WO2000027890A1 - Tensioactifs polymerisables - Google Patents

Tensioactifs polymerisables Download PDF

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Publication number
WO2000027890A1
WO2000027890A1 PCT/GB1999/003574 GB9903574W WO0027890A1 WO 2000027890 A1 WO2000027890 A1 WO 2000027890A1 GB 9903574 W GB9903574 W GB 9903574W WO 0027890 A1 WO0027890 A1 WO 0027890A1
Authority
WO
WIPO (PCT)
Prior art keywords
polymerisable
group
polymerisable surfactant
groups
catalyst
Prior art date
Application number
PCT/GB1999/003574
Other languages
English (en)
Inventor
Peter David Hasling
Original Assignee
Albright & Wilson Uk Limited
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
Priority claimed from GBGB9824267.0A external-priority patent/GB9824267D0/en
Priority claimed from GBGB9913034.6A external-priority patent/GB9913034D0/en
Application filed by Albright & Wilson Uk Limited filed Critical Albright & Wilson Uk Limited
Priority to AU63599/99A priority Critical patent/AU6359999A/en
Priority to EP99951024A priority patent/EP1175447A1/fr
Publication of WO2000027890A1 publication Critical patent/WO2000027890A1/fr

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Classifications

    • 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
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic

Definitions

  • the present invention relates to polymerisable surfactants comprising at least one hydrophobic polymerisable group which is linked by polyalkyleneoxy groups to a hydrophilic group.
  • the surfactants are particularly useful in emulsion-polymerised surface coatings.
  • the present invention also relates to a method of making the polymerisable surfactants, to uses thereof, and to surface coatings including the surfactants.
  • the object of the present invention is to provide a polymerisable surfactant which is particularly suitable for use in surface coatings, which has improved water resistance and which reduces the problems of "bloom” and “blush” in coatings.
  • a method of making such a polymerisable surfactant is also provided.
  • X is between 5 and 40
  • R H or CH 3 or COOR'
  • R' H or CH 3
  • R" H, CH 3 or C 2 H 5
  • R" ' d - C 20 alkyl
  • the hydrophobic polymerisable group may alternatively be maleate, fumarate, crotonate or isocrotonate.
  • x is between 10 and 30, more preferably 17 and 22, most preferably x is 20.
  • the oxyalkylene groups represented by [CH 2 CHR"O] comprise mainly propyleneoxy groups.
  • the oxyalkylene groups may be propyleneoxy groups.
  • at least 90%, more preferably at least 95% and most preferably at least 98% of the oxyalkylene groups are propyleneoxy groups.
  • the balance of the oxyalkylene groups not being propyleneoxy groups is preferably selected from ethyleneoxy or butyleneoxy groups.
  • the hydrophilic group represented by PO (OY) m is a phosphate group, i.e. Y represents hydrogen.
  • the hydrophilic group may be a water-soluble phosphate salt group, for example alkali metal phosphate, in which Y represents an alkali metal atom.
  • surfactants according to the present invention exhibit improved water-resistance in comparison with prior-art surfactants because they do not include a non-ionic hydrophilic group, such as polyethylene oxide.
  • a hydrophilic non-ionic group is present which can give rise to poor water sensitivity in a final coating. Ionic groups are only hydrophilic when ionised and therefore the resultant dried coatings are less hydrophilic and less water sensitive than coatings including non- ionic hydrophiles.
  • the present invention provides a method of making a polymerisable surfactant according to the first aspect of the present invention, the method comprising the steps of:
  • the polyalkoxylation process step may be carried out with the aid of a catalyst.
  • the catalyst is preferably a catalyst for alkoxylation which does not catalyse the polymerisation of unsaturated groups of the hydrophobic group.
  • a preferred catalyst for alkoxylation is a strong Lewis acid such as boron trifluoride.
  • a portion, most preferably a small portion, of the catalyst for alkoxylation is added to the unsaturated carboxylic acid before the alkylene oxide.
  • the bulk of the catalyst is added with the alkylene oxide.
  • a remaining portion of the catalyst is preferably added after completion of addition of the alkylene oxide to maximise conversion as the catalyst has a short active life.
