EP2176302A2 - Copolymerlatex, verfahren zu seiner herstellung und seine verwendung zur beschichtung von papier und pappe - Google Patents

Copolymerlatex, verfahren zu seiner herstellung und seine verwendung zur beschichtung von papier und pappe

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Publication number
EP2176302A2
EP2176302A2 EP08826710A EP08826710A EP2176302A2 EP 2176302 A2 EP2176302 A2 EP 2176302A2 EP 08826710 A EP08826710 A EP 08826710A EP 08826710 A EP08826710 A EP 08826710A EP 2176302 A2 EP2176302 A2 EP 2176302A2
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EP
European Patent Office
Prior art keywords
monomers
weight
optionally substituted
latex
copolymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP08826710A
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English (en)
French (fr)
Inventor
Laurence Couvreur
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema France SA
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Arkema France SA
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Filing date
Publication date
Application filed by Arkema France SA filed Critical Arkema France SA
Publication of EP2176302A2 publication Critical patent/EP2176302A2/de
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Classifications

    • 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
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
    • 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
    • C08F212/00—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 an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • 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
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/38—Thiocarbonic acids; Derivatives thereof, e.g. xanthates ; i.e. compounds containing -X-C(=X)- groups, X being oxygen or sulfur, at least one X being sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/39—Thiocarbamic acids; Derivatives thereof, e.g. dithiocarbamates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene
    • C08L9/08—Latex
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/22—Polyalkenes, e.g. polystyrene
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/24—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/58—Polymers or oligomers of diolefins, aromatic vinyl monomers or unsaturated acids or derivatives thereof
    • 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
    • C08F2438/00—Living radical polymerisation
    • C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/3188—Next to cellulosic
    • Y10T428/31895—Paper or wood

Definitions

  • the present invention relates to copolymer latexes (s) made using halogen-free molecular weight chain transfer agents or regulators that can be used for paper coating applications, particularly in the field of odor-sensitive applications (eg food packaging).
  • Latexes that can be used for the coating of paper and board must have good mechanical properties (printability, resistance to tearing of the coating). For this purpose, it is necessary to control the molecular weight of the copolymer latex (s) during the polymerization using regulators or chain transfer agents (CTA).
  • CTA chain transfer agents
  • organohalogen compounds have been widely used as chain transfer agents (eg carbon tetrachloride, carbon tetrabromide) and have been banned for some years for ecological reasons and replaced by sulfur transfer agents.
  • chain transfer agents eg carbon tetrachloride, carbon tetrabromide
  • sulfur transfer agents eg carbon tetrachloride, carbon tetrabromide
  • mercaptan type and in particular by tert-dodecyl mercaptan (TDM).
  • TDM tert-dodecyl mercaptan
  • Mercaptans perform very well their role in action on the control of the molecular weight of the chains in the copolymer latex (s) and make it possible to obtain latexes which have good resistance to tearing in the dry state or wet.
  • No. 5,837,762 discloses the use of chain transfer agents derived from rosin for the manufacture of the copolymer latex (s).
  • the regulation efficiency of rosin is much lower than that of mercaptans. It is therefore necessary to use up to 9% of rosin during the polymerization of the latex to reach acceptable values of resistance to dry tearing of coated paper.
  • rosin is a natural product whose quality varies greatly depending on the source.
  • rosin has a strong clean color (yellow to brown), which can be a drawback in coated paper, given the amounts of rosin that are implemented.
  • FR 2,665,450 discloses a very broad family of organosulfide transfer agents which are substituted diphenyl disulfides and are used as transfer agents for the preparation of low-odor latex since they have little or no undesirable residual odor.
  • this patent discloses that diphenyl disulfide alone is not sufficiently effective as a CTA and other organic disulfides, known as molecular weight regulators, such as thiuram disulfide, diethyl xanthogen disulfide and diphenyl substituted with amines. These additives are rather known as retarders and produce undesirable odors.
