Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D19/00—Degasification of liquids
  • B01D19/02—Foam dispersion or prevention
  • B01D19/04—Foam dispersion or prevention by addition of chemical substances
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/72—Ethers of polyoxyalkylene glycols
  • C11D1/721—End blocked ethers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D19/00—Degasification of liquids
  • B01D19/02—Foam dispersion or prevention
  • B01D19/04—Foam dispersion or prevention by addition of chemical substances
  • B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/0005—Other compounding ingredients characterised by their effect
  • C11D3/0026—Low foaming or foam regulating compositions
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
  • D21C3/00—Pulping cellulose-containing materials
  • D21C3/22—Other features of pulping processes
  • D21C3/28—Prevention of foam
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
  • D21H21/06—Paper forming aids
  • D21H21/12—Defoamers

Definitions

• the present invention relates to a polyalkylene glycol for use as a foam control agent, and more particularly, for use as a foam control agent in aqueous systems of the pulp and paper industry.
• Co- and homopolymers of alkylene oxide are widely used as non-ionic surfactants, foam control agents, mineral wetting agents, emulsifiers, de-emulsifiers, dispersants and synthetic lubricants.
• polyoxyalkylene copolymers made from ethylene oxide, propylene oxide and 1,2-butylene oxide represent a major class of such materials.
• An example of such compounds are those of the Formula (I) R'KOR' OR 1 [ ) g (OR 12 ) h OH]i (I) wherein R 9 is a Cj to C o alkyl or Cj to C 0 acyl group, or an aliphatic hydrocarbon having 1-6 valencies.
• R is an alkylene group having 2 to 4 carbon atoms
• R u is an alkylene group having 2 to 4 carbon atoms
• R is an alkylene group having 2 to 4 carbon atoms
• f, g and h are integers of 0 to 80
• i is an integer of 1 to 6.
• Polylalkylene glycol derivatives are also known to be useful for lubricating applications.
• JP 09-117608 discloses a very broad class of defoaming agents which have only a slight susceptibility to combustion or ignition.
• the agents are polymers of one or more monomers and, if they are copolymers, they can be random or block copolymers. They may be terminated by a hydrogen atom or an organic group with not more than 24 carbon atoms, and they may contain ester, ether or methane linkages.
• a first aspect of the present invention comprises the use of a block copolymer containing two blocks and having the general formula (III) R 13 [(OR 14 ) j (OR 16 ) ⁇ OR 17 ] m (III) wherein R 13 is the residue of an organic initiator; R 14 is one or more C 2 -C 4 alkylene groups;
• R 16 is one or more C 2 -C 4 alkylene groups; provided that R 14 and R 16 must be different from each other;
• R 17 is a Ci-Cio alkyl group; j is an integer of 5 to 80; 1 is an integer of 1 to 80; and m is an integer of 1 to 6; as a foam control agent.
• R 17 is a methyl group.
• a further aspect of the invention provides a method of controlling foam in an aqueous environment, comprising incorporating into said environment a compound having the formula (III).
• a composition which comprises, as a foam control agent, a compound of the general formula III.
• a detergent composition may for example contain, in addition to the compound of the general formula III, a surfactant of either ionic or non-ionic character.
• the above compounds may for example be us in detergent formulations, especially industrial detergents, bottle washing and pulp and paper mill defoamers. They are particularly useful for controlling foam in aqueous industrial environments, particularly such environments having conditions of high pH and/or temperature, for example temperatures in excess of 100°C and a pH up to 14, such as in paper mill or pulp mill processing. Generally, they are effective in decreasing the foam level of aqueous media and in maintaining low foam levels, particularly in extreme media, typically media having a pH of less than 4 or greater than 10, for example black liquor produced in the pulp and paper industry.
• the compounds of formula III may be used with or without the presence of an additional anti-foaming compound, but it is a particular merit of the present invention that they may be used when appropriate as the only anti-foaming compound present.
• Polyalkylene glycol derivatives of the formula (III) can be prepared by suitable methods known in the art, for example as described in WO 01/57164 or in Methods A, B and C of EP 634467 A.
• the copolymer is prepared by first polymerising an alkylene oxide or mixture of alkylene oxides using an organic initiator corresponding to the group R .
• R may for example represent (i) an alkyl group which may be unsubstituted or substituted by one or more, preferably one or two, substituents selected from optionally alkyl -substituted cycloalkyl, aryl or heteroaryl groups; (ii) an optionally alkyl-substituted cycloalkyl, aryl or heteroaryl group; or (iii) an acyl group; each having up to 20 carbon atoms.
• the group R 13 has 1-6 valencies.
• the initiator may be mono-functional; examples include alcohols, amines, mercaptans, phenols, amino alcohols and mercapto alcohols. Hydroxyl and amino terminated initiators are preferred.
• the initiator may alternatively be polyfunctional.
• Preferred polyfunctional initiators have from 2 to 6 reactive hydrogens in the form of hydroxyl groups.
• the polyfunctional initiators include compounds of the formula R 20 (YH) P wherein R 20 is an aliphatic, aromatic or heterocyclic radical, p is at least 2, and each Y is O, S, NH or 1 1
• NR where R is hydrocarbyl.
• Preferred such initiators are diols, polyols, diamines, hydroxyamines and thiols, such as ethylene/propylene glycol, diethylene/dipropylene glycol, glycerine, trimethylol propane, pentaerythritol, ethylene diamine etc. Di- and, especially, tri-functional initiators are preferred for some applications. Mixtures of organic initiators may be employed.
