EP0830413A1 - Epaississants du type polyurethane avec des extremites protegees par des groupes hydrophiles - Google Patents

Epaississants du type polyurethane avec des extremites protegees par des groupes hydrophiles

Info

Publication number
EP0830413A1
EP0830413A1 EP96919209A EP96919209A EP0830413A1 EP 0830413 A1 EP0830413 A1 EP 0830413A1 EP 96919209 A EP96919209 A EP 96919209A EP 96919209 A EP96919209 A EP 96919209A EP 0830413 A1 EP0830413 A1 EP 0830413A1
Authority
EP
European Patent Office
Prior art keywords
thickener composition
acid
diisocyanate
polyether polyol
diglycidal ether
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Withdrawn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
EP96919209A
Other languages
German (de)
English (en)
Other versions
EP0830413A4 (fr
Inventor
Randolph B. Krafcik
Revathi Tomko
Paul M. Kayima
Anthony B. Sharrotta
Hyeong-Chan Youn
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.)
Sherwin Williams Co
Original Assignee
Sherwin Williams Co
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 Sherwin Williams Co filed Critical Sherwin Williams Co
Publication of EP0830413A1 publication Critical patent/EP0830413A1/fr
Publication of EP0830413A4 publication Critical patent/EP0830413A4/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/43—Thickening agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes

Definitions

  • This invention relates to hydrophilically end-capped polyurethane thickeners having particular utility in paints, coatings and other aqueous systems.
  • Thickeners have been known for use in paints and coatings for many years. They can be naturally occuring or synthetically manufactured. Examples of naturally occuring thickeners include alginates, casein, gum karaya, locust bean gum, cellulosics such as methyl cellulose, hydroxyethyl cellulose and hydroxypropylmethyl cellulose.
  • Examples of synthetic thickeners include the compositions of U.S. patent 4,079,028 (Emmons et al.), U.S. patent 4,180,491
  • U.S. patent 4,079,028 purports to teach latex systems containing a low molecular weight polyurethane thickener characterized by at least three hydrophobic groups interconnected by hydrophilic polyether groups.
  • U.S. patent 4,180,491 purports to teach nonionic polyurethane thickeners for print pastes, which thickeners are characterized by a molecular weight of at least 10,000 and having at least three hydrophobic branching groups linked through hydrophilic polyether segments.
  • U.S. patent 4,327,008 purports to teach rheology modifiers useful in water-based and organic solvent-based compositions, which modifiers are derived from the reaction of polyalkylene oxide, polyfunctional material (such as polyol, amine, amine alcohol, thiol or polyisocyanate) , diisocyanate, water and a monofunctional active hydrogen-containing compound or monoisocyanate.
  • U.S. patent 4,373,083 purports to teach a process for making rheology modifiers (particularly those of U.S. patent 4,079,028) useful in water and organic solvent-based compositions, which modifiers are derived from the reaction of polyalkylene oxide, polyfunctional material (such as polyol, amine, amine alcohol, thiol or polyisocyanate) , diisocyanate, water and end-capping compounds in an organic solvent.
  • U.S. patent 4,426,485 purports to teach water soluble, thickeners for aqueous systems which are characterized by deliberate, arranged bunches of hydrophobes bonded to a water- soluble backbone.
  • U.S. patent 4,496,708 purports to teach water-soluble comb polyurethane thickeners having hydrophilic polyether backbones and pendant monovalent hydrophobic groups.
  • U.S. patent 4,514,552 purports to teach alkali soluble thickeners which are aqueous emulsion copolymers of a,b- monoethylenically unsaturated carboxylic acid, monoethylenically unsaturated monomer (such as ethyl acrylate) , nonionic urethane monomer which is the reaction product of a monohydric surfactant and a monoisocyanate, and optionally a polyethylenically unsaturated monomer.
  • the present invention relates to hydrophilically end-capped polyurethane thickener compositions which are particularly suited for use in paint and coating compositions .
  • the patents discussed above all teach the use of hydrophobic end-capping groups to attain thickening efficiency, the present invention utilizes hydrophilic end groups.
  • compositions of this invention are the reaction product of:
  • an isocyanate functional material preferably a diisocyanate
  • polyether polyol preferably a polyalkylene oxide such as polyethylene glycol having a molecular weight between about 1000 and about 20,000, and
  • a difunctional hydrophilic endcapping material that is reactive with isocyanate groups, preferably a C4- C20 linear diol having hydroxy groups which are positioned at or near the ends of the diol chain.
  • compositions of this invention can be linear, branched, comb-type or other complex structures, however, the linear compositions are preferred.
  • the compositions of this invention are excellent thickeners and rheology modifying agents. These compositions are characterized by hydrophilic end caps which provide a definite and desirable impact on the compositions rheology modifying properties.
  • compositions of this invention are hydrophilically-modified polyurethane thickeners which are the reaction product of: (1) an isocyanate functional material, preferably a diisocyanate, (2) a polyether polyol, preferably a polyalkylene oxide such as polyethylene glycol having a molecular weight between about 1000 and about 20,000, and (3) a difunctional hydrophilic endcapping material that is reactive with isocyanate groups, preferably a C4-
  • the first starting material an isocyanate-functional material
  • the isocyanate-functional material should have at least two or more reactive isocyanate groups.
  • Exemplary diisocyanates include the aliphatic, cycloaliphatic and aromatic diisocyanates either alone or in admixture.
  • diisocyanates have the formula OCN-R-NCO where
  • R is arylene (e.g. phenylene and diphenylene) , alk larylene
  • R can be a hydrocarbon group containing ester or ether linkages.
  • diisocyanates include 1,4-tetramethylene diisocyanate, 1,6- hexamethylene diisocyanate, 2,2,4-trimethyl-l,6-diisocyanato hexane, 1,10-decamethylene diisocyanate, 1,4-cyclohexylene diisocyanate, 4,4' -methylene bis (isocyanato cyclehexane) , p- phenylene diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, xylene diisocyanate, isophorone diisocyanate, bis para-isocyanato cyclohexylmethane, 4,4-biphenylene diisocyanate, 4,4-methylene diphenyl isocyanate, 1,5- naphthalene diisocyanate, benzene 1,3-bis (1-isocyanato-1- methylethy
  • suitable triisocyanates include aromatic triisocyanate adduct of trimethylol propane and tolylene diisocyanate sold under the brand name Mondur CB- 75, and aliphatic triisocyanate product of the hydrolytic trimerization of l,6-hexamethylene diisocyanate, sold under the brand name Desmodur N.
  • dicyclohexylmethane-4,4'-diisocyanate sold under the brand name Desmodur W
  • isophorone diisocyanate diphenylmethane-4,4'-diisocyanate sold under the brand name Mondur XP744
  • isocyanurate trimer of hexamethylene diisocyanate sold under the brand name Desmodur N-3300.
  • the isocyanate-functional material should be used in an amount of between about 30.0% to about 50.0% (molar percent of all reactants) , preferably between about 35.0% to about 45.0%.
  • the second starting material, the polyether polyol is preferably a polyalkylene oxide such as polyethylene glycol having a molecular weight between about 1000 and about 20,000.
  • Suitable materials include the adducts of an aliphatic, cycloaliphatic or aromatic polyhydroxy compound such as a polyhydric alcohol or polyhydric alcohol ether and an alkylene oxide such as ethylene oxide or propylene oxide. Or, they may be hydroxyl-terminated prepolymers of such adducts and an organic polyisocyanate.
