NO145510B - RETAINABLE ACRYLSTER COPOLYMERIZATES. - Google Patents

RETAINABLE ACRYLSTER COPOLYMERIZATES. Download PDF

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Publication number
NO145510B
NO145510B NO1990/73A NO199073A NO145510B NO 145510 B NO145510 B NO 145510B NO 1990/73 A NO1990/73 A NO 1990/73A NO 199073 A NO199073 A NO 199073A NO 145510 B NO145510 B NO 145510B
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Prior art keywords
acid
units
ester
carbon atoms
monomer
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NO1990/73A
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Norwegian (no)
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NO145510C (en
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Rolf Reinecke
Karl-Josef Rauterkus
Werner Schmieder
Eleonore Lutz
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Hoechst Ag
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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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/064—Copolymers with monomers not covered by C09J133/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Polymerisation Methods In General (AREA)
  • Dental Preparations (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Description

Oppfinnelsen vedrører fornettbare acrylesterkopoly-raerisater spesielt for anvendelse som fast kleber (Haftkleber), The invention relates to crosslinkable acrylic ester copolymers especially for use as a permanent adhesive (Self-adhesive),

Fornettbare acrylesterkopolymerisater er i og for seg kjent. Sammenstilling av nettdannelsesmuligheter er f.eks. omtalt i UB-A 1.805.370 samt i J. Paint Technology 42, side 346 Crosslinkable acrylic ester copolymers are known per se. Compilation of network formation possibilities is e.g. discussed in UB-A 1,805,370 as well as in J. Paint Technology 42, page 346

(1970) og J. Paint Technology 42, 45-50 (1971). Prinsippielt adskiller man derved to metoder for nettdannelse: Nettdannelse under fremstilling og etterfølgende nettdannelse. Nettdannelsen under fremstilling med polyfunk-sjonelle monomere som diallylforbindelser, diacrylater eller dimetacrylater fører til kopolymerisater av bestemt, men etterpå ikke mer påvirkbar kohesjon. En etterfølgende nettdannelse av kopolymerisater ved hjelp av reaktive monomere byr derimot på for-delen med en eventuell mulig innstilling av kohesjonen av kopolymerisatene. Slike reaktive monomere er f.eks. hydroksy-, epoksy-, halogenhydrin- eller aktiverte halogenforbindelser. Kopolymere, som inneholder disse reaktive monomere kan etterpå nettdannes med egnede komponenter og eventuelt under tilsetning &v egnede katalysatorer. Som eksempler skal det nevnes nettdannelse av hydroksylgruppeholdige kopolymere med diisocyanater eller av epoksydgruppeholdige kopolymerisater med diaminer. Alt etter reaksjonstype (addisjon, kondensasjon) og katalysator-system foregår nettdannelsen ved værelsestemperatur eller ved forhøyet temperatur. Termiske nettdannelsesmekanismer er ikke egnet for forskjellige anvendelsesområder, da det ofte inntrer en uønsket misfarvning (guldannelse). På mange anvendelsesområder anvendes på grunn av deres fordelaktige forarbéidelsesegen-skaper som luktfrihet og oppløsningsmiddelfrihet i økende grad polymerisater i form av deres vandige dispersjoner. For slike kunststoffdispersjoner er det ønskelig med nettdannelsesmekanismer som er anvendbare direkte i dispersjonen og som ikke krever noen termisk aktivering, hvilket er inter-essant for mange av disse dispersjoners anvendelsesformål. Fra tysk patent nr. 1.204.407 er det kjent vandige dispersjoner av acrylsyreestere, monokloreddiksyre vinylester og eventuelt ytterligere kopolymeriserbare monomere. Polymerisatet blandes imidlertid etter adskillelse av den vandige fase tilsvarende som syntesekautsjuk med vanlige kautsjuk-hjelpemidler og vulkaniseres ved temperaturer på ca. l60°C, idet det oppstår elastomere formmasser. (1970) and J. Paint Technology 42, 45-50 (1971). In principle, two methods of netting are thus distinguished: netting during manufacture and subsequent netting. The network formation during production with polyfunctional monomers such as diallyl compounds, diacrylates or dimethacrylates leads to copolymers of specific, but subsequently no more influenceable cohesion. A subsequent network formation of copolymers using reactive monomers, on the other hand, offers the advantage of possibly setting the cohesion of the copolymers. Such reactive monomers are e.g. hydroxy, epoxy, halohydrin or activated halogen compounds. Copolymers, which contain these reactive monomers, can then be net-formed with suitable components and possibly with the addition of suitable catalysts. Examples include cross-linking of copolymers containing hydroxyl groups with diisocyanates or of copolymers containing epoxide groups with diamines. Depending on the type of reaction (addition, condensation) and catalyst system, the network formation takes place at room temperature or at an elevated temperature. Thermal net formation mechanisms are not suitable for various areas of application, as undesirable discoloration (yellowing) often occurs. Polymers in the form of their aqueous dispersions are increasingly used in many areas of application due to their advantageous processing properties such as odorlessness and solvent-freeness. For such plastic dispersions, it is desirable to have net-forming mechanisms which can be used directly in the dispersion and which do not require any thermal activation, which is interesting for many of the application purposes of these dispersions. From German patent no. 1,204,407, aqueous dispersions of acrylic acid esters, monochloroacetic acid are known vinyl ester and possibly further copolymerizable monomers. However, after separation of the aqueous phase, the polymer is mixed similarly to synthetic rubber with common rubber auxiliaries and vulcanized at temperatures of approx. l60°C, as elastomeric molding compounds are produced.