  • Hydroquinone is preferably added to the reaction mixture after the addition of the remaining portion of the catalyst. The hydroquinone is added to inhibit autopolymerisation of the unsaturated groups of the hydrophobic group. Any unreacted alkylene oxide may be removed, preferably by sparging with air.
  • the reaction of the unsaturated carboxylic acid and the alkylene oxide is carried out in an inert atmosphere, for example under nitrogen.
  • the reaction mixture may be stirred.
  • moisture is excluded from the reaction mixture.
  • the alkylene oxide is added continuously at a constant rate over a given time period, suitably 90 minutes.
  • the phosphation step is preferably carried out by means of phosphorus pentoxide.
  • the most preferred form of phosphorus pentoxide is the solid form.
  • the phosphorus pentoxide may be added over a given period of time, preferably one hour.
  • the resulting mixture is maintained at an elevated temperature, such as 80°C, for about 4 hours, with stirring.
  • the product of the phosphation step is treated to remove any free phosphoric acid.
  • the presence of phosphoric acid can be detrimental to the final product containing the surfactant.
  • Deionised water may be used to wash the product.
  • the present invention provides a coating including a polymerisable surfactant according to the first or second aspect of the invention.
  • the coating is an acrylic coating, an acrylic or vinyl halide latex composition, a latex paint, a coating for contact lenses, a coating to modify the surface properties of organic polymers, glass, graphite, metals, a coating to convert hydrophilic articles to hydrophobic articles and vice versa, a coating for fabrics.
  • the coating is an emulsion polymerised coating.
  • the present invention also provides adhesives, flocculants, resinous binders, polymer materials for medical or dental use and oil-displacing fluids including the polymerisable surfactant of the present invention.
  • a reactor comprising a 1 -litre jacketed vessel fitted with overhead stirrer, septum cap, nitrogen bleed, condenser, peristaltic addition tube and thermometer was heated to 120°C for 1 hour under nitrogen and the flask lid flamed to ensure dryness. The reactor was then cooled to room temperature.
  • Methacrylic acid 28.3g, 0.329 mol
  • boron trifluoride etherate 1.0 ml
  • Propylene oxide was then added to the stirred reaction mixture at a constant rate over 90 minutes, using a peristaltic pump.
  • the remainder of the BF 3 was added over 120 minutes via a screw-feed syringe pump.
  • the additions commenced the temperature rose to 40 °C and the reactor jacket was cooled to - 5°C. Care was taken to ensure that the reaction temperature was maintained between 40 and 50 °C throughout the propylene oxide addition.
  • Butylene oxide 142. Og (1.970 mol)
  • a reactor comprising a 1-litre jacketed vessel fitted with overhead stirrer, septum cap, nitrogen bleed, condenser, peristaltic addition tube and thermometer was heated to 120°C for 1 hour under nitrogen and the flask lid flamed to ensure dryness. The reactor was then cooled to room temperature.
  • Methacrylic acid 28.3g, 0.329 mol
  • boron trifluoride etherate 1.0 ml
  • Propylene oxide 114.5g
  • butylene oxide 142. Og
  • the remainder of the BF 3 was added over 120 minutes, via a screw-feed syringe pump.
  • the additions commenced the temperature rose to 40° C and the reactor jacket was cooled to -5°C. Care was taken to ensure that the reaction temperature was maintained between 40 and 50°C throughout propylene oxide and butylene oxide addition.
  • Example 7 The procedure of Example 7 (above) was repeated using 5.6g Empimin OT60 (a dialkyl sulfosuccinate made by Albright & Wilson Limited) in place of PP20MP.
  • Empimin OT60 a dialkyl sulfosuccinate made by Albright & Wilson Limited
  • the gloss was measured at 20°C and 60°C using a Rhopoint "Novo-Gloss" glossmeter.
  • Adhesion was tested on panels of mild steel and aluminium by applying emulsion to the panels as described in (a) and according to BS 39000: E6 : 1992.
  • Example 7 The polymer latex prepared in Example 7 having 1.5% and 3.0% polymer has been compared with that produced in Example 8.
  • the coatings produced from dried films of the latices have also been compared.
  • the latex produced using PP20MP (Example 7) has higher gloss, reduced water- sensitivity and increased adhesion to aluminium and steel substrates than that prepared with Empimin OT60 (Example 8) .