  • the amounts of transfer agent recommended in the patent for the polymerization are between 0.5% and 10%, with an optimum between 0.5% and 5% to obtain a paper having satisfactory properties (printability, resistance to abrasion). removal of the coating) close to the treated paper with obtained with TDM.
  • JP 7166496, JP 7278213 and JP 2001/003298 disclose the use of alpha-methylstyrene dimer alone or in admixture as a transfer agent for latices for coated paper applications. However, because of the low efficiency of these products, quantities much higher than those usually used must be implemented to arrive at good final properties of the materials.
  • EP 1 380 597 describes the use of several types of peroxides used as chain transfer agents (such as di-tert-butyl peroxide, cumol hydroperoxide, or di-tert-butyl, etc.).
  • the amount of peroxides used must be twice as great as that of TDM in order to obtain quasi-similar performances (particle size, glass transition temperature (Tg), gel ratio and intrinsic properties of the coated paper).
  • TDM glass transition temperature
  • Tg glass transition temperature
  • US 6,369,158 claims the use of dibenzyl trithiocarbonate (DBTTC) for the synthesis of SBR type latex ("styrene-butadiene rubber”) of high molecular weight which is mainly in pneumatic applications. It is well known that these elastomeric type products are characterized by low glass transition temperatures, incompatible with applications in which the elastomeric type products are not sought.
  • DBTTC dibenzyl trithiocarbonate
  • the problem is to look for variants of regulatory systems that do not contain halogen, do not present an odor as undesirable and marked as that of mercaptans while being suitable for making copolymer latexes (s) having a strength of sufficient bonding (i.e. tear resistance) and thus can be used in the area of odor-sensitive applications for coating paper and board.
  • the subject of the invention is a copolymer latex (s) intended to be used for coating paper and board, where the copolymer latex (s) has a glass transition temperature between -30 ° C. and 70 ° C. C, preferably between -20 ° C and 40 ° C, manufactured with at least one chain transfer agent and comprising in polymerized form: a) from 10% by weight to 80% by weight of one or more vinyl monomers ; b) from 20% by weight to 70% by weight of one or more conjugated diene monomers; c) and optionally up to 70% by weight of one or more monomers comprising at least one ethylenic unsaturation copolymerizable, chosen from acrylic monomers, ethylene-type unsaturated dicarboxylic acid monomers, monomers further bearing at least one nitrile function, the monomers of vinyl esters, the monomers of
  • (meth) acrylamide characterized in that the at least one chain transfer agent can be represented by the formula: where R is selected from -CH 2 RI, -CHR1 R'1 and -CR1 R'1 R "1, with R1, R'1 and R 11 I 1 identical or different, each independently represent each other , a group chosen from optionally substituted alkyl, a saturated, unsaturated or aromatic carbocyclic or heterocyclic ring, optionally substituted, optionally substituted alkylthio, optionally substituted alkoxy group, optionally substituted dialkylamino, organometallic group, acyl, acyloxy, carboxy (and its esters and / or salts), sulphonic acid (and its salts and or sulphonates), alkoxy- or aryloxycarbonyl, and polymer chain prepared by any polymerization mechanism, wherein Z is selected from hydrogen, halogen (chlorine, bromine, iodine), optionally substituted alkyl, optionally substituted
  • the group R as defined above can be released in the form of a radical R " , which initiates free radical polymerization.
  • Dithioesters which can be advantageously used in the context of the invention are those corresponding to the following formula (I):
  • Z represents a group chosen from -C 6 H 5 , -CH 3 , a pyrrole group, -OC 6 F 5 , a pyrrolidinone group, -OC 6 H 5 , -OC 2 H 5 , -N (C 2 H 5 ) 2, and advantageously the group -S-CH 2 -C 6 H 5 (dibenzyl trithiocarbonate or DBTTC) of formula (II) below:
  • chain transfer agents as defined above which are fat-soluble, and of little or no water-soluble nature.
