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WO1998031655A1 - Procede d'hydroxyalkylation de matieres fonctionnalisees par de l'acide carboxylique - Google Patents

Procede d'hydroxyalkylation de matieres fonctionnalisees par de l'acide carboxylique Download PDF

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Publication number
WO1998031655A1
WO1998031655A1 PCT/US1998/000862 US9800862W WO9831655A1 WO 1998031655 A1 WO1998031655 A1 WO 1998031655A1 US 9800862 W US9800862 W US 9800862W WO 9831655 A1 WO9831655 A1 WO 9831655A1
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Prior art keywords
poly
carboxylic acid
functionalized
group
process according
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PCT/US1998/000862
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English (en)
Inventor
John G. Woods
Susanne D. Morrill
Anthony F. Jacobine
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Loctite Corporation
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Application filed by Loctite Corporation filed Critical Loctite Corporation
Priority to EP98902804A priority Critical patent/EP0973721A4/fr
Priority to JP53456598A priority patent/JP2001509205A/ja
Priority to AU59610/98A priority patent/AU5961098A/en
Priority to US09/341,287 priority patent/US7354977B1/en
Publication of WO1998031655A1 publication Critical patent/WO1998031655A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/30—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
    • C08C19/34—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with oxygen or oxygen-containing groups
    • C08C19/36—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with oxygen or oxygen-containing groups with carboxy radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3234—Polyamines cycloaliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen

Definitions

  • the present invention relates broadly to a process for hydroxyalkylating carboxylic acid-functionalized materials. More specifically, this invention provides a process for preparing primary hydroxyl -terminated polymers from carboxylic acid-terminated polymers, such as carboxylic acid-terminated butadiene nitrile co-polymers ("CTBNs"), using a carbocyclic carbonate, such as ethylene carbonate, or a carbocyclic sulfite, such as ethylene sulfite.
  • CBNs carboxylic acid-terminated butadiene nitrile co-polymers
  • HTBNs are known, and are generally useful as extenders with difunctional polymerizable materials to add toughness to adhesive compounds, caulking compounds and potting compounds. HTBNs react rapidly through their terminal hydroxyl groups with, for instance, organic diisocyanates to form solid, high molecular weight materials of low fusibility. [See e.g. , U.S. Patent No. 3,551,472 (Siebert).] They are also used in particular to form block prepolymer resins, as taught by U.S. Patent No. 4,295,909 (Baccei), the disclosure of which is hereby incorporated herein by reference .
  • Another method of preparing HTBNs from CTBNs involves the use of diols.
  • B.F. Goodrich 's '472 patent discloses such a method, employing diols having three to six carbon atoms in an acid-catalyzed direct esterification to yield primary hydroxyl -terminated materials with a straight -chain three to six carbon atom unit between the carboxylic acid linkage and the hydroxyl terminus.
  • this process has certain undesirable features, namely the use of a large excess of the diol which is particularly troublesome to remove upon completion of the reaction, and trans-esterification which results in an increase of the molecular weight of the so- formed HTBN which in turn increases the viscosity and reduces the hydroxyl number of the resultant HTBN.
  • Hydroxyamide-terminated equivalents to HTBN have also been prepared by amidation of CTBN with aminoalcohols . See B.F. Goodrich's U.S. Patent No. 4,489,008 (Riew) .
  • such process is not particularly suitable for large-scale commercial production as aminoalcohols are not only toxic, but are used in molar. excess to CTBN. Since residual aminoalcohols are difficult to remove, the final polymer is frequently treated with maleate esters and the like to ensure complete aminoalcohol removal . This results in the formation of low molecular weight reactive plasticizers , which adversely affect the toughness of urethane resins produced from the so-prepared hydroxyamide-terminated material .
  • U.S. Patent No. 4,310,707 (Strege) , however, speaks to and claims a method of hydroxyalkyating phenols and thiophenols using cyclic organic carbonate compounds and sodium stannate as the catalyst.
  • U.S. Patent No. 4,261,922 (Kern) also relates to hydroxyl alkylation reactions to prepare ether compounds from cyclic organic carbonate compounds and phenols contacted in the presence of potassium iodide catalyst.
  • U.S. Patent No. 4,266,046 (Wu) speaks to and claims a process for preparing esters of polycarboxylic acids which includes reacting cyclic carbonates with a polycarboxylic acid in the presence of an alkylammonium halide.
  • polycarbocyclic acids are exemplified as hydrocarbon radicals having from two to four carboxylic acid groups, and are selected from substituted aromatic acids, cyclohexyl acids and short chain acids.
  • hydrocarbon radicals having from two to four carboxylic acid groups, and are selected from substituted aromatic acids, cyclohexyl acids and short chain acids.
