EP0594596A1 - Monomere d'imidazolidinone copolymerisable - Google Patents

Monomere d'imidazolidinone copolymerisable

Info

Publication number
EP0594596A1
EP0594596A1 EP91904976A EP91904976A EP0594596A1 EP 0594596 A1 EP0594596 A1 EP 0594596A1 EP 91904976 A EP91904976 A EP 91904976A EP 91904976 A EP91904976 A EP 91904976A EP 0594596 A1 EP0594596 A1 EP 0594596A1
Authority
EP
European Patent Office
Prior art keywords
monomer
latex
copolymer
alkyl
carbon
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Withdrawn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
EP91904976A
Other languages
German (de)
English (en)
Inventor
Thomas O. Murdock
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.)
HB Fuller Licensing and Financing Inc
Original Assignee
HB Fuller Licensing and Financing Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by HB Fuller Licensing and Financing Inc filed Critical HB Fuller Licensing and Financing Inc
Publication of EP0594596A1 publication Critical patent/EP0594596A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
    • C07D207/22—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D207/24—Oxygen or sulfur atoms
    • C07D207/26—2-Pyrrolidones
    • C07D207/263—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms
    • C07D207/27—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms with substituted hydrocarbon radicals directly attached to the ring nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D205/00—Heterocyclic compounds containing four-membered rings with one nitrogen atom as the only ring hetero atom
    • C07D205/02—Heterocyclic compounds containing four-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings
    • C07D205/06—Heterocyclic compounds containing four-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D205/08—Heterocyclic compounds containing four-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with one oxygen atom directly attached in position 2, e.g. beta-lactams
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D229/00—Heterocyclic compounds containing rings of less than five members having two nitrogen atoms as the only ring hetero atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D233/28—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/30—Oxygen or sulfur atoms
    • C07D233/32—One oxygen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D233/28—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/30—Oxygen or sulfur atoms
    • C07D233/32—One oxygen atom
    • C07D233/36—One oxygen atom with hydrocarbon radicals, substituted by nitrogen atoms, attached to ring nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D233/28—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/30—Oxygen or sulfur atoms
    • C07D233/42—Sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D263/16—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D263/18—Oxygen atoms
    • C07D263/20—Oxygen atoms attached in position 2
    • C07D263/22—Oxygen atoms attached in position 2 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to other ring carbon atoms
    • 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
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof

