WO1999040134A1 - Procede de polymerisation en suspension de monomeres (meth)acryliques utilisant de la dextrine et des billes de polymere obtenues par ce procede - Google Patents

Procede de polymerisation en suspension de monomeres (meth)acryliques utilisant de la dextrine et des billes de polymere obtenues par ce procede Download PDF

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Publication number
WO1999040134A1
WO1999040134A1 PCT/US1998/002024 US9802024W WO9940134A1 WO 1999040134 A1 WO1999040134 A1 WO 1999040134A1 US 9802024 W US9802024 W US 9802024W WO 9940134 A1 WO9940134 A1 WO 9940134A1
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WIPO (PCT)
Prior art keywords
meth
acrylate
acrylic acid
polymer beads
dextrin
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PCT/US1998/002024
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English (en)
Inventor
Yvan A. Bogaert
Eric B. T. Moonen
Robert R. L. Smolders
François C. D'HAESE
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Minnesota Mining And Manufacturing Company
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Publication date
Application filed by Minnesota Mining And Manufacturing Company filed Critical Minnesota Mining And Manufacturing Company
Priority to JP2000530560A priority Critical patent/JP2002502898A/ja
Priority to US09/381,112 priority patent/US6245838B1/en
Priority to AU60551/98A priority patent/AU6055198A/en
Priority to PCT/US1998/002024 priority patent/WO1999040134A1/fr
Publication of WO1999040134A1 publication Critical patent/WO1999040134A1/fr

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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
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/18—Suspension polymerisation
    • 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
    • C08F20/00—Homopolymers and 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 a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/12—Esters of monohydric alcohols or phenols

Definitions

  • the present invention relates to a novel method for aqueous bead-type suspension polymerization of (meth)acrylic monomers to prepare non-agglomerating, storage stable (meth)acrylic polymer beads which are extrudable at low temperatures.
  • the invention also relates to the polymer beads which are obtainable by said method and to their use as adhesive and further to adhesive compositions comprising the polymer beads.
  • Known polymerization processes in heterogeneous aqueous dispersions comprise emulsion polymerization, dispersion polymerization, and bead-type suspension polymerization (see C.E. Schild necht, Ed., Polymerization Processes, John Wiley & Sons, 1977, p. 106 and 107).
  • the polymers obtained via emulsion polymerization comprise fine particles ofpolymer stabilized by an emulsifier or surfactant and dispersed uniformly in the aqueous phase.
  • the polymer product obtained is often referred to as a "latex", and the particle size is generally in the range of 0.05 to 0.2 ⁇ m. No beads are obtained during emulsion polymerization.
  • dextrin in emulsion polymerization methods in order to form adhesive compositions is known.
  • US-A-5,004,768 discloses an adhesive composition
  • an adhesive composition comprising dextrin, a surfactant, and a polymer at least some of the repeating units of which are derived from an acrylate of at least one saturated aliphatic alcohol having from 4 to 12 carbon atoms.
  • the manufacture of the composition may be carried out in any manner suitable for preparing acrylic polymers in the presence of a surfactant, emulsion polymerization being preferred.
  • EP-A-0 351 193 discloses a composition comprising dextrin, a surfactant, a polymer a major proportion of the repeating units of which are derivable from an acrylate of at least one saturated aliphatic alcohol having from two to twelve carbon atoms, and, optionally, a tackifier. If a tackifier is present, the dextrin level may be up to 7%, based on the total weight of dextrin, surfactant, and acrylate polymer. In the absence of tackifier, the 2
  • maximum dextrin level is 3.5%. Preparation of the composition by emulsion polymerization is preferred.
  • Polymers obtained via dispersion polymerization are in the form of viscous, latex-like dispersions having a particle size in the range of 0.5 to lO ⁇ m.
  • dextrin as a "protective colloid" in this type of polymerization is also known.
  • US-A-5, 004,767 teaches an aqueous acrylate polymer dispersion having a total solids content of 30 to 60% by weight, which has been made by polymerizing one or more acrylate monomers optionally together with other olefinically unsaturated monomer(s) in the presence of a dextrin, at least 70% of the dextrin having a molecular weight in the range of 1000 to 25000 and not more than 10% of the dextrin having a molecular weight above 25000.
  • US-A-4, 560,724 discloses a process for the preparation of aqueous polymer dispersions comprising polymerizing compounds with unsaturated ethylenic bonds at a temperature of 10° to 100°C in the presence of an at least partially water-soluble free-radical initiator and at least one starch and/or starch derivative.
  • Bead-type suspension polymerization in general is a well known method of polymerization in which the polymer formed is obtained as spherical beads or pearls. Various different methods of avoiding agglomeration of the beads have been disclosed.