  • the present invention is directed to a process for hydroxyalkylating carboxylic acid group-functionalized material. More specifically, this invention provides a process for preparing an hydroxyl-functionalized material, which includes the step of reacting a carboxylic acid-functionalized material with an amount of a carbocyclic carbonate or carbocyclic sulfite in the presence of a phase transfer catalyst under conditions sufficient to form the hydroxyl-functionalized material.
  • the funtionalized material should be a nitrile rubber, such as those found in a liquid or melt phase.
  • the amount of carbocyclic carbonate or carbocyclic sulfite should of course be sufficient to convert the carboxylic acid groups of the carboxylic acid-functionalized material into an hydroxyl-functionalized material .
  • a carboxylic acid-functionalized material is converted into an hydroxyl-functionalized material having a lower alkyl linkage (such as a two or three carbon alkyl linkage) between the prior carboxylic acid group (now an ester linkage) and the newly- formed hydroxyl group.
  • the present invention provides a method of using carbocyclic carbonates or carbocyclic sulfites, such as eth ⁇ lene carbonate or propylene carbonate (such as 1 , 3-propylene carbonate), or ethylene sulfite or propylene sulfite (such as 1 , 3 -propylene sulfite) , respectively, in the presence of a phase transfer catalyst as a replacement reactant in synthetic schemes presently calling for the use of carbocyclic oxides, such as ethylene oxide or propylene oxide, respectively.
  • carbocyclic carbonates or carbocyclic sulfites such as eth ⁇ lene carbonate or propylene carbonate (such as 1 , 3-propylene carbonate), or ethylene sulfite or propylene sulfite (such as 1 , 3 -propylene sulfite) , respectively.
  • the carbocyclic carbonates or carbocyclic sulfites are capable of introducing an alkyl hydroxyl group to a reactive group having an acidic hydrogen, such as a carboxylic acid group .
  • the present invention also provides a method of purifying the so- formed hydroxylated material which includes the step of contacting the reaction mixture with an appropriate amount of an amphoteric treating agent. This purifying treatment method avoids ' the conventional use of a solvent to accomplish that objective.
  • the process of the present invention treats a carboxylic acid-functionalized material, such as CTBN, with an hydroxyalkylating reagent, such as a carbocyclic carbonate or carbocyclic sulfite, in the presence of a phase transfer catalyst to provide a corresponding hydroxyl-functionalized material, such as HTBN, in a manner which is simple, safe and commercially viable.
  • a carboxylic acid-functionalized material such as CTBN
  • an hydroxyalkylating reagent such as a carbocyclic carbonate or carbocyclic sulfite
  • urethane block co-polymers may be prepared therefrom with improved toughness .
  • the hydroxyalkylating reagent, as well as the phase transfer catalyst are non-toxic and require neither special handling conditions nor equipment.
  • the process according to this invention also does not require a solvent for reaction and in one aspect does not require a solvent for separation or purification.
  • at least the prior process which employs ethylene oxide also requires a trialkyl amine catalyst, the entire removal of which at the completion of the reaction is difficult and the presence of which (even in residual amounts) frequently results in premature polymerization of block resins formed from HTBN.
  • this invention relates to a process for reacting carboxylic acid-functionalized polymeric materials, such as terminal and/or pendant carboxylic acid-functionalized materials, with an amount of carbocyclic carbonate or carbocyclic sulfite, such as ethylene carbonate or ethylene sulfite, respectively, sufficient to cause formation of hydroxyl-functionalized materials by conversion of carboxylic acid groups to hydroxyl groups with a lower alkyl linkage between the ester linkage and the newly- formed hydroxyl group.
  • carboxylic acid-functionalized polymeric materials such as terminal and/or pendant carboxylic acid-functionalized materials
  • carbocyclic carbonate or carbocyclic sulfite such as ethylene carbonate or ethylene sulfite
  • the hydroxyalkylating reagent appropriate to convert terminal carboxylic acid groups to corresponding terminal hydroxyl groups may be chosen from a variety of materials. Of particular interest are carbocyclic carbonates and carbocyclic sulfites. For instance, where a primary hydroxyl is desirable as a terminal group, an unsubstituted carboxylic material may be chosen. That is, in the event a two or a linear three carbon linkage is desired between the ester linkage and the terminal hydroxyl group, and carbocyclic carbonate is desired as the hydroxyalkylating reagent, ethylene carbonate or
  • 1, 3 -propylene carbonate should be used.
  • 2 -methyl-1 , 2 -ethylene carbonate or 3 -methyl -1 , 3 -propylene carbonate should be used.
  • 1 , 2 -dimethyl -1 , 2 -ethylene carbonate or 1, 3 -dimethyl -1, 3 -propylene carbonate should be used.
  • 1, 1-dimethyl -1, 2 -ethylene carbonate or 1 , 1-dimethyl -1 , 3 -propylene carbonate should yield a mixture of primary and tertiary hydroxyl end groups; 1, 1 , 2-trimethyl-l, 2 -ethylene carbonate or 1, 1, 2 -trimethyl-1 , 3 -propylene carbonate should yield a mixture of secondary and tertiary hydroxyl end groups; and 1, 1, 2 , 2-tetramethyl-l, 2 -ethylene glycol or
  • 1, 1, 2, 2-tetramethyl-l, 3 -propylene glycol should yield tertiary hydroxyl end groups.