Definitions

  • This invention relates generally to polymer dispersions and solutions and to monomers used to prepare these dispersions and solutions. More specifically, the present invention relates to copolymerizable monomers which promote wet adhesion in any variety of polymeric compositions including sealants, coatings, paints, and adhesives among others.
  • Haskins et al U.S. Patent No. 2,727,01c discloses acrylamides of N-aminoalkyl alkylene urea polymers useful in coating compositions. Hurwitz, U.S. Patent No. 3,369,008 also discloses N(cyclic ureidoalkyl)crotonamide ⁇ polymers useful in coating compositions.
  • Dixon et al U.S. Patent No. 4,111,877 disclose allyl esters of N-alkyl-omega-(alkyleneureido ⁇ a ic acids useful for imparting wet adhesion properties re emulsion systems. Sims, U.S. Patent No.
  • the present invention provides a polymerizable monomer for the promotion of wet adhesion having the formula: R' 0
  • the monomer may also be synthesized to have vinyl acrylic functionality.
  • the monomer of the present invention can be used either alone or polymerized in any given polymer system.
  • the polymerizable monomer of the present invention provides far superior wet adhesion when compared to polymers presently commercially available and commonly used in the coatings and paint industries .
  • the present invention discloses monomers useful in polymeric materials, the monomers providing enhanced wet adhesion and scrub resistance.
  • the enhanced wet adhesion monomers of the present invention may be polymerized into polymeric materials or polymers that may be added to other polymers.
  • the instant monomer can be used in polymeric matrices which result in any number of adhesives, caulks, latexes, paints, coatings, and sealants among other matrices.
  • the wet adhesion monomers of the present invention can be used in polymeric compositions that are applied to any number of substrates and subjected to any number of environmental factors.
  • the instant wet adhesion monomer may be applied in any number of ways. Wet adhesion monomers can be copolymerized in latex compositions, paint compositions, coating compositions, and film compositions.
  • the Monomer is a monomer for the promotion of wet adhesion having the formula:
  • the monomer may also be synthesized to have vinyl acrylic functionality.
  • Synthesis of the monomer of the present invention is initiated by reacting any compound having an active vinyl group and a reactive isocyanate group with a backbone compound having an active hydrogen in the form of a reactive hydroxyl group or a ine group.
  • a backbone compound having an active hydrogen in the form of a reactive hydroxyl group or a ine group Generally, isocyanate-type compounds and monomers have been found useful to this end.
  • the preferred isocyanate compound useful in the invention is a compound having a single polymerizable vinyl group and a single monoisocyanare group.
  • a vinyl compound such as alpha, alpha-dimethyl meta-isopropenyl benzyl isocyanate (m-TMI) is combined with a backbone heterocyclic compounds such as oxazolidinone in the presence of an organic solvent and heat.
  • organic solvents found useful in synthesizing the monomer of the present invention include ethyl acetate, hexane, chloroform and the like.
  • a reaction catalyst such as dibutyl tin dilaurate may also be used.
  • Backbone compounds which may be allowed to react with m-TMI include any variety of heterocyclic or heteroaliphatic compounds including 1-(2-hydroxyethyl) imidazolidin-2-one, N,N-diethylethylenediamine, 2-(2-aminoethyl)imidazolidin-2-one and the like which when reacted with m-TMI produce polymerizable compounds which are capable of being used in all acrylic systems .
  • the monomer of the present invention may be synthesized in any manner which permits its use in vinyl acrylic systems.
  • compounds such as 2-vinyl-4,4-dimethyl-2-oxazolin-5-one may be combined with backbone compounds such as N-(2-hydroxyethyl)oxazolidin-2-one, N,N-diethylethylenediamine and 2-(2-aminoethyl) imidazolidin-2-one in a manner that provides the polymerizable compound useful in vinyl acrylic systems.
  • the 2-vinyl-4,4-dimethyl-2-oxazolin-5-one has a reactive carbonyl in the five position which results in the five member ring opening when combined with the reactive amine moiety of the backbone compound.
  • the resulting monomer is an imidazoline type compound having an amide linkage which is terminated by a polymerizable olefin group at one end of the monomer.
  • This monomer may then be polymerized with compounds such as vinyl acetate and n-butyl acrylate to provide an emulsion polymer useful again in any type of latex, caulk, adhesive, or other film forming compositions.
  • the polymerizable compound of the present invention may be combined with any number of monomers to form a copolymer.
