Classifications

• • 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
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
  • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
  • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
  • C08J9/143—Halogen containing compounds
  • C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
• • 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
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
  • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
  • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
  • C08J9/142—Compounds containing oxygen but no halogen atom
• • 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
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
  • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
  • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
  • C08J9/143—Halogen containing compounds
  • C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
  • C08J9/145—Halogen containing compounds containing carbon, halogen and hydrogen only only chlorine as halogen atoms
• • 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
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
  • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
  • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
  • C08J9/149—Mixtures of blowing agents covered by more than one of the groups C08J9/141 - C08J9/143
• • 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
  • C08G2101/00—Manufacture of cellular products
• • 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
  • C08J2203/00—Foams characterized by the expanding agent
  • C08J2203/12—Organic compounds only containing carbon, hydrogen and oxygen atoms, e.g. ketone or alcohol
• • 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
  • C08J2203/00—Foams characterized by the expanding agent
  • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
  • C08J2203/146—Saturated hydrocarbons containing oxygen and halogen atoms, e.g. F3C-O-CH2-CH3
• • 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
  • C08J2203/00—Foams characterized by the expanding agent
  • C08J2203/16—Unsaturated hydrocarbons
  • C08J2203/162—Halogenated unsaturated hydrocarbons, e.g. H2C=CF2
• • 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
  • C08J2205/00—Foams characterised by their properties
  • C08J2205/04—Foams characterised by their properties characterised by the foam pores
  • C08J2205/044—Micropores, i.e. average diameter being between 0,1 micrometer and 0,1 millimeter
• • 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
  • C08J2205/00—Foams characterised by their properties
  • C08J2205/04—Foams characterised by their properties characterised by the foam pores
  • C08J2205/052—Closed cells, i.e. more than 50% of the pores are closed
• • 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
  • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
  • C08J2375/04—Polyurethanes

Definitions

• the present invention relates to hydrochlorofluoroolefin blowing agent compositions and the use of hydrochlorofluoroolefin blowing agent compositions for the production of two component polyurethane foam blasks.
• the invention also provides certain particular blowing agent compositions suitable for the above-mentioned use.
• Methods of making polyurethane foams are known and generally consist in reacting an organic isocyanate compound with a polyol or a mixture of polyols in the presence of a blowing agent.
• Single-component formulations for which the isocyanate compound and the polyol compound are blended prior to foam expansion
• two-component formulations for which the isocyanate compound and the polyol compound are blended during foam expansion
• HFCO-1233zd is a high-performance compound for polyurethane foams, due in particular to its low thermal conductivity.
• this compound is problematic in certain applications, and in particular in the context of the production of two-component polyurethane foam spray (generally called "spray foam" in English).
• the projected two-component polyurethane foam is produced from two precursor products, namely a composition (A) comprising an isocyanate and a composition (B) comprising a polyol formulated with a blowing agent.
• the two compositions are projected, generally by means of a gun equipped with an internal mixer, and the mixture between the two compositions is therefore performed at the time of projection.
• HFCO-1233zd tends to evaporate at the most common operating temperatures. This poses specific problems in the packaging, handling and implementation of precursor products of the foam; thus, cooling may be necessary during conditioning to avoid losses of HFCO-1233zd, there is a risk of overpressure occurring in containers of precursor products during storage or transport and a significant portion of the agent Expansion may be lost during the manufacture of the projected two-component foam (i.e., during spraying). The same problems arise, even more acute, for 2-chloro-3,3,3-trifluoropropene (HFCO-1233xf), whose boiling temperature is still lower than that of HFCO-1233zd.
• HFCO-1233xf 2-chloro-3,3,3-trifluoropropene
• the invention relates first of all to the use of a composition as a blowing agent for a projected two-component polyurethane foam, said composition comprising 1-chloro-3,3,3-trifluoropropene and / or 2-chloro-3,3,3-trifluoropropene.
• the boiling temperature can be determined as described below in Example 1.
• the boiling point of the composition is greater than or equal to 21 ° C, preferably greater than or equal to 22 ° C, preferably greater than or equal to 23 ° C, preferably greater than or equal to 24 ° C, preferably greater than or equal to 25 ° C, preferably greater than or equal to 26 ° C, and preferably less than or equal to 30 ° C.
