EP1218424A1 - Polyacrylates biodegradables pour la detergence - Google Patents
Polyacrylates biodegradables pour la detergenceInfo
- Publication number
- EP1218424A1 EP1218424A1 EP00956634A EP00956634A EP1218424A1 EP 1218424 A1 EP1218424 A1 EP 1218424A1 EP 00956634 A EP00956634 A EP 00956634A EP 00956634 A EP00956634 A EP 00956634A EP 1218424 A1 EP1218424 A1 EP 1218424A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polymers according
- hydrophilic polymers
- bond
- monomers
- biodegradable
- Prior art date
- Legal status (The legal status 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 status listed.)
- Withdrawn
Links
- 239000003599 detergent Substances 0.000 title abstract description 8
- 229920000058 polyacrylate Polymers 0.000 title description 19
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 230000003647 oxidation Effects 0.000 claims abstract description 3
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 3
- 229920000642 polymer Polymers 0.000 claims description 25
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 11
- 229920001477 hydrophilic polymer Polymers 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 11
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 7
- 238000005904 alkaline hydrolysis reaction Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 238000012546 transfer Methods 0.000 claims description 3
- PSYGHMBJXWRQFD-UHFFFAOYSA-N 2-(2-sulfanylacetyl)oxyethyl 2-sulfanylacetate Chemical compound SCC(=O)OCCOC(=O)CS PSYGHMBJXWRQFD-UHFFFAOYSA-N 0.000 claims description 2
- NTYQWXQLHWROSQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;2,2,2-tris(sulfanyl)acetic acid Chemical compound OC(=O)C(S)(S)S.CCC(CO)(CO)CO NTYQWXQLHWROSQ-UHFFFAOYSA-N 0.000 claims description 2
- VLCCKNLIFIJYOQ-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] 2,2,3,3-tetrakis(sulfanyl)propanoate Chemical compound OCC(CO)(CO)COC(=O)C(S)(S)C(S)S VLCCKNLIFIJYOQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 150000001993 dienes Chemical class 0.000 claims description 2
- 230000002255 enzymatic effect Effects 0.000 claims description 2
- 230000007071 enzymatic hydrolysis Effects 0.000 claims description 2
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 238000007248 oxidative elimination reaction Methods 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 150000007970 thio esters Chemical class 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims 1
- 125000004434 sulfur atom Chemical group 0.000 claims 1
- 229920002988 biodegradable polymer Polymers 0.000 abstract description 6
- 239000004621 biodegradable polymer Substances 0.000 abstract description 6
- 230000007062 hydrolysis Effects 0.000 abstract description 2
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- 230000029058 respiratory gaseous exchange Effects 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 239000008363 phosphate buffer Substances 0.000 description 6
- 101710125690 50S ribosomal protein L17, chloroplastic Proteins 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- 101001075055 Spinacia oleracea 50S ribosomal protein L19, chloroplastic Proteins 0.000 description 4
- 101000725126 Spinacia oleracea 50S ribosomal protein L35, chloroplastic Proteins 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 238000004811 liquid chromatography Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 230000002906 microbiologic effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- HNSDLXPSAYFUHK-UHFFFAOYSA-N 1,4-bis(2-ethylhexyl) sulfosuccinate Chemical compound CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC HNSDLXPSAYFUHK-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- VSZSIEBALNXIFG-UHFFFAOYSA-N 2-hydroxyethyl 2,2-bis(sulfanyl)acetate Chemical compound OCCOC(=O)C(S)S VSZSIEBALNXIFG-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 241000222178 Candida tropicalis Species 0.000 description 1
- 108090000371 Esterases Proteins 0.000 description 1
- PWGOWIIEVDAYTC-UHFFFAOYSA-N ICR-170 Chemical compound Cl.Cl.C1=C(OC)C=C2C(NCCCN(CCCl)CC)=C(C=CC(Cl)=C3)C3=NC2=C1 PWGOWIIEVDAYTC-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 108091005804 Peptidases Proteins 0.000 description 1
- 102000035195 Peptidases Human genes 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000004365 Protease Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- JOBBTVPTPXRUBP-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS JOBBTVPTPXRUBP-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 239000007003 mineral medium Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000004172 nitrogen cycle Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- 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
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
-
- 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
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/04—Acids; Metal salts or ammonium salts thereof
- C08F120/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- 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
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/06—Butadiene
-
- 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
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/08—Isoprene
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/12—Hydrolysis
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
-
- 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
- C08J3/12—Powdering or granulating
- C08J3/126—Polymer particles coated by polymer, e.g. core shell structures
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
Definitions
- the invention relates to the field of detergency and in particular to biodegradable detergent compositions. It more particularly describes biodegradable polymers containing branches based on polyacrylates.
