WO2002036654A2 - Dispersion polyurethane anionique - Google Patents

Dispersion polyurethane anionique Download PDF

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Publication number
WO2002036654A2
WO2002036654A2 PCT/US2001/050532 US0150532W WO0236654A2 WO 2002036654 A2 WO2002036654 A2 WO 2002036654A2 US 0150532 W US0150532 W US 0150532W WO 0236654 A2 WO0236654 A2 WO 0236654A2
Authority
WO
WIPO (PCT)
Prior art keywords
hydroxylated
dispersion
prepolymer
accordance
compound
Prior art date
Application number
PCT/US2001/050532
Other languages
English (en)
Other versions
WO2002036654A3 (fr
Inventor
Ibrahim Bechara
Biau-Hung Chang
Pavel Ilmenev
Original Assignee
Crompton Corporation
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 Crompton Corporation filed Critical Crompton Corporation
Publication of WO2002036654A2 publication Critical patent/WO2002036654A2/fr
Publication of WO2002036654A3 publication Critical patent/WO2002036654A3/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • 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
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • 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
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
    • 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
    • C08G18/69—Polymers of conjugated dienes
    • C08G18/698—Mixtures with compounds of group C08G18/40

Definitions

  • the present invention is directed to an anionic polyurethane dispersion having high functionality. More specifically, the present invention is drawn to an anionic polyurethane dispersion having excellent adhesion to non-polar substrates.
  • Other problems associated with polyurethane dispersion coatings and adhesives are their poor performance when blended with non-polar materials, such as polyolefin emulsions, and their poor acid and alkaline resistance.
  • U.S. Patent 5,672,653 discloses an anionic waterborne dispersion which includes hydroxy- terminated polybutadiene to produce films and adhesives.
  • Other solutions are provided in other U.S. patents.
  • U.S. Patent 4,240,944 describes a binder composition and a method of employing that composition in glass fiber sizing compositions.
  • the binder composition of the '944 patent is an aqueous emulsion containing isotactic carboxylated polypropylene, base and surfactant.
  • U.S. Patent 4,507,430 sets forth a water-based polyurethane emulsion containing a hydrogenated polyalkadiene polyol component.
  • U.S. Patent 4,728,573 is drawn to an aqueous treating composition which includes at least one amino coupling agent and an aqueous emulsion of an acid or anhydride-modified polyolefin containing one or more surfactants.
  • the polyolefin is neutralized with an organic or inorganic base having a basicity less than the basicity of the amino moiety of the coupling agent.
  • the aqueous treating composition further comprises a binder stabilizer, one or more film-forming polymers and water.
  • a new anionic polyurethane dispersion has now been developed which provides enhanced functionality so that improved compatibility and adhesivity of polyurethane dispersions to non-polar substrates, such as polyolefins, is provided.
  • an anionic polyurethane dispersion is provided.
  • the dispersion is a reaction product of a prepolymer and a chain extender.
  • the prepolymer is a reaction product of a hydroxylated polymer selected from the group consisting of polyether polyols, polyester polyols and mixtures thereof, a polyisocyanate, and a hydroxylated compound having a pendent sulfonic acid group.
  • a second preferred embodiment of the anionic polyurethane dispersion of the present invention is again provided by a reaction product of a prepolymer and a chain extender.
  • the prepolymer is a reaction product of a hydroxylated polymer selected from polyols the group consisting of polyether polyols, polyester polyols, and mixtures thereof, a polyisocyanate, a hydroxylated compound having a pendent carboxylic acid group and an ester of a fatty acid having about 12 to about 20 carbon atoms which contains hydroxyl groups.
  • a third preferred embodiment of the anionic polyurethane dispersion is provided.
  • the dispersion is a reaction product of a prepolymer and a hydroxylated amine chain extender.
  • the prepolymer is a reaction product of a hydroxylated polymer selected from the group consisting of a polyether polyol, a polyester polyol and mixtures thereof, a hydroxylated compound containing a hydrocarbon group of at least about 15 carbon atoms, a polyisocyanate and a hydroxylated compound having a pendent acid group.
  • the anionic polyurethane dispersion having enhanced functionality of the present invention is a reaction product of a prepolymer and a chain extender.
  • the first component of the prepolymer is a hydroxylated polymer which may be a polyether polyol, a polyester polyol or mixtures thereof.