• composition used as expansion agent :
• GWP has a GWP of less than or equal to 150, preferably less than or equal to 100, preferably less than or equal to 50, preferably less than or equal to 25;
• a proportion of closed cells greater than or equal to 90%, preferably greater than or equal to 95%, particularly preferably greater than or equal to 99%;
• a change in volume after 48 hours at -20 ° C. of less than or equal to 3%, preferably less than or equal to 1%;
• a thermal conductivity at 10 ° C. after aging of less than or equal to 28 mW / mK; and or a compressive strength in the direction parallel to the expansion greater than or equal to 100 kPa, preferably greater than or equal to 130 kPa; and or
• a compressive strength in the direction perpendicular to the expansion greater than or equal to 90 kPa, preferably greater than or equal to 100 kPa.
• the invention also relates to a process for manufacturing polyurethane foam involving an expansion agent according to the invention.
• This process comprises:
• composition A comprising an isocyanate compound
• composition B comprising a polyol compound and an expanding agent
• composition A and composition B spraying and mixing composition A and composition B, and reacting compositions A and B to provide the polyurethane foam;
• blowing agent is a composition comprising 1-chloro-3,3,3-trifluoropropene and / or 2-chloro-3,3,3-trifluoropropene and at least one additional compound selected from hydrochlorofluoroolefins, hydrofluoroolefins, hydrochloroolefins, hydrofluorocarbons, hydrochlorofluorocarbons, hydrocarbons, substituted or unsubstituted ethers, substituted or unsubstituted alcohols, substituted or unsubstituted aldehydes, substituted or unsubstituted ketones and substituted or unsubstituted esters, said composition having a boiling temperature greater than or equal to 20 ° C.
• the boiling point of the blowing agent is greater than or equal to 21 ° C., preferably greater than or equal to 22 ° C., preferably greater than or equal to 23 ° C. ° C, preferably greater than or equal to 24 ° C, preferably greater than or equal to 25 ° C, preferably greater than or equal to 26 ° C, and preferably less than or equal to 30 ° C.
• the blowing agent :
• GWP has a GWP of less than or equal to 50, preferably less than or equal to 25;
• the polyurethane foam has: a cell size of 0.05 to 1 mm; and or
• a proportion of closed cells greater than or equal to 90%, preferably greater than or equal to 95%, particularly preferably greater than or equal to 99%;
• a change in volume after 48 hours at -20 ° C. of less than or equal to 3%, preferably less than or equal to 1%;
• a compressive strength in the direction parallel to the expansion greater than or equal to 100 kPa, preferably greater than or equal to 130 kPa;
• a compressive strength in the direction perpendicular to the expansion greater than or equal to 90 kPa, preferably greater than or equal to 100 kPa.
• the additional compound is chosen from 1, 2-transdichloroethylene, ethyltetrafluoroethylether, methylacetate, methylformate, dimethoxymethane, nonafluoroethoxybutane, 1, 1 , 1,3,3-pentafluorobutane and mixtures thereof.
• the blowing agent comprises:
• the subject of the invention is also a particular composition for carrying out the above process, comprising 1-chloro-3,3,3-trifluoropropene and at least one additional compound chosen from nonafluoroethoxybutane and ethyltetrafluoroethylether.
• this composition comprises:
• the subject of the invention is also another particular composition for carrying out the above process, comprising 2-chloro-3,3,3-trifluoropropene and at least one additional compound chosen from methyl acetate and methylformate. dimethoxymethane, transdichloroethylene, ethyltetrafluoroethyl ether and nonafluoroethoxybutane.
• this composition comprises:
• one of the above compositions further comprises a polyol compound, preferably in a mass content of 60 to 90%.
• the present invention overcomes the disadvantages of the state of the art. It provides more particularly an expansion agent for the production of two-component polyurethane foam projected, said expansion agent to avoid the packaging problems, handling and use encountered with HFCO-1233zd or HFCO-1233xf. This is accomplished by adding at least one co-blowing agent in combination with HFCO-1233zd or HFCO-1233xf, whereby the resulting mixture has a higher boiling temperature than HFCO-1233zd alone (about 18 ° C. ) or HFCO-1233xf alone (about 13 ° C), and more particularly a boiling temperature above room temperature in the majority of situations.
• the invention also has one or preferably more of the advantageous features listed below.
• the blowing agent according to the invention has acceptable properties vis-à-vis environmental constraints (including low GWP), toxicity and safety (non-flammability). It is soluble in polyols.
• the polyurethane foam obtained by virtue of the invention has acceptable properties of thermal conductivity, density, dimensional stability, cell structure and compressive strength; preferably, these properties are as satisfactory or nearly as satisfactory as the properties of a projected two-component polyurethane foam obtained with HFCO-1233zd alone (respectively with HFCO-1233xf alone) as the blowing agent.
• Blending of the blowing agent with the polyol compound can be carried out at room temperature without risking too much loss of blowing agent, which is more economical and facilitates the use of the blowing agent. .
