Classifications

• • 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
• • 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

Definitions

• the invention relates to biodegradable polymers and in particular to polyacrylates with improved biodegradability.
• the polyacrylates of the invention can be used in various applications and in particular in detergent compositions.
• 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.
• hydrophilic polymers such as polyvinyl alcohol
• acrylic polyacids with an average mass by weight of less than 1000 have better biodegradability than their superior counterparts (Swift, Ecoiogical Assessment of Polymer 1 5, 291-306, 1 997).
• 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 531 871 9 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 that the degradability of the polymers described above can be improved by inserting brittleness sites into the main chain. These sites will be rapidly broken down by microorganisms in the natural environment, to lead to acrylic sequences of sufficiently low mass to be easily biodegradable.
• the Applicant has found that the fact of inserting electron-rich centers, such as double bonds, in an acrylic chain, makes the acrylic chain more fragile with respect to microorganisms and thus improves its biodegradability.
• the invention relates to hydrophilic polymers with improved biodegradability, in particular polyacrylates containing sites rich in readily oxidizable electrons.
• the polymers of the invention contain:
• the final polymer must remain hydrophilic.
• the monomer A is chosen from the group consisting of monomers carrying at least one carboxylic acid and their derivatives such as salts and acid anhydrides.
• carboxylic acid and their derivatives such as salts and acid anhydrides.
• the preferred monomer A according to the invention is acrylic acid.
• the monomer B is chosen from the group consisting of: by the monomers carrying two conjugated double bonds such as butadiene, isoprene, chloroprene, dimethylbutadiene, cyclohexandiene, butadiene carboxylic acid and butadiene dicarboxylic acid, and by monomers bearing a triple bond such as acetylene, acetylene carboxylic acid and acetylene dicarboxylic acid.
• the preferred monomer B of the invention is isoprene.
• the monomer C, different from A and B, is chosen from the group containing the monomers copolymerizable with A and B such as vinyl, acrylic, styrene monomers and their derivatives.
• the distribution in the final polymer of the fragile sites provided by the monomer B depends both on the relative reactivity specific to the different monomers present, and on the ratio of the relative concentrations of monomer A, monomer B and possibly other monomers C.
• the polymers of the invention can be linear or branched. They can also be partially crosslinked.
• the polyacids partially neutralized and crosslinked using a molecule containing at least two reactive functions with carboxylic acids and containing the fragile sites described above, constitute a perfect example of branched polymers with improved biodegradability according to the invention.
• SAP super absorbents
• the polymers of the invention can be obtained by the joint polymerization: from 70 to 99% by weight of at least one monomer A, from 1 to 30% by weight of at least one monomer B, and from 0 to 29% by weight of at least one monomer C.
• the monomers A, B and C are those described above.
• the polymerization can be carried out in solution in an organic solvent or in the presence of water. For information, these two modes of synthesis are described below for obtaining a linear product:
• the polymerization takes place in tetrahydrofuran (THF).
• THF tetrahydrofuran
• AIBN azo-bis-isobutyronitrile
• ATG thioglycolic acid
• the reaction is started by raising the temperature to 70 ° C.
• the monomers A, B and optionally C can be introduced continuously using a metering pump into the reactor throughout the reaction with the aim of better distributing the functional monomer throughout the chain and obtaining thus a more homogeneous polymer in composition.
• the polymer After reaction and concentration of THF on a rotary evaporator, the polymer is precipitated and dried in an oven under vacuum.
• the reaction After degassing and placing under nitrogen, the reaction is started by raising the temperature to 70 or 80 ° C. After polymerization, the product is recovered by evaporation and drying under vacuum.
• This test is intended to assess the sensitivity of new sequences to the action of oxidative degradation of microbial enzymes.
• test method described below uses metal complexes, analogs of oxidation enzymes and in particular TPEN N, N , N ', N' tetramethylpyridine 1, 2- ethylene diamine or N, N, N ', N' tetrakis- (2 pyridylmethyl) ethane 1, 2 diamine.
• reaction conditions used for the degradability test are as follows:
• 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.
• Candida tropicalis cultures are carried out on a liquid medium comprising malt extract (20 g. H) and incubated at 30 ° C. with axial shaking for 48 hours.
• Warburg method The evaluation of the respiration of C. tropicalis on a polyacrylate is carried out in Warburg flasks (total capacity of 3 ml) comprising 1, 3 ml of phosphate buffer 0, 1 pH6, 1 ml of yeast suspension (about 3 mg dry weight) and 0.5 ml of polyacrylate at 1, 1 2 g. H (final concentration of 200 ppm). Control tests are carried out in parallel:
• the vials are shaken in a water bath at 30 ° C. Measurements of pressure variations due to the appearance of CO2, revealing the metabolism of acrylate by yeast, are carried out every 1 5 minutes.
• cultures comprising exclusively polyacrylate as carbon source and cultures associating it with yeast extract.
• the first case reveals the use of the compound by the microorganism.
• the second aims to optimize this use in order to increase the degradation yield by promoting the development of yeast.
• these media comprise a conventional mineral medium (MgS ⁇ ; 7H2O 3 g; CaCl2 2H2O 0.1 g: NaCl 1 g; FeS ⁇ 4 7H2O 0.1 g; ZnSO 4 7H2O 0.1 g; C0CI2 0.1 g ; CUSO4 5H2O 1 0 mg; AIK (SO 4 ) 2 1 2 H 2 O 10 mg; H3BO3 10 mg; Na 2 MoO 4 2H 2 O 2 mg; qs 1 I distilled water) combined with phosphate buffer 0, 1. M; pH6 in the proportions 2/98.
• the polyacrylate is at a final concentration of 500 ppm.
• the yeast extract optionally added has a final concentration of 200 ppm.
• the principle of this test consists in measuring the capacity of a given polymer to prevent the formation of a precipitate of CaSO4 from sodium sulphate and calcium chloride.
• Solution A CaCI 2 , 2H 2 O 64.9 g / 1 + MgCl2 0.5 g / 1
• Solution B Na2SO4 62.7 g / 1
• the ion concentration is measured by emission spectrometry using the ICP (Inductively Coupled Plasma) technique.
• the results obtained are expressed in ppm of calcium in the solutions at time 0 and after 7 days of contact.
• reaction mixture is degassed by a succession of vacuum and nitrogen cycles, then placed in an oil bath thermostatically controlled at 70 ° C. After 12 hours of reaction, the reaction mixture is concentrated on a rotary evaporator then precipitated (2 times), filtered (frit 5), and dried in an oven under vacuum (5.1 0 " 2 bar) for a minimum of six hours.
• the product obtained has a degradability index oOO equal to 56, which is a result superior to the reference polyacrylates whose oOO is killed between 18 and 26 under the same conditions.
• reaction mixture is degassed by a succession of vacuum and nitrogen cycles, then placed in an oil bath thermostatically controlled at 70 ° C. After 12 hours of reaction, the reaction mixture is concentrated on a rotary evaporator and then precipitated. (2 times), filtered (frit 5), and dried in the vacuum oven (5 * 10 _ 2 bar) for a minimum of six hours.
• the reactor is hermetically closed by an 8-screw cover surmounted by a pressure gauge and a valve usable for the introduction of liquids and for degassing the reactor.
• the pressure is raised to 2.5 bars in the reactor by the introduction of nitrogen.
• the reactor is placed in an ice bath in order to reduce the internal pressure, after 30 minutes it is degassed.
• reaction mixture is concentrated on a rotary evaporator then precipitated (2 times), filtered (frit 5), and dried in an oven under vacuum (5 * 10 ⁇ 2 bar) for a minimum of six hours.
• the AA / lsoprene copolymer (BG70) was also evaluated for microbiological degradation under the conditions described above. Two types of results were obtained. a - Breathing test The copolymer was used as a carbon substrate for Candida tropicalis cultures, compared to easily metabolized control glucose substrate and to a reference polyacrylate.
• the copolymer with isoprene has a specific respiration rate close to 30% that of glucose, which indicates a marked improvement in biodegradability.
• the copolymer was used as a carbon substrate for Candida tropicalis cultures of greater duration, and analyzed by liquid chromatography in a comparative manner, after 15 days of culture.
• the copolymers obtained are dissolved in 0.1 M sodium hydroxide before analysis, then brought back to the pH of the test.
• the measurable level of calcium after 7 days of contact indicates the ability of the polymer evaluated to inhibit its precipitation in the form of CaSO4.
• the table below indicates that the effect persists up to 0.25 ppm of AA / isoprene copolymer under the conditions of the test, and up to a value similar to the reference polyacrylate, then no effect is measured for the witness.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Life Sciences & Earth Sciences (AREA)
• Polymers & Plastics (AREA)
• Medicinal Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Engineering & Computer Science (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Biological Depolymerization Polymers (AREA)
• Detergent Compositions (AREA)

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• 1998
  • 1998-06-03 FR FR9806939A patent/FR2779435B1/fr not_active Expired - Fee Related
• 1999
  • 1999-06-01 EP EP99922242A patent/EP1091985A1/fr not_active Withdrawn
  • 1999-06-01 AU AU39365/99A patent/AU3936599A/en not_active Abandoned
  • 1999-06-01 WO PCT/FR1999/001279 patent/WO1999062971A1/fr not_active Application Discontinuation
  • 1999-06-01 CN CNB998092886A patent/CN1158316C/zh not_active Expired - Fee Related
  • 1999-06-01 JP JP2000552178A patent/JP3659888B2/ja not_active Expired - Fee Related
  • 1999-06-01 US US09/701,681 patent/US6900171B1/en not_active Expired - Fee Related
  • 1999-06-01 CA CA002334091A patent/CA2334091A1/fr not_active Abandoned

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