in the second step. Typically, this gradient zone can be detected by DSC.
- Example 4a which comprises a copolymer with well-defined end blocks exhibits good overall PSA properties, especially cohesion.
- Example 4a has a superior overall PSA performances to Comp A with a higher level of adhesion on both polar and non-polar substrates.
- PSA properties can be further improved by modifying the amount and type of tackifier used in the formulation.
- the shear level (Test (i)) is improved to more than 10,000 minutes.
- adhesive transfer is observed during peel on polar substrate, a very high level of adhesion on high density polyethylene substrate is attained and the cohesion is as good as with Comp A.
- very high adhesion on both stainless steel (polar substrate) and polyethylene (low surface energy) is observed compared to Comp A.
- improved SAFT values and cohesion levels may be obtained by improving the phase separation between the domains of low T g and high T g . which may also allow selective compatibility with the tackifier.
- thermoplastic shell domain comprises only Copolymers 5, 6 or 7 which were obtained from methyl methacrylate monomers only. Improvement of the phase separation of these formulations was shown by AFM images and mechanical analysis.
- Examples 5a and 5b based various formulations of Copolymer 5 derived from 2HEA/MA and MMA monomers show improved properties over formulations based on copolymers of nBuA, MMA, IBMA.
- the values of the more severe shear test (Test (ii) - 1 kg x 0.25 inch 2 ) confirm the high level of cohesive strength of these formulations. Improved SAFT are also shown with these systems.
- Example 6 is more preferred formulation of the invention which uses Copolymer 6, a modified version of Copolymer 5 where T g in the elastomeric blocks is lowered to reduce zipping and where the length of the PMMA blocks has increased to maintain or improve cohesive strength.
- Addition of only 5 phr of plasticizer (Edelex 945) to the Formulation of Example 6 leads to good level of shear strength together with clean peel and loop-tack tests as otherwise slip-stick is observed during peel tests.
- Examples 7a to 7d were prepared and tested in order to evaluate the influence of tackifier level on a given base polymer and this data is shown Table 6.
- Examples 8a to 8d were prepared. These use a copolymer of hydroxy functionalized acrylate (HBA) with MMA (Copolymer 8) so that thermoplastic domains could then be chemically cross linked with polyisocyanates.
- HBA hydroxy functionalized acrylate
- MMA Copolymer 8
- formulations with star-shaped all-acrylic block copolymers of the present invention exhibit improved adhesion and SAFT values on both polar and non-polar substrates compared to prior art formulations such as Comp A and Comp B.
- a further advantage of materials of the present invention is their ease of synthesis compared to materials (such as Comp B) produced by living anionic polymerization.
- the all-acrylic block copolymers of the invention can be used also as compatibilising agent between two otherwise non-compatible acrylic polymers. This is shown when
- Copolymer 7 is formulated with two incompatible polymer Polyl and Poly2 which form a hazy film when formulated together.
- Polyl is a high molecular weight (M n of 5.1 x 10 4 daltons) acrylic copolymer obtained from 2EHA, MA, AA, HBA monomers, having a low Tg of -26.5°C and a polydispersity of 20.9.
- Poly 2 is a methacrylic copolymer obtained from MMA and IBA monomers, having M n of 7.8 x 10 3 daltons, a high Tg of 103°C and a polydispersity of 3.7.
- AAAI denotes an aluminium acetylacetonate cross-linker Table 9
- Copolymer 7 When cross-linked with AAAI, Poly 1 behaves as a PSA with modest performance.
- Poly 2 acts as a hardener to significantly improves the cohesive strength and SAFT of Examples 9b and 9c, without significantly reducing other PSA properties. This illustrates that copolymers of the invention can act as compatibilising agents between two otherwise non compatible acrylic polymers and that blending high and low Tg (meth)acrylic polymers allows cohesive and adhesive character of a formulation to be separated when they are normally inter-related in classical acrylic PSA.
- Table 11 shows that viscosity of a formulated full-acrylic thermoplastic elastomer of the invention (such as Example 4c) is lower than that of Comp A.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Graft Or Block Polymers (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2004561393A JP2006511640A (en) | 2002-12-23 | 2003-12-19 | adhesive |
AT03795941T ATE545668T1 (en) | 2002-12-23 | 2003-12-19 | ADHESIVES |
EP03795941A EP1581570B1 (en) | 2002-12-23 | 2003-12-19 | Adhesives |
US10/537,157 US7465767B2 (en) | 2002-12-23 | 2003-12-19 | Adhesives |
AU2003298220A AU2003298220A1 (en) | 2002-12-23 | 2003-12-19 | Adhesives |
MXPA05006723A MXPA05006723A (en) | 2002-12-23 | 2003-12-19 | Adhesives. |
CA002511433A CA2511433A1 (en) | 2002-12-23 | 2003-12-19 | Adhesives |
Applications Claiming Priority (2)
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EP02028900.5 | 2002-12-23 | ||
EP02028900A EP1433799A3 (en) | 2002-12-23 | 2002-12-23 | Star shaped acrylic block copolymer |
Publications (2)
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WO2004056898A2 true WO2004056898A2 (en) | 2004-07-08 |
WO2004056898A3 WO2004056898A3 (en) | 2004-11-11 |
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PCT/EP2003/014658 WO2004056898A2 (en) | 2002-12-23 | 2003-12-19 | Adhesives |
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US (1) | US7465767B2 (en) |
EP (2) | EP1433799A3 (en) |
JP (1) | JP2006511640A (en) |
KR (1) | KR20050084471A (en) |
CN (1) | CN1732194A (en) |
AT (1) | ATE545668T1 (en) |
AU (1) | AU2003298220A1 (en) |
CA (1) | CA2511433A1 (en) |
MX (1) | MXPA05006723A (en) |
WO (1) | WO2004056898A2 (en) |
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WO2007029783A1 (en) * | 2005-09-07 | 2007-03-15 | Kuraray Co., Ltd. | Acrylic adhesive composition and adhesive product |
DE102008034106A1 (en) | 2008-07-21 | 2010-01-28 | Evonik Röhm Gmbh | Block copolymers based on (meth) acrylate with A-P structure |
CN101189268B (en) * | 2005-08-31 | 2010-07-14 | Evonik罗麦斯添加剂有限公司 | Oil soluble polymers |
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JP2023524454A (en) * | 2020-04-30 | 2023-06-12 | ダウ グローバル テクノロジーズ エルエルシー | Method for preparing olefin-acrylate block copolymers by ATRP |
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- 2003-12-19 MX MXPA05006723A patent/MXPA05006723A/en unknown
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Also Published As
Publication number | Publication date |
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US20060074210A1 (en) | 2006-04-06 |
WO2004056898A3 (en) | 2004-11-11 |
EP1433799A3 (en) | 2004-07-14 |
US7465767B2 (en) | 2008-12-16 |
AU2003298220A1 (en) | 2004-07-14 |
EP1581570B1 (en) | 2012-02-15 |
EP1433799A2 (en) | 2004-06-30 |
CN1732194A (en) | 2006-02-08 |
KR20050084471A (en) | 2005-08-26 |
MXPA05006723A (en) | 2005-09-08 |
EP1581570A2 (en) | 2005-10-05 |
ATE545668T1 (en) | 2012-03-15 |
JP2006511640A (en) | 2006-04-06 |
CA2511433A1 (en) | 2004-07-08 |
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