  • carbocyclic sulfites ethylene sulfite and propylene sulfites (such as 1 , 2 -propylene sulfite and 1 , 3 -propylene sulfite) should be used.
  • carbocyclic carbonates and carbocyclic sulfites may also be used.
  • a stoichiometric or a slight excess amount of the carbocyclic carbonate or carbocyclic sulfite may be used for each equivalent of carboxylic acid group present on the carboxylic acid-functionalized material.
  • a slight excess may be used, such as about 2.2 equivalents for each equivalent of carboxylic acid-functionalized material having two carboxylic acid groups.
  • the reaction desirably proceeds in the presence of a phase transfer catalyst.
  • the catalyst may be any material capable of accelerating the rate of hydroxyalkylation and minimizing undesirable side reactions .
  • the catalyst is a quaternary ammonium halide and may be used in an amount in the range of about 0.005 to about 0.5 equivalents, with about 0.01 to about 0.1 equivalents being preferred, for each equivalent of the carboxylic " acid-functionalized material.
  • Phosphonium halides such as triphenyl phosphonium halides like triphenyl phosphonium bromide
  • sulfoniun halides may also be used. See e.g., the '046 patent, the disclosure of which is hereby expressly incorporated herein by reference.
  • quaternary ammonium halides include alkaryl ammonium halides, such as benzyltrimethyl ammonium chloride and tetralkyl ammonium halides, such as tetraethyl ammonium halides or tetrabutyl ammonium halides like bromides or iodides.
  • alkaryl ammonium halides such as benzyltrimethyl ammonium chloride
  • tetralkyl ammonium halides such as tetraethyl ammonium halides or tetrabutyl ammonium halides like bromides or iodides.
  • Other desirable materials useful as the phase transfer catalyst include crown ethers and calixarenes. Of course, combinations of these materials may also be used.
  • a particularly desirable catalyst in connection with the process of the present invention is tetraethyla monium iodide.
  • the carboxylic acid-functionalized materials used in the process of the present invention may be selected from a wide variety of carboxylic acid-functionalized polymers having mono- or poly-carboxylic acid groups. Included among such materials are alkenoic carboxylic acid-functionalized materials, polymers of dienes, such as butadiene, co-polymers of dienes and vinylnitriles , such as butadiene-acrylonitrile, and alkyl acrylates, which may be prepared, for example, by known processes, such as described in B.F. Goodrich 1 s U.S. Patent No. 3,285,949 (Siebert) , and the like.
  • suitable materials include carboxylic acid-functionalized versions of liquid and solid polymers of conjugated diene monomers or mixtures of these monomers with co-polymerizable monomers.
  • suitable materials include olefins (e.g. , isobutylene) , aryl olefins and substituted aryl olefins (e.g. , styrene, p-chlorostyrene, p-methoxystyrene , alpha methyl styrene, vinyl naphthalene, and the like); unsaturated organic acids (e.g. , acrylic and methacrylic acids) ; alkyl esters of acrylic and methacrylic acids (e.g.
  • liquid or solid polymers may be prepared by conventional methods including mass, emulsion and solution polymerization methods. See U.S. Patent No. 3,346,631 (Boyer) , the disclosure of which is hereby expressly incorporated herein by reference.
  • a general representation of certain desirable carboxylic acid-functionalized polymers suitable for use with the subject invention include those within structure:
  • R and R 1 may be the same or different and may be selected from COOH or CAA 1 -X-COOH, where A and A 1 may be the same or different and may be selected from hydrogen, halogen, cyano, or linear or branched alkyl groups having from 1 to about 5 carbon atoms and X may be selected from linear or branched alkyl groups having from 2 to about 5 carbon atoms, such as methylene, ethylene, propylene and the like .
  • Examples of carboxylic-acid functionalization through the CAA' -X-COOH group include
  • carboxylic acid-functionalized polymers which may benefit from the process of the present invention include acrylic and methacrylic acid polymers and co-polymers, carboxylic acid-functionalized hydrogenated butadiene nitrile co-polymers, carboxylic acid-terminated poly (isobutylene) , carboxylic acid-terminated polyesters, polyamides, polyurethanes and polymeric acids derived from maleic anhydride co-polymers, and carboxylic acid-terminated polyethylene, polybutadiene, polyisoprene, poly (butadiene-co-acrylonitrile) , poly (isobutylene) , poly (butadiene-co-styrene) , poly (butadiene-co-acrylonitrile-c ⁇ -acrylic acid), poly (ethyl acrylate), poly(ethyl acrylate-co-n-butyl acrylate), poly(n-butyl acrylate-co-acrylonitrile) ,
  • CTBN carboxylic acid-functionalized block and graft co-polymers
  • HYCAR carboxylic acid-functionalized block and graft co-polymers
  • CTBN available commercially from B.F. Goodrich under the "HYCAR" trademark, such as "HYCAR” 1300X31.