  • US-A-4,833,179 and US-A-4,952,650 teach a method for suspension polymerization of pressure-sensitive acrylate copolymer beads having a glass transition temperature of 0°C or less.
  • the copolymer beads are prepared by an aqueous suspension polymerization technique utilizing a modifier moiety selected from polystyryl macromers, reactive zinc salts, and hydrophobic silica.
  • the modifier moiety is used in an amount sufficient to render the copolymer beads non-agglomerating at room temperature for handling and transportation purposes.
  • Beads formed without vinyl acetate which are storage stable must have an inherent viscosity that is so high (e.g., 1.1) that they can only be extruded at high temperatures.
  • Suspension beads which do not contain vinyl acetate can be prepared which are extrudable at low temperatures but which are not storage stable (IV 0.7dl/g) (see US- A-5,292,844, column 11, lines 26-35).
  • the adhesives formed from the beads comprising vinyl acetate as taught in US-A- 5,292,844 typically have inherent viscosities of about 0.6 to about 1.5 dl/g in ethyl acetate, preferably about 0.65 to about 0.8 dl/g in order to facilitate extrusion at low temperatures (below about 170°C).
  • this invention provides a method of suspension polymerization of
  • (meth)acrylic monomers wherein a monomer premix comprising (i) at least one (meth)acrylic acid ester of at least one nontertiary alkyl alcohol, the alcohol having from 1 to 18 carbon atoms; and
  • At least one free-radical initiator is polymerized in an aqueous medium in the presence of at least one stabilizer selected from dextrins and dextrin derivatives and said monomer premix further comprising at least one polar monomer or polar macromer copolymerizable with the (meth)acrylic acid ester and/or said aqueous medium further comprising a water soluble or water dispersible polymeric costabiliser.
  • the monomer premix may further comprise other monomers and/or additives such as chain transfer agents, water soluble inhibitors, and crosslinking agents.
  • this invention also provides the use of a dextrin or a derivative thereof as stabilizer in the suspension polymerization of (meth)acrylic monomers.
  • this invention provides polymer beads comprising a (meth)acrylic polymer of (i) at least one (meth)acrylic acid ester of at least one nontertiary alkyl alcohol, the alcohol having from 1 to 18 carbon atoms; said polymer beads having on their surface a layer comprising at least one stabilizer selected from dextrins and dextrin derivatives and optionally a water soluble or water dispersible polymeric costabiliser.
  • Particularly preferred are polymer beads wherein the 5
  • (meth)acrylic polymer is a copolymer of (i) at least one (meth)acrylic acid ester of at least one nontertiary alkyl alcohol, the alcohol having from 1 to 18 carbon atoms; and (ii) at least one polar monomer or polar macromer copolymerizable with the (meth)acrylic acid ester.
  • the polymer beads exhibit a broad range of inherent viscosities and exhibit both good storage stability, in particular in a wet state at room temperature (20-30°C), and low temperature extrudability.
  • polymer beads in connection with the present invention is meant polymer particles that are simple to isolate e.g. by filtering or centrifuging.
  • the polymer beads in connection with the present invention typically have a diameter of at least 50 ⁇ m, preferably at least lOO ⁇ m. Generally, the beads have a diameter between 150 and 5000 ⁇ m.
  • this invention also provides the use of said polymer beads as an adhesive, in particular as a pressure sensitive adhesive.
  • This invention also provides an adhesive composition comprising polymer beads as defined above and further, a coated material comprising on a substrate the adhesive composition.
  • the adhesive composition is a pressure sensitive adhesive composition.
  • Dextrins and their derivatives useful in the present invention to stabilize the bead-type suspension polymerization can be used as the only stabilizer and can be linear or cyclic.
  • Dextrins are the degradation products of starches of different origin (e.g., potatoes and corn) obtained by dry thermal treatment in the presence or absence of a certain amount of acid or other chemical reagent or of an enzyme (see, e.g., ISO NORM 1227-1979).
  • Linear dextrins are commonly classified in white, yellow, and pyro dextrins.
  • the linear dextrins used in the present invention are preferably not completely water soluble at room temperature.
  • Cyclic dextrins are cyclic torusshaped oligosaccharides which are formed by the decomposition of starch by a bacterial enzyme called cyclodextrin glycosyltransferase.
  • Maltodextrins are low molecular weight dextrin derivatives. 6
  • dextrins and dextrin derivatives useful in this invention include linear dextrins such as Tackidex® grades available from Roquette, France, Dextrin available from Aldrich, Belgium; cyclic dextrins, such as ALPHA W6, BETA W7 and GAMMA W8, from Wacker-Chemie GmbH, Germany and Maltodextrins such as Glucidex® grades from Roquette.