• the vapor pressure of the polyol formulated with the blowing agent is lower, which limits the risk of reaching pressures above the operating pressure of the containers (drums) used.
• the invention is based on the use of 1-chloro-3,3,3-trifluoropropene (HFCO-1233zd) or 2-chloro-3,3,3-trifluoropropene (HFCO 1233xf) compositions and minus one co-blowing agent (additional compound) as blowing agent in the production of the projected two-component polyurethane foam.
• HFCO-1233zd 1-chloro-3,3,3-trifluoropropene
• HFCO 1233xf 2-chloro-3,3,3-trifluoropropene
• the additional compound is chosen such that its boiling point is greater than that of HFCO-1233zd, so that the boiling point of the composition comprising HFCO-1233zd and the additional compound (s) is greater than that of HFCO-1233zd. or equal to 20 ° C or 21 ° C or 22 ° C or 23 ° C or 24 ° C or 25 ° C or 26 ° C, and preferably less than or equal to 30 ° C.
• the blowing agent may especially be a binary composition consisting essentially of HFCO-1233zd and a single additional compound, or a binary composition consisting essentially of HFCO-1233xf and a single additional compound, or a ternary composition consisting essentially of HFCO-1233zd and two additional compounds, or a ternary composition consisting essentially of HFCO-1233xf and two additional compounds, or a ternary composition consisting essentially of HFCO-1233zd, HFCO-1233xf and a single additional compound.
• composition may optionally comprise, in addition to the abovementioned compounds, a proportion of impurities or other additives of less than or equal to 1%, preferably less than or equal to 0.5%, or even less or equal to 0.1%.
• HFCO-1233zd is preferably in its trans form, which has the advantage of being less toxic than the cis form.
• the trans form advantageously represents at least 80% by weight of HFCO-1233zd, preferably at least 90% by weight, more preferably at least 95% by weight, for example at least 98% by weight.
• essentially all of the HFCO-1233zd is in trans form.
• the additional compounds are generally chosen from hydrochlorofluoroolefins (alkenes having chlorine and fluorine substituents), hydrofluoroolefins (alkenes having fluorine substituents), hydrochloroolefins (alkenes having chlorine substituents), saturated or non-saturated hydrocarbons (especially alkanes).
• hydrofluorocarbons hydrocarbons having fluorine substituents
• hydrochlorofluorocarbons hydrocarbons having fluorine and chlorine substituents
• substituted or unsubstituted ethers especially halogenated ethers containing chlorine and / or fluorine substituents
• substituted or unsubstituted alcohols especially halogenated alcohols containing chlorine and / or fluorine substituents
• substituted or unsubstituted aldehydes in particular halogenated aldehydes containing chlorine and / or fluorine substituents
• substituted or unsubstituted ketones in particular halogenated ketones containing chlorine substituents and and / or fluorine
• substituted or unsubstituted esters in particular halogenated esters containing chlorine and / or fluorine substituents
• the preferred additional compounds are 1,2-transdichlorethylene (or TDCE), ethyltetrafluoroethylether (or ETFEE), methylacetate, methylformate, dimethoxymethane, nonafluoroethoxybutane (or HFE-7200) and 1,1,1,3 , 3-pentafluorobutane (or HFC-365mfc), their mixtures.
• TDCE 1,2-transdichlorethylene
• ETFEE ethyltetrafluoroethylether
• methylacetate methylformate
• dimethoxymethane dimethoxymethane
• HFE-7200 nonafluoroethoxybutane
• HFC-365mfc 1,1,1,3 , 3-pentafluorobutane
• composition is preferably non-flammable (and this in view of the risks associated with the vapor emissions during spraying) and that Preferably the GWP of the composition is as low as possible (preferably less than or equal to 150 or 100 or 50 or 25).
• the flammability or non-flammability of the composition is determined on the liquid phase of the composition, according to ASTM D3828.
• the global warming potential is defined with respect to the carbon dioxide and with respect to a duration of 100 years, according to the method indicated in "The scientific assessment of ozone depletion, 2002, a report of the World Meteorological Association's Global Ozone Research and Monitoring Project.
• the nature and the amount of the additional compound (s) are chosen so that preferably the polyurethane foam obtained by reacting an isocyanate compound and a polyol compound in the presence of the expansion of the invention has the following properties:
• 90 kPa preferably greater than or equal to 100 kPa.
• HFCO-1233zd or HFCO-1233xf generally provides excellent properties for polyurethane foam (in terms of thermal conductivity, density, dimensional stability, cell structure and compressive strength). It is therefore desired that the blowing agent used according to the invention provide the polyurethane foam with properties as close as possible to those obtained with HFCO-1233zd (respectively with HFCO-1233xf), in particular with regard to thermal conductivity, density, dimensional stability, cell structure and compressive strength.