  • the transfer agent of formula (II) responds particularly to these conditions.
  • chain transfer agents dibenzyl trithiocarbonate (DBTTC) and its derivatives are particularly suitable.
  • the quantities of chain transfer agents used generally range from 0.1 to 10% by weight, preferably from 0.1 to 5% by weight, particularly from 0.1 to 3% by weight, relative to to 100% by weight of monomer (s) a) to c).
  • the amounts of chain transfer agents above allow the synthesis of copolymer (s) copolymer (s) whose (s) copolymer (s) free (fractions extracted from the copolymer (s) isolated (s) at room temperature. ambient temperature with toluene for 24 hours) have the following characteristics: 5,000 ⁇ Mn ⁇ 80,000, preferably 5,000 ⁇ Mn ⁇ 50,000, and 10,000 ⁇ Mw ⁇ 270,000, preferably 10,000 ⁇ Mw ⁇ 200,000, where Mn and Mw respectively represent the molar masses in number and in weight.
  • the quantities used of the chain transfer agents defined above can be less than those used with conventionally used chain transfer agents (mercaptans, di- and trithiols, and others), while retaining the mechanical properties of the copolymers (such as bond strength, tear resistance, and others).
  • the vinyl monomers a) comprise, in particular, vinyl aromatic monomers such as styrene, ⁇ -methylstyrene, para-ethylstyrene, ter-butylstyrene and / or vinyltoluene. Mixtures of one or more vinyl monomers may also be used.
  • the preferred monomers are styrene and ⁇ -methylstyrene.
  • the monomer (s) a) are generally used in a range from 10% to 80% by weight, preferably from 25% to 75% by weight, most preferably 35% to 70% by weight, based on to the total weight of the monomers.
  • Conjugated diene monomers b) suitable for the manufacture of latices include conjugated diene monomers such as ⁇ j
  • the amount of conjugated diene monomer (s) present in the polymer phase ranges from 20% to 70% by weight, preferably from 20% to 65% by weight, more preferably from 20% to 70% by weight. % to 55% by weight, more preferably 30% to 50% by weight, most of the time 30% to 45% by weight, based on the total weight of the monomers.
  • the acrylic monomers c) usable in the present invention as copolymerizable comonomers include in particular acrylic acid, methacrylic acid, alkyl (meth) acrylates, hydroxyalkyl and / or alkoxyalkyl (meth) acrylates, where the alkyl group (n-alkyl, / -sat-alkyl or terf-alkyl) has 1 to 20 carbon atoms of alkyl and is optionally substituted by at least one epoxy group, amide, and / or at least one amino group; the reaction product of (meth) acrylic acid with the glycidyl ester of a neoacid such as versatic acids, neodecanoic acids or pivalic acid and mixtures thereof.
  • the preferred acrylic monomers are acrylic, methacrylic, alkyl and / or hydroxyalkyl and / or alkoxyalkyl (meth) acrylates, wherein the alkyl group is C1-C10, preferably
  • Ci-Cs As examples of preferred acrylic monomers, mention may be made especially of acrylic acid, methacrylic acid, n-butyl acrylate, sec-butyl acrylate, ethyl acrylate and hexyl acrylate. tert-butyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate,
  • the most preferred acrylic monomers are acrylic acid, methacrylic acid, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate.
  • the amount of acrylic monomer (s) optionally present in the polymer phase depends on the monomer or monomers chosen; however, the typical range can be up to 70% by weight, preferably from 1 to 70% by weight, preferably from 1 to 60% by weight, most preferably from 0 to 51% by weight, by weight. relative to the total weight of the monomers.
  • the unsaturated dicarboxylic acid monomers of the ethylene type that can be used as copolymerizable comonomers c) within the scope of the present invention comprise, in addition to the ethylenically unsaturated dicarboxylic acids, their monoesters and / or their anhydrides.