  • linear dextrins such as Tackidex® grades available from Roquette, France, Dextrin available from Aldrich, Belgium
  • cyclic dextrins such as ALPHA W6, BETA W7 and GAMMA W8, from Wacker-Chemie GmbH, Germany
  • Maltodextrins such as Glucidex® grades from Roquette.
  • dextrins and dextrin derivatives include linear dextrins, such as Tackidex® 035, Tackidex® 133, Tackidex® 050 and Tackidex® M332F and cyclic dextrins, such as ALPHA W6 and BETA W7.
  • the dextrins yield hazy solutions when dissolved at 22°C rather than clear solutions.
  • compositions according to the invention generally contain about 0.1 to about 10% by weight of dextrin based on the total amount of monomers and macromers. Preferably about 0.3% to about 2% by weight of dextrin is used.
  • the (meth)acrylic acid ester monomers useful in the present invention include monofunctional ethylenically unsaturated esters of (meth)acrylic acid and/or substituted (meth)acrylic acid and alcohols comprising about 1 to about 18 carbon atoms, preferably about 1 to about 12 carbon atoms.
  • the alcohols are advantageously straight or branched chain aliphatic alcohols, are preferably monohydroxy alcohols and preferably free from other functional substituent groups.
  • Useful monomers include but are not limited to those selected from methyl (meth)acrylate, n-butyl (meth)acrylate, ethyl (meth)acrylate, 2- methylbutyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, hexyl (meth)acrylate, isobornyl (meth)acrylate, octadecyl (meth)acrylate, phenoxyethyl (meth)acrylate, alkoxylated alkyl(meth)acrylates such as e.g.
  • Preferred (meth)acrylic acid ester monomers include those selected from methyl (meth)acrylate, butyl (meth)acrylate e.g. n-butyl (meth)acrylate, ethyl (meth)acrylate, 2- 7
  • methylbutyl (meth)acrylate isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, hexyl (meth)acrylate, isobornyl ( eth)acrylate, octadecyl (meth)acrylate, phenoxyethyl (meth)acrylate, and mixtures thereof.
  • the polymer beads of the present invention are copolymers of (meth)acrylic acid esters and optionally one or more additional monomers.
  • (Meth)acrylic acid ester monomers generally comprise from about 60 to about 100 parts by weight based on 100 parts total monomer content, preferably from about 70 parts to about 98 parts based on 100 parts total monomer content.
  • Copolymerizable polar monomers can be selected from both strongly and moderately polar copolymerizable monomers.
  • the polar monomers preferably have one or more hydrophilic groups such as hydroxy, thiol, amino, amid, ionic groups such as an acid, e.g. carboxylic acid, sulphonic acid, phosphonic acid, phosphoric acid and salts thereof, an ammonium group etc., or one or more polar groups such as a nitrile.
  • polar monomers examples include methacrylic acid, acrylic acid, itaconic acid, hydroxyalkyl (meth)acrylates, ⁇ -carboxy ethyl (meth)acrylate, styrene sulfonic acid or the sodium salt thereof, maleic acid, fumaric acid, (meth)acrylamides and substituted (meth)acrylamides, N- vinylpyrrolidone, N-vinyl caprolactam, acrylonitrile, dimethyl amino propyl methacrylate.
  • Prefe ⁇ ed polar monomers include acrylic acid, methacrylic acid, (meth)acrylamide and substituted (meth)acrylamide.
  • Polar monomers generally are comprised from about 1 to about 40 parts by weight based on the total monomer content, preferably from about 2 to about 30 parts by weight.
  • Copolymerizable polar macromers are preferably water soluble or water dispersible polymers or oligomers that contain a polymerizable group.
  • a macromer useful in preparing copolymer beads contains a single polymerizable group such as a vinyl group.
  • the polar macromer contains a plurality of hydrophilic sites which impart the required hydrophilicity of the macromer to make it water soluble or water dispersible.
  • a polar macromer in connection with this invention may be represented by the general formula I 8
  • X is a structural element comprising a moiety copolymerizable with the (meth)acrylic acid ester
  • Y is a divalent linking group
  • Z is the hydrophilic site and comprises a water-dispersible or water soluble polymeric or oligomeric moiety, i.e. one containing two or more monomer units which are essentially unreactive under free radical initiated copolymerizing conditions employed to form the copolymer beads.
  • a preferred X group of the polar macromer is a vinyl group of the general formula II
  • R 1 is a hydrogen atom or a methyl group.
  • a preferred Y group is a divalent carbonyl group.