  • CTBN generally has a number average molecular weight in the range of about 3,100 to about 4,200, with about 3,800 being desirable, an AN content in the range of 0 to about 26% by weight, with about 10% being desirable [polymer without AN in the case of CTBN, is carboxy-terminated polybutadiene (CTB) ] , and terminal groups R and R 1 as shown above.
  • the process of the present invention may be performed by contacting together the carboxylic acid-functionalized polymer, such as CTBN, a carbocyclic carbonate, such as ethylene carbonate, and a phase transfer catalyst, such as tetrabutyl ammonium iodide, for a period of time in the range of about 0.5 hours to about 2 hours, with about 1 hour being desirable, at a temperature in the range of about 125 to about 150°C.
  • a phase transfer catalyst such as tetrabutyl ammonium iodide
  • the so-formed hydroxyl-functionalized polymer such as HTBN
  • HTBN hydroxyl-functionalized polymer
  • liquid media such as methanol and/or water
  • the so-formed hydroxyl-functionalized material may be treated with an amphoteric treating agent, as discussed infra, followed by physical separation, such as filtration.
  • reaction conditions may be desirable to alter the reaction conditions in order to suit the particular reagents chosen.
  • a liquid medium such as a solvent, ordinarily is not required to perform the process of this invention, one may be desirable if, for instance, the carboxylic acid-functionalized polymer chosen is solid at the reaction temperature or if the hydroxyalkylating reagent is insoluble in the carboxylic acid-functionalized polymer at that temperature.
  • Appropriate solvents or liquid media capable of dissolving or dispersing the carboxylic acid-functionalized polymer and the hydroxyl-functionalized polymer formed therefrom include acetone, methyl ethyl ketone, cyclohexanone , tetrahydrofuran, dioxane, toluene, xylene(s) and combinations thereof.
  • the hydroxyalkylating reagent such as carbocyclic carbonate, may be used in an excess amount to ensure fluidity and accomplish satisfactpry heat transfer.
  • hydroxyl-functionalized polymers produced by the process of the present invention include, of course, hydroxyalkylated versions of any of the wide variety of carboxylic acid-functionalized polymers indicated above.
  • hydroxyalkylated versions of the carboxylic acid-functionalized polymer include those where R and R 1 may be selected from COO-X'-OH or CAA'-X-COO-X'-OH, where A, A 1 and X are as defined above and X 1 is as defined by X.
  • hydroxyalkylated versions of carboxylic acid-functionalized polymers through the COO-X'-OH or the CAA'-X-COO-X'-OH group therefore include
  • hydroxyl-functionalized copolymers of butadiene containing in excess of about 50% by weight of butadiene with the remainder being at least one co-polymerizable olefinically unsaturated monomer, such as acrylonitrile , alkyl acrylates and methacrylates , acrylic and methacrylic acid, and other materials known to free-radically co-polymerize with butadiene, such as styrene (s) and derivatives thereof, and other related polymerizable materials, such as are disclosed, for instance, in the '909 patent.
  • co-polymerizable olefinically unsaturated monomer such as acrylonitrile , alkyl acrylates and methacrylates , acrylic and methacrylic acid, and other materials known to free-radically co-polymerize with butadiene, such as styrene (s) and derivatives thereof, and other related polymerizable materials, such as are disclosed, for instance, in the '90
  • hydroxyl-functionalized polymers After the hydroxyl-functionalized polymers are formed, they are separated from the reaction mixture by precipitation in a suitable non-solvent, such as methanol.
  • a suitable non-solvent such as methanol.
  • This provides purified polymer free of a phase transfer catalyst, ethylene carbonate and ethylene glycol (if ethylene carbonate is used as the carbocylic carbonate) , after removal of solvent.
  • the so- formed polymer may also be purified through contact with an amphoteric treating agent, which removes all or substantially all of the catalyst.
  • amphoteric treating agents and general uses therefor are discussed in detail in U.S. Patent Nos. 5,371,181 (Glaser) and 5,399,624 (Glaser) .
  • amphoteric treating agents so noted may be chosen from silicated magnesium oxide, magnesium oxide, magnesium hydroxide, calcium hydroxide, barium oxide and barium hydroxide. Of course, combinations thereof may also be employed, if desired.
  • the average particle size of the amphoteric treating agent should be in the range of about 2 to about 200 microns.
  • a particularly desirable amphoteric treating agent is "MAGNESOL" Polysorb 30/40 hydrated silicated magnesium oxide (commercially available from The Dallas Group of America Inc., Liberty Corner, New Jersey) , which has a particle size in the range of from about 2 to about 200 microns, and an average particle size of about 50 microns .