  • unsaturated dicarboxylic acid of ethylene type mention may be made of fumaric acid, crotonic acid, maleic acid and maleic anhydride.
  • nitrile monomers usable as copolymerizable comonomers c) in the context of the present invention comprise polymerizable unsaturated aliphatic nitrile monomers which contain from 2 to 4 carbon atoms in a linear or branched arrangement and which may be optionally substituted by acetyl or additional nitrile groups.
  • These nitrile monomers include, for example, acrylonitrile, methacrylonitrile and fumaronitrile, with acrylonitrile being preferred.
  • These nitrile monomers (if used) can be included up to about 25 parts by weight, preferably from 0 to 15 parts by weight, based on 100 parts by weight of monomers.
  • the vinyl ester monomers useful as the coolymerizable monomers c) include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, vinyl 2-ethylhexanoate, vinyl stearate and vinyl esters. versatic acid.
  • the preferred vinyl ester monomer for use in the present invention is vinyl acetate.
  • the amount of vinyl ester monomer (if used), which is present in the polymer phase ranges from 0 to 45% by weight, preferably from 0 to 35% by weight, based on the total weight monomers.
  • the monomers of (meth) acrylamide that can be used as coolmeasurable monomers c) include the ⁇ , ⁇ -olefin unsaturated carboxylic acid amides, such as, for example, acrylamide, methacrylamide and diacetone-acrylamide.
  • the preferred (meth) acrylamide monomer is acrylamide.
  • the amount of (meth) acrylamide monomer (if used), which is present in the polymer phase depends on the monomer chosen, but the typical range is from 0 to 10% by weight, preferably from 0 to 5% by weight, most preferably from 0 to 2% by weight relative to the total weight of the monomers.
  • Another subject of the invention is a process for producing a copolymer latex (s) as defined above from:
  • copolymerizable monomers c) chosen from acrylic monomers, ethylene-type unsaturated dicarboxylic acid monomers, nitrile monomers, vinyl ester monomers, monomers of (meth) acrylamide, and
  • CTA chain transfer agent
  • the size or average diameter of the latex particles, measured by light scattering, is generally between 50 and 200 nm.
  • the copolymer latex composition (s) of the present invention can be manufactured according to polymerization processes which are known in the field of polymerization, and in particular according to the latex emulsion polymerization processes, in particular the latex polymerizations carried out. with seeding latexes. Representative methods include those described in US 4,478,974, US 4,751,111, US 4,968,740, US 3,563,946 and US 3,575,913 and DE-A-19 05 256. These methods may be suitable for the polymerization of the previously described monomers. The method of introducing monomers and other ingredients such as polymerization aids is not particularly critical. The polymerization is then carried out under customary conditions, until the desired degree of polymerization is obtained.
  • Crosslinking agents and auxiliaries well known for latex polymerization such as initiators, surfactants and emulsifiers may be used depending on requirements.
  • Primers useful in the context of the present invention include water-soluble and / or fat-soluble initiators, which are effective for the purpose of polymerization.
  • Representative initiators are well known in the art and include, for example, azo compounds (such as AIBN) and persulfates (such as, for example, potassium persulfate, sodium persulfate and ammonium persulfate).
  • the initiator (s) are used in an amount sufficient to initiate the creation of polymerization at a desired rate; in general, an amount of initiator of 0.05 to 5% by weight, preferably 1 to 4% by weight, based on the weight of the total polymer, is sufficient.
  • the amount of initiator reaches from 0.1 to 3% by weight, relative to the total weight of the polymer.
  • any type of usual surfactant known in the field of polymerization processes may be used.
  • the surfactant (s) may be added to the aqueous phase and / or to the phase of the monomer (s).
  • the amount of surfactant (s) is generally chosen to promote the stabilization of the particles in the form of colloid and / or to reduce the contact between the particles and / or prevent coagulation. In an uninoculated process, the amount of surfactant (s) is generally selected to influence particle size.