  • Polyhydric alcohols include not only the simple glycols such as ethylene glycol, polyethylene glycol, propylene glycol and polypropylene glycol, but also hydroxy compounds having three or more hydroxyl groups such as polyalkylolalkanes (e.g. trimethylolpropane, pentaerythritol) and polyhydroxyalkanes (e.g. glycerol, erythritol, sorbitol, mannitol, and the like) . Most preferred are the polyethylene and polypropylene oxides having molecular weights of between about 4,000 and about 20,000. Most preferred is polyethylene glycol having a molecular weight of about 8,000.
  • the polyether polyol component should be used in an amount of between about 14.0% to about 35.0% (molar percent of all reactants), preferably about 17.5% to about 25.0%.
  • the third starting material is a difunctional hydrophilic endcapping material that is reactive with isocyanate groups. It is preferably either a C4-C20 linear diol wherein the hydroxy groups are positioned at or near the ends of the diol chain or a di-functional amine wherein the amino groups are positioned at or near the ends of the diamine chain.
  • 1,2-hexanediol is readily commercially available, it is not acceptable for use herein due to the positioning of the hydroxy groups on the adjacent Cl and C2 carbons. Instead, diols such as 1,6-hexanediol and 1,10- decanediol are highly preferred. These diols have the hydroxy groups positioned on the terminal carbon atoms (Cl, C6 and Cl, CIO respectively). Unlike the 1,2-hexanediol, which results in a thickener which has a pendant five carbon chain as shown in Figure I, the use of 1,6-hexanediol results in a hydroxy- terminated polymer having a six carbon chain included in the backbone as shown in Figure II.
  • Diamines which are acceptable for use herein include 1,4- diaminobutane, 1, 5-diaminopentane, 1, 6-diaminohexane, 1,7- diaminoheptane , 1, 8-diaminooctane, 1, 9-diaminononane, 1,10- diaminodecane , 1 , 12 - diaminodode cane , 4, 4' - diaminodicyclohexylmethane and mixtures thereof.
  • the hydrophilic endcapping material are also suitable for use as the hydrophilic endcapping material.
  • the dithiols, dimercaptans, dicarboxylic acids and bisepoxies having functionality at or near the end of their respective chains.
  • useful dithiols include 1,4- butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1,7- heptanedithiol, 1, 8-octanedithiol, 1,9-nonanedithiol and 1,10- decanedithiol.
  • Useful dicarboxylic acids include 1,4- butanedicarboxylic acid, 1,5-pentanedicarboxylic acid, 1,6- hexanedicarboxylic acid, 1,7-heptanedicarboxylic acid, 1,8- octanedicarboxylic acid, 1,9-nonanedicarboxylic acid and 1,10- decanedicarboxylic acid.
  • Useful diepoxy compounds include 1,4- butanediol diglycidal ether, 1,5-pentanediol diglycidal ether, l,6-hexanediol diglycidal ether, l,7-heptanediol diglycidal ether, 1,8-octanediol diglycidal ether, 1,9-nonanediol diglycidal ether, 1,10-decanediol diglycidal ether and bisphenol A diepoxide.
  • the hydrophilic endcapping material is preferably used in an amount of between about 4.5% and about 40.0% (molar percent of all ⁇ reactants), preferably between about 30.0% and about 39.0%.
  • the preferred reaction procedure comprises charging the polyether polyol to a reactor equipped with a nitrogen blanket along with an optional, though preferred, solvent.
  • the solvent should be selected so as to be nonreactive with the isocyanate- functional material. It should be compatible with the polyether polyol material and capable of dissolving the resultant urethane products.
  • Suitable solvents include benzene, toluene, xylene, and other well-known non-active hydrogen solvents high in aromatic hydrocarbon contents such as Solvesso ® 100 and Solvesso ® 150, ethyl acetate, butyl acetate, and dialkyl ethers of alkylene glycol, dialkylene glycol, dipropyleneglycol monomethyletheracetate, N-methylpyrrolidone and the like.
  • the polyether polyol should be stirred and heated to about 100-120 degrees C. Any residual water in the reaction vessel or reactants should be azeotropically removed at this time.
  • the temperature of the reactor is then reduced to a temperature of about 65-75 degrees C and the isocyanate-functional material is added, followed by a catalyst such as dibutyl tin dilaurate.
  • a catalyst such as dibutyl tin dilaurate.
  • the polymerization is carried out over a time period of about three hours and the percent of free isocyanate is about 0.3- 0.6% by weight of reaction mixture present.
  • a diol can be added to the reaction mixture along with the polyether polyol and isocyanate-functional materials to provide hydrophobic moieties along the polymer backbone.
  • the polyether polyol, the isocyanate-functional material and the optional diol undergo a polymerization reaction to build a compound with an average molecular weight distribution of between about 10,000 and about 30,000 (Mn by gel permeation chromatography) .
  • the molecular weight of the compound is partially controlled by the ratio of equivalents of OH:NCO of the starting materials. Higher molecular weight polymers are produced when the OH:NCO ratio approaches 1:1.
  • the hydrophilic endcapper In a separate container, blend the hydrophilic endcapper along with an optional solvent selected from the group described above, such as toluene. This mixture is added quickly to the reaction vessel, preferably over a time period of less than about five minutes. Hold the reaction temperature at 65-75 degrees C for about one hour and thirty minutes or until the percent of free isocyanate is about 0%. The actual amount of free isocyanate left after the polymerization is dependent upon the level of endcapping material added to the reaction vessel.
  • the hydrophilic endcapping material is present in a sufficient quantity so as to provide about twice the number of equivalents as are required to theoretically react all of the isocyanate-functional material. This ensures that all molecules are terminated with the hydrophilic material.
  • the solvent can be removed by standard methods known in the industry and the thickener can be diluted to the desired solids level in Butyl Carbitol ® and water.
  • NCO Desmodur W ® (dicyclohexylmethane-4,4' - diisocyanate)
  • 1,10 DIOL is 1,10-decanediol
  • Paint viscosities were measured after 24 hours by a Stormer visc ⁇ meter (50 to 200 sec “1 shear rate, Krebs Units) and a cone and plate rheometer (10,000 sec “1 shear rate) and tabulated as follows: EX__ KU Hi ⁇ h Shear Vise (10.000 sec "1 )

