WO1993018851A2 - Agent tensioactif - Google Patents

Agent tensioactif Download PDF

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Publication number
WO1993018851A2
WO1993018851A2 PCT/GB1993/000524 GB9300524W WO9318851A2 WO 1993018851 A2 WO1993018851 A2 WO 1993018851A2 GB 9300524 W GB9300524 W GB 9300524W WO 9318851 A2 WO9318851 A2 WO 9318851A2
Authority
WO
WIPO (PCT)
Prior art keywords
surfactant
dispersion
residue
chains
carboxylic ester
Prior art date
Application number
PCT/GB1993/000524
Other languages
English (en)
Other versions
WO1993018851A3 (fr
Inventor
Derrick Clifford Dobson
Original Assignee
Imperial Chemical Industries Plc
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 Imperial Chemical Industries Plc filed Critical Imperial Chemical Industries Plc
Priority to CA002131895A priority Critical patent/CA2131895A1/fr
Priority to EP93905578A priority patent/EP0631522A1/fr
Priority to JP5516348A priority patent/JPH07504846A/ja
Priority to KR1019940703246A priority patent/KR100250545B1/ko
Priority to AU36463/93A priority patent/AU672598B2/en
Publication of WO1993018851A2 publication Critical patent/WO1993018851A2/fr
Publication of WO1993018851A3 publication Critical patent/WO1993018851A3/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
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/34—Higher-molecular-weight carboxylic acid esters
    • 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
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
    • C08G81/025—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/246—Intercrosslinking of at least two polymers