  • surfactants mention may be made of ethylenically saturated and unsaturated sulphonic acids or their salts, including, for example, hydroxycarboxylic-sulphonic acids, such as vinylsulphonic acid, allylsulfonic acid and methallylsulphonic acid, and their salts.
  • aromatic hydroxycarboxylic acids such as, for example, para-styrenesulfonic acid, naphthalenesulfonic acid and vinyloxybenzenesulphonic acid and their salts
  • sulfoalkyl esters of acrylic acid and methacrylic acid such as, for example, sulfoethyl methacrylate and sulfopropyl methacrylate and their salts, and 2-acrylamido-2-methylpropanesulphonic acid and its salts
  • fatty alcohol (poly) ether sulphates such as, for example, para-styrenesulfonic acid, naphthalenesulfonic acid and vinyloxybenzenesulphonic acid and
  • the type and concentration of surfactant (s) typically depends on the content of solid polymers: a higher content of solid polymers generally increases the need for surfactant (s).
  • the surfactant (s) are used at concentrations ranging from 0.05 to 20, preferably from 0.05 to 10, more preferably from 0.05 to 5 parts by weight, relative to the weight total monomers.
  • Suitable colloids include partially acetylated polyvinyl alcohol, casein, hydroxyethyl starch, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose and gum arabic; the preferred protective colloids are carboxymethylcellulose, hydroxyethylcellulose and hydroxypropylcellulose.
  • these protective colloids are used at contents ranging from 0 to 10, preferably from 0 to 5, more preferably from 0 to 2 parts by weight, relative to the total weight of the monomers.
  • additives can be incorporated to make the latex composition of the present invention.
  • additives include, for example, antifoaming agents, wetting agents, thickeners, plasticizers, fillers, pigments, crosslinking agents, antioxidants and metal chelating agents.
  • anti-foaming agents include silicone oils and acetylene glycols.
  • Typical known wetting agents include alkyl phenol ethoxylates, alkali metal dialkyl sulfosuccinates, acetylene glycols and alkali metal alkyl sulfates.
  • Typical thickeners include polyacrylates, polyacrylamides, xanthan gums, modified cells or particulate thickeners such as diatomaceous earths and clays.
  • Typical plasticizers include mineral oil, liquid polybutenes, liquid polyacrylates and lanolin. Zinc oxide, titanium dioxide, aluminum hydrate, and calcium carbonate and clay are typically used fillers.
  • the object of the invention is also the use of the copolymer latices (s) defined above for the coating of paper and cardboard.
  • the latexes of copolymer (s) comprising at least one unsaturated carboxylic acid monomer of the ethylene type, whether it is an acrylic monomer and / or that it is an unsaturated dicarboxylic acid monomer of the ethylene type, improves strongly.
  • the stability of the latex and the adhesion of the latex films which makes the latex particularly suitable for use in paper coating formulations.
  • monocarboxylic acid monomers include, for example: acrylic acid, methacrylic acid and examples of dicarboxylic acid monomers include, for example: fumaric acid, crotonic acid, maleic acid and maleic anhydride.
  • ethylenically unsaturated carboxylic acid monomer (s) influences the properties of the polymer dispersion and the coatings produced therefrom, typically, when the amount of unsaturated carboxylic acid monomer (s) is present.
  • Ethylenically ranges from 1 to 20% by weight, preferably from 1 to 10% by weight, relative to the total weight of the monomers.
  • the copolymer latex composition (s) of the present invention prepared from styrene, butadiene, and acrylic acid, preferably copolymerized in the presence of DBTTC as a chain transfer agent.
  • Example 1 (comparative) - styrene latex
  • a solution is prepared containing 0.24 g of Na HCO 3 (buffer), 8 g of surfactant SLS (Sodium Lauryl Sulfate) and 540 g of distilled water; the mixture is stirred and heated (approximately 50 ° C.) until the surfactant is completely dissolved.