  • a preferred Z moiety is an oligomeric/polymeric material with a molecular weight of 300 to 30,000g/mol.
  • the Z moiety is a polyethyloxazoline or a poly-N- vinylpyrrolidone or a polyalkyleneoxide structure.
  • a Z component which is a copolymer of different monomers, e.g. a copolymer of one or more of the above listed polar monomers such as a copolymer of a N-vinylpyrrolidone and acrylamide.
  • a number of macromers of the type useful for the invention are available commercially.
  • One method of preparing macromers uses commercially available preformed polymeric Z moieties and conventional chemical reactions for modifying them.
  • a mono- methoxypolyethyleneglycolacrylate macromer can be prepared by esterification of a monohydroxyl-terminated poly(C ⁇ -Cs alkylene oxide) compound in an appropriate solvent.
  • ⁇ , ⁇ -unsaturated carboxylic acid preferably in presence of p-toluene sulfonic acid and refluxed for generally 16 to 18 hours. Excess acid is neutralized and the precipitate is filtered off.
  • Suitable monohydroxyl terminated poly(d- Cs alkylene oxides) which may be used to prepare the macromers using the above described procedure include CarbowaxTM 750, CarbowaxTM 550 and CarbowaxTM 350.
  • the macromer can also be prepared by an addition reaction in which an isocyanate is reacted with a monohydroxyl or monoamine terminated poly(C ⁇ -Cs alkylene oxides) as well as other Z moieties as described above.
  • an isocyanate is reacted with a monohydroxyl or monoamine terminated poly(C ⁇ -Cs alkylene oxides) as well as other Z moieties as described above.
  • a benzylisocyanate having a vinylic double bond in the side chain may be reacted with a monoamine terminated 9
  • poly(C ⁇ -C 5 alkylene oxide) The components are mixed and reacted for a few hours for quantitative conversion.
  • a suitable monoamino terminated poly(C ⁇ -C 5 alkylene oxide) is for example JeffamineTM M 600.
  • the macromers can be also prepared by first synthesizing a suitable Z moiety and then converting it to a macromer using known methods.
  • the Z moiety may be formed by radical polymerization of N-vinylpyrrolidone and acrylamide in the presence of a chain transfer agent for example amino-ethanethiol, using a radical chain initiator for example azobisisobutyronitrile in an appropriate organic solvent.
  • a chain transfer agent for example amino-ethanethiol
  • a radical chain initiator for example azobisisobutyronitrile
  • a suitable reagent for introducing the X and Y groups is vinyl azlactone (available from SNPE, France). The vinyl-azlactone ring can be opened yielding the macromer.
  • polar, comonomers or comacromers can be used together with the (meth)acrylic acid esters and/or the polar comonomers or polar macromers.
  • examples include monomers selected from styrene, alpha-methyl " styrene, vinyl acetate, and vinyl ester monomers such as vinyl 2-ethyl hexanoate and derivatives thereof, and comacromers such as a polystyrene macromer, a polymethylmethacrylate macromer or a polyphenyleneoxide macromer etc....
  • Such optional comonomers/comacromers can generally be used in a range up to about 40 parts by weight based on the total monomer and/or macromer content.
  • the costabiliser is an optional component.
  • the costabiliser is preferably a synthetic water soluble or water dispersible polymer such as e.g. a polyvinylalcohol, a polyvinylacetate, a poly-N-vinylpyrrolidone, a poly(meth)acrylic acid etc... or mixtures thereof.
  • the costabiliser can be used in an amount of 0.1% by weight to 10% by weight, preferably 0.3% to 2% by weight based on the total weight of monomers and/or macromers.
  • Initiators for polymerizing the monomers to provide the polymer beads of the invention are those which are normally suitable for free-radical polymerization of acrylate monomers 10
  • initiators are azo-initiators and include 2,2'-azobisisobutyronitrile, commercially available from E.I. Dupont de Nemours as VazoTM 64 and 2,2'-azobis(2,4-dimethyl valeronitrile), available from Wako as V-65.
  • the initiator can generally be present in an amount of from about 0.01 to 1 parts by weight based on 100 parts of monomer content.
  • Useful chain transfer agents include mercaptans, alcohols, carbon tetrabromide, and mixtures thereof. Isooctyl thioglycolate and carbon tetrabromide are preferred.
  • the chain transfer agent can generally be present in an amount of from about 0.01 to about 0.5 parts by weight preferably from about 0.01 to about 0.2 parts, based on 100 parts total monomer content.
  • a water soluble inhibitor can be added to inhibit polymerization in the water phase in order to prevent the formation of too much polymer by emulsion and/or solution polymerization in the water phase, which can result in bead agglomeration or emulsion type polymerization.