  • the polyether polyol be a polyalkylene glycol.
  • the polyalkylene glycol is preferably polyethylene glycol, polypropylene glycol or mixtures thereof.
  • the polyester polyol be a polyester glycol.
  • preferred polyester glycols are poly(hexamethylene adipate/isophthalate) glycol and poly(hexamethylene orthophthalate)glycol.
  • a second component, common to all embodiments of the present invention, that reacts to form the reaction product of the prepolymer, is a polyisocyanate.
  • a polyisocyanate any compound possessing at least two isocyanate groups is within the contemplation of the present invention, it is preferred that the polyisocyanate be a diisocyanate.
  • Both aliphatic and aromatic polyisocyanates may be utilized in the formation of the prepolymer.
  • aliphatic polyisocyanates are preferred.
  • such aliphatic diisocyanates as isophorone diisocyanate (IPDI), hexamethylene diisocyanate, dicyclohexylmethane-4,4-diisocyanate and the like are preferred for inclusion in the prepolymer reaction product.
  • the third component of the prepolymer reaction product is a hydroxylated compound containing a pendent sulfonic acid group.
  • the prepolymer of the first embodiment of the present invention may be limited to the aforementioned three components, one or more additional components, which generically can be defined as a hyroxylated compound containing a hydrocarbon segment having at least about 12 carbon atoms, can also be provided.
  • One preferred class of hydroxylated compounds containing a hydrocarbon segment is a hydroxylated polyalkadiene.
  • the hydroxylated polyalkadiene may or may not be hydrogenated. If hydrogenated, the degree of hydrogenation maybe partial or complete.
  • a preferred class of hydroxylated polyalkadienes is the class of polyalkadiene diols.
  • a particularly preferred class of hydroxylated polyalkadienes are hydroxylated polybutadienes.
  • Another class of preferred hydroxylated compounds containing a hydrocarbon segment is a class of esters of a fatty acid having about 12 to about 20 carbon atoms containing hydroxyl groups. More preferably, this class of esters of fatty acids having about 15 to about 20 carbon atoms and contains hydroxyl groups. Still more preferably, an ester is a fatty acid having about 18 carbon atoms containing hydroxyl groups is utilized. Thus, a particularly preferred ester for use in the prepolymer reaction product is glycerol monostearate (GMS).
  • GMS glycerol monostearate
  • the chain extender which reacts with the prepolymer to form the polyurethane dispersion, is preferably an amine compound. More preferably, a diamine, whether aliphatic or aromatic, is utilized. Of the diamines, the simplest and one that is particularly preferred is hydrazine.
  • the prepolymer reaction product includes the aforementioned hydroxylated polymer polyisocyanate components, as defined in the discussion of the first embodiment.
  • the employment of a hydroxylated compound containing a hydrocarbon segment is not optional. Rather, it is essential. Specifically, in this embodiment an ester of a hydroxylated fatty acid containing about 12 to about 20 carbon atoms is required.
  • the preferred and more preferred embodiments of this class of compounds discussed above, are applicable.
  • glycerol monostearate is a particularly preferred component of the prepolymer reaction product of this second embodiment.
  • the second embodiment is broader than the first embodiment insofar as a requirement of the first embodiment, that the prepolymer include a hydroxylated compound containing a pendent sulfonic acid group, is, in the second embodiment, extended to any hydroxylated compound containing a pendent acid group.
  • this component may be a hydroxylated compound containing a pendent sulfonic acid group as well a hydroxylated compound containing a pendent carboxylic acid group.
  • DMPA dimethylol propionic acid
  • the prepolymer is a reaction product of a hydroxylated polymer, a polyisocyanate, a hydroxylated compound containing a pendent acid group and a hydroxylated compound including a hydrocarbon segment containing at least about 12 carbon atoms. It is emphasized that the latter component may be a hydroxylated polyalkadiene, an ester of a fatty acid or both.
  • the chain extender is limited to functionalized amine compounds.
  • a diamine albeit functionalized, is preferred.
  • Preferred functionalized amines include hydroxylated amines, such as aminoethylaminoethanol, and unsaturated amines, such as diethylene triamine.
  • IPDI isophorone diisocyanate
  • DMPA dimethylol propionic acid
  • M-Pyrol 1- methyl-2-pyrrolidinone
  • the thus formed prepolymer was thereupon dispersed in water (648.46 g) to which triethylamine (29.18 g) (TEA) and a defoamer (0.8 g) was added.
  • TEA triethylamine
  • defoamer 0.8 g
  • the completely dispersed prepolymer was extended employing the hydroxylated amine, aminoethylaminoethanol (18.78 g).