  • Na HCO 3 buffer
  • surfactant SLS Sodium Lauryl Sulfate
  • the transfer agent (DBTTC or TDM) / monomer (styrene) mixture is prepared, the CTA being introduced in the proportions indicated in Table 1 below; - Introduction of 2 mixtures above in a jacketed reactor of 1 L pre-vacuum, with stirring at 150 rpm and heated to 65 0 C;
  • the medium is deoxygenated with 3 cycles of evacuation and then under nitrogen to inert the reactor, it is left under vacuum at 65 ° C. before introduction of the initiator;
  • a solution containing the initiator is prepared, ie 0.2 g of PRS in 15 g of water (ie 82.6 mol% of PRS relative to DBTTC);
  • This mixture is introduced into an airlock under nitrogen flushing and then injected into the reactor by nitrogen thrust; rinse the lock with 45 g of water still under nitrogen and injection into the reactor;
  • the dried polymers are analyzed by steric exclusion chromatography (SEC) in THF at 40 ° C. at 1 g / l with a flow rate of 1 mL / min in a set of 2 Plgel MIXED B columns (30 cm) with a refractometric and UV detector.
  • SEC steric exclusion chromatography
  • the results of the molar masses and distribution are expressed in polystyrene equivalent (PS)
  • the vacuum is again made in the capacity and the capacity of liquid butadiene is pressurized with nitrogen (0.3 MPa).
  • the scale is weighed under the capacity of the monomers and then 209.5 g of butadiene are introduced. This monomer capacity is then pressurized to 1 MPa with nitrogen.
  • the butadiene capacity is degassed by nitrogen sweeping and stops cooling.
  • the following mixture is prepared that is introduced into the reactor 1 L provided with a jacket at 50 0 C under vacuum and with stirring at 150 rpm:
  • the reactor is heated to 80 ° C. and the initiator is prepared with 1.46 g of Na 2 S 2 O 8 and 15 g of water.
  • the boot is introduced through an airlock under N 2 of the initiator and the airlock is then rinsed with 20 g of water also introduced into the medium.
  • the pressure is then close to 0.57 MPa.
  • the polymerization is allowed to start so as to have a "seed", there is a drop in pressure of 0.02 MPa for about 30 minutes.
  • the reactor is cleaned with water at 70 ° C. and then with THF at 50 ° C., then dried and disassembled for manual cleaning. Residual monomer capacity is degassed and cleaned by rinsing with acetone.
  • Malvern (Zetasizer 5000) after dilution of the latex to adjust to the concentration required in the measuring cell of the device. They can also be measured by CHDF. Values of 171 nm measured with Zetasizer and 156 nm with CHDF are typically obtained.
  • the final raw latex is placed so as to have 6 to 7 g of dry product: approximately 14 g of latex per dish, which is allowed to dry slowly by evaporation in a hood for 3 days. Then drying is continued in a ventilated oven at 50 ° C. for 1 day. Carefully take off the film obtained which is put on the back for additional drying of a day still in an oven at 50 ° C.
  • % free polymer 100 x (m latex - dry m) / m latex 53.39 99.86
  • the measurement of the gel level serves to determine the insoluble fraction of a polymer in a specific solvent and the crosslinking of the copolymer latex (s). It corresponds to the gel portion of the polymer not solubilized in toluene after 24 hours in the cold. As a solvent, toluene is then used. The swelling is done on films that have been manufactured as described above. The toluene insoluble gel is filtered off, dried and weighed. The gel content is defined as the quotient of the weight of the dried gel divided by the weight of the original latex film (before swelling with toluene) and is indicated in%.
  • the free polymer (previously extracted in toluene after 24 hours of reflux with Soxhlet) is recovered in PTFE cups by evaporation of toluene in a ventilated oven at 50 ° C. for 2 days.