Oppfinnelsen vedrører fornettbart acrylesterpoly-merisat bestående av The invention relates to crosslinkable acrylic ester polymer consisting of

a) enheter av minst en acrylsyreester og/eller metacrylsyreester av en mettet alifatisk alkohol a) units of at least one acrylic acid ester and/or methacrylic acid ester of a saturated aliphatic alcohol

med 4-12 karbonatomer, with 4-12 carbon atoms,

b) enheter av en monomer valgt blant styren, metylmetacrylat, acrylnitril, metacrylnitril, vinylacetat, vinylpropionat, acrylamid og metacryl-amid, idet denne monomer er forskjellig fra b) units of a monomer selected from styrene, methyl methacrylate, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate, acrylamide and methacrylamide, this monomer being different from

monomeren ifølge a), the monomer according to a),

c) enheter av en a-halogenalkankarboksylsyrevinyl-ester med formel (I) c) units of an α-haloalkanecarboxylic acid vinyl ester of formula (I)

idet og hver betyr hydrogen eller en alkylrest med 1-5 karbonatomer og X betyr fluor, klor, wherein and each means hydrogen or an alkyl residue with 1-5 carbon atoms and X means fluorine, chlorine,

brom eller jod, bromine or iodine,

samt enheter av ytterligere monomere, idet polymerisatet erkarakterisert vedat sistnevnte er as well as units of further monomers, the polymer being characterized by the latter being

d) enheter av en a,g-etylenisk umettet karboksyl-syre med 3-8 karbonatomer eller dens partialester d) units of an a,g-ethylenically unsaturated carboxylic acid with 3-8 carbon atoms or its partial esters

med en mettet alifatisk alkohol med 1-20 karbonatomer og with a saturated aliphatic alcohol of 1-20 carbon atoms and

e) enheter av en hydroksylgruppeholdig monomer med formel (II) e) units of a hydroxyl group-containing monomer of formula (II)

hvori Rj betyr hydrogen, en metylgruppe eller gruppen -COORg, R^ og Rj- betyr hver hydrogen wherein R 1 means hydrogen, a methyl group or the group -COOR 8 , R 1 and R 1 - each means hydrogen

eller en metylgruppe og Rg betyr hydrogen eller or a methyl group and Rg means hydrogen or

en alkylgruppe med 1-12 karbonatomer, an alkyl group with 1-12 carbon atoms,

og at mengden av a) utgjør 50-95 vekt-?, av b) 0,5-25 vekt-?, av c) 0,5-8 vekt-?, av d) 0,5-5 vekt-? og av e) 0,1-5 vekt-?. and that the amount of a) amounts to 50-95 wt-?, of b) 0.5-25 wt-?, of c) 0.5-8 wt-?, of d) 0.5-5 wt-? and of e) 0.1-5 wt.

Som acrylsyre- eller metacrylsyreester kommer det i betraktning estrene av mettede, rettlinjede eller for-grenede alifatiske alkoholer med 4-12 C-atomer, f.eks. n-butylacrylat, i-butylacrylat, 2-etylheksylacrylat, lauryl-acrylat og/eller laurylmetacrylat. As acrylic acid or methacrylic acid esters, the esters of saturated, linear or branched aliphatic alcohols with 4-12 C atoms come into consideration, e.g. n-butyl acrylate, i-butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate and/or lauryl methacrylate.

Som ytterligere kopolymeriserbare. monomere anvendes slike, hvis homopolymere har glasstemperaturer mellom -40°C og'+150°C, fortrinnsvis mellom 0°C og 110°C og som under polymerisasjonsbetingelsene ikke inngår annen reaksjon med monomerene av de andre grupper a), c), d) og e). Eksempler hertil er styren, metylmetacrylat, acrylnitril, metacrylnitril, vinylacetat, vinylpropionat, acrylamid eller met-acrylamid. De anvendes i mengder fra 0-40 vekt-?, fortrinnsvis 0,5-25 vekt-?, referert til monomerblandingen. As further copolymerizable. monomers are used whose homopolymers have glass transition temperatures between -40°C and +150°C, preferably between 0°C and 110°C and which, under the polymerization conditions, do not undergo any other reaction with the monomers of the other groups a), c), d ) And e). Examples of this are styrene, methyl methacrylate, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate, acrylamide or meth-acrylamide. They are used in amounts from 0-40% by weight, preferably 0.5-25% by weight, referred to the monomer mixture.