• the copolymers of the present invention consist of two distinct blocks. Two or more alkylene oxides may be present in the first block of the polymer. A random configuration of the first block is obtained by polymerising more than one alkylene oxide simultaneously. Thus the initiator is reacted with one of ethylene oxide, propylene oxide, or butylene oxide, or a mixture thereof.
• the resulting product is then reacted with a different alkylene oxide or mixture of alkylene oxides to produce a two-block polymer.
• the resulting product will comprise a polyalkylene block copolymer terminating in a hydroxy group.
• This product is subsequently reacted further such that the hydrogen atom of the hydroxy group is converted to a Ci-Cjo alkyl group R .
• the H is converted to an alkyl group by reaction with, for example, the appropriate chloride.
• the polymerisation of alkylene oxides may be carried out in the presence of a catalyst. Any catalyst capable of promoting the necessary polymerisation reaction may be employed. Representative catalysts include alkali metal and alkaline earth hydroxides, and Lewis acids.
• Preferred catalysts are alkali hydroxides, particularly potassium hydroxide (KOH). Typical concentrations of catalysts are approximately 0.001 to 2 wt%, with approximately 0.01 to 1.0 wt% preferred. Catalyst neutralisation may be required prior to recovery.
• the copolymer of the present invention may be prepared at a reaction temperature of 75 to 175°C, preferably 85 to 150°C. These temperature ranges may be suitable for the formation of both blocks of the copolymer of the present invention. Reaction pressures range from, but are not limited to, 1 to 15 bar, preferably 6 to 10 bar. Preferably anhydrous conditions are employed. The reaction may be performed on a batch, semicontinuous, or continuous basis.
• R i3 represents a monovalent C 8 -C ⁇ 8 , preferably C 12 -C 13 , alkyl group; j is an integer 8 to 43; and 1 is an integer 1 to 10.
• R 14 is butylene oxide or, preferably, propylene oxide, or a mixture of the two, and R 16 is ethylene oxide.
• such a polymer has a molecular weight of 200 to 6000, preferably 400 to 4000, and most preferably 500 to 2500.
• the molecular weight of the first block is typically 200 to 5000, preferably 500 to 3000, most preferably 1000 to 2000; whilst the molecular weight of the second block is typically no more than 3000, preferably less than 1000 and most preferably less than 500.
• Such materials are especially suitable for use as a foam control agent for aqueous paper / pulp systems.
• R represents a polyvalent alkyl group, preferably a di- or especially, tri-valent alkyl group, preferably having from 2 to 6, especially three, carbon atoms; j is an integer 11 to 45; and 1 is an integer 35 to 52.
• R 14 is ethylene oxide and R 16 is butylene oxide or, preferably, propylene oxide, or a mixture of the two.
• a polymer has a molecular weight of 200 to 6000, preferably 400 to 5000, and most preferably 1000 to 5000.
• the molecular weight of the first block is typically 200 to 5000, preferably 500 to 3000, most preferably 500 to 2000; whilst the molecular weight of the second block is typically no more than 5000, preferably less than 4000 and most preferably less than 3000.
• Such materials are especially suitable for use in detergents, especially industrial detergents. Such materials can also find application in pulp and paper manufacture.
• the initiator is preferably reacted with a higher molecular weight alkylene oxide, for example propylene oxide, followed by reaction with a lower molecular weight alkylene oxide, for example ethylene oxide.
• the initiator is preferably reacted with a lower molecular weight alkylene oxide, for example ethylene oxide, followed by reaction with a higher molecular weight alkylene oxide, for example propylene oxide.
• Potassium hydroxide was added to glycerol as a catalyst. To this mixture was added ethylene oxide (26.2 parts molar) in a pressurised vessel inerted with nitrogen, reaction occurring at 120 to 130°C until a constant pressure was achieved. Propylene oxide (40 parts molar) was then added, reaction was maintained at a temperature of 120 to 130°C until the vessel pressure remained constant, such that the final product had a block structure with a theoretical molecular weight of 3563.
• Example 1 The polymers of Examples 1 and 2 were tested according to the following procedure, which is a variation of the standard test method IP 146/73. For comparison, the uncapped polymer prepared as an intermediate (i.e. prior to the reaction with methyl chloride) in Example 1 was also tested.
• the apparatus for performing the foaming test comprised a 1000 ml measuring cylinder immersed in a water bath at the appropriate temperature. 200ml of black liquor obtained from a Canadian mill were placed in the measuring cylinder and allowed to reach a temperature of 80°C. An air pipe having a diffuser stone at its open end was placed into the sample, and air blown through at a fixed rate for a set period of time. After a measured length of time the height of foam in the measuring cylinder was recorded. The results are shown in the following Table.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Dispersion Chemistry (AREA)
• Toxicology (AREA)
• Health & Medical Sciences (AREA)
• Polyethers (AREA)
• Detergent Compositions (AREA)
• Paper (AREA)
• Degasification And Air Bubble Elimination (AREA)

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• 2003
  • 2003-03-03 GB GBGB0304788.3A patent/GB0304788D0/en not_active Ceased
• 2004
  • 2004-03-02 EP EP04716269A patent/EP1599267A1/de not_active Withdrawn
  • 2004-03-02 CA CA002517973A patent/CA2517973A1/en not_active Abandoned
  • 2004-03-02 JP JP2006505903A patent/JP2006523527A/ja not_active Withdrawn
  • 2004-03-02 CN CNA2004800056815A patent/CN1756580A/zh active Pending
  • 2004-03-02 WO PCT/GB2004/000871 patent/WO2004078312A1/en not_active Ceased
  • 2004-03-02 RU RU2005129779/04A patent/RU2005129779A/ru not_active Application Discontinuation
  • 2004-03-02 KR KR1020057016344A patent/KR20050106074A/ko not_active Withdrawn

Non-Patent Citations (1)

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