  • Suitable inhibitors include those selected from thiosulfates, thiocyanates and nitrites.
  • the water soluble inhibitor can generally be added in an amount of from about 0.01 to about 1 parts by weight based on 100 parts total monomer content.
  • Crosslinking agents can also be used in the present invention.
  • Preferred crosslinking agents include copolymerizable aromatic ketone monomers, especially acryloxybenzophenone and derivatives, triazine crosslinking agents such as those taught in US-A-4,330,590 (Vesley) and US-A-4,329,384 (Vesley et al.), and combinations thereof.
  • the crosslinking agent generally comprises from about 0.01 to about 5 parts weight based on 100 parts total monomer content.
  • additives can optionally be used in combination with dextrins, e.g., borax, urea, glyoxal and urea formaldehyde resin.
  • Biocides both bactericides and fungicides can also be added, in order to prevent microbial growth in the finished product and during its use.
  • the monomers, free-radical initiator, and any optional materials can be mixed together in the prescribed ratio to form a premix.
  • Dextrin or a derivative of dextrin can be combined 1 1
  • Bead-type suspension polymerization in accordance with the present invention is typically a thermally initiated polymerization and is preferably carried out with agitation for about 2 to about 16 hours at a temperature between about 40°C and 90°C.
  • the polymers made by the method of the present invention are preferably soluble in ethyl acetate and typically have an inherent viscosity between about 0.4 and 2.2 dl/g, (measured in ethyl acetate). The inherent viscosity of the polymers can be varied according to particular needs, e.g., by changing the amount of chain transfer agent utilized.
  • the polymer beads prepared by the method of the present invention are useful in any application in which acrylate adhesives and adhesive formulations, in particular pressure sensitive adhesive compositions, otherwise produced may be used.
  • the polymer beads can be extruded at temperatures below 180°C.
  • the polymer beads can be coated from water or solvents by conventional methods such as roller coating or dip coating. Extrusion or coating results in the formation of a continuous film of adhesive.
  • These adhesive compositions can be applied to a backing, e.g., polyethylene terephthalate (PET) liner, or to a release liner such as a silicone-coated paper to form a tape or a transfer tape.
  • PET polyethylene terephthalate
  • Tacky bead-type suspension polymers that can be obtained in connection with the present invention can optionally be compounded with tackifying agents in order to improve tack and adhesive strength.
  • Useful tackifying agents include rosin and rosin derivatives, hydrocarbon tackifiers such as polyterpenes, synthetic hydrocarbon resins, and modified phenolic resins.
  • Preferred tackifiers include hydrocarbon resins, such as Regalrez® and Regalite® (Hercules); phenol terpene tackifiers, such as SP 553 and SP 560
  • the tackifying agent comprises about 0 to about 60 parts by weight, preferably about 10 to 12
  • compositions of the present invention include additives such as pigments, dyes, viscosity builders, viscosity stabilizers, antioxidants, matting agents, inert fillers and waxes.
  • test methods used for determining peel adhesion and shear of adhesive formulations made from the polymer beads prepared according to the method of the present invention are based on those described by the Pressure- Sensitive Tape Council (Test Methods for Pressure-Sensitive Tapes, Ninth Edition, August 1989), with some deviations as outlined below.
  • Peel adhesion is the force required to remove a coated flexible sheet material from a test panel measured at a specific angle and rate of removal. In the following Examples, this force is expressed in Newtons per decimeter width (N/dm) of coated sheet.
  • 12.5 mm width of the coated sheet is applied to the horizontal surface of a clean test plate with at least 12.7 lineal cm in firm contact.
  • a hard rubber roller is used to apply the strip.
  • the free end of the coated strip is doubled back, and the free end is attached to the adhesion tester scale.
  • the angle of removal is 90° or 180°, as indicated in the experiments.
  • the test plate is clamped in the jaws of the tensile testing machine which is capable of moving the plate away from the scale at a constant rate of 300 mm/min.
  • the scale rating in Newtons is recorded as the tape is peeled from the surface.
  • the data are recorded as the average value of the range of numbers observed during the test.
  • Shear strength is a measure of the cohesiveness or internal strength of an adhesive. It is based upon the amount of force 13
  • the panel with coated strip attached is held in a rack such that the panel forms an angle of 178° with the extended tape free end which is then tensioned by application of a force of one kilogram (test at room temperature) or 0.5 kilogram (test at 70°C) applied as a hanging weight from the free end of the coated strip.
  • An angle of 178° is used to negate any peel forces, thus ensuring that only the shear forces are measured in an attempt to more accurately determine the holding power of the tape being tested.