Av a-halogenalkankarboksylsyrevinylestrene Of the α-haloalkanecarboxylic acid vinyl esters

med formel I som anvendes i mengder fra 0,1-10 vekt-?, fortrinnsvis 0,5-8 vekt-?, referert til monomerblandingen, skal det eksempelvis nevnes monohalogeneddiksyre- og a-halogen-propionsyrevinylester. Foretrukket er monofluor-, monoklor-, monombrom- og monojodeddiksyrevinylester, spesielt monokloreddiksyrevinylester. with formula I which is used in amounts from 0.1-10% by weight, preferably 0.5-8% by weight, referred to the monomer mixture, monohaloacetic acid and α-halopropionic acid vinyl ester should be mentioned, for example. Preferred are monofluoro, monochloro, monobromo and monoiodoacetic acid vinyl ester, especially monochloroacetic acid vinyl ester.

Eksempler for de som ytterligere reaktivmono-mere anvendte a,3-etylenisk umettede karboksylsyrer er mono-karboksylsyrene acrylsyre, metacrylsyre og krotonsyre, di-karboksylsyrene maleinsyre og fumarsyre og deres halvestere med alkoholer av kjedelengder 1-20, f.eks. monometylmaleinat, monoisooktylmaleinat og monolaurylmaleinat, samt itakonsyre. Fortrinnsvis anvendes monokarboksylsyre, spesielt acrylsyre. De umettede karboksylsyrer anvendes i mengder fra 0,1-10 vekt-?, fortrinnsvis 0,5-5 vekt-?, referert til monomerblandingen. Examples of the α,3-ethylenically unsaturated carboxylic acids used as additional reactive monomers are the monocarboxylic acids acrylic acid, methacrylic acid and crotonic acid, the dicarboxylic acids maleic acid and fumaric acid and their half-esters with alcohols of chain lengths 1-20, e.g. monomethyl maleinate, monoisooctyl maleinate and monolauryl maleinate, as well as itaconic acid. Monocarboxylic acid, especially acrylic acid, is preferably used. The unsaturated carboxylic acids are used in amounts from 0.1-10% by weight, preferably 0.5-5% by weight, referred to the monomer mixture.

Som hydroksylgruppeholdig monomere med formel II kan det f.eks. anvendes hydroksyetylacrylat, hydroksyety1- metacrylat, hydroksypropylacrylat, hydroksypropylmetacrylat, krotonsyre-2-oksetylester, 2-etylheksyl-2-oksetylmaleinat eller metyl-2-oksetylmaleinat. Deres mengder utgjør 0-10 vekt-?, fortrinnsvis 0,1-5 vekt-?, referert til monomerblandingen. As hydroxyl group-containing monomers with formula II, it can e.g. hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, crotonic acid 2-oxetyl ester, 2-ethylhexyl-2-oxetyl maleate or methyl 2-oxetyl maleate are used. Their amounts amount to 0-10% by weight, preferably 0.1-5% by weight, referred to the monomer mixture.

Dispersjoner av fornettbart acrylesterkopolymerisat ifølge oppfinnelsen fremstilles ved radikalisk polymerisasjon av de monomere i vandig dispersjon under anvendelse av emulgatorer, beskyttelseskolloider og eventuelt regulatorer, idet det benyttes de kjente fremgangsmåter fra doseringsteknikken (f.eks. foremulgering eller monomerdosering). Dispersions of crosslinkable acrylic ester copolymer according to the invention are produced by radical polymerization of the monomers in an aqueous dispersion using emulsifiers, protective colloids and possibly regulators, using the known methods from the dosing technique (e.g. pre-emulsification or monomer dosing).

Som initiatorer anvendes uorganiske og organiske perforbindelser som ammoniumpersulfat, kaliumpersulfat, na-triumperfosfat, organiske peroksyder, som dibenzoylperoksyd, perestere som perisooktoat, perisopivalat eventuelt i kombi-nasjon med reduksjonsmidler som natriumdisulfit, natriumfor-maldehydsul.foksy lat, f ormamidinsulf insyre , hydrazin, hydrok-sylamin og katalytiske mengder akselleratorer som jern-, kobolt-, cerium-, vanadylsalter. Polymerisasjonstempera-turen ligger mellom 0 og 100°C, fortrinnsvis mellom 20 og 80°C. Som emulgatorer anvendes fortrinnsvis anioniske, f.eks. alkalisalter av svovelsyrehalvestere av alkylfenoler eller alkoholer, idet alkylfenolene og alkoholene eventuelt dessuten kan omsettes med mindre mengder etylenoksyd samt alkyl- og arylsulfonater eller sulforavsyremono- og -diester. Eksempler hertil er alkalisalter av svovelsyrehalvesteren As initiators, inorganic and organic compounds such as ammonium persulphate, potassium persulphate, sodium perphosphate, organic peroxides, such as dibenzoyl peroxide, peresters such as perisooctoate, perisopivalate are used, possibly in combination with reducing agents such as sodium disulfite, sodium formaldehyde sulphoxylate, formamidinesulfinic acid, hydrazine, hydroxylamine and catalytic amounts of accelerators such as iron, cobalt, cerium, vanadyl salts. The polymerization temperature is between 0 and 100°C, preferably between 20 and 80°C. Anionic emulsifiers are preferably used, e.g. alkali salts of sulfuric acid half-esters of alkylphenols or alcohols, the alkylphenols and alcohols possibly also being reacted with smaller amounts of ethylene oxide as well as alkyl and arylsulfonates or sulforaic acid mono- and -diesters. Examples of this are alkali salts of the sulfuric acid half-ester