- detergent compositions involve a number of chemicals. These must be biodegradable so as not to harm the environment.
- detergent compositions and cleaning agents contain phosphates. These are very effective and relatively non-toxic, however they cause eutrophication of natural aquatic environments.
- the phosphates have been partly replaced in the formulations for detergency by polymers such as polyacrylic acids or copolymers based on acrylic acid and maleic anhydride. Although the polyacrylates currently used do not pose this problem, their lack of rapid biodegradability causes accumulation in the natural environment (Swift, polymer Degradation and Stability 45, 215 - 231, 1994).
- hydrophilic polymers such as polyvinyl alcohol
- acrylic polyacids with an average mass of less than 1000 by weight have better biodegradability than their superior counterparts (Swift, Ecological Assessment of Polymer 15, 291-306, 1997).
- EP 049761 1 describes the preparation of biodegradable terpolymers and compositions containing them. These terpolymers are based on vinyl acetate, acrylic acid and maleic anhydride. They have average masses by weight of less than 20,000. US 5318719 describes a new class of biodegradable materials based on the grafting of polymers containing acid functions on a biodegradable support based on polyoxyalkylene.
- the Applicant has now found an effective solution for preparing biodegradable polymers for detergency.
- biodegradable polymers constituting one of the objects of the invention consist of hydrophilic acrylic polymers carrying carboxylic functions, the structure of which is characterized by a biodegradable core (A) to which at least two polycarboxylic chains (B) are attached. bonds (C) degradable by hydrolysis or by oxidative cleavage.
- A biodegradable core
- B polycarboxylic chains
- These polymers are also characterized by the fact that each polycarboxylic chain has a degree of polymerization which gives it good biodegradability, and which gives the assembly good functional properties with respect to the detergent composition.
- the polymers of the invention have the following general structure:
- Heart A is generally a biodegradable molecule branched or capable of giving rise to at least two branches, chosen from the group containing pentaerythritol, trimethylol propane, ethylene glycol.
- Polymer B is either an acrylic polyacid or a polymer containing acrylic acid and at least one monomer chosen from the group containing: unsaturated carboxylic monomers other than acrylic acid, maleic anhydride, vinyl or acrylic monomers or diene monomers such as isoprene or butadiene.
- B generally has a weight average mass of between 100 and
- the function C linking the polymer B to the biodegradable core is a brittle bond hydrolysable by alkaline or enzymatic route such as an ester, amide, thioester or thioamide bond or breakable by chemical or biological oxidation such as a double or triple bond.
- biodegradable polymers of the invention can be prepared in different ways.
- they are prepared in the following manner:
- the B— X sequence is firstly prepared, taking care to terminate it with a reactive function, by radical polymerization of the monomer (s) in the presence of a reactive transfer agent, in this case a mercaptan. .
- the functionalized sequence is reacted with the core A.
- the respective amounts of A and B are defined so as to have the desired number of branches.
- Another variant of synthesis consists in first modifying the heart so as to prepare:
- the degradation level obtained is evaluated by liquid chromatography under the following conditions:
- the column is calibrated using polyacrylate standards (Polymer Laboratories).
- the degradability of the polymer under the conditions of the test is measured by the displacement of the peak observed in liquid chromatography towards the lower molecular weights.
- the polymer sample is dissolved in a 0.08 M pH 12 borate buffer at a rate of 10 mg of polymer for 10 ml of buffer solution. Each test is then placed under magnetic stirring in a bath thermostatically controlled at the desired temperature for a determined time.
- the analysis is carried out by liquid chromatography (see above) directly on a sample of the reaction medium after neutralization with 0.1 M HCl, at the rate of 1 ml of HCl for 1 ml of sample.
