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
  • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
  • C09K5/20—Antifreeze additives therefor, e.g. for radiator liquids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
  • C08L71/02—Polyalkylene oxides
• • 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
  • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
  • C08G2650/50—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing nitrogen, e.g. polyetheramines or Jeffamines(r)

Definitions

• the present invention relates to the use as antifreeze agent of a composition containing at least one polymer having a critical temperature of solubility in water, called LCST (Lower Critical Solution Temperature), ranging from 20 to 80 ° C.
• LCST Lower Critical Solution Temperature
• the field of the invention is more particularly that of antifreeze additives for compositions of the coolant type and in particular dedicated to use in the automotive, electronic or electrotechnical fields.
• the fluids used are typically mixtures of 60% by volume of water and 40% by volume of glycol.
• glycol in the water, such as ethylene glycol or propylene glycol, prevents the cooling fluid from freezing during storage at low temperatures.
• glycols would also have a protective effect against corrosion of the walls of the exchangers, in contact with these coolants.
• the presence of glycol in water has the major disadvantage of significantly reducing the thermal conductivity of the new fluid thus obtained. Since the thermal conductivity of the distilled water is 0.608 Wm ⁇ .K “1 for distilled water and 0.208 Wm ⁇ .K “ 1 for a glycol, it follows that the thermal conductivity of a A mixture of 60% by volume of water and 40% by volume of ethylene glycol is only 0.40 WV.K -1 , which is about 30% lower than that of water.
• thermal conductivity performances of the fluid therefore have a direct impact on the volume of the coolant reservoir, in particular on the gain of weight or space, but also on the recirculation pumps which will be less powerful (global energy balance).
• glycol (s) as anti-freeze additive has the major disadvantage of generating an additional cost in terms of electrical consumption of the recirculation pumps or in sizing of the installation, the weight and the congestion being added in addition. Therefore, there remains to this day a need for antifreeze additive to guarantee fluids containing the container, maintaining its fluidity at low temperatures with a thermal conductivity as close as possible to that of water.
• the present invention specifically aims to meet this need.
• the present invention relates to the use as antifreeze agent of a composition containing at least one polymer having a critical temperature of solubility in water, called LCST, ranging from 20 to 80 ° C. vs.
• LCST critical temperature of solubility in water
• the present invention relates to the use as anti-freeze agent of a composition containing at least one polymer chosen from polyetheramines having a critical water solubility temperature, termed LCST, ranging from 20 to 80 ° C. .
• LCST critical water solubility temperature
• the polymer in question according to the invention is used in an aqueous composition.
• LCST polymers considered according to the invention are therefore polymers which by a reversible phase change mechanism (hydrophilic / hydrophobic) separate from the water when the temperature of the fluid begins to heat above 20 ° C., thus creating a colloidal sol of hydrophobic particles.
• This phase change temperature is called LCST (Lower Critical Solution Temperature).
• the polymer shows a very high affinity with water which makes it completely soluble, and above this same temperature there is phase separation.
• this di-phasic medium is a significant increase in the volume concentration of water of the mixture and, consequently, in the thermal conductivity of the mixture, which then becomes almost equal to that of the distilled water.
• the system becomes monophasic again.
• the phenomenon is more specifically detailed in the examples which follow and which show that for aqueous compositions containing a compound having an LCST, the measured thermal conductivities increase significantly when the temperature is higher than its LCST.
• an aqueous composition containing a polymer as a polyetheramine having a LCST at 32 ° C shows a thermal conductivity greater than 16% based on the mixture 60% H 2 0 and 40%> propylene glycol at 45 ° C.
• polymers with an LCST have the particularity of not having the same rheological behavior below and above the hydrophilic / hydrophobic transition temperature.
• the present invention relates to an aqueous composition, useful as an antifreeze agent, comprising at least one polymer having a critical water solubility temperature, called LCST, ranging from 20 to 80 ° C and at least one alcohol.
• LCST critical water solubility temperature
• such a composition is dedicated to be diluted with water before use.
• the present invention relates to an aqueous composition useful as antifreeze agent comprising from 20 to 50% by weight of at least one polymer having a critical temperature of solubility in water, called LCST, ranging from 20 to 80 ° C and at least one alcohol.
• LCST critical temperature of solubility in water
• the present invention relates to an aqueous composition as defined above in which the polymer has a critical solubility temperature in water, called LCST, ranging from 25 to 50 ° C., preferably from 30 to 45 ° C. ° C, or even 30 to 40 ° C.
• LCST critical solubility temperature in water
• the present invention relates to an aqueous composition, as defined above, in which the polymer is chosen from polyetheramines, poly (N-isopropylacrylamide), polyvinylcaprolactams, polyvinylmethylether, polyoxazolines and hydroxyalkylcelluloses, and their copolymers.