Definitions

  • This invention relates to a surfactant, a method of making it, a dispersion containing the surfactant and a dispersed solid, a polymer composition that comprises the surfactant and a plasticiser, a method for making the dispersion, a dispersible solid comprising the surfactant, and a product coated with material comprising the discontinuous phase of the dispersion.
  • a surfactant is characterised by a plurality of addition-copolymer chains, on each chain an average of at least 0.5 adsorptive or chemisorptive groups and at least one monovalent polyether residue; and between the chains at least one divalent polyether residue.
  • adsorptive and chem isorpt ive herein indicate that the chains of the surfactant are capable of adsorption or chemisorption to the surface of a phase other than that which is or comprises the surfactant.
  • the surfactant has sufficient solubility as such or as a salt in a liquid to exert surface activity, either in that liquid or on the surface of a sol id to which it is applied by way of such a solution.
  • the surfactant is mainly a two-dimensional molecule, it may be at least partly three-dimensional, provided that it has sufficient solubility.
  • the addition-copolymer chains may consist of
  • the carboxyl-carrying units may be for example (meth)acrylic units, but are preferably 1,2-dicarboxylic units such as maleic units.
  • the number of such carboxyl groups per 100 addition-copolymerised monomer residues in their overall relative proportions is preferably in the range of 25 to 60, especially 45 to 55.
  • the acid value of the addition-copolymer chains, assuming hydrolysis of any anhydride units is suitably in the range of 150-350, especially 250-310, mg KOH/g.
  • the free carboxylic acid groups in each chain are optionally salified with for example a plurality of monovalent cations such as alkali metal, e.g. sodium, or ammonium ions.
  • the other units may for example comprise ethylene, vinyl esters, vinyl ethers or acrylic esters, but are most conveniently styrene.
  • the average molecular weight of each of the addition-copolymer chains is suitably in the range of 1000 to 5000, especially 1500 to 300.
  • the monovalent polyether residue is suitably derived from an ether-terminated polyalkylene glycol.
  • Such polyalkylene glycol (apart from its terminating hydrocarbyloxy group) has an oxygen-to-carbon ratio preferably in the range of 0.25 to 0.33. Its average molecular weight is preferably in the range of 250 to 5000, especially 300 to 400 including the terminating hydrocarbyloxy group.
  • That group is preferably C 1-4 (lower) alkyl or phenyl.
  • the divalent polyether residue is conveniently the same in oxygen-to-carbon ratio as the monovalent residue.
  • Its average molecular weight is preferably in the range of 150 to 1000, especially 150 to 300.
  • the invention provides in its second aspect a method of making the the above particular embodiment of the surfactant of the present invention which is characterised inter alia by: (i) a plurality of copolymer chains; and
  • step (b) reacting the product of step (a) in esterifying conditions with a divalent polyether alcohol.
  • esterifying includes transesterifying and the term “esterifiable” includes transesterifiable.
  • the addition-copolymer of carboxyl-carrying and other ethylenic monomers may be a commercially available addition-copolymer, such as SMA 3000A (Atochem UK Limited).
  • the addition-copolymer may be prepared by the prior process step of copolymerising ethylenic monomers corresponding to the carboxyl-carrying and other monomers of the addition-copolymer chains. Conventional procedures using e.g. peroxide catalysts may be used.
  • the copolymerisation reaction is preferably controlled to give an average molecular weight of each of the addition-copolymer chains in the relevant above ranges.
  • both reaction steps may be carried out concurrently, but preferably step (a) is substantially completed before adding the divalent polyether alcohol.
  • step (a) in step (a), some of the carboxy l ic groups are left for esterification in step (b).
  • step (a) a great proportion or all of the carboxyl groups are reacted in step (a), and the divalent polyether alcohol reacts by transesterification in step (b).
  • the carboxyl-carrying monomer unit is preferably a 1,2-dicarboxylic unit such as maleic anhydride; in such case, esterification in step (a) (e.g. with or with a derivative of an ether-terminated polyalkylene glycol), and preferably also in step (b) is carried out by ring-opening.
  • esterification in step (a) e.g. with or with a derivative of an ether-terminated polyalkylene glycol
  • step (b) is carried out by ring-opening.
  • the necessary control of the reaction is preferably effected by control of the proportions of the reactants.
  • alkali e.g. sodium hydroxide or ammonia (e.g. at 20 to 100, typically 60oC in the case of alkali) to increase solubility in water.
  • alkali e.g. sodium hydroxide or ammonia (e.g. at 20 to 100, typically 60oC in the case of alkali) to increase solubility in water.
  • the relative proportions of the addition-copolymer, the monovalent polyether alcohol and the divalent polyether alcohol should be such as to
  • (b) suitably not give more than 10 of such chains per surfactant molecule, because of the resulting high viscosity.
  • the proportions are preferably in the following ranges defined by mole equivalent fractions of esterifiable carboxyl and alcoholic hydroxyl:
  • step (a) and step (b) both reaction steps are carried out at temperatures typically in the range of 140o - 180oC.
  • a solvent for example a hydrocarbon boiling in that range may be present, but it is usually preferred to carry it out in the melt.
  • One embodiment of the particular surfactant of the present invention is characterised by a carboxylic ester group having as its alcohol residue e.g. C 1-20 hybrocarbyl.
  • Such an ester group may be incorporated in the surfactant molecule by esterification or by use of a corresponding monomer in the production of the initial addition-copolymer.
  • the invention in a third aspect provides a dispersion in a liquid characterised by containing a dispersion-stabilising quantity of the surfactant.
  • the dispersion is characterised by containing a dispersion-stabilising quantity of the particular surfactant of the present invention
  • the dispersion may also contain a minor proportion of a material characterised by the following features:
  • the surfactant of the present invention i.e. an uncrosslinked form of the surfactant of the present invention, which may e.g. be present in the product of the present method for the particular embodiment of the surfactant of the present invention.
  • the material of the discontinuous phase of the dispersion is preferably an inorganic solid, especially a crystalline oxide or combination of oxides, particularly having at least on its surface, a combination of a volatile oxide and an involatile oxide.
  • the material of the discontinuous phase of the dispersion is preferably an inorganic crystalline carbonate, basic carbonate or hydroxide. It preferably has a crystallographic face similar to the 001 face of calcite.
  • the involatile oxide component of such material of the discontinuous phase of the dispersion is preferably at least as strong a base as magnesium oxide.
  • Other oxides include those of aluminium, copper, zinc, vanadium, chromium, manganese, iron, cobalt and nickel and compounds which include mixtures thereof, such as clays, spinel precursors and malachites.