  • the resultant stable dispersion product had a solids content of 34.4%, a pH of 8.7 and viscosity of 140 cps (Brookfield 7 LV, spindle #3 at 60 rpm). This dispersion is summarized in Table 1.
  • Example 1 was substantially identically reproduced. However, the aminoethylaminoethanol chain extender of that example was replaced with a 35% solution of aqueous hydrazine (16.45 g).
  • Example 1 and Comparative Example 1 were cast on glass plates.
  • the dispersions disposed on glass plates were dried to form films having thicknesses of about 5 mils.
  • the thus formed films were removed from the glass plates upon which they were cast and cut into samples using a standard die-cut knife.
  • compositions were formed into films in accordance with the procedure of Example 2.
  • the films were tested in accordance with the procedure of Example 2.
  • Example 3 is summarized in Table 2.
  • the final product was a stable, viscous dispersion having a solids content of 61.9% and a pH of 7.7.
  • a polyurethane dispersion substantially identical to the polyurethane dispersion of Example 4 but for the omission of GMS was prepared in accordance with the procedure of Example 4.
  • the resultant composition was cast upon an untreated polypropylene sheet (30 mils thick) and dried at room temperature. Following drying, the resultant cast sheet was annealed by subjecting it to a temperature of 248° F for 15 minutes. The cast sheet was thereupon laminated to another 30 mil thick polypropylene sheet under a pressure of 60 psi at 300° F for 30 seconds.
  • glycerol monostearate improves the adhesivity of a blend of wax and the anionic polyurethane dispersion of Example 4 to the non-polar substrate polypropylene, as manifested by the peel adhesion test relative to the prior art anionic polyurethane dispersion of Comparative Example 2 in which it is omitted.
  • This is so insofar as the sole distinction between the polyurethane dispersion of Example 4 and the polyurethane dispersion of Comparative Example 2 is the presence of glycerol monostearate. Indeed, the absence of glycerol monostearate, as illustrated by the results summarized in Table 4, is essential to effective adhesive properties.
  • the reactor was then heated at 80°C for about 3 hours at which time the resultant prepolymer reached the NCO calculated value of 4.43%.
  • the prepolymer was dispersed in water (355.32 g) containing defoamer (0.8 g). After the polymer was completely dispersed, the prepolymer was extended with a 35% aqueous solution of hydrazine (11.58 g).
  • an anionic polyurethane dispersion was stable having a 38.1% solids content, a pH of 6.5 and a viscosity of 500 cps (Brookf ⁇ eld ® LV, spindle #3 at 60 rpm).
  • Example 6 was substantially reproduced but for the substitution of
  • An anionic polyurethane dispersion was prepared in accordance with the procedure employed in the formation of the polyurethane dispersion of Example 6 but for two distinctions. The first was the substitution of the hydroxylated polyester Fomrez ® 8066-37, within the scope of the present invention, for the polypropylene glycol diol, Poly-G ® 20-56. The second distinction was the absence of the hydroxylated polybutadiene, Poly bd ® R45HTOL.
  • compositions comprising equal weight mixtures of an aqueous emulsion of carboxylated polypropylene wax and the polyurethane dispersions of Examples 4 and 6 and Comparative Examples 1 to 4 were prepared. These compositions, as well as neat carboxylated polypropylene wax, were sandwiched between polypropylene sheets in accordance with the procedure of Example 5.
  • the comparison between the polyurethane dispersions of Example 6 and Comparative Example 3 illustrates the improved result obtained by utilizing a hydroxylated compound with a pendent sulfonic acid group, compared to a hydroxylated compound with a pendent carboxylic acid group, as a stabilizer in providing unexpectedly improved adhesion.
  • the unexpected improved peel strength of the PUD of Example 6 over that of Comparative Example 3 is solely due to the only distinction between the two PUD's, the employment of BES, a compound with a pendent sulfonic acid group, in the PUD of Example 6, compared to the inclusion of DMPA, a compound with a pendent carboxylic acid group, in the PUD of Comparative Example 3.
  • the unexpected result, in comparing the polyurethane dispersions of Example 6 and Comparative Example 4, is the failure mode.
  • the polyurethane dispersion of Comparative Example 4 failed adhesively whereas the polyurethane dispersion of Example 6 failed cohesively.
  • a cohesive failure indicates that adhesion of the polyurethane wax blend to the polypropylene substrate exceeds the strength of the polymer itself. This demonstrates that the polypropylene dispersion of Example 6 provides higher adhesion that does the polyurethane dispersion of Comparative Example 4.