• the polymer is chosen from polyetheramines, poly (N-isopropylacrylamide), polyvinylcaprolactams, polyvinylmethylether, polyoxazolines and hydroxyalkylcelluloses, and their copolymers.
• the present invention relates to an aqueous composition, useful as antifreeze agent, comprising from 20 to 50% by weight of at least one polymer selected from polyetheramines and at least one alcohol.
• the present invention relates to an aqueous composition, as defined above, wherein the polymer is O- (2-Aminopropyl) -O '- (2-methoxyethyl) polypropylene glyco 1.
• a composition according to the invention comprises at least one polymer having a critical temperature of solubility in water, called LCST, ranging from 20 to 80 ° C.
• critical water solubility temperature or "LCST” (Lower Critical Solution Temperature) means the critical temperature above which the polymer loses its solubility in water and below which it becomes soluble in water. 'water. According to the invention, this process is reversible.
• the polymer used in the context of the present invention has a critical solubility temperature in water, called LCST, ranging from 25 to 50 ° C., preferably from 30 to 45 ° C., or even from 30 to 40 ° C. vs.
• LCST critical solubility temperature in water
• the polymers considered according to the invention are uncrosslinked.
• the polymer having a critical solubility temperature in water, called LCST, ranging from 20 to 80 ° C. can be chosen from:
• non-crosslinked homopolymers or copolymers of monomers comprising at least one ether group such as poly (ethylene oxide),
• non-crosslinked homopolymers or copolymers of monomers comprising at least one alcohol group such as poly (hydroxyalkylacrylate),
• Polyetheramines poly (N-isopropylacrylamide) polyvinylcaprolactams, polyvinylmethylether, polyoxazolines and hydroxyalkylcelluloses and their copolymers are particularly suitable for the invention.
• polyetheramines and their copolymers which are suitable for the invention, mention may be made more particularly of monoamine polyetheramines and more particularly O- (2-aminopropyl) -O '- (2-methoxyethyl) polypropylene glycol which has an LCST at 32 ° C.
• polyetheramines particularly suitable for the invention can be used, for example those sold under the name Jeffamine ® M-600 ® or XTJ- ® 505, Jeffamine ® M-1000 ® or XTJ-506 ®, Jeffamine ® M-2005 ® and Jeffamine ® M-2070 ® , marketed by Huntsman.
• poly (N-isopropylacrylamide) and their copolymers that are suitable for the invention mention may be made more particularly of those having a molecular weight greater than 200 and less than 50,000, such as non-crosslinked homopolymers or copolymers of monomers containing an amide group such as poly (N-substituted acrylamide), homopolymers poly (N-isopropylacrylamide), copolymers of N-isopropyl-acrylamide and (meth) acrylic acid ester C 1 -C 1 s (by butyl acrylate) and copolymers of N-isopropylacrylamide and methacrylic acid.
• amide group such as poly (N-substituted acrylamide), homopolymers poly (N-isopropylacrylamide), copolymers of N-isopropyl-acrylamide and (meth) acrylic acid ester C 1 -C 1 s (by butyl acrylate) and copolymers of N-isoprop
• polyoxazolines and their copolymers that are suitable for the invention, mention may be made more particularly of polyalkyloxazolines with a molecular weight greater than 200 and less than 50000, such as N-ethyl / N-propyl or N-isopropyl copolymers.
• hydroxyalkylcelluloses and their copolymers that are suitable for the invention, mention may be made more particularly of hydroxypropylmethylcelluloses, ethylhydroxyethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose and methylcellulose.
• polymer chosen from poly (N-substituted acrylamide), poly (N-isopropylacrylamide) homopolymers, copolymers of N-isopropyl-acrylamide and of acid ester ( C1-C18 meth) acrylic (eg butyl acrylate) and copolymers of N-isopropylacrylamide and methacrylic acid, and O- (2-Aminopropyl) -O '- (2-methoxyethyl) polypropylene glycol .
• the polymer is chosen from polyetheramines.
• the polymer is O- (2-Aminopropyl) -O '- (2-methoxyethyl) polypropylene glyco 1.
• This polyetheramine is especially sold under the names Jeffamine ® M-600 ® or XTJ-505 ® , marketed by Huntsman.
• the composition according to the invention is aqueous and comprises from 20 to 50% by weight of the polymer having a critical temperature of solubility in water, called LCST, ranging from 20 to 80 ° C.
• LCST critical temperature of solubility in water
• the measured thermal conductivities of the aqueous compositions containing a compound having an LCST of 20 to 80 ° C increase significantly beyond the LCST.
• the thermal conductivity is measured by the hot filament technique using the Lambda 1 ® equipment marketed by F5Tech.
• the polymer having an LCST of 20 to 80 ° C, can be used for purposes of antifreeze additives as such, or in a form associated with a conventional antifreezing additive such as an alcohol and more particularly a glycol as defined below.
• a conventional antifreezing additive such as an alcohol and more particularly a glycol as defined below.