• the proportion of HFCO-1233zd and / or HFCO-1233xf in the blowing agent composition is greater than or equal to 50%, and preferably greater than or equal to 55% or 60%. or 65% or 70% or 75% or 80%.
• compositions are as follows:
• HFCO-1233xf and TDCE 70 to 80% HFCO-1233xf and 20 to 30% TDCE.
• the upper bounds of the HFCO-1233zd contents in the above preferred compositions are mainly dictated by the boiling temperature criterion, which is desired to be greater than or equal to about 20 ° C.
• a HFCO-1233zd / TDCE binary mixture contains less than 75% HFCO-1233zd, the dimensional stability of the polyurethane foam is lost.
• a HFCO-1233zd / ETFEE binary mixture contains less than 30% HFCO-1233zd, the mixture is flammable.
• a binary HFCO-1233zd / methylacetate mixture contains less than 58% HFCO-1233zd, the mixture is flammable.
• HFCO-1233zd / methylformate binary mixture contains less than 71% HFCO-1233zd, the mixture is flammable.
• the projected two-component polyurethane foam is made from a composition A comprising an isocyanate compound and a composition B comprising a polyol compound and the above blowing agent. Both compositions are sprayed and mixed at the time of spraying (usually by a gun with an internal mixer). The reaction between the polyol compound and the isocyanate compound to form the polyurethane takes place in situ, i.e. where the foam is applied.
• the "two-component polyurethane foam sprayed” can also be called spray foam (or “spray foam”). It is distinguished from the one-component polyurethane foam (or "OCF") which is manufactured by means of an aerosol in which are mixed both the formulated polyol and the isocyanate, the blowing agent then acting as a propellant (In one-component foams, it is desirable to have a low boiling blowing agent, such as trans-HFO-1234ze having a boiling point of -19 ° C).
• a low boiling blowing agent such as trans-HFO-1234ze having a boiling point of -19 ° C.
• composition B preferably comprises from 60 to 90% of polyol compound and from 5 to 30% of blowing agent.
• polyol compound is meant a polyol or a mixture of polyols.
• polyols examples include glycerol, ethylene glycol, trimethylolpropane, pentaerythritol, polyether polyols, for example those obtained by condensation of an alkylene oxide or a mixture of alkylene oxides with glycerol.
• Polyether polyols obtained by adding alkylene oxides, in particular ethylene oxide and / or propylene oxide, to the aromatic amines, in particular the mixture of 2,4-toluene diamine and 2,6-toluene diamine; toluene diamine, are also suitable. Polyether polyols are particularly preferred.
• Composition B may also comprise one or more surfactants and one or more catalysts as is known in the art, preferably in a total amount of between 5 and 20%.
• Composition A comprises an isocyanate compound which is preferably an organic polyisocyanate.
• organic polyisocyanate mention may be made of aliphatic polyisocyanates having a hydrocarbon group comprising up to 18 carbon atoms, cycloaliphatic polyisocyanates having a hydrocarbon group comprising up to 15 carbon atoms, and aromatic polyisocyanates having a hydrocarbon group comprising from 6 to 15 carbon atoms. to 15 carbon atoms and arylaliphatic polyisocyanates having a hydrocarbon group comprising from 8 to 15 carbon atoms.
• the preferred polyisocyanates are 2,4-diisocyanato-toluyl and 2,6-diisocyanato-toluyl, diphenylmethane diisocyanate, polymethylenepolyphenyl isocyanate and mixtures thereof.
• Modified polyisocyanates such as those comprising carbodiimide groups, urethane groups, isocyanurate groups, urea groups or biurea groups may also be suitable.
• Example 1 boiling temperatures of blowing agents
• the technique used for measuring the temperature of the compositions is the method of ebulliometry.
• An ebulliometer consisting of a flask maintained at ambient pressure (1.013 bar) and surmounted by a condenser is charged with at least 50% of its volume in HFCO-1233zd (or in HFCO-1233xf). HFCO-1233zd is heated to boiling and the temperature is measured. The flask is cooled and another component is added to the flask in small amounts determined. After each addition, the mixture is boiled and the temperature of the medium is measured.
• the measured temperature of the composition is corrected according to the measured temperature of HFCO-1233zd.

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• Materials Engineering (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Polyurethanes Or Polyureas (AREA)
• Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

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• 2010
  • 2010-03-09 FR FR1051683A patent/FR2957350B1/fr active Active
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