  • the monomer of the present invention may be polymerized with virtually any other vinyl monomer.
  • Examples of the broad classes of such vinyl monomers include alpha-olefins, vinyl chlorides, vinylidene chlorides, vinyl aromatic monomers, polymerizable alpha, beta-unsaturated carboxylic acids and esters, and other well known monomers.
  • the vinyl unsaturated monomer can be an alpha-olefin monomer such as ethylene, propylene, butylene, isobutylene, hexene; styrene, alpha methylstyrene, vinyl chloride, vinyl acetate, acrylonitrile, ricinoleic acid, oleic acid, linoleic acid, butadiene, and the like.
  • Alpha-olefins that can also be used in the invention include other C ⁇ ,. alpha-olefins such as cyclopentene, cyclopentadiene, 1,3-butadiene, 1-hexene, norbornene, etc.
  • Useful acrylic monomers include methylacrylate, methyl methacrylate, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, butyl acrylate, hexyl acrylate, cyclohexylacrylate, (2-hydroxyethyl) methacrylate,
  • Useful unsaturated dicarboxylic acids include itaconic acid, cinnamic acid, crotonic acid, mesaconic acid, maleic acid, fumaric acid, and the like; alpha, beta unsaturated dicarboxylic acid esters of the dicarboxylic acid esters described above including aromatic esters, cycloalkyl esters, alkyl esters, hydroxy alkyl esters, alkoxy alkyl esters, and the like.
  • Vinyl aromatic monomers that can be used with the monomer of this invention include monomers that comprise at least one aromatic group and at least one polymerizable vinyl group. Typical examples of aromatic groups include phenyl, substituted phenyl, naphthyl, phenanthryl, and others.
  • Preferred vinyl aromatic monomers include the styrene family including such monomers as styrene, methyl styrene (vinyl toluene), ethyl styrene, isopropyl styrene, tertiary butyl styrene, etc. 4-hydroxy styrene, 4-chlorostyrene, and styrene with other common ring substituents.
  • the proportions of each monomer can vary widely.
  • the vinyl monomer may range generally from 1-99 mole-% and the monomer of the present invention may generally range from 0.05-15 mole-%, preferably from about 0.1 mole-% to 9 mole-% and most preferably for reasons of economy and efficacy from about 0.5 mole-% to 3 mole-%.
  • the molar proportions will vary according to the necessary wet adhesion action and scrub properties desired, and the economics of employing a larger amount of the active monomer of the present invention and the requirements of the physical properties.
  • the monomer of the present invention may be polymerized into either a latex or solution compositions.
  • Polymerization can generally be carried out in a closed vessel under heated conditions.
  • the solution polymeriza ⁇ tion reaction is generally carried out with the monomers in solution in an inert organic solvent such as tetrahydro- furan, methyl ethyl ketone, acetone, ethyl acetate, or other suitable organic solvents such as organic C-C 2 __ alkanols.
  • Organic solvents can also be mixed with compatible amounts of water in emulsions or inverse emulsion systems. Preferred solvents are non-toxic and odorless.
  • Pre-polymer monomeric starting materials used to form polymeric pre-emulsion compositions using the monomer of the present invention are typically dissolved or suspended in the solvent to a desired concentration.
  • the polymerization of the invention is typically performed at a concentration of about 10 wt-% to 70 wt-% of the monomers in the solvent material, although somewhat higher or lower concentrations may be employed in some cases .
  • Polymerization reactions are typically initiated in a conventional manner, preferably by use of a suitable initiator.
  • suitable initiators include 2,2'-azobis(2-methylpropane nitrile) (AIBN) , dibenzoyl peroxide tertiary butyl peroctoate, cumene hydroperoxide, diisopropyl percarbonate, ammonium persulfate, and the like, per se or in combination with a reducing agent in the form of an oxidation reduction catalyst system.
  • the reaction mixture may be agitated and heated preferably in an inert atmosphere (purging with nitrogen, argon, etc.), to about 50-100°C, controlling the reaction temperature to avoid destructive exother s, preferably to about 75-95°C.
  • an inert atmosphere purging with nitrogen, argon, etc.
  • the polymer may contain anywhere from about 0.05 wt-% to 15.0 wt-% of the monomer of the present invention, preferably from about .10 wt-% to 9.0 wt-% of the present monomer, and most preferably about .5 wt-% to 3.0 wt-% of the monomer of the present invention.
  • this concentration may vary given the physical properties to be imparte ⁇ to the final system.
  • the molecular weights of the resulting polymers may vary. However, the molecular weight of the resulting solution copoly er is preferably at least approximately 3000. However the molecular weight of these polymers may generally range from 1000 to 1,000,000.