  • amphoteric treating agents allows for adsorption of the catalyst from the reaction mixture and avoids the introduction of a solvent, such as methanol, which must thereafter be removed, and which is flammable. After treatment, the amphoteric treating agents may be removed by * physical means, such as filtration.
  • the desirability of using the amphoteric treating agents is therefore seen not only as a purification measure, but also as a safety measure, as well as a cost-saving measure. Accordingly, it is seen that a number of significant advantages may be realized by the process of the present invention, particularly when compared with known processes. For instance, a relatively innocuous coreactant is employed in the process hereof (i.e.
  • a carbocyclic carbonate such as ethylene carbonate
  • a carbocyclic sulfite such as ethylene sulfite
  • Another significant advantage is that fewer impurities are formed through the use of a carbocyclic carbonate or carbocyclic sulfite reagent, and impurities originating from ethylene oxide or the amine catalyst used therewith are no longer present.
  • Block prepolymer resins may be viewed as one-component , polymerizable block co-polymers having rigid and flexible segments, with block resins having flexible segments derived from HTBN being particularly useful in the preparation of structural " anaerobic adhesives. Products derived from such resins are ordinarily characterized by a combination of high adhesive strength, good cure through depth (surface activation) and outstanding cohesive toughness. See the ' 909 patent .
  • an additional aspect of this invention provides an adhesive and sealant composition having improved thermal and impact properties and curable though gaps of more than 40 mils.
  • a composition includes a reaction product of the hydroxyl-functionalized material formed from reacting a carboxylic acid-functionalized material with an hydroxyalkylating reagent in the presence of a phase transfer catalyst under conditions sufficient to form the hydroxyl-functionalized material; a molar excess of polyisocyanate and polyol , with the so- formed reaction product subsequently being reacted with a molar excess of a hydroxyalkyl or amino acrylate, or methacrylate; and an initiator .
  • the carboxylic acid-functionalized material may be one within the structure below:
  • the hydroxylating reagent may be selected from carbocyclic carbonates and carbocyclic sulfites.
  • the polyisocyanate and the polyol may be ones which are aromatic or cycloaliphatic .
  • the initiator may be a free-radical initiator or a photoinitiator .
  • a desirable adhesive and sealant composition along these lines includes one where the polyisocyante is toluene diisocyanate or 4 , ' -diisocyanate diphenyl methane and the reaction product is one from the reaction of isocyantate-terminated hydrogenated bisphenol-A with toluene diisocyanate .
  • HTBNs formed in accordance with the present invention may be used to form block prepolymer resins in accordance with the teaching of the '909 patent, such as by chemically- linking two "pre-polymers” which are subsequently “capped” with acrylate or methacrylate functionality.
  • a "flexible" polymeric butadiene polyol segment of relatively low molecular weight is reacted with a molar excess of a "rigid” diisocyanate, such as toluene diisocyanate or methylene diisocyanate, thereby forming urethane linkages.
  • the resin structures include a central flexible low glass transition linear polymer which is chemically linked to relatively short rigid segments, located at either end of the linear polymer through urethane groups and capped with acrylate or methacrylate groups.
  • rigid segment as used herein with respect to block resins includes a segment or segments containing aromatic, heterocyclic” or cycloaliphatic rings, with multiple segments joined by either fusing the rings or by a minimum number of carbon atoms (e.g. , 1 to 2 , if linear, or 1 to about 6, if branched) such that there is little or no flexing of the segments.
  • flexible segment as used herein with respect to block resins includes a segment of primarily linear aliphatic moieties containing internal unsaturation, with pendant functional groups, such as aromatic, heterocyclic , cycloaliphatic, and the like, as well as branching, also incorporated therein, provided no substantial interference exists with the flexible nature of the linear portion.
  • the flexible polybutadiene or copolybutadiene having functional groups containing an active hydrogen may be reacted with a molar excess (e.g . , about 0.05 to about 6) of polyisocyanate as to the concentration of the active hydrogen-containing groups on the polybutadiene. In this way, a product is assured which has an isocyanate group at each end of the polybutadiene segment .
  • the rigid segment may be derived from the reaction of cycloaliphatic diols, such as hydrogenated bis-phenol A, with two equivalents of a diisocyanate, such as toluene diisocyanate.
  • the urethane resins are synthesized in the presence of diluent monomers, such as triethylene glycol dimethacrylate, which also have a significant influence on the cured material properties.
  • diluent monomers such as triethylene glycol dimethacrylate
  • the material properties" of the cured resins may be optimized for adhesive applications. And in order to ensure rapid and complete incorporation of the flexible segment into the urethane polymer, it is desirable for the terminal hydroxyl groups of the HTBN to be primary, rather than secondary or tertiary.
  • Block resins may be prepared at temperatures within the range of from about room temperature to about
  • the reaction should be allowed to continue to proceed for a period of time of about 0.1 to about 24 hours.