  • the dispersion is especially suitable for solid particles of high aspect ratio, for example 5:1 to 50:1.
  • the distance between the carboxyl groups of the surfactant is chosen to match the crystallographic lattice parameters of the dispersed material.
  • the carboxyl groups in the addition-copolymer chains are su itab ly separated by 4 ethylene oxide residues. It is believed that the surfactant is then substantially completely adsorbed on the dispersed phase, thereby leading to an acceptable charge density at the surface, tending to act against flocculation and for low viscosity. If the number of carboxyl groups per unit length of the surfactant molecule chains were too great, the surfactant would not be uniformly and completely adsorbed.
  • the adsorption may actually be chemisorptive in nature.
  • the liquid forming the continuous phase of the dispersion typically is or comprises water, but may be or comprise a highly polar organic liquid.
  • the dispersion may comprise other ingredients, such as pigments, texturising agents, perfumes and disinfectants, and other surfactants and polymers.
  • a preferred dispersion has a high solids content of 20-80% w/w, especially 25-75% w/w.
  • the dispersion may typically have a relatively low viscosity, and its rheological properties may be adjusted with considerable freedom by means of additives.
  • the dispersion of the present invention may have any rheology between mobile and thixotropic using additives.
  • the dispersion is suitable for coating solid substrate surfaces with the dispersed solid.
  • a dispersion comprising fine particles is especially suitable as a printing ink of low viscosity with good stability against flocculation, e.g. for wallpapers, or for applying surface fire-proofing or making abrasive papers.
  • the dispersion may be caused or allowed to settle and the precipitate may be collected and dried.
  • the dried material may, optionally after milling, be redispersed.
  • the material may be redispersed in an organic medium, especially a plasticised polymer.
  • the invention accordingly provides in its fourth aspect a composition, characterised in that it comprises a polymer containing a plasticiser and a solid dispersed material having a surfactant of the present invention adsorbed on its surface.
  • the polymer is especially polyvinyl chloride or a copolymer of vinyl chloride, and the plasticiser is especially a dialkyl phthalate, e.g. dioctyl phthalate.
  • the invention in a fifth aspect provides a method for making a dispersion according to the third aspect, characterised by incorporating with the sol id a quantity of a surfactant of the present invention to adsorb onto the surface of the solid to an extent which is sufficient to stabilise a dispersion of the solid in the liquid.
  • this is a quantity such as to adsorb onto at least half of the relevant adsorptive sites on the surface.
  • incorporation of the surfactant of the present invention may include intensive mixing with the solid, for example homogenisation under high shear to break down secondary aggregates of the solid and/or to effect further comminution.
  • the surfactant of the present invention is in the form of a salt, and the nature of the interaction between the surfactant and the solid is chemisorptive, it may be desirable to include pH adjustment in the incorporation method to neutralise alkali or ammonia liberated by chemisorption of carboxylic acid groups to the solid surface.
  • the invention in its sixth aspect provides a redispersible solid comprising fine particles having a surfactant of the present invention adsorbed or chemisorbed on its surface.
  • the surfactant will be adsorbed in a quantity which is sufficient to stabilise a dispersion of the solid in a liquid, preferably sufficient to adsorb or chemisorb onto at least half of the relevant adsorptive or chemisorptive sites on the surface.
  • the redispersible solid is most conveniently made by drying the dispersion of the third aspect of the invention, but may be made by dry-mixing or melt-mixing of the solid with the surfactant.
  • the invention in a seventh aspect provides a method of coating a substrate with the discontinuous phase of a dispersion of the third aspect of the invention, which comprises applying the dispersion to the substrate.
  • Any convenient method may be used, for example intaglio printing, padding, brushing, spraying, doctoring and reverse-roll coating.
  • the process may include preliminary adjustment of the rheology of the dispersion using additives.
  • the liquid forming the continuous phase of the dispersion typically is removed during the coating process e.g. by evaporation.
  • the dispersion is especially suitable for roller-coating paper at a shear rate of less than l sec - 1 .
  • the invention accordingly provides in its eighth aspect a product coated with material comprising the discontinuous phase of the dispersion of the third aspect of the invention.
  • Examples of such products include in particular printed papers, e.g. wallpapers, fire-proofed papers and abrasive papers.
  • the present invention is illustrated by the following Example.
  • SMA styrene maleic anhydride addition-copolymer
  • MeOPEG methoxy polyethylene glycol
  • PEG polyethylene glycol
  • the mixture remained liquid and of stable viscosity.
  • the product was cooled to 120oC and poured out.
  • a sample was dissolved over several hours in dilute sodium hydroxide at 60oC to give a solution of salified surfactant of final pH of 7.5 to 8.5.
  • This surfactant is referred to as "B" below.
  • aqueous slurries l and Il were made up using 100g solids in aqueous solutions of surfactants made according to (a) above: l "Ultracarb", 30% w/w sol ids content (RTM, commercially available from Microfine Ltd, a naturally occurring crystalline mineral composed of approximately equal amounts of huntite and hydromagnesite with a lamellar crystal habit with an aspect ratio in the range of 5:1 to 20:1 which consequently forms aqueous slurries of high viscosity) with
  • Surfactant A 1.5% w/w on Ultracarb.
  • Il "Calopake F” 46.8% w/w solids content (commercially available from Rhone-Poulenc, a precipitated calcium carbonate of particle size 2.1 ⁇ Stokes equivalent diameter) with
  • Surfactant B 1.5% w/w on Calopake F. Addition was made stirring at first at 250 rpm, increasing to 500 rpm, as the viscosity rose; the product was stirred for a further 10 min.
  • the dispersion was then stored at room temperature for up to 6 days.
  • the viscosity was measured at intervals using a Brookf ield viscometer at two rpm levels.
  • Precipitated calcium carbonate of particle size 4.5 ⁇ was aqueous slurried at a solids content of 14.9% w/w and heated with agitation to 85oC.
  • a control sample was made by applying 1.6% w/w of stearic acid to the precipitated calcium carbonate by slurrying in ammonium stearate solution, then filtering, drying and milling in the same way.
  • a PVC masterbatch was prepared from: Corvic P706 emulsion PVC (ICI) 406G
  • the formulations were prepared by mixing and then triple roller-milling the following:
  • the rheological properties of these formulations were measured using a Carri-Med rheometer in controlled stress mode.
  • the measuring system was a 4cm parallel plate with a 200 ⁇ gap.
  • a linked flow/creep shear stress programme was used with the fol lowing parameters:
  • the PVC plastisol formulation using surfactant B gave a Daniel gauge measurement of 1mm compared with 9mm for the control formulation using stearic acid.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