- Control tests are carried out in parallel: - a flask containing only phosphate buffer (2.8 ml) makes it possible to measure the variations in atmospheric pressure, endogenous respiration is measured in a flask containing only phosphate buffer (1, 8 ml) and the yeast suspension (1 ml), respiration due to contaminants possibly present in the acrylate solution is also evaluated by a test comprising the acrylate (0.5 ml) and the phosphate buffer (2.3 ml), the flasks are stirred in a water bath at 30 ° C, the pressure variation measurements due to the appearance of CO2, revealing the metabolism of acrylate by yeast, are carried out every 1 5 minutes.
- Assimilation test complex flora cultures on polyacrylate These cultures are used on a conventional mineral medium (MgS0 4 7H 2 0 3 g; CaCl 2 2H 2 0 0.1 g; NaCl 1 g; FeS0 4 7H 2 0 0.1 g; ZnS0 7H 2 0 0.1 g; CoCI 2 0.1 g; CuS0 4 5H 2 0 10 mg; AI (S0 4 ) 2 12 H 2 0 10 mg; H3BO3 10 mg; Na 2 Mo0 4 2H 2 0 2 mg; qs 1 liter of distilled water) associated with 0.1 M phosphate buffer pH 7 in the proportions 2/98.
- the polyacrylate tested is at a final concentration of 500 ppm.
- the sludge from the purification station * is diluted to a third in 0.1 M phosphate buffer, pH 7, with 100 mg.H of polyacrylate sample to be tested, then the culture is subcultured on a 500 mg medium. H of polyacrylate to be tested.
- the flasks are incubated at 30 ° C in Monod tubes with transverse shaking and subcultured after one week. The cultures then continue for 30 days under the same conditions.
- the principle of this test consists in measuring the capacity of a given polymer to prevent the formation of a precipitate of CaS ⁇ 4 from sodium sulphate and calcium chloride.
- THF tetrahydrofuran
- acrylic acid multifunctional transfer agent
- AIBN Azo bis-
- reaction mixture is degassed by a succession of vacuum and nitrogen cycles, then placed in an oil bath thermostatically controlled at 70 ° C. Polymerization takes place in batch at reflux of the solvent (THF). After 12 hours of reaction, the reaction mixtures are concentrated on a rotary evaporator then precipitated in ethyl ether, filtered (frit No. 5), and dried in an oven under vacuum (5.10 -2 bar) for a minimum of 6 hours.
- BG104 and 106 as CL19 are built on penta-erythritol-tetramercaptopropionate.
- CL17 is built on glycol-dimercaptoacetate.
- CL35 is built on tri methylol propane-tri mercaptoacetate.
- the poly-telomer BG104 was also used as a carbon substrate for Candida tropicalis cultures compared to easily metabolized control glucose and a reference polyacrylate.
- the respiration values are as follows:
- the poly-telomer BG104 Compared to a standard polyacrylate which does not cause respiration, the poly-telomer BG104 has a specific respiration rate close to 18% of that of glucose, which indicates a marked increase in biodegradability.
- the poly-telomer BG104 was used as carbonaceous substrate for cultures of microorganisms originating from sludges from treatment plants, and analyzed by liquid chromatography in a comparative manner after 1 5 days of culture.
- aqueous solutions are prepared from distilled water, to contain the following salts:
- Solution A CaCl2,2H20 64.9 g / 1 + MgCl2 0.5g / l
- the ion concentration is measured by emission spectrometry using the ICP (Inductively Coupled Plasma) technique.