  • the time (min) elapsed for each tape example to separate from the test panel is recorded as the shear strength.
  • the inherent viscosity of the polymers was measured by conventional means using a Cannon-Fenske # 50 viscosimeter in a water bath controlled at 25°C to measure the flow time of 10 ml of a polymer solution (0.15 g of polymer in 100 ml ethyl acetate). Inherent viscosity is recorded as dl/g.
  • FUSOAM90g polyalkylene oxide containing acrylate macromer obtained from Shinnakamura 14
  • FUSOM90g polyalkylene oxide containing methacrylate macromer obtained from Shinnakamura
  • CW750AM mono-methoxypolyethyleneglycol acrylate prepared from
  • CarbowaxTM 750 (Union Carbide) in accordance with the procedure set out at column 10 of US 5.380.779
  • SSS sodium salt of styrene sulphonate
  • IOTG isooctylthioglycolate, available from Elf Atochem
  • ABP acryloxybenzophenone
  • WPI Watts per inch rpm : rotations per minute
  • IBA isobornyl acrylate
  • PAA polyacrylic acid
  • PVA polyvinylalcohol (88% hydrolysed) obtained from Janssen Chimica
  • PETP pentaerythritol tetrakis mercaptopropionate (obtained from Aldrich)
  • Suspension polymer beads were made using the general method as described below : the reaction was carried out in a two liter flask equipped with a condenser, nitrogen inlet, 15
  • thermowell stainless steel motor-driven stirrer, and a heating unit with temperature control.
  • the reaction flask was charged with deionized water and an amount of dextrin or a derivative of dextrin, as indicated in the specific examples.
  • the resulting mixture was heated to 45°C with agitation while purging with nitrogen.
  • a premixed charge of monomers, initiator, and optional chain transfer agent, water soluble inhibitor and photocrosslinker was added while stirring vigorously at a rate between about 600 and 750 rpm.
  • the temperature of the reaction mixture was adjusted to 45°C or 55°C (depending on the initiator). Reaction was continued with nitrogen purging until completion.
  • the copolymer beads thus formed may be coated from water. Alternatively, they could be collected by filtration and dried in an air ventilated oven, after which they could be coated via extrusion or could be dissolved in solvent and coated as a solution in a solvent.
  • the polymer beads were extruded at a temperature below 180°C.
  • the samples could be formulated with tackifying agent, which was added to the molten extruder contents.
  • An adhesive layer was formed onto a backing. If the adhesive composition was to be used as a tape, it was coated onto a flexible carrier web; if it was to be used as a transfer tape, it was applied to a release liner such as a silicone-coated paper.
  • the adhesive coatings were laminated against both sides of a flexible carrier, such as, e.g., a flexible polyvinyl chloride (PVC) or polypropylene carrier.
  • PVC polyvinyl chloride
  • UV-cure lamps e.g., AUV 6A/300WPI, available from American Ultraviolet Company, USA; or F- 600 D-bulb, available from Fusion GmbH, Germany
  • Examples 1 to 4 were made essentially according to the above-described general procedure for the bead-type suspension polymerization with a premixed charge of 96% IOA and 4% MAA, along with the amounts of IOTG and sodium thiosulfate shown in 16
  • Comparative Examples C-1 and C-2 were made in the same way, but with conventional suspending agents such as hydroxyethylcellulose (Natrosol® 250 MBR, available from AQUALON, Germany) in C-1 and hydroxypropylcellulose (Klucel L®, available from AQUALON, Germany) in C-2, instead of using dextrin.
  • Table 1 Bead-type Suspension Polymerization, Stabilized with Dextrin
  • Example 4 also contaii is 0.3% Al BP
  • Examples 5 to 11 were made in order to evaluate dextrins from different sources (available from Roquette, France, as different Tackidex® grades) and having different solubilities in water (at 22°C).
  • the polymerization reactions were carried out essentially according to the general method described above.
  • the premixed monomer charge contained 96% IOA, 4% MAA, 0.16% IOTG, 016% STS, and 0.3% V-65. In all 17
  • suspension polymer beads were prepared of IOA/MAA 96/4 essentially according to the above-described general procedure, using 0.6% Tackidex® 035 as the stabilizer.
  • the amount of chain transfer agent was varied in order to make various polymers beads with different inherent viscosities.
  • the compositions and inherent viscosities (IV) of the samples are given in Table 3.
  • suspension polymer beads were formed that were non-agglomerating and stable for more than 4 weeks. Su ⁇ risingly, even the polymer beads with very low IV (0.4) were stable and non-agglomerating.