av en med 4-5 mol etylenoksyd omsatt nonylfenol, natrium-laurylsulfat, natriumsaltet av et laurylalkoholetersulfat med 10 mol etylenoksyd, natriumdodecylbenzensulfonat, na-triumtetrapropylenbenzensulfonat eller natriumsaltet av sulforavsyrediheksylester. Mengden av disse emulgatorer utgjør fortrinnsvis 0,1-5 vekt-?, referert til den monomere. Eventuelt kan det dessuten i tillegg anvendes ikke ioniske emulgatorer av typen oksetylerte alkylfenoler, f.eks. nonylfenol med 30 ml etylenoksyd eller kondensasjonsprodukter av etylenoksyd og propylenoksyd. Som beskyttelseskolloider kan det f.eks. anvendes polyvinylalkoho1, poly-N-vinyl- of a nonylphenol reacted with 4-5 mol of ethylene oxide, sodium lauryl sulfate, the sodium salt of a lauryl alcohol ether sulfate with 10 mol of ethylene oxide, sodium dodecylbenzenesulfonate, sodium tetrapropylenebenzenesulfonate or the sodium salt of sulforaic acid dihexyl ester. The amount of these emulsifiers preferably amounts to 0.1-5% by weight, referred to the monomer. Optionally, non-ionic emulsifiers of the oxytylated alkylphenol type can also be used, e.g. nonylphenol with 30 ml of ethylene oxide or condensation products of ethylene oxide and propylene oxide. As protective colloids, it can e.g. polyvinylalcohol1, poly-N-vinyl-

pyrrolidon, hydroksyetylcellulose, karboksymetylcellulose eller kopolymerisater av maleinsyre med vinylforbindelser som vinyletere, styren, propylen eller etylen i mengder på 0,01-2 vekt-?, referert til den monomere. pyrrolidone, hydroxyethyl cellulose, carboxymethyl cellulose or copolymers of maleic acid with vinyl compounds such as vinyl ethers, styrene, propylene or ethylene in amounts of 0.01-2 wt.-?, referred to the monomer.

Dispersjonenes faststoffinnhold ligger mellom 30 og 70?, fortrinnsvis mellom 40 og 60?. The solids content of the dispersions is between 30 and 70%, preferably between 40 and 60%.

Dispersjonene er fornettbare ved hjelp av alkali, idet kohesjonen resp. nettdannelsesgraden kan styres ved den tilsatte alkalimengde resp. pH-verdien. Ved innpolymeri-sasjon av i tillegg dessuten hydroksylgruppeholdige monomere oppnås et optimum av de adhesive og kohesive egenskaper. The dispersions can be cross-linked by means of alkali, as the cohesion resp. the degree of network formation can be controlled by the added amount of alkali or the pH value. By incorporating monomers that also contain hydroxyl groups, an optimum of the adhesive and cohesive properties is achieved.

Nettdannelsen av de således fremstilte dispersjoner foregår ved hjelp av ammoniumhydroksyd, alkalihydrok-syd eller jordalkalihydroksyd, fortrinnsvis ved hjelp av natriumhydroksyd eller kal iumhydroksyd, som settes til dis-pers jonen i form av vandige oppløsninger. Dispersjonens pH-verdi innstilles derved fra til å begynne med 2 til 3 The network formation of the thus prepared dispersions takes place with the aid of ammonium hydroxide, alkali hydroxide or alkaline earth hydroxide, preferably with the aid of sodium hydroxide or potassium hydroxide, which is added to the dispersion in the form of aqueous solutions. The dispersion's pH value is thereby set from 2 to 3 to begin with

til 6 til 12, fortrinnsvis 7 til 11, alt etter ønsket kohesjon og adhesjon. to 6 to 12, preferably 7 to 11, depending on the desired cohesion and adhesion.

De nettdannede kopolymerisater ifølge oppfinnelsen utmerker seg ved fremragende kohesjon. De kan anvendes som lakkråstoffer, klebestoffer, pigmentbindere, flor-bindere samt i tetnings- og overtrekksmasser. Forenligheten med de vanlige tilsetningsstoffer som pigmenter, fyllstoffer, harpikser, mykningsmidler osv. er god. The net-formed copolymers according to the invention are distinguished by excellent cohesion. They can be used as lacquer raw materials, adhesives, pigment binders, flour binders and in sealing and coating compounds. Compatibility with the usual additives such as pigments, fillers, resins, plasticizers, etc. is good.