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Paints Or Removers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Cette invention a trait à un tensioactif polymérisable possédant au moins un groupe polymérisable hydrophobe lié par des groupes polyalkylèneoxy à un groupe hydrophile. Ce tensioactif polymérisable correspond à la formule générale: (RCH = CR'COO [CH2CHR''O]x)nPO (OY)m, formule dans laquelle n + m = 3, et où la valeur de x est comprise entre 5 et 40, R représente H ou CH3 ou COOR''', R' représente H ou CH3, R'' représente H, CH3 ou C2H5, R''' représente un alkyle porteur de 1 à 20 atomes de carbone et Y représente H ou un atome de métal alcalin.ette invention porte également sur un procédé de fabrication de ces tensioactifs et sur leur utilisation dans des revêtements de surface, afin d'améliorer l'imperméabilité à l'eau et de réduire la formation de « voile » et de « nébulosité » dans ces revêtements.
PCT/GB1999/003574 1998-11-06 1999-10-28 Tensioactifs polymerisables WO2000027890A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU63599/99A AU6359999A (en) 1998-11-06 1999-10-28 Polymerisable surfactants
EP99951024A EP1175447A1 (fr) 1998-11-06 1999-10-28 Tensioactifs polymerisables

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GBGB9824267.0A GB9824267D0 (en) 1998-11-06 1998-11-06 Polymerisable surfactants
GB9824267.0 1998-11-06
GB9913034.6 1999-06-05
GBGB9913034.6A GB9913034D0 (en) 1999-06-05 1999-06-05 Polymerisable surfactants

Publications (1)

Publication Number Publication Date
WO2000027890A1 true WO2000027890A1 (fr) 2000-05-18

Family

ID=26314620

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1999/003574 WO2000027890A1 (fr) 1998-11-06 1999-10-28 Tensioactifs polymerisables

Country Status (3)

Country Link
EP (1) EP1175447A1 (fr)
AU (1) AU6359999A (fr)
WO (1) WO2000027890A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8022238B2 (en) 2009-03-20 2011-09-20 E. I. Du Pont De Nemours And Company Phosphate surfactants
US8163204B2 (en) * 2006-03-14 2012-04-24 Tda Research Nanoporous polymer electrolyte
CN109072020A (zh) * 2016-04-28 2018-12-21 日本瑞翁株式会社 自粘合性层

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3855364A (en) * 1973-01-05 1974-12-17 Alcolac Inc Phosphate esters of hydroxyalkyl acrylates and hydroxyalkyl methacrylates
FR2325662A1 (fr) * 1975-09-25 1977-04-22 Synres Internationaal Nv Procede de preparation d'emulsions aqueuses de polymeres d'addition avec emulsifiant incorpore
EP0458245A1 (fr) * 1990-05-21 1991-11-27 Nippon Paint Co., Ltd. Composition de revêtement aqueuse

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3855364A (en) * 1973-01-05 1974-12-17 Alcolac Inc Phosphate esters of hydroxyalkyl acrylates and hydroxyalkyl methacrylates
FR2325662A1 (fr) * 1975-09-25 1977-04-22 Synres Internationaal Nv Procede de preparation d'emulsions aqueuses de polymeres d'addition avec emulsifiant incorpore
EP0458245A1 (fr) * 1990-05-21 1991-11-27 Nippon Paint Co., Ltd. Composition de revêtement aqueuse

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8163204B2 (en) * 2006-03-14 2012-04-24 Tda Research Nanoporous polymer electrolyte
US8022238B2 (en) 2009-03-20 2011-09-20 E. I. Du Pont De Nemours And Company Phosphate surfactants
CN109072020A (zh) * 2016-04-28 2018-12-21 日本瑞翁株式会社 自粘合性层
US20190092980A1 (en) * 2016-04-28 2019-03-28 Zeon Corporation Self-adhesive layer
CN109072020B (zh) * 2016-04-28 2021-08-03 日本瑞翁株式会社 自粘合性层

Also Published As

Publication number Publication date
AU6359999A (en) 2000-05-29
EP1175447A1 (fr) 2002-01-30

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