  • the reaction may be catalyzed, and unreactive diluents may also be used to control viscosity, bearing in mind of course that the presence of unreactive diluents may affect material properties of the cured resins.
  • the product of this reaction may be reacted with at least a molar equivalence, based on isocyanate group content, of an hydroxy or aminoalkyl acrylate or methacrylate to form an adhesive/sealant monomer (or prepolymer) capped at both ends with acrylate or methacrylate functionality, respectively.
  • Esters suitable for such use are of a wide variety, although particularly desirable ones may be represented by:
  • R J may be hydrogen, halides (e.g. , chlorine) and alkyl groups (e.g. , methyl and ethyl) ; and R 4 may be lower alkyl groups, such as linear, branched, or cyclic groups having 1 to about 8 carbon atoms, phenylene and naphthalene .
  • the fully-prepared monomeric block prepolymers may be represented by:
  • R 3 and R 4 are as defined above;
  • A is a polyisocyanate linkage;
  • D is an aromatic, heterocyclic or cycloaliphatic polyol or polyamine group (e.g. , a diol of a cycloaliphatic compound) ;
  • Z is a polymeric or copolymeric polyol or poly radical of butadiene, the latter having a degree of polymerization of from about 5 to about 150 and at least about 70 percent of the polybutadiene portion of the 1, -configuration;
  • z is an integer corresponding to the valency of Z;
  • d is either 0 or 1; and
  • i is 0 when d is 0, and otherwise is one less than the number of reactive hydrogen atoms of D.
  • An asterisk indicates a urethane (-NH-COO-) or ureide (-NH-CO-NH-) linkage.
  • the block prepolymer resins cure to a hard, tough resin, using any of a wide variety of known free radical initiators, which may be activated by redox, thermal or photo-initiated mechanisms.
  • free radical initiators include (a) ones which perform through a redox mechanism such as benzoyl peroxide/N, N-dimethyl-p-toluidine , cumene hydroperoxide/o-benzoyl sulfimide/N, N-dimethyl-p-toluidine , and tributyl borane ; (b) ones which perform under elevated temperature conditions such as benzoyl peroxide, and 2 , 2 ' -azobisisobutylnirtile; and (c) ones which perform through photo-initiators 2 , 2-dimethoxy-2-phenylacetophenone and benzoyl cyclohexanol .
  • a redox mechanism such as benzoyl peroxide/N, N-dimethyl-p-toluidine , cumene hydroperoxide/o-benzoyl sulfimide/N, N-dimethyl-p-toluidine , and tributy
  • one aspect of the present invention as exemplified in the illustrative examples is directed to a novel process for the preparation of HTBN, as noted above, it may also be used to convert a wide range of carboxylic acid functionalized polymers and oligomers to the corresponding hydroxylated derivatives.
  • the X H NMR spectrum of the HTBN product showed neither the starting reagents, ethylene carbonate and phase transfer catalyst, nor ethylene glycol, a potential hydrolysis by-product . Residual methanol from the purification step was also shown to have been removed. The spectral characteristics of the HTBN product obtained by this method were observed to be similar to those obtained from the "HYCAR" 1300X29 HTBN product.
  • the solution was then transferred to an evaporating dish and warmed to a temperature of about 45 °C to remove most of the methylene chloride, and then heated to a temperature of about 60 °C under vacuum for a period of time of about 8 hours to yield about 140.89 grams of HTBN corresponding to an about 89% recovery.
  • the warm polymer was then transferred to a distillation flask and heated on a rotary evaporator at a temperature of about 95 °C for a period of time of about 3.5 hours under reduced pressure.
  • the product obtained was found by NMR and IR analyses to be identical to the product described in Example 1.
  • HTBN produce was not detected until the reaction mixture had been heated for a period of time of about 1.5 hours.
  • that reaction was performed with an about 2 -fold molar excess of ethylene carbonate, substantially complete conversion of CTBN to HTBN was observed after a period of time of about 1 hour. This indicates that the reaction rate is significantly enhanced by employing excess ethylene carbonate.
  • Example 1 supra was repeated with the temperature of the mixture being maintained in the range of about 100 to about 107°C throughout the heating period. NMR analysis indicated that no HTBN product had formed after a period of time of about 1 hour.
  • Example 1 supra was again repeated with the temperature of the mixture being maintained in the range of about 155 to about 160°C throughout the heating period.
  • the temperature of the mixture was increased to about 135°C, with continued stirring and heating for a total period of time of about one hour while maintaining the reaction temperature in the range_ of about 134 to about
  • the contents of the reactor were cooled to about 60 °C and about 49 grams of magnesium silicate ("MAGNASOL” Polysorb 30/40) was added. The mixture was stirred for a period of time of about 4 hours and centrifuged for a period of time of about 10 minutes at a rate of about 2,500 rpm to separate the silicate.
  • Carboxylic acid-functionalized materials other than HTBN were treated with hydroxyalkylating agents in accordance with the process of the present invention to yield corresponding hydroxyl-functionalized materials.