Un agent tensioactif se caractérise par la présence de plusieurs chaînes copolymères d'addition, par la présence, sur chaque chaîne, en moyenne d'au moins un demi-groupe permettant l'adsorption chimique et d'au moins un résidu de polyéther monovalent, et par la présence, entre ces chaînes, d'au moins un résidu de polyéther divalent. On décrit le procédé permettant de fabriquer cet agent, une dispersion qui contient l'agent et un solide dispersé, une composition à base de polymères comprenant l'agent et un plastifiant, un procédé de fabrication de cette dispersion, un solide à mettre en dispersion et qui contient cet agent, ainsi qu'un produit recouvert d'un matériau qui comprend cette dispersion en phase discontinue.
PCT/GB1993/000524 1992-03-16 1993-03-12 Agent tensioactif WO1993018851A2 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
CA002131895A CA2131895A1 (fr) 1992-03-16 1993-03-12 Surfactif
EP93905578A EP0631522A1 (fr) 1992-03-16 1993-03-12 Agent tensioactif
JP5516348A JPH07504846A (ja) 1992-03-16 1993-03-12 界面活性剤
KR1019940703246A KR100250545B1 (ko) 1992-03-16 1993-03-12 계면활성제
AU36463/93A AU672598B2 (en) 1992-03-16 1993-03-12 Surfactant