  • polymerization towards the formulation of latex or dispersion polymers may be completed under substantially similar circumstances except that the medium of polymerization is aqueous instead of organic .
  • the molecular weights of the resulting latex polymers may vary generally from 1000 to 2 million with about 50,000 being a preferred weight.
  • these polymers form a colloidal dispersion suspended in an aqueous carrier which, once applied, forms a readily wetting and scrub resistant film.
  • the emulsion polymer may be formulated into any number of compositions including paints, film coatings, sealants, adhesives, caulks, or the like.
  • the formulation of these systems will vary depending upon the application of the system, i.e., the systems final end use. However, formulation processes include those found within the following examples, as well as those generally known within the art.
  • the monomer will have a concentration with the final system which may range from about 0.001 wt-% to 10.0 wt-%, preferably from about .01 wt-% to 7.0 wt-%, and most preferably from about .10 wt-% to 5.0 wt-%.
  • concentration with the final system which may range from about 0.001 wt-% to 10.0 wt-%, preferably from about .01 wt-% to 7.0 wt-%, and most preferably from about .10 wt-% to 5.0 wt-%.
  • the wet adhesion monomer of the present invention was synthesized using various feed stocks including N-(2- hydroxyethyl)oxazolidin-2-one or N,N-diethylethylenediamine in combination with alpha, alpha-dimethyl meta-isopropenyl benzyl isocyanate (m-TMI) in the presence of an organic solvent.
  • feed stocks including N-(2- hydroxyethyl)oxazolidin-2-one or N,N-diethylethylenediamine in combination with alpha, alpha-dimethyl meta-isopropenyl benzyl isocyanate (m-TMI) in the presence of an organic solvent.
  • the Carbon 13 spectra of the sample exhibits both the proper number of nonequivalent carbons and the correct number of attached protons recorded by the monomer. Upon determination, the melting point of the monomer was 129.0 to 130.0°C.
  • Example 2 The monomer of Example 2 was then characterized using
  • NMR spectra provided the following data (C-13, PPM): Carbon No. 1 at 21.9; Carbon No. 2 at 29.5; Carbon No. 3 at 38.2; Carbon No. 4 or 5 at 43.1; Carbon No. 5 or 4 at 45.4; Carbon No. 6 at 55.2; Carbon NO. 7 at 61.9; Carbon No. 8 at 112.5; Carbon No. 9 at 122.1; Carbon No. 10 at 124.0; Carbon No. 11 at 124.1; Carbon No. 12 at 128.3; Carbon No. 13 at 141.4; Carbon No. 14 at 143.6; Carbon No. 15 at 147.3; Carbon No. 16 at 154.9; Carbon No.
  • Example 3 A similar monomer synthesized in Example 3 was then synthesized using meta-TMI and 2-(2-aminoethyl) imidazolidin-2-one (AEI) using the following procedure. Using a 500 ml 3-necked roundbottom flask equipped with a pressure equalizing addition funnel, magnetic spin bar, thermometer and a N, inlet was added m-TMI (80.4 g, 0.40 mol.) was added to the flask with 100 ml of chloroform. A solution of AEI (55.6 g, 0.40 mol) in 100 ml of chloroform was added dropwise to the flask over a 1 hour interval while maintaining the reaction temperature between 20-25 c C with an ice/water bath.
  • AEI 2-(2-aminoethyl) imidazolidin-2-one
  • Example 4 A scale up of Example 4 was then attempted using 1- (2-aminoethyl)imidazolidin-2-one, m-TMI, and the following procedure. Using a 2 liter 3-necked roundbottom flask equipped with a mechanical stirrer, reflux condenser, pressure equalizing addition funnel and a N 2 inlet, a solution of l-(2-aminoethyl)imidazolidin-2-one (173.6 g, 1.34 mol) was added in 500 ml of chloroform to the flask.. A solution of m-TMI (275.5 g, 1.38 mol) in 250 ml of chloroform was added to the flask at a rate such that the temperature of the reaction mixture did not exceed 25°C.
  • the flask was cooled with an ice-water bath. Once completely added, the mixture crystallized. An additional 300 ml CHC13 was added and the mixture was stirred at 25°C. for 2 hours. The mixture was then analyzed by TLC. The slurry of the product in CHC13 was dissolved by warming with a hot water bath. The clear solution was filtered into an Erlenmeyer flask and allowed to cool to 25°C, and subsequently placed in the freezer. A white crystalline solid was isolated by suction filtration and the crude product had a melting point of 138-143°C. The solid was recrystallized and recovered from ethyl acetate/isopropanol (60:40).
  • C13 NMR spectroscopy provided the following chemical shift data: Carbon No. 1, 21.5; Carbon No. 2, 30.0; Carbon Nos . 3 or 4, 37.2; Carbon Nos. 4 or 3, 37.4; Carbon Nos. 5 or 6, 43.6; Carbon Nos. 6 or 5, 44.7; Carbon Nos. 7, 54.0; Carbon No. 8, 112.1; Carbon No. 9, 121.7; Carbon No. 10, 122.7; Carbon No. 11, 124.1; Carbon No. 12, 127.7; Carbon No. 13, 139.9; Carbon No. 14, 143.0; Carbon No.
  • Carbon 13 spectra of the sample exhibit both the proper number of nonequivalent carbons and the correct number of attached protons required by the formula of this monomer.
  • the reaction flask was rinsed with 100 ml of ethyl acetate and then it was poured over the crystals in the Buchner funnel.
  • the melting point of the recovered white solid was 138.5-142.0°C.
  • the filter cake was broken up and dried by pulling air through the pulverized solid for 30 minutes with a water aspirator.
  • the weight of the solid was 232.4 g.
  • the filtrate was concentrated and an additional 6.8 g of solid was obtained.
  • the solid was further dried by spreading on a sheet of release paper to obtain 159.8 g of product.
  • the residue collected by concentrating the mother liquor was a mixture of a crystalline compound and an oil. The material was not characterized further.
  • Emulsion Polymers were then synthesized using the monomers of Working Examples 1, 2, 3 and 6.
  • emulsion polymers containing the monomer of the present invention were polymerized by charging a reactor with water, a surfactant based defoamer such as Balab 748, commercially available from Witco Chemical Co. , and diammonium phosphate.
  • a catalyst was then charged into the reactor over a delayed period of time as a water carried system of ammonium persulfate and sodium metabisulfite.
  • the pre-emulsion was prepared by first forming a solution of the monomer of the present invention with a surfactant sucr.
  • Example 1 and 6 were used to form a pre- emulsion composition base for Examples 9 and 10.
  • pigments grinds were formulated by first weighing water, a dispersant, preservative, surfactants, and defoamers to the composition. The pigments were weighed in a separate container and using a cowles blade gradually added to the liquid phase. Titanium dioxide was added to the liquid phase first, then adding the extenders in any order after the Ti0 2 . Once the pigment had been wet out, the remaining amount of defoamer was added. The pigment composition was then ground at high speed (about 4,000 rpms) for 15 to 20 minutes. Listed below are the constituents of the individual grinds.
  • Nopcosperse 44 (dispersant, 7.7
  • Tamol 731 (dispersant, 8.6 Rohm & Haas)
  • Igepal CO-630 (surfactant, 3.5 GAF Corp. )
  • Paint systems, semigloss as well as flat, were then formulated using the polymeric systems of Working Examples 7-10 and pigment grinds previously formulated by weighing the latex polymer and defoamer into a lined can or stainless steel beaker. The system was then mixed with a three bladed paddle and the pigment grind and water was added to the latex. Cellulosic NatrosolTM thickeners were added along with the propylene glycol and TexanolTM. The mixture was slowly and continuously mixed until a vortex formed with agitation increased as needed. The composition was mixed for 10 minutes or until the thickener dissolved. Once formulated, the paint was covered and let stand for 24 hours prior to testing. This process was used to formulate the exterior flat and semi-gloss paint of Examples 11 and 12.
  • Example 9B Latex Pol mer Example 10 Latex
  • Propylene Glycol Texanol (coalescent, from Texaco Inc.)
  • Caulk compositions were then prepared using the wet adhesion monomer synthesized in Example 6.
  • the caulk of Working Examples 13A and 13B were synthesized by charging a reactor with 400 parts of water, 10 parts of acrylic acid, adjusting with a buffer to a pH of 7 or 8 and then raising the reactor temperature to 80°C under a nitrogen purge.
  • 3.3 parts of Igepal CA-520 (from GAF Corp.) were added to a reactor.
  • the pre- emulsion composition was added to the reactor with the immediate addition of a potassium persulfate catalyst.
  • the pre-emulsion composition was added at a rate of 5% over 15 minutes with the remaining 95% being completely added at the end of 3-1/2 hours.
  • the reactor temperature was maintained at a temperature of between
  • Example 13B The caulk compositions containing emulsion polymers having the monomer of the present invention (Example 13B) were shown to improve adhesion to a variety of surfaces when compared to caulk formulations containing polymers without a wet adhesion monomer (Example 13A) .
  • a solution polymer for a coating composition was then prepared using the monomer of Example 6 in a 1 liter three-necked roundbottom flask equipped with a mechanical stirrer, addition funnels, reflux condenser and a thermometer. Toluene (150 g ) and the Pre-Solution
  • composition 50 gm was then added to the flask.
  • the reaction mixture was warmed to reflux (approx. H0°C) and the remainder of the Pre-Solution mixture was added over a 4 hour interval and the peroxide initiator was added over a
  • Aromatic 100 (hydrocarbon solvent 4.0 from Worum)
  • the coating samples were prepared in a glass jar and applied to a green alkyd base painted wood surface with a bird type applicator. Wet film thickness was 6 ml. The samples were placed in a drying oven at 140°C for 20 minutes. The samples were allowed to equilibrate for two days at ambient temperature and humidity. A Crosshatch wa; scribed into the coating with a razor blade and 1/2 of the board was immersed in water for 30 minutes. The adhesion of the coating to the alkyd was determined with a 3E Company, 610 tape test. No dela ination from the alkyd coated surface was noted from the control or the experimental coating.
  • the vinyl monomer of this set was synthesized from feed compounds such as 2-vinyl-4,4- dimethyl-2-oxazolin-5-one which were then allowed to react with a feed stock of an imidazolidine compound such as l-(2-amino ethyl)-imidazolidin-2-one (AEI). After a given reaction period in an organic medium, the solid precipitate was generally isolated by filtration. The precipitate was then generally purified by washing and characterized through chemical analysis.
  • feed compounds such as 2-vinyl-4,4- dimethyl-2-oxazolin-5-one which were then allowed to react with a feed stock of an imidazolidine compound such as l-(2-amino ethyl)-imidazolidin-2-one (AEI).
  • AEI imidazolidine compound
  • the solid precipitate was generally isolated by filtration.
  • the precipitate was then generally purified by washing and characterized through chemical analysis.
  • the reaction mixture was stirred at 25°C. for 4 hours and the white solid was isolated by suction filtration.
  • the filter cake was washed once with 100 ml of hexane.
  • the melting point of the solid was 188.5-189.5°C.
  • the compounc was soluble in water.
  • the monomer of Working Example 1, Set II was characterized to carbon 13 nuclear magnetic resonance spectra, melting point, and infrared scan.
  • the NMR spectrum provided the following data (reported in carbon 13 ppm) : Carbon number 1 at 27.2; carbon number 2 at 40.1; carbon number 3 at 40.8; carbon number 4 at 44.9; carbon number 5 at 48.7; carbon number 6 at 59.5; carbon number 7 at 130.5; carbon number 8 at 132.8; carbon number 9 at 167.5; carbon number 10 at 170.3; and carbon number 11 at 179.9.
  • the melting point of the monomer was found to be 188.5 to 189.5°C.
  • VDM vinyl dimethyl azlactone
  • the white crystalline solid was isolated by suction filtration and washed with 100 ml of hexane.
  • the crude material had a melting point of 182-185°C.
  • the crude product was recrystallized from a mixture of isopropanol and methanol to afford white crystals having a melting point of 195.0- 196.0°C.
  • the pre-emulsion was prepared by first forming a solution of the monomer of the present invention with a surfactant such as Igepal CA897 (from GAF) and other polymerizable monomers constituents listed below and subsequently adding the solution of monomers and surfactant to a beaker containing water which was being agitated with a paddle-type blade stirrer. The reactor was then charged with 4.24 parts of potassium persulfate catalyst and heated to 80°C. with a nitrogen purge. The pre-emulsion composition was then fed into the reactor at a rate of 3% over 15 minutes, another 5 wt-% over the next 30 minutes, and the remaining 92 wt-% over the balance of 3 1/2 hours. The reactor was maintained at about 80 C C. during the feed and the nitrogen purge was shut off.
  • a surfactant such as Igepal CA897 (from GAF) and other polymerizable monomers constituents listed below
  • Igepal CA897 ethoxylated phenol surfactant from GAF Corporation
  • TRITON X200 sodium alkyl aryl polyether sulfonate surfactant from Rohm & Haas
  • pigment grinds were formulated by first weighing water, a dispersant, preservative, surfactants, and defoamers to the composition. The pigments were weighed in a separate container and using a cowles blade gradually added to the liquid phase. Titanium dioxide was added to the liquid phase first adding the extenders in any order after Ti0 2 . Once the pigment had been wet out any remaining amount of defoamer was added. The pigment composition was then ground at high speed (about 4,000 rpms) for 15 to 20 minutes. Listed below are the constituents of the individual grinds. Interior Flat Grind (Parts By Weight)
  • Tamol 731 (dispersant, Rohm & Haas) 9.2
  • Igepal CO-630 (GAF Corp.) 3.5 AMP 95 (dispersant, Angus Chemical Co.) 2.0 Ti0 2 190.0
  • Attagel 50 thickener, Engelhard Corp.
  • Drew L464 defoamer, Drew Industrial Div.
  • Tamol SG-1 (dispersant, Rohm & Haas) 7.2
  • PD-124 (BHO-20) (latex, H.B.
  • Working Examples 4B and 4C had greater adhesion properties than control Working Example 5A.
  • Working Example 4B containing the monomer of the present invention had superior scrub resistance to the control Working Example 4A.

Landscapes

  • 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)

Abstract

L'invention concerne un monomère ainsi que des polymères obtenus de ce monomère, lequel a la formule (I), dans laquelle n = 1 ou 2; m = 1 ou 2; R' = H ou CH3; X = -O-, -CH2, -NR-; R = H, -alkyle, -aryle, -CH2(CH2)y-C = N, -CH2O alkyle, -(CH2)yOH, -CH2CH(OH)CH3 où y = 1 - 12; A = phénylène ou alkylène; Y = -O-, -NH-, -NHNH-, -O-M-, -NH-M-, ou -NH-NH-M-; Z = -O- ou -S-, et M = (a), (b), (c) et (d) où x = 2 - 5.
EP91904976A 1990-02-14 1991-02-12 Monomere d'imidazolidinone copolymerisable Withdrawn EP0594596A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US47971890A 1990-02-14 1990-02-14
US479718 1990-02-14
PCT/US1991/000939 WO1991012243A2 (fr) 1990-02-14 1991-02-12 Monomere d'imidazolidinone copolymerisable

Publications (1)

Publication Number Publication Date
EP0594596A1 true EP0594596A1 (fr) 1994-05-04

Family

ID=23905129

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91904976A Withdrawn EP0594596A1 (fr) 1990-02-14 1991-02-12 Monomere d'imidazolidinone copolymerisable

Country Status (4)

Country Link
EP (1) EP0594596A1 (fr)
JP (1) JPH05503941A (fr)
CA (1) CA2074098A1 (fr)
WO (1) WO1991012243A2 (fr)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5496907A (en) * 1993-03-02 1996-03-05 H. B. Fuller Licensing & Financing, Inc. Wet adhesion monomers with ureido functionality and polymers prepared therefrom
US5399706A (en) * 1993-03-02 1995-03-21 H. B. Fuller Licensing & Financing, Inc. Imidazolidinone diamine and derivatives thereof
DE69726160T2 (de) 1996-06-24 2004-08-26 Cytec Technology Corp., Wilmington Neue polymerisierbare acylimidazolidinonmonomere
EP0912522B1 (fr) * 1996-06-24 2003-10-08 Cytec Technology Corp. Derives d'acylimidazolidinone a fonctions de reticulation multiples
CN1094488C (zh) * 1996-06-24 2002-11-20 Cytec技术有限公司 可聚合的脲/脲基官能单体
US6630599B1 (en) 1998-01-06 2003-10-07 Cytec Technology Corp. Process for preparing derivatives of isopropenyl-α, α-dimethylbenzyl isocyanate
US6069275A (en) * 1998-01-28 2000-05-30 Rhodia Inc. Monomers and polymers and latices therefrom
DE19830555A1 (de) 1998-07-08 2000-01-13 Basf Ag Verwendung wässriger Polymerzubereitungen für die Beschichtung polyurethanhaltiger Substanzen
DE19924790A1 (de) * 1999-05-29 2000-11-30 Bayer Ag Polymerisierbare, olefinisch ungesättigte Monomere
TW201604173A (zh) * 2014-06-12 2016-02-01 Koei Chemical Co 鎓鹽及含有該鎓鹽之丙烯酸共聚物以及含有其等之抗靜電劑
US12552931B2 (en) 2019-01-25 2026-02-17 Isp Investments Llc Dihydroxy lactam based polymers, compositions and applications thereof

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2727016A (en) * 1955-12-13 Hjnan
US3369008A (en) * 1964-05-26 1968-02-13 Rohm & Haas N-(cyclic ureidoalkyl) crotonamides and polymers thereof
US4032638A (en) * 1974-10-29 1977-06-28 E. I. Du Pont De Nemours And Company Heterocyclic ureas
US4111877A (en) * 1976-07-29 1978-09-05 Air Products & Chemicals, Inc. Allyl esters of n-alkyl-omega-(alkyleneureido) amic acids and their synthesis and use in aqueous emulsion polymer systems
US4104220A (en) * 1976-07-29 1978-08-01 Air Products & Chemicals, Inc. Alkenyl 1-(2-Aminoethyl) alkyleneureido succinamates, their synthesis, and use in aqueous emulsion polymer systems
US4632957A (en) * 1984-09-04 1986-12-30 Ppg Industries, Inc. Ethylenically unsaturated ethylene and propylene ureas containing alkylene urea groups or alkylene urethane groups, useful in coating compositions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9112243A3 *

Also Published As

Publication number Publication date
WO1991012243A3 (fr) 1991-10-03
WO1991012243A2 (fr) 1991-08-22
CA2074098A1 (fr) 1991-08-15
JPH05503941A (ja) 1993-06-24

Similar Documents

Publication Publication Date Title
US4151142A (en) Wet adhesion emulsions of polymer resins systems employed in water-based paint and coating compositions comprising as a component thereof monomer containing an ethylenic double bond and a ureido group polymerized therein
US4319032A (en) Derivatives of aminoalkyl alkylene ureas
US4504635A (en) Process for the preparation of polymeric compositions
CA1243026A (fr) Imidazolidones avec insaturations ethyleniques, renfermant des groupes d'alcoylene-uree ou d'alcoylene-urethane
US4521565A (en) Aqueous dispersion
US5115025A (en) (N-substituted carbamoyloxy)alkanoyloxyalkyl acrylate polymers and compositions made therefrom
EP0594596A1 (fr) Monomere d'imidazolidinone copolymerisable
CA2350881C (fr) Momnomere a adhesion humide et copolymeres derives pour des peintures au latex
US6166220A (en) Ethylenically unsaturated imidazidolidinone monomers
EP0103199B1 (fr) Revêtements résistants à l'humidité employant des polymères ramifiés de t-butyl acrylate
EP0581466A2 (fr) Compositions à base de polymères contenant un groupe acétoacétate et de polyformals
GB2112773A (en) Polymer-forming imidazolidinone and hexahydropyrimidone derivatives
US4314067A (en) Monomeric compounds having vinyl and imidazolidin-2-one terminal groups
US4429095A (en) Polymerizable compositions comprising derivatives of mono-(alkylene ureido alkyl) ureas and bis-(alkylene ureido alkyl) ureas
JP2001520285A (ja) ３−ブテンエステルのポリマー、その製造及び使用
US4340743A (en) Derivatives of mono-(alkylene ureido alkyl) ureas, and bis-(alkylene ureido alkyl) ureas
KR20010030851A (ko) 스크럽 내성 라텍스
US6630599B1 (en) Process for preparing derivatives of isopropenyl-α, α-dimethylbenzyl isocyanate
US4426503A (en) Derivatives of aminoalkyl alkylene ureas and their use as wet adhesion promoters
DE69110244T2 (de) Bei Raumtemperatur härtende Beschichtungszusammensetzungen mit zwei Komponenten.
US5342891A (en) (N-substituted carbamoyloxy) alkanoyloxyalkyl acrylate polymers and compositions made therefrom
US5679738A (en) Aqueous polymeric emulsions incorporating polymerized units of michael adducts of N-vinylformamide
CA1307370C (fr) Procede de fabrication de produits liants durcissant en presence d'humiditeet usages qui en sont faits
US4617364A (en) Wet adhesion promoters for emulsion polymers
US5728789A (en) Powder coating compositions containing copolymers having hydroxyl and carboxylic acid anhydride groups as binders

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

17P Request for examination filed

Effective date: 19920804

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LI LU NL SE

18W Application withdrawn

Withdrawal date: 19940425