  • Examples 21 to 24 were made in order to evaluate derivatives of dextrins such as maltodextrin (available as Glucidex® grades from Roquette, France) and beta-cyclo dextrin (available from Wacker Chemie, Germany).
  • dextrin derivatives were evaluated in the suspension polymerization of IOA/MAA 98/2, essentially according to the above-described general procedure (with addition of 0.2% STS, 0.3% V-65, and 0.017% IOTG). 0.6% dextrin derivative was used. The results are given in Table 4.
  • Suspension polymers were made from the monomers indicated in Table 5, essentially according to the general method described above. 0.3% V-65, and the amounts of IOTG, STS, and ABP indicated in Table 5 were used. Examples 25 and 26 were made with Tackidex® 133 stabilizer (0.8% and 0.6% respectively); the other examples were made with Tackidex® 035 (0.6%). The composition and IV of the polymers are shown in Table 5. Table 5 : Bead-type Suspension Polymerization of Various Monomers in the
  • the suspension polymerization in accordance with the present invention allows for the preparation of polymer beads comprising high levels (more than 20 parts) of polar monomers.
  • the suspension polymer beads were stable for more than 4 weeks.
  • Examples 34 to 37 were made following the general procedure for the bead-type suspension polymerization as set out above.
  • a monomer premix of phenoxyethylacrylate and isobomylacrylate in a molar ratio of 50/50 was prepared. 0.3% V-65 initiator was used. This premix was added to a mixture of 0.5% Tackidex® 035 and 0.5% of a polymeric stabilizer as indicated in table 6.
  • Example 37 also contained 0.05% IOTG. The 20
  • a costabiliser is needed in case a monomer premix is used that does not include a polar monomer or polar macromer.
  • Polymer beads were prepared using the general procedure for the bead-type suspension polymerization as set out above.
  • a monomer premix of ethylacrylate/methylmethacrylate/isobomylacrylate/acrylic acid in a mol ratio 50/30/10/10 was used.
  • 0.3% V-65 initiator was used.
  • This premix was added to a mixture of 0.45% Tackidex® 035 and 0.13% of PVA.
  • the initiation temperature was 55°C.
  • Stable beads were obtained. This example illustrates that a co-stabiliser may also be used in case the premix contains a polar monomer.
  • Polymer beads were prepared using the general procedure for the bead-type suspension polymerization as set out above.
  • the premix contained IOA/IBA/AA in a mol ratio 95/4.75/0.25 along with 0.1% ABP, 0.02% IOTG and 0.3% V-65 initiator.
  • the stabiliser 21
  • Examples 40 to 46 were made following the general procedure for the bead-type suspension polymerization with a monomer mixture as given in table 7. In all cases 0.6%
  • Tackidex® 035 was used as stabilizer. 0.3% V-65 initiator was used and initiation temperature was 50°C.
  • OK means that free flowing beads in a wet state were obtained;
  • examples 44, 47b compared to example 43, 47a use of SSS (sodiumstyrene sulfonate) improves the stability of the reaction mixture. More homogeneous bead- size is obtained and the waterphase is completely water clear.
  • SSS sodiumstyrene sulfonate
  • suspension polymer beads were prepared essentially according to the general procedure, starting from IOA/MAA 96/4 and using
  • suspension polymer beads were in some cases formulated with tackifying agent during extrusion.
  • the resulting adhesive formulations were coated onto a silicon-coated paper liner and laminated against a PET liner. The adhesives were tested before and after crosslinking under high intensity UV light. The results are given in Table 8.
  • Adhesion to SS 180° peel adhesion, measured at 300 mm/min
  • Examples 60 to 63 were made essentially according to the above-described general procedure using IOA/MAA 98/2 monomer mixture, 0.017% IOTG, 0.16% STS, 0.3% 24
  • the IV of the resulting polymer was 1.35.
  • Examples 64 and 65 were made essentially the same way, but starting from a monomer mixture of IOA/iBA/MAA 92/6/2. The resulting IV was 1.5.
  • the polymer beads were formulated with tackifying agent and in some cases with 2,4-bistrichloromethyl-6(4- methoxyphenyl)s-triazine crosslinking agent (XL), during extrusion at a temperature of 120-180°C.
  • the resulting adhesive formulations were coated onto silicon coated paper liner. Double coated tapes were made by laminating the adhesive against both sides of a PVC or microvoided polypropylene (Teslin) liner. The thickness of the adhesive layer was 0.08 mm.
  • the resulting adhesive properties are given in Table 9.
  • suspension polymers having a high inherent viscosity could be extruded at low temperature.