- ICP Inductively Coupled Plasma
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Detergent Compositions (AREA)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9910433A FR2797448B1 (fr) | 1999-08-12 | 1999-08-12 | Polyacrylates biodegradables pour la detergence |
| FR9910433 | 1999-08-12 | ||
| PCT/FR2000/002265 WO2001012683A1 (fr) | 1999-08-12 | 2000-08-07 | Polyacrylates biodegradables pour la detergence |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP1218424A1 true EP1218424A1 (fr) | 2002-07-03 |
Family
ID=9549102
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP00956634A Withdrawn EP1218424A1 (fr) | 1999-08-12 | 2000-08-07 | Polyacrylates biodegradables pour la detergence |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US6818700B1 (ko) |
| EP (1) | EP1218424A1 (ko) |
| JP (1) | JP2003507501A (ko) |
| KR (1) | KR20020019618A (ko) |
| CN (1) | CN1379789A (ko) |
| AU (1) | AU6851200A (ko) |
| FR (1) | FR2797448B1 (ko) |
| WO (1) | WO2001012683A1 (ko) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105102600A (zh) | 2013-03-28 | 2015-11-25 | 宝洁公司 | 包含聚醚胺、去垢性聚合物和羧甲基纤维素的清洁组合物 |
| US20150275143A1 (en) | 2014-03-27 | 2015-10-01 | The Procter & Gamble Company | Cleaning compositions containing a polyetheramine |
| CA2941253A1 (en) | 2014-03-27 | 2015-10-01 | Frank Hulskotter | Cleaning compositions containing a polyetheramine |
| EP3152288A1 (en) | 2014-06-06 | 2017-04-12 | The Procter & Gamble Company | Detergent composition comprising polyalkyleneimine polymers |
| JP6479959B2 (ja) | 2014-08-27 | 2019-03-06 | ザ プロクター アンド ギャンブル カンパニー | カチオン性ポリマーを含む洗剤組成物 |
| WO2016032992A1 (en) | 2014-08-27 | 2016-03-03 | The Procter & Gamble Company | Detergent composition comprising a cationic polymer |
| WO2016032991A1 (en) | 2014-08-27 | 2016-03-03 | The Procter & Gamble Company | Detergent composition comprising a cationic polymer |
| JP6400837B2 (ja) | 2014-08-27 | 2018-10-03 | ザ プロクター アンド ギャンブル カンパニー | 布地の処理方法 |
| EP3197992B1 (en) | 2014-09-25 | 2023-06-28 | The Procter & Gamble Company | Fabric care compositions containing a polyetheramine |
| CN106749981B (zh) * | 2016-12-29 | 2019-02-01 | 中科院广州化学有限公司南雄材料生产基地 | 一种低缓凝高分散聚羧酸超塑化剂及其制备方法和应用 |
| JP6871399B2 (ja) * | 2017-09-29 | 2021-05-12 | 富士フイルム株式会社 | 水性組成物及び高分子化合物 |
| US11286322B2 (en) * | 2018-08-31 | 2022-03-29 | Dow Global Technologies Llc | Branched polymeric dispersants, aqueous pigment dispersions, and aqueous coating compositions thereof |
| CA3228918A1 (en) | 2021-08-10 | 2023-02-16 | Nippon Shokubai Co., Ltd. | Polyalkylene-oxide-containing compound |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3620149A1 (de) * | 1986-06-14 | 1987-12-17 | Roehm Gmbh | Geruchsarmes wasserloesliches polymerisat oder copolymerisat, seine herstellung und verwendung |
| GB9711849D0 (en) * | 1997-06-06 | 1997-08-06 | Unilever Plc | Polymeric materials |
| FR2779435B1 (fr) * | 1998-06-03 | 2005-03-11 | Atochem Elf Sa | Polyacrylates a biodegradabilite amelioree |
-
1999
- 1999-08-12 FR FR9910433A patent/FR2797448B1/fr not_active Expired - Fee Related
-
2000
- 2000-08-07 WO PCT/FR2000/002265 patent/WO2001012683A1/fr not_active Application Discontinuation
- 2000-08-07 JP JP2001517579A patent/JP2003507501A/ja not_active Withdrawn
- 2000-08-07 US US10/049,377 patent/US6818700B1/en not_active Expired - Fee Related
- 2000-08-07 AU AU68512/00A patent/AU6851200A/en not_active Abandoned
- 2000-08-07 EP EP00956634A patent/EP1218424A1/fr not_active Withdrawn
- 2000-08-07 CN CN00814262A patent/CN1379789A/zh active Pending
- 2000-08-07 KR KR1020027001813A patent/KR20020019618A/ko active IP Right Grant
Non-Patent Citations (1)
| Title |
|---|
| See references of WO0112683A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20020019618A (ko) | 2002-03-12 |
| JP2003507501A (ja) | 2003-02-25 |
| US6818700B1 (en) | 2004-11-16 |
| FR2797448B1 (fr) | 2001-09-14 |
| CN1379789A (zh) | 2002-11-13 |
| FR2797448A1 (fr) | 2001-02-16 |
| AU6851200A (en) | 2001-03-13 |
| WO2001012683A1 (fr) | 2001-02-22 |
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