  • the masses and distribution by steric exclusion chromatography (SEC) in THF at 40 ° C. and at 1 g / L are determined with a flow rate of 1 mL / min over a set of 2 Plgel MIXED B columns (30 cm) with a refractometric and UV detector.
  • SEC steric exclusion chromatography

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Paper (AREA)
  • Polymerisation Methods In General (AREA)
EP08826710A 2007-07-25 2008-07-24 Copolymerlatex, verfahren zu seiner herstellung und seine verwendung zur beschichtung von papier und pappe Withdrawn EP2176302A2 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0756723A FR2919290B1 (fr) 2007-07-25 2007-07-25 Latex de copolymeres, leur procede de preparation et leur utilisation pour le couchage du papier et du carton.
PCT/FR2008/051390 WO2009016320A2 (fr) 2007-07-25 2008-07-24 Latex de copolymère(s), leur procédé de préparation et leur utilisation pour le couchage du papier et du carton

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FR2934861B1 (fr) * 2008-08-05 2012-12-28 Arkema France Nouveaux modifiants chocs du type coeur-ecorce pour matrices polymeres transparentes.
MX384775B (es) * 2012-02-10 2025-03-14 Arkema Inc Polimeros de emulsion de multiples fases para composiciones de recubrimiento acuosas que contienen poco o ningun solvente organico.
CN118079099A (zh) 2015-10-18 2024-05-28 阿利吉安斯公司 水基水凝胶共混涂料和施加到弹性体制品上的方法
EP3472212A4 (de) * 2016-06-15 2020-02-19 Rhodia Operations Hochleistungsfähige tensidfreie latexe für verbesserte wasserbeständigkeit
WO2019017470A1 (ja) * 2017-07-21 2019-01-24 デンカ株式会社 クロロプレン系重合体及びその製造方法
CN113795527A (zh) 2019-04-16 2021-12-14 罗地亚管理公司 使用选择性亲水大分子-raft试剂制备高固体、低粘度胶乳的方法
KR102714209B1 (ko) * 2019-12-18 2024-10-04 주식회사 엘지화학 고흡수성 수지의 제조 방법
KR102822965B1 (ko) * 2020-02-24 2025-06-19 주식회사 엘지화학 고흡수성 수지
JP7700786B2 (ja) * 2020-04-23 2025-07-01 東亞合成株式会社 カルボキシル基含有架橋重合体又はその塩及びその利用
WO2025129421A1 (en) * 2023-12-19 2025-06-26 Specialty Operations France Aqueous barrier coating and the recyclable article prepared from the same

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FR2665450B1 (fr) * 1990-08-01 1994-04-08 Rhone Poulenc Chimie Procede de preparation de dispersions aqueuses de copolymeres.
CA2091871A1 (en) * 1992-03-18 1993-09-19 Shigeo Suzuki Copolymer latex, production and use thereof
US5837762A (en) * 1993-07-08 1998-11-17 The Dow Chemical Company Latex-based coating composition
US5834762A (en) * 1994-12-13 1998-11-10 Minolta Co., Ltd. Image reading apparatus and method
US6369158B1 (en) * 1999-12-22 2002-04-09 The Goodyear Tire & Rubber Company Dibenzyltrithiocarbonate molecular weight regulator for emulsion polymerization
KR100409076B1 (ko) * 2000-12-20 2003-12-11 주식회사 엘지화학 종이 코팅용 라텍스의 제조방법
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FR2893025B1 (fr) * 2005-11-10 2010-12-03 Arkema Procede de preparation d'esters de type trithiocarbonate sans odeur ou a odeur attenuee

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JP2010534264A (ja) 2010-11-04
FR2919290A1 (fr) 2009-01-30
US20100255329A1 (en) 2010-10-07
FR2919290B1 (fr) 2009-10-02
WO2009016320A3 (fr) 2009-04-23

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