Kopolymerisatene ifølge oppfinnelsen egner seg spesielt som fastkleber for selvklebende gulvbelegg, selvklebende etiketter av papir eller metallfolier, for skum-stoffer, tapeter eller klebebånd. Varmebestandigheten av klebningen er utmerket, som skallbilde iakttas også ved forhøyet temperatur adhesjonsbrudd. Misfarvningstendensen av alkalisk innstilte filmer er lite. Hvis nødvendig kan polymerisatene dessuten modifiseres ved tilsetning av pigmenter, fyllstoffer eller klebrige harpikser. The copolymers according to the invention are particularly suitable as adhesives for self-adhesive floor coverings, self-adhesive labels made of paper or metal foils, for foam materials, wallpaper or adhesive tape. The heat resistance of the adhesion is excellent, as a shell pattern is also observed at elevated temperatures. The discoloration tendency of alkaline-set films is small. If necessary, the polymers can also be modified by adding pigments, fillers or sticky resins.

Anvendbarheten av polymerisatene ifølge oppfinnelsen forutsetter at det iakttas de for fagfolk kjente generelle sammenhenger mellom polymeroppbygning og egenskaps- bilder. Dette gjelder spesielt glasstemperaturen av kopolymeri-satet, som alt etter anvendelsesformål av disse kopolymerisater innstilles ved de kjente metoder, således at det for ethvert anvendelsesformål lar seg fremstille et polymerisat med opti-malt egenskapsbilde. The applicability of the polymers according to the invention presupposes that the general relationships between polymer structure and properties known to those skilled in the art are observed. This applies in particular to the glass transition temperature of the copolymer, which, depending on the purpose of use of these copolymers, is set by the known methods, so that a polymer with optimal properties can be produced for any purpose of use.

Oppfinnelsen skal forklares nærmere ved hjelp av noen eksempler. The invention will be explained in more detail with the help of some examples.

Eksempel 1. Example 1.

fremstilles en stabil monomeremulsjon. I en med nitrogen spylt trehalskolhe med tilbakeløpskjøler og termomenter haes 150 vektdeler vann, 5 vektdeler av overnevnte emulgator og 100 vektdeler av monomeremulsjonen. Det oppvarmes til 60°C og tilsettes initiatoroppløsningen a stable monomer emulsion is produced. 150 parts by weight of water, 5 parts by weight of the above-mentioned emulsifier and 100 parts by weight of the monomer emulsion are placed in a nitrogen-flushed three-neck boiler with a reflux cooler and thermostats. It is heated to 60°C and the initiator solution is added

Etter 15 minutter foregår under en nitrogenatmosfære tildosering av den resterende mor.cmeremulsjon, idet det sam-tidig tildoseres initiatoroppløsningene After 15 minutes, the remaining mother emulsion is dosed under a nitrogen atmosphere, while the initiator solutions are dosed at the same time

0,66 vektdeler ammoniumpersulfat i 60 vektdeler vann og 0,33 vektdeler natriumdisulfit i 60 vektdeler vann. Etter 2 timers etterreaksjon ved 60°C avkjøles. pH-verdien innstilles med 5-10>!-ig natroniut til den ønskede verdi. 0.66 parts by weight of ammonium persulfate in 60 parts by weight of water and 0.33 parts by weight of sodium disulfite in 60 parts by weight of water. After 2 hours of post-reaction at 60°C, cool. The pH value is adjusted with 5-10 µg sodium chloride to the desired value.

Den dannede dispersjon er koagulatfri, stabil. pH-verdien utgjør ca. 2,5. Dispersjonens faststoffinnhold utgjør 53,5%. The resulting dispersion is coagulant-free, stable. The pH value is approx. 2.5. The solids content of the dispersion amounts to 53.5%.

I følgende ekseirpler gjennomføres tilsvarende som i eksempel 1, idet det ble anvendt følgende monomerbland3nger: In the following examples, the same is carried out as in example 1, in that the following monomer mixtures were used:

Eksempel 2. Example 2.

84? 2-etylheksylacrylat, 9,5? acrylnitril, 3? acrylsyre, 3,5? monokloreddiksyrevinylester. 84? 2-ethylhexyl acrylate, 9.5? acrylonitrile, 3? acrylic acid, 3.5? monochloroacetic acid vinyl ester.

Eksempel 3- Example 3-

83? 2-etylheksylacrylat, 9% acrylnitril, 3? acrylsyre, 1,5? hydroksypropylmetacrylat, 3,5? monokloreddiksyrevinylester. 83? 2-ethylhexyl acrylate, 9% acrylonitrile, 3? acrylic acid, 1.5? hydroxypropyl methacrylate, 3.5? monochloroacetic acid vinyl ester.

Eksempel 4. Example 4.

85? 2-etylheksylacrylat, 9,5? acrylnitril, 2,5? acrylsyre, 2,0? monokloreddiksyrevinylester, 1,0? hydroksypropylmetacrylat . 85? 2-ethylhexyl acrylate, 9.5? acrylonitrile, 2.5? acrylic acid, 2.0? monochloroacetic acid vinyl ester, 1.0? hydroxypropyl methacrylate.

Eksempel 5. Example 5.

86? 2-etylheksylacrylat, 9,5? acrylnitril, 3,0? acrylsyre, 1,Q? monokloreddiksyrevinylester, 0,5? hydroksypro-pylmotacrylat. 86? 2-ethylhexyl acrylate, 9.5? acrylonitrile, 3.0? acrylic acid, 1,Q? monochloroacetic acid vinyl ester, 0.5? hydroxypropyl mothacrylate.

