Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
• • 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
  • C08F2/00—Processes of polymerisation
  • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
• • 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
  • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
  • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
  • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials

Definitions

• the subject of the present invention is a copolymer with surfactant blocks prepared by controlled radical polymerization, as well as a process for the preparation of said copolymers.
• the subject of the present invention is therefore a surfactant block copolymer comprising at least one hydrophilic block and at least one hydrophobic block and prepared by a so-called living preparation process using a transfer agent, said copolymer having:
• a glass transition temperature of the hydrophobic block of less than 30 ° C, preferably less than 25 ° C and more than -100 ° C, and - a surface tension less than 60 millinewton per meter (mN / m), preferably less at 50 mN / m, measured at a concentration in demineralized water less than or equal to 10 ⁇ 4 mole / l, at 20 ° C and under an atmosphere.
• mN / m millinewton per meter
• the transfer agent located at one of the ends of the molecule, chemically inert or else to destroy said agent.
• the block surfactant copolymers comprising at least one hydrophilic block and at least one hydrophobic block, are prepared by a so-called living or controlled radical polymerization process involving the use of a transfer agent precisely for the control of said radical polymerization.
• the above block copolymers can be obtained by any so-called living or controlled polymerization process such as, for example: - radical polymerization controlled by xanthates according to the teaching of application WO 98/58974,
• the preferred transfer agents for carrying out the controlled polymerization process are chosen from dithioesters, thioethers-thiones, dithiocarbamates, and xanthates.
• the preferred polymerization is living radical polymerization using xanthates.
• the invention further relates to a process for the preparation of these block polymers. This process consists of:
• R represents an R2O-, R2R'2N- or R3- group with:
• R2 and R'2 identical or different, representing a group (i) alkyl, acyl, aryl, alkene or alkyne, or a carbon ring (ii), saturated or not, optionally aromatic, or a heterocycle (iii), saturated or no, these groups and cycles (i), (ii) and (iii) can be substituted,
• R3 representing H, Cl, an alkyl, aryl, alkene or alkyne group, a saturated or unsubstituted (hetero) ring, optionally substituted, an alkylthio, alkoxycarbonyl, aryloxycarbonyl, carboxy, acyloxy, carbamoyl, cyano, dialkyl- or diaryl-phosphonato group , dialkyl- or diaryl-phosphinato, a polymer chain,
• R1 represents a group (i) alkyl, acyl, aryl, alkene or alkyne optionally substituted, or a carbon ring (ii), saturated or unsaturated, optionally substituted or aromatic, or a heterocycle (iii), saturated or unsaturated, optionally substituted, or a polymer chain, and
• the groups R1, R2, R'2 and R3 can be substituted by alkyl groups, substituted phenyls, substituted aromatic groups or groups: oxo, alkoxycarbonyl or aryloxycarbonyl (-COOR), carboxy (-COOH), acyloxy (-O2CR ), carbamoyl (-CONR2), cyano (-CN), alkylcarbonyl, alkylarylcarbonyl, arylcarbonyl, arylalkylcarbonyle, isocyanato, phtalimido, male ⁇ mido, succinimido, amidino, guanidino, hydroxy (