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB929205701A GB9205701D0 (en) 1992-03-16 1992-03-16 Surfactant
GB9205701.7 1992-03-16

Publications (2)

Publication Number Publication Date
WO1993018851A2 true WO1993018851A2 (fr) 1993-09-30
WO1993018851A3 WO1993018851A3 (fr) 1993-10-28

Family

ID=10712227

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1993/000524 WO1993018851A2 (fr) 1992-03-16 1993-03-12 Agent tensioactif

Country Status (8)

Country Link
EP (1) EP0631522A1 (fr)
JP (1) JPH07504846A (fr)
KR (1) KR100250545B1 (fr)
AU (1) AU672598B2 (fr)
CA (1) CA2131895A1 (fr)
GB (1) GB9205701D0 (fr)
NZ (1) NZ249574A (fr)
WO (1) WO1993018851A2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5703167A (en) * 1993-12-24 1997-12-30 Marubishi Oil Chemical Co., Ltd. Modifier for resin and rubber

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0064225A2 (fr) * 1981-04-27 1982-11-10 Hoechst Aktiengesellschaft Utilisation d'oxalkylates estérifiés comme adjuvants pour colorants et les préparations tinctoriales correspondantes
EP0131558A2 (fr) * 1983-07-06 1985-01-16 Bergvik Kemi AB Agent dispersant
EP0233684A1 (fr) * 1986-01-30 1987-08-26 Imperial Chemical Industries Plc Agent dispersant
EP0373621A2 (fr) * 1988-12-16 1990-06-20 Nippon Oil And Fats Company, Limited Copolymère d'un éther polyoxyalkylène alkényl et d'un ester d'acide maléique et son utilisation
EP0403197A2 (fr) * 1989-06-16 1990-12-19 ARCO Chemical Technology, L.P. Compositions de polymères-polyol contenant un agent de dispersion polyol-polyacrylate greffé
EP0459651A2 (fr) * 1990-05-16 1991-12-04 Shell Internationale Researchmaatschappij B.V. Dispersions de copolymère acrylique stable

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0064225A2 (fr) * 1981-04-27 1982-11-10 Hoechst Aktiengesellschaft Utilisation d'oxalkylates estérifiés comme adjuvants pour colorants et les préparations tinctoriales correspondantes
EP0131558A2 (fr) * 1983-07-06 1985-01-16 Bergvik Kemi AB Agent dispersant
EP0233684A1 (fr) * 1986-01-30 1987-08-26 Imperial Chemical Industries Plc Agent dispersant
EP0373621A2 (fr) * 1988-12-16 1990-06-20 Nippon Oil And Fats Company, Limited Copolymère d'un éther polyoxyalkylène alkényl et d'un ester d'acide maléique et son utilisation
EP0403197A2 (fr) * 1989-06-16 1990-12-19 ARCO Chemical Technology, L.P. Compositions de polymères-polyol contenant un agent de dispersion polyol-polyacrylate greffé
EP0459651A2 (fr) * 1990-05-16 1991-12-04 Shell Internationale Researchmaatschappij B.V. Dispersions de copolymère acrylique stable

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0631522A1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5703167A (en) * 1993-12-24 1997-12-30 Marubishi Oil Chemical Co., Ltd. Modifier for resin and rubber

Also Published As

Publication number Publication date
KR950700785A (ko) 1995-02-20
CA2131895A1 (fr) 1993-09-30
GB9205701D0 (en) 1992-04-29
AU672598B2 (en) 1996-10-10
NZ249574A (en) 1996-12-20
AU3646393A (en) 1993-10-21
JPH07504846A (ja) 1995-06-01
WO1993018851A3 (fr) 1993-10-28
KR100250545B1 (ko) 2000-04-01
EP0631522A1 (fr) 1995-01-04

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