• the present invention also relates to an aqueous composition, useful as an antifreeze agent, comprising at least one polymer having a critical water solubility temperature called LCST ranging from 20 to 80 ° C and at least one alcohol.
• LCST critical water solubility temperature
• this additive as well as its amount will be adjusted so as not to affect, at least significantly, the thermal conductivity gain provided by the LCST-containing polymer.
• the alcohols can be mentioned in particular.
• glycols As polyalcohols that are particularly suitable for the invention, there may be mentioned glycols.
• glycol is intended to mean any organic molecule comprising at least two free hydroxyl groups.
• a glycol that is suitable for the invention may be a linear, branched or cyclic alkyl compound, saturated or unsaturated, bearing on the alkyl chain at least two -OH functions, in particular at least three -OH functions.
• glycols which are advantageously suitable for the formulation of the compositions according to the present invention are those having in particular 2 to 16 carbon atoms, preferably 2 to 4 carbon atoms.
• the glycol may be, for example, chosen from ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, polyethylene glycol, butylene glycol, isoprene glycol and pentylene glycol. hexylene glycol, glyceryl triacetate, and mixtures thereof.
• the alcohol is a glycol.
• the glycol is chosen from ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol and mixtures thereof.
• the glycol is selected from ethylene glycol and propylene glycol.
• the polymer and the alcohol, and more particularly the glycol are present in a volume ratio polymer (s) / alcohol (s) greater than or equal to 0.1, more particularly varying 0.3 to 3, and preferably 1.
• composition considered according to the invention advantageously also comprises one or more additive (s).
• composition according to the invention may further comprise any additive usually used with an antifreeze additive.
• this additional additive can also be conditioned by the nature of the fluid in which it is dedicated to be added, or even the field of application of this fluid.
• this additional additive may be chosen in particular from anti-foam agents, dyes, biocides, buffering agents, anticorrosion agents and mixtures thereof.
• anti-foam agents By way of illustration of anti-foam agents, mention may in particular be made of polysiloxanes, oxyalkylated polysiloxanes, and fatty acid amides derived from vegetable or animal oils.
• anti-corrosion agents By way of illustration of anti-corrosion agents, mention may especially be made of those selected from the group consisting of amines, succinimides, alkenylsuccinimides, polyalkylamines, polyetheramines, and polyalkyl polyamines. It may also be alkaline salts, nitrates, carbonates or silicates.
• biocides By way of illustration of biocides, particular mention may be made of bacteriostats and / or bactericides or fungistats and / or fungicides.
• Percentages are percentages by volume.
• the LCST polymer used is 0- (2-Aminopropyl) -0 '- (2-methoxyethyl) polypropylene glycol sold under the name Jeffamine ® M-600 ® from Huntsman, and which has a LCST at 32 ° C.
• Aqueous compositions were prepared from this polymer, at different concentrations, in the presence or absence of a glycol.
• glycols used are ethylene glycol and propylene glycol, marketed by Aldrich, Fluka.
• Control compositions that is to say without LCST polymer, with one of the above glycols were prepared in parallel.
• compositions tested are heated respectively to the temperatures of 25 ° C. and 45 ° C. in a double-jacketed reactor connected to a Julabo thermo-cryostat and their thermal conductivity is evaluated at each of these two temperatures.
• Thermal conductivities are measured by the hot filament technique on Lambda System 1 ® equipment marketed by F5 Technology.
• Thermal conductivity K Thermal conductivity K at 25 ° C to 45 ° C (T> LCST) in mW.K ⁇ .rn 1 in mW.K ⁇ .rn 1
• Control composition 1 100%
• Control Composition 2 60% H 2 0
• Control composition 3 60% H 2 O
• composition 4 according to the invention
• composition 5 according to the invention
• composition 6 according to the invention
• the thermal conductivities measured for the compositions according to the invention vary greatly as a function of the temperature.
• compositions 4 to 6 of Example 1 as well as the two compositions which follow were tested for their rheological performance as a function of temperature.
• composition 7 60% H 2 0, 30% Ethylene Glycol and 10% Jeffamine ® M-600 ® (H 2 0-EG-Jeff 60-30- 10)
• Composition 8 60%> H 2 0, 20%> Propylene Glycol and 20%> Jeffamine ® M-600 ® (H 2 O-Jeff-PG 60-20-20)
• Figure 1 depicts the viscosity versus temperature curves of compositions 4-8.
• compositions no longer exhibit the same rheological behavior below and above the hydrophilic / hydrophobic transition temperature of the polymer considered in the composition.

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• Chemical & Material Sciences (AREA)
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• 2011
  • 2011-04-15 FR FR1153303A patent/FR2974105B1/fr not_active Expired - Fee Related
• 2012
  • 2012-04-12 JP JP2014504433A patent/JP2014514406A/ja active Pending
  • 2012-04-12 WO PCT/IB2012/051804 patent/WO2012140600A1/fr not_active Ceased
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