Eksempel 6. Example 6.

85? 2-etylheksylacrylat, 9,5? metylmetacrylat, 2,5? acrylsyre, 2,0? monokloreddiksyrevinylester, 1,0? hydroksypropylmetacrylat . 85? 2-ethylhexyl acrylate, 9.5? methyl methacrylate, 2.5? acrylic acid, 2.0? monochloroacetic acid vinyl ester, 1.0? hydroxypropyl methacrylate.

Eksempel 7• Example 7•

85? 2-etylheksylacrylat, 9,5? styren, 2,5? acrylsyre, 2,0? monokloreddiksyrevinylester, 1,0? hydroksypropylmetacrylat . 85? 2-ethylhexyl acrylate, 9.5? styrene, 2.5? acrylic acid, 2.0? monochloroacetic acid vinyl ester, 1.0? hydroxypropyl methacrylate.

Eks_ empel 8. Example 8.

85? 2-etylheksylacrylat, 9,5? acrylnitril, 2,5? acrylsyre, 2,0? monokloreddiksyrevinylester, 1,0? hydroksy-etylmetacrylat. 85? 2-ethylhexyl acrylate, 9.5? acrylonitrile, 2.5? acrylic acid, 2.0? monochloroacetic acid vinyl ester, 1.0? hydroxyethyl methacrylate.

Eksempel 9- Example 9-

85? 2-etylheksylacrylat, 9,5? acrylnitril, 2,5? acrylsyre, 2,0? monokloreddiksyrevinylester, 1,0? hydroksyetylacrylat. 85? 2-ethylhexyl acrylate, 9.5? acrylonitrile, 2.5? acrylic acid, 2.0? monochloroacetic acid vinyl ester, 1.0? hydroxyethyl acrylate.

Eksempel 10. Example 10.

85? 2-etylheksylacrylat, 9,5? acrylnitril, 2,5? acrylsyre, 2,0? monokloreddiksyrevinylester, 1,0? maleinsyre-metyl-2-oksetylester. 85? 2-ethylhexyl acrylate, 9.5? acrylonitrile, 2.5? acrylic acid, 2.0? monochloroacetic acid vinyl ester, 1.0? maleic acid methyl-2-oxyethyl ester.

Eksempel 11. Example 11.

85? 2-etylheksylacrylat, 9,5? acrylnitril, 2,5? acrylsyre, 2,0? monokloreddiksyrevinylester, 1,0? kroton- 85? 2-ethylhexyl acrylate, 9.5? acrylonitrile, 2.5? acrylic acid, 2.0? monochloroacetic acid vinyl ester, 1.0? croton

syreoksetylester. acid oxyethyl ester.

Eksempel 12. Example 12.

84,5? 2-etylheksylacrylat, 9,5? acrylnitril, 2,5? acrylsyre, 2,0? monokloreddiksyrevinylester, 1,5? maleinsyre-2-etylheksyloksetylester. 84.5? 2-ethylhexyl acrylate, 9.5? acrylonitrile, 2.5? acrylic acid, 2.0? monochloroacetic acid vinyl ester, 1.5? maleic acid 2-ethylhexyloxyethyl ester.

Eksempel 13. Example 13.

84,2? 2-etylheksylacrylat, 9,4? acrylnitril, 2,8? acrylsyre, 2,8? monojodeddiksyrevinylester, 0,8? hydroksypropylmetacrylat . 84.2? 2-ethylhexyl acrylate, 9.4? acrylonitrile, 2.8? acrylic acid, 2.8? monoiodoacetic acid vinyl ester, 0.8? hydroxypropyl methacrylate.

Eksempel 14. Example 14.

84,2? 2-etylheksylacrylat, 9,4? acrylnitril, 2,8? acrylsyre, 2,8? monobromeddiksyrevinylester, 0,8? hydroksypropylmetacrylat. 84.2? 2-ethylhexyl acrylate, 9.4? acrylonitrile, 2.8? acrylic acid, 2.8? monobromoacetic acid vinyl ester, 0.8? hydroxypropyl methacrylate.

Eksempel 15- Example 15-

94,5? laurylmetacrylat, 2,5? acrylsyre, 2? monokloreddiksyrevinylester, 1,0? hydroksypropylmetacrylat. Sammenligningseksempel 1. 94.5? lauryl methacrylate, 2.5? acrylic acid, 2? monochloroacetic acid vinyl ester, 1.0? hydroxypropyl methacrylate. Comparative example 1.

86? 2-etylheksylacrylat, 9,5? acrylnitril, 3,0? acrylsyre, 1,5? hydroksypropylmetacrylat. 86? 2-ethylhexyl acrylate, 9.5? acrylonitrile, 3.0? acrylic acid, 1.5? hydroxypropyl methacrylate.

Sammenligningseksempel 2. Comparative example 2.