  • trans-3 -hexenoic acid a low molar mass model compound for HTBN
  • ethylene carbonate about 0.97 grams; about 0.001 moles
  • phase transfer catalyst was added to a 25 ml reaction flask containing a magnetic stirrer. The mixture was stirred at elevated temperature conditions to effect the hydroxyethylation reaction of the hexenoic acid. The reaction yields were estimated from the X H NMR spectrum of the crude product mixture .
  • Hydroxyl Number We also determined the hydroxyl number for HTBN prepared by the process of the present invention and its commercial counterpart .
  • the hydroxyl number is a measure of the concentration of hydroxyl groups on the polymeric structure and is desirable to ensure that the stoichiometric equivalent of diisocyanate be employed in the production of the block-prepolymer intermediate. Hydroxyl numbers were determined here by standard titration techniques and are reported here as mg of KOH/g of polymer.
  • the acid number is the amount of free carboxylic acid and is used to determine residual unreacted carboxylic acid at the completion of the reaction. It is desirable for the HTBN to have a low acid number, particularly when the HTBN is to be used to prepare urethane resins, because acid functionalized polymers (e.g. , CTBN) react only slowly and incompletely with isocyanates . We found the process of the present invention to provide materials essentially free of carboxylic acid functionality, which compares favorably with values obtained from commercial HTBN.
  • the process of the present invention provides greater than a twenty fold decrease in residual acid, which results in a cleaner urethane product and is 5 desirable to ensure that the stoichiometric equivalent of diisocyanate be employed in the production of the block-prepolymer intermediate.
  • Presence of Residual Glycol 0 1 H NMR analysis of commercial HTBN showed the presence of ethylene glycol in an amount in the range of about 0.29 to about 0.43 by weight percent.
  • the presence of ethylene glycol in HTBN prepared from CTBN and excess ethylene oxide is not entirely surprising as residual 5 ethylene oxide may be converted to ethylene glycol by hydrolysis.
  • the presence of ethylene glycol in the HTBN is disadvantageous for certain applications to the extent that it reduces the toughness of block resins derived from HTBN. While this attribute may be beneficial in certain applications, in other applications where enhanced stiffness or reactivity is required, it is desirable to have the choice of whether or not a less tough material is to be formed.
  • Block resins were prepared from HTBN prepared by 5 the process of the present invention as follows.
  • reaction mixture indicated that all of the isocyanate was consumed (through the disappearance of the absorption band of the isocyanate at 2265 cm "1 ) .
  • Resin A to have a number average molecular weight of about
  • glycol (“EG) center segment having the following structure :
  • ethylene glycol has substantially equivalent reactivity to the HTBN resin and results in the formation of a short, and hence rigid, urethane oligomer which in turn results in adhesive products with reduced toughness. Further, if the concentration of the ethylene glycol varies, then adhesive products with variable rheological and mechanical properties will be produced. Such variations is often viewed as unacceptable.
  • the molecular weight of the EG prepolymer is significantly lower than that of the HTBN material, it is to be expected that the molecular weight of a blend of the EG and HTBN products will be lower than that of the HTBN formed in accordance with this invention, such as the HTBN used to prepare Resin A.
  • block resins prepared from the HTBN formed in accordance with the process of this invention i.e. , Resin A
  • This difference may provide further opportunities for block resins prepared from HTBN formed in accordance with this invention, such as where improved thoughness and elongation are desirable properties to extend the range of applications for adhesives, protective coatings and sealant compositions.
  • the mechanical properties of the cured films were determined from (1) stress-strain measurements using an Instron universal tensile tester operating at a strain rate of about 0.2"/min., with a film size of about 101.6 X 6.35 mm 2 and (2) dynamic mechanical analysis (“DMA”) using a
  • both cured resins show two distinct transitions in the DMA spectrum, a low temperature transition, designated T g l , and a high temperature transition, designated T g 2.
  • the two transitions are indicative of a two-phase morphology.
  • the similarity of the DMA parameters indicates a similar structure for the cured resins .
  • the low temperature transition (at about -55°C) occurs at about the same temperature for both of the cured resins and is associated with the rubbery central segment derived from HTBN.
  • the high temperature transition (at about +100°C) is associated with the stiffer urethane end segments and is lower for cured Resin A than for cured Resin B.
  • the lower T g 2 value for cured Resin A may be attributed to the absence of ethylene glycol in the HTBN prepared by the process of the present invention (and hence the absence of the corresponding rigid short chain urethane oligomer present in Resin B) . This result correlates well with the increased toughness associated with cured Resin A.
  • Amine analysis also indicated the presence of residual amine in the commercial HTBN product .
  • This amine impurity is known to cause premature polymerization and formation of urethane/isocyanate by-products, particularly when (meth) acrylate capping reagents and diluents are employed with respect to the production of urethane prepolymers . Accordingly, it is desirable and advantageous to first remove or neutralize the amine catalyst, prior to the introduction of isocyanate monomers.