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne des épaississants du type polyuréthane particulièrement utiles pour les peintures et les revêtements, comprenant le produit de réaction d'un composé à groupes isocyanate fonctionnels, d'un polyéther polyol et d'un composé hydrophile difonctionnel protecteur, capable de réagir avec les isocyanates, aux extrémités.
EP96919209A 1995-06-07 1996-06-06 Epaississants du type polyurethane avec des extremites protegees par des groupes hydrophiles Withdrawn EP0830413A4 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US48380395A 1995-06-07 1995-06-07
US483803 1995-06-07
PCT/US1996/009514 WO1996040820A1 (fr) 1995-06-07 1996-06-06 Epaississants du type polyurethane avec des extremites protegees par des groupes hydrophiles

Publications (2)

Publication Number Publication Date
EP0830413A1 true EP0830413A1 (fr) 1998-03-25
EP0830413A4 EP0830413A4 (fr) 1998-07-01

Family

ID=23921599

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96919209A Withdrawn EP0830413A4 (fr) 1995-06-07 1996-06-06 Epaississants du type polyurethane avec des extremites protegees par des groupes hydrophiles

Country Status (5)

Country Link
EP (1) EP0830413A4 (fr)
JP (1) JPH11507405A (fr)
AU (1) AU6160696A (fr)
BR (1) BR9609025A (fr)
WO (1) WO1996040820A1 (fr)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5973063A (en) * 1997-09-24 1999-10-26 Rheox, Inc. Polyurethane thickeners useful for clear and high gloss aqueous based systems a process for providing rheological properties to clear aqeous-based systems using such thickeners and clear aqueous-based systems containing such thickeners
US6433056B1 (en) 1997-10-17 2002-08-13 Hercules Incorporated Fluidized polymer suspension of hydrophobically modified poly(acetal- or ketal-polyether) polyurethane and polyacrylate
DE19945574A1 (de) * 1999-09-23 2001-04-05 Basf Coatings Ag Verwendung assoziativer Verdickungsmittel auf Polyurethanbasis und/oder von Dipropylenglykolmonoalkylethern zur Unterdrückung optischer Fehlstellen in farb- und/oder effektgebenden Mehrschichtlackierungen oder deren Reparaturlackierungen
GB0222522D0 (en) * 2002-09-27 2002-11-06 Controlled Therapeutics Sct Water-swellable polymers
US8691907B2 (en) 2010-11-23 2014-04-08 Valspar Sourcing, Inc. Water-borne primer
JP6072001B2 (ja) * 2012-03-13 2017-02-01 住友精化株式会社 化粧料組成物
KR101630161B1 (ko) * 2014-07-25 2016-06-14 한국화학연구원 열안정성이 우수한 탄성 폴리우레탄의 중합 방법 및 이로부터 제조된 탄성 폴리우레탄 중합체
JPWO2020121577A1 (ja) * 2018-12-13 2021-10-21 Jnc株式会社 エポキシ化合物
FR3111893B1 (fr) * 2020-06-30 2023-04-28 Coatex Sas Composé triuréthane modificateur de rhéologie
CN112961317B (zh) * 2021-02-07 2022-06-10 武汉纺织大学 具有阴阳两性离子核的星型聚氨酯增稠剂及其制备方法
CN112898529B (zh) * 2021-02-07 2022-06-07 武汉纺织大学 具有阳离子核的非对称星型聚氨酯增稠剂及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4298511A (en) * 1980-08-01 1981-11-03 Ppg Industries, Inc. Urethane rheology modifiers and compositions containing same
EP0307775A2 (fr) * 1987-09-18 1989-03-22 Rheox International, Inc. Agent épaississant d'un polyuréthane modifié dispersible dans l'eau ayant une viscosité améliorée à taux de cisaillement élevé dans des systèmes aqueux
EP0639595A1 (fr) * 1993-08-16 1995-02-22 Bayer Ag Polyuréthanes utilisés comme agents d'épaississant et leur utilisation pour épaississement des systèmes aqueux

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3607822A (en) * 1967-03-23 1971-09-21 Takeda Chemical Industries Ltd Thixotropical polyurethane compositions
US3923926A (en) * 1974-01-29 1975-12-02 Dai Ichi Kogyo Seiyaku Co Ltd Thixotropic polyurethane composition

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4298511A (en) * 1980-08-01 1981-11-03 Ppg Industries, Inc. Urethane rheology modifiers and compositions containing same
EP0307775A2 (fr) * 1987-09-18 1989-03-22 Rheox International, Inc. Agent épaississant d'un polyuréthane modifié dispersible dans l'eau ayant une viscosité améliorée à taux de cisaillement élevé dans des systèmes aqueux
EP0639595A1 (fr) * 1993-08-16 1995-02-22 Bayer Ag Polyuréthanes utilisés comme agents d'épaississant et leur utilisation pour épaississement des systèmes aqueux

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO9640820A1 *

Also Published As

Publication number Publication date
JPH11507405A (ja) 1999-06-29
AU6160696A (en) 1996-12-30
WO1996040820A1 (fr) 1996-12-19
EP0830413A4 (fr) 1998-07-01
BR9609025A (pt) 1999-06-29

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