87,5? 2-etylheksylacrylat, 9,5? acrylnitril, 3,0? acrylsyre. 87.5? 2-ethylhexyl acrylate, 9.5? acrylonitrile, 3.0? acrylic acid.

Sammenligningseksempel 3- Comparison example 3-

88,5? 2-etylheksylacrylat, 9,5? acrylnitril, 2,0? monokloreddiksyrevinylester. 88.5? 2-ethylhexyl acrylate, 9.5? acrylonitrile, 2.0? monochloroacetic acid vinyl ester.

Til undersøkelse av fastklebeegenskaper av disse polymerisater anvendes følgende prøvemetoder: The following test methods are used to examine the adhesive properties of these polymers:

a) Måling av skallfasthet (kp/2,5 cm): a) Measurement of shell strength (kp/2.5 cm):

En polyetylentereftalatfolie av 2,5 cm x 20 cm A polyethylene terephthalate foil of 2.5 cm x 20 cm

'størrelse utstyres med en klebepåføring av 0,3 mm sjikttykk-else (våtpåføring). Etter tørkning klebes folien under lett trykk på en omhyggelig renset stålblikk. Etter en times lag-ring ved værelsestemperatur skalles forklebningen ved en 'size is equipped with an adhesive application of 0.3 mm layer thickness (wet application). After drying, the foil is glued under light pressure to a carefully cleaned steel sheet. After one hour's storage at room temperature, the bonding shall be done at a

skallehastighet på 300 mm/min. ved en avtrekningsvinkel på skull speed of 300 mm/min. at a pull-off angle of

>90°-I tillegg vurderes sammenklebningens bruddbilde. >90°-In addition, the joint's fracture pattern is assessed.

Denne måling gjennomføres ved de to temperaturer 70°C og 10°C. This measurement is carried out at the two temperatures 70°C and 10°C.

b) Varmestandfasthet (timer): b) Heat resistance (hours):

En polyetylentereftalatfolie belegges som i overnevnte tilfelle med kleberen og etter tørkning av klebesjiktet klebes således på et stålblikk, at det oppstår en overlappings-flate på 2,5 cm p. Sammenklebningen belastes deretter ved en vinkel på 0° med en vekt på 500.g. Måletemperaturen utgjør 100°C. Det bestemmes den tid innen hvilke .sammenklebningen er løsnet. A polyethylene terephthalate foil is coated as in the above case with the adhesive and after drying the adhesive layer is glued to a steel sheet in such a way that an overlapping surface of 2.5 cm p is created. The bonding is then loaded at an angle of 0° with a weight of 500 g . The measuring temperature is 100°C. The time within which the adhesion is released is determined.

c) Bestemmelse av nettdannelse: c) Determination of net formation:

Dispersjonen og den av dispersjonen dannede film The dispersion and the film formed by the dispersion

ekstraheres med dioksan. Det bestemmes den oppløselig del i vekt-? av faststoffinnveiningen. Innen feilgrensen er begge ekstraksjonsverdier like. is extracted with dioxane. It is determined the soluble part in weight-? of the solids weighing. Within the margin of error, both extraction values are equal.

Sammenklebningens egenskaper er oppført i følgende tabeller. The bonding properties are listed in the following tables.

pH-verdiens innvirkning på nettdannelsen sees tyde-lig. Alle monohalogeneddiksyrevinylestere og et, f5-umettede syreholdige polymerisater gir med økende pH-verdi avtagende oppløseligheter. The effect of the pH value on the network formation is clearly seen. All monohaloacetic acid vinyl esters and et, f5-unsaturated acidic polymers give decreasing solubilities with increasing pH value.

At denne avhengighet er å tilskrive reaktivmonomerkombinasjonen fremgår av sammenligningseksemplene. Således viser hverken prøven med sammensetningen 2-etylheksylacrylat/ acrylnitril/acrylsyre eller prøven som i tillegg dessuten inneholder hydroksypropylmetacrylat, og heller ikke prøven som riktignok inneholder monohalogenvinylester, men ingen syre, That this dependence is attributable to the reactive monomer combination is evident from the comparison examples. Thus, neither the sample with the composition 2-ethylhexyl acrylate/acrylonitrile/acrylic acid nor the sample which additionally contains hydroxypropyl methacrylate, nor the sample which does contain monohalogen vinyl ester but no acid,

en slik påvirkning av pH-verdien på kopolymerisatets oppløse-lighet. such an influence of the pH value on the solubility of the copolymer.

I tillegg til reaktivmonomerkombinasjonen halogen-ester/syre virker et innhold av hydroksylgruppeholdige monomere positivt på de adhesive og kohesive egenskaper av kopolymeri-satet. Således ligger de målte skallfastheter på grunn av deres høye kohesjon også dessuten ved 70°C meget høyt, idet det i alle tilfeller som bruddtype iakttas adhesjonsbrudd (pH 7 innstilling). Ved innstilling pH 3 iakttas som ventet ved 70°C rent kohesjonsbrudd, da polymerisatets kohesjon ikke er tilstrekkelig på grunn av manglende nettdannelse. In addition to the reactive monomer combination halogen ester/acid, a content of monomers containing hydroxyl groups has a positive effect on the adhesive and cohesive properties of the copolymer. Thus, due to their high cohesion, the measured shell strengths are also very high at 70°C, as in all cases the fracture type observed is adhesion fracture (pH 7 setting). At a setting of pH 3, pure cohesion failure is observed at 70°C, as expected, as the cohesion of the polymer is insufficient due to a lack of network formation.