Abstract

L'invention concerne une dispersion polyurethane anionique compatible avec et pouvant adhérer à des substrats non polaires, tels que des polyoléfines. La dispersion polyurethane anionique comprend un produit réactionnel d'un prépolymère et un allongeur de chaîne. Le prépolymère comprend un polymère hydroxylé, un polyisocyanate et un composé hydroxylé comprenant un groupe acide pendant. Dans une forme de réalisation, le prépolymère est limité par la condition que le groupe acide pendant du composé hydroxylé soit un groupe acide sulfonique. Dans une autre forme de réalisation, le prépolymère est limité par la condition que le produit réactionnel comprenne un ester d'un acide gras hydroxylé présentant environ 12 à 20 atomes de carbone. Dans une troisième forme de réalisation, la dispersion est limitée par la condition que le produit réactionnel du prépolymère comprenne un segment hydrocarboné ccontenant au moins environ 12 atomes de carbone et que l'allongeur de chaîne soit un composé amine hydroxylé.
PCT/US2001/050532 2000-10-30 2001-10-19 Dispersion polyurethane anionique WO2002036654A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US69980800A 2000-10-30 2000-10-30
US09/699,808 2000-10-30

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WO2002036654A2 true WO2002036654A2 (fr) 2002-05-10
WO2002036654A3 WO2002036654A3 (fr) 2003-01-03

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6774181B1 (en) 2003-07-01 2004-08-10 Crompton Corporation Process for the preparation of a self-emulsifiable polyolefin emulsion and hybrid polyolefin-polyurethane dispersion derived therefrom
US7160944B2 (en) 2003-06-17 2007-01-09 Crompton Corporation Process for the preparation of a polyolefin emulsion and hybrid polyolefin-polyurethane dispersion derived therefrom
WO2007023655A1 (fr) * 2005-08-24 2007-03-01 Daicel Chemical Industries, Ltd. Polyester polyol et resine polyurethanne

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4277380A (en) * 1979-03-29 1981-07-07 Textron, Inc. Water-dispersible urethane polymers and aqueous polymer dispersions
US4307219A (en) * 1980-04-30 1981-12-22 Minnesota Mining And Manufacturing Company Aqueous solvent dispersible linear polyurethane resins
US4870129A (en) * 1986-09-04 1989-09-26 Bayer Aktiengesellschaft Adhesive and use of the adhesive for the formation of bonds
EP0640632A1 (fr) * 1993-08-31 1995-03-01 The Thompson Minwax Company Compositions de poly(uréthane-urée) dispersables dans l'eau
EP0794203A2 (fr) * 1996-03-05 1997-09-10 H.B. FULLER LICENSING & FINANCING, INC. Adhésifs stratifiés pour emballage souple
WO1999048941A1 (fr) * 1998-03-25 1999-09-30 Elf Atochem S.A. Dispersions aqueuses de polyurethane et leur procede de preparation
EP1172389A1 (fr) * 2000-07-12 2002-01-16 Solutia Austria GmbH Dispersions aqueuses de polyuréthane contenant des composants de polybutadiène

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4277380A (en) * 1979-03-29 1981-07-07 Textron, Inc. Water-dispersible urethane polymers and aqueous polymer dispersions
US4307219A (en) * 1980-04-30 1981-12-22 Minnesota Mining And Manufacturing Company Aqueous solvent dispersible linear polyurethane resins
US4870129A (en) * 1986-09-04 1989-09-26 Bayer Aktiengesellschaft Adhesive and use of the adhesive for the formation of bonds
EP0640632A1 (fr) * 1993-08-31 1995-03-01 The Thompson Minwax Company Compositions de poly(uréthane-urée) dispersables dans l'eau
EP0794203A2 (fr) * 1996-03-05 1997-09-10 H.B. FULLER LICENSING & FINANCING, INC. Adhésifs stratifiés pour emballage souple
WO1999048941A1 (fr) * 1998-03-25 1999-09-30 Elf Atochem S.A. Dispersions aqueuses de polyurethane et leur procede de preparation
EP1172389A1 (fr) * 2000-07-12 2002-01-16 Solutia Austria GmbH Dispersions aqueuses de polyuréthane contenant des composants de polybutadiène

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7160944B2 (en) 2003-06-17 2007-01-09 Crompton Corporation Process for the preparation of a polyolefin emulsion and hybrid polyolefin-polyurethane dispersion derived therefrom
US6774181B1 (en) 2003-07-01 2004-08-10 Crompton Corporation Process for the preparation of a self-emulsifiable polyolefin emulsion and hybrid polyolefin-polyurethane dispersion derived therefrom
WO2007023655A1 (fr) * 2005-08-24 2007-03-01 Daicel Chemical Industries, Ltd. Polyester polyol et resine polyurethanne
JPWO2007023655A1 (ja) * 2005-08-24 2009-03-26 ダイセル化学工業株式会社 ポリエステルポリオール及びポリウレタン系樹脂
US7674930B2 (en) 2005-08-24 2010-03-09 Daicel Chemical Industries, Ltd. Polyester polyol and polyurethane resin

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Publication number Publication date
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