  • the adhesive formulations prepared had high overall performance.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne un nouveau procédé de polymérisation en suspension de type billes aqueuses de monomères (méth)acryliques pour préparer des billes de polymère (méth)acryliques qui ne s'agglomèrent pas et à stockage stable. Ces billes sont extrudables à basses températures. L'invention concerne aussi les billes de polymère en soi et leur utilisation comme adhésif, plus particulièrement comme adhésif autocollant. L'invention concerne en outre des compositions adhésives comprenant les billes de polymère.
PCT/US1998/002024 1998-02-03 1998-02-03 Procede de polymerisation en suspension de monomeres (meth)acryliques utilisant de la dextrine et des billes de polymere obtenues par ce procede WO1999040134A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2000530560A JP2002502898A (ja) 1998-02-03 1998-02-03 デキストリンを用いる（メタ）アクリル酸モノマーの懸濁重合の方法、及びその方法から得られるポリマービーズ
US09/381,112 US6245838B1 (en) 1998-02-03 1998-02-03 Method of suspension polymerization of (meth)acrylic monomers using dextrin, and polymer beads resulting from that method
AU60551/98A AU6055198A (en) 1998-02-03 1998-02-03 Method of suspension polymerization of (meth)acrylic monomers using dextrin, andpolymer beads resulting from that method
PCT/US1998/002024 WO1999040134A1 (fr) 1998-02-03 1998-02-03 Procede de polymerisation en suspension de monomeres (meth)acryliques utilisant de la dextrine et des billes de polymere obtenues par ce procede

Applications Claiming Priority (1)

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PCT/US1998/002024 WO1999040134A1 (fr) 1998-02-03 1998-02-03 Procede de polymerisation en suspension de monomeres (meth)acryliques utilisant de la dextrine et des billes de polymere obtenues par ce procede

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1247820A1 (fr) * 2001-03-29 2002-10-09 Agfa-Gevaert Méthode de préparation de particules de polymères à distribution étroite de la taille
US6800709B2 (en) 2001-03-29 2004-10-05 Agfa-Gevaert N.V. Method of preparing polymer particles having narrow particle size distribution
US20220002445A1 (en) * 2020-07-01 2022-01-06 Nanjing Wurui Biodegradable New Material Research Institute Co., Ltd. Thermoplastic starch and starch-based biodegradable film

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011074308A (ja) * 2009-10-01 2011-04-14 Three M Innovative Properties Co 透明粘着シート及びそれを含む画像表示装置
JP6325653B2 (ja) * 2014-03-31 2018-05-16 リンテック株式会社 粘着性組成物、粘着剤および粘着シート

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Publication number Priority date Publication date Assignee Title
US2857367A (en) * 1954-06-10 1958-10-21 Diamond Alkali Co Polymerization process utilizing dextran as a primary dispersing agent
US4833179A (en) * 1987-07-27 1989-05-23 Minnesota Mining And Manufacturing Company Suspension polymerization
EP0334515A1 (fr) * 1988-03-21 1989-09-27 Cerestar Holding Bv Compositions de polymères
EP0853092A1 (fr) * 1997-01-14 1998-07-15 Minnesota Mining And Manufacturing Company Procédé de polymérisation en suspension de monomères (meth)acryliques utilisant dextrine et perles de polymérisation préparés de cette méthode

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2857367A (en) * 1954-06-10 1958-10-21 Diamond Alkali Co Polymerization process utilizing dextran as a primary dispersing agent
US4833179A (en) * 1987-07-27 1989-05-23 Minnesota Mining And Manufacturing Company Suspension polymerization
EP0334515A1 (fr) * 1988-03-21 1989-09-27 Cerestar Holding Bv Compositions de polymères
EP0853092A1 (fr) * 1997-01-14 1998-07-15 Minnesota Mining And Manufacturing Company Procédé de polymérisation en suspension de monomères (meth)acryliques utilisant dextrine et perles de polymérisation préparés de cette méthode

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1247820A1 (fr) * 2001-03-29 2002-10-09 Agfa-Gevaert Méthode de préparation de particules de polymères à distribution étroite de la taille
US6800709B2 (en) 2001-03-29 2004-10-05 Agfa-Gevaert N.V. Method of preparing polymer particles having narrow particle size distribution
US20220002445A1 (en) * 2020-07-01 2022-01-06 Nanjing Wurui Biodegradable New Material Research Institute Co., Ltd. Thermoplastic starch and starch-based biodegradable film
US11732058B2 (en) * 2020-07-01 2023-08-22 Nanjing Wurui Biodegradable New Material Research Institute Co., Ltd. Thermoplastic starch and starch-based biodegradable film

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JP2002502898A (ja) 2002-01-29

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