Claims (1)

Fornettbart acrylesterkopolymerisat bestående av a) enheter av minst en acrylsyreester og/eller metacrylsyreester av en. mettet alifatisk alkohol med 4-12 karbonatomer, b) enheter av en monomer valgt blant styren, metylmetacrylat, acrylnitril, metacrylnitril, vinylacetat, vinylpropionat, acrylamid og metacryl-amid, idet denne monomer er forskjellig fra monomeren ifølge a), c) enheter av en ot-halogenalkankarboksylsyrevinyl-ester med formel (I)Crosslinkable acrylic ester copolymer consisting of a) units of at least one acrylic acid ester and/or methacrylic acid ester of one. saturated aliphatic alcohol with 4-12 carbon atoms, b) units of a monomer selected from styrene, methyl methacrylate, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate, acrylamide and methacrylamide, this monomer being different from the monomer according to a), c) units of an o-haloalkanecarboxylic acid vinyl ester of formula (I) idet og Rg hver betyr hydrogen eller en alkylrest med 1-5 karbonatomer og X betyr fluor, klor, brom eller jod,and Rg each means hydrogen or an alkyl residue with 1-5 carbon atoms and X means fluorine, chlorine, bromine or iodine, samt enheter av ytterligere monomere, karakt eris errt ved at sistnevnte er d) enheter av en a,g-etylenisk umettet karboksyl-syre med 3-8 karbonatomer eller dens partialester med en mettet alifatisk alkohol med 1-20 karbonatomer og . e) enheter av en hydroksylgruppeholdig monomer med formel (II)as well as units of further monomers, characterized by the latter being d) units of an a,g-ethylenic unsaturated carboxylic acid with 3-8 carbon atoms or its partial ester with a saturated aliphatic alcohol with 1-20 carbon atoms and . e) units of a hydroxyl group-containing monomer of formula (II) hvori R^betyr hydrogen, en metylgruppe eller gruppen -COORg, R^ og R^betyr hver hydrogen eller en metylgruppe og Rg betyr hydrogen eller en alkylgruppe med 1-12 karbonatomer,wherein R^ means hydrogen, a methyl group or the group -COORg, R^ and R^ each means hydrogen or a methyl group and Rg means hydrogen or an alkyl group of 1-12 carbon atoms, og at mengden av a) utgjør 50-95 vekt-?, av b) 0,5~25 vekt-?, av c) 0,5-8 vekt-?, av d) 0,5-5 vekt-? og av e) 0,1-5 vekt-?.and that the amount of a) amounts to 50-95 wt-?, of b) 0.5-25 wt-?, of c) 0.5-8 wt-?, of d) 0.5-5 wt-? and of e) 0.1-5 wt.
NO1990/73A 1972-05-15 1973-05-14 RETAINABLE ACRYLSTER COPOLYMERIZATES. NO145510C (en)

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DE2364364C3 (en) * 1973-12-22 1980-04-24 Hoechst Ag, 6000 Frankfurt Crosslinkable aqueous vinyl ester copolymer dispersions
DE2459160C3 (en) * 1974-12-14 1984-10-18 Basf Ag, 6700 Ludwigshafen Process for the preparation of aqueous dispersions of copolymers of non-tertiary acrylic acid esters
DE2636970A1 (en) * 1976-08-17 1978-02-23 Texaco Ag COLD CROSS-LINKING DISPERSION ADHESIVES
DE2636934A1 (en) * 1976-08-17 1978-02-23 Texaco Ag COLD CROSS-LINKING DISPERSION ADHESIVES
US4204023A (en) * 1978-07-07 1980-05-20 The Kendall Company Mixed sulfonated emulsifying agents used to produce adhesive compositions from acrylic monomers and adhesive tape using the compositions
DE2929793A1 (en) * 1979-07-23 1981-02-12 Basf Ag THICKENING AGENT FOR PHYSICAL DRYING COATING MATERIALS AND METHOD FOR THE PRODUCTION THEREOF
DE3333503A1 (en) * 1983-09-16 1985-04-18 Röhm GmbH, 6100 Darmstadt THICKENING AGENTS AND BINDERS GELLING IN GASOLINE
JPS6243475A (en) * 1985-08-20 1987-02-25 Mitsui Toatsu Chem Inc Adhesive composition
JP6293503B2 (en) * 2014-01-30 2018-03-14 デンカ株式会社 Acrylic elastomer, acrylic elastomer composition and laminate
JPWO2019003342A1 (en) * 2017-06-28 2020-04-23 株式会社大阪ソーダ Acrylic rubber and its rubber cross-linked product
CN112679913B (en) * 2020-12-28 2023-01-24 上海昭和高分子有限公司 High-toughness vinyl ester resin

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