  • the HTBN prepared in accordance with this invention is also substantially free of carboxylic acid functionalized materials.
  • Carboxylic acids are undesirable, since they are known to compete with hydroxyl groups for isocyanate and result in the formation of complex mixtures of ureas, anhydrides, amides and carbon dioxide.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention se rapporte à un procédé d'hydroxyalkylation de groupes acides carboxyliques terminaux. Plus précisément, cette invention se rapporte à un procédé de préparation de matières fonctionnalisées par des groupes hydroxyle, à partir de matières fonctionnalisées par de l'acide carboxylique, telles que des polymères nitrile-butadiène, au moyen d'un carbonate carbocyclique, tel que le carbonate d'éthylène, ou un sulfite carbocyclique, tel que le sulfite d'éthylène.
PCT/US1998/000862 1997-01-17 1998-01-16 Procede d'hydroxyalkylation de matieres fonctionnalisees par de l'acide carboxylique WO1998031655A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP98902804A EP0973721A4 (fr) 1997-01-17 1998-01-16 Procede d'hydroxyalkylation de matieres fonctionnalisees par de l'acide carboxylique
JP53456598A JP2001509205A (ja) 1997-01-17 1998-01-16 カルボン酸官能基を有する物質をヒドロキシアルキル化する方法
AU59610/98A AU5961098A (en) 1997-01-17 1998-01-16 Process for hydroxyalkylating carboxylic acid-functionalized materials
US09/341,287 US7354977B1 (en) 1998-01-16 1998-01-16 Process for hydroxyalkylating carboxylic acid-functionalized materials

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US3571797P 1997-01-17 1997-01-17
US60/035,717 1997-01-17

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WO1998031655A1 true WO1998031655A1 (fr) 1998-07-23

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1059308A4 (fr) * 1998-02-27 2003-05-21 Kaneka Corp Polymere et composition solidifiable
EP2868676A1 (fr) 2013-10-30 2015-05-06 LANXESS Deutschland GmbH Caoutchouc copolymère fonctionnalisé contenant des groupes nitrile

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4266046A (en) * 1976-09-17 1981-05-05 Phillips Petroleum Company Esterification process
US4310707A (en) * 1980-08-18 1982-01-12 The Dow Chemical Company Sodium stannate catalyst for hydroxyalkylation of phenols or thiophenols
US4513146A (en) * 1982-09-23 1985-04-23 Ppg Industries, Inc. Method for producing esters from highly hindered carboxylic acids or their salts, and carbonates
US5019629A (en) * 1988-11-10 1991-05-28 Loctite Corporation Polymerizable styryloxy resins and compositions thereof

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3588100T2 (de) * 1984-02-17 1996-08-29 Cytec Tech Corp Carbamidsäureester-Derivate, Mittel und Herstellungsverfahren
FR2579611B1 (fr) * 1985-03-28 1987-08-21 Saint Gobain Vitrage Couche adhesive utilisee dans la fabrication de vitrages feuilletes et vitrages feuilletes comprenant une telle couche
US4713188A (en) * 1986-01-10 1987-12-15 Chevron Research Company Carbonate treated hydrocarbyl-substituted amides
US4769419A (en) * 1986-12-01 1988-09-06 Dawdy Terrance H Modified structural adhesives
US5399624A (en) * 1990-12-21 1995-03-21 Loctite Corporation High purity resins for thiol-ene polymerizations and method for producing same
US5556927A (en) * 1994-06-16 1996-09-17 Daicel Chemical Industries, Ltd. Carbonate group-modified epoxy resin, a process for the preparation thereof, and a heat-curable resin composition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4266046A (en) * 1976-09-17 1981-05-05 Phillips Petroleum Company Esterification process
US4310707A (en) * 1980-08-18 1982-01-12 The Dow Chemical Company Sodium stannate catalyst for hydroxyalkylation of phenols or thiophenols
US4513146A (en) * 1982-09-23 1985-04-23 Ppg Industries, Inc. Method for producing esters from highly hindered carboxylic acids or their salts, and carbonates
US5019629A (en) * 1988-11-10 1991-05-28 Loctite Corporation Polymerizable styryloxy resins and compositions thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0973721A4 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1059308A4 (fr) * 1998-02-27 2003-05-21 Kaneka Corp Polymere et composition solidifiable
US6964999B1 (en) 1998-02-27 2005-11-15 Kaneka Corporation Polymer and curable composition
EP2868676A1 (fr) 2013-10-30 2015-05-06 LANXESS Deutschland GmbH Caoutchouc copolymère fonctionnalisé contenant des groupes nitrile

Also Published As

Publication number Publication date
EP0973721A4 (fr) 2000-05-10
AU5961098A (en) 1998-08-07
JP2001509205A (ja) 2001-07-10
EP0973721A1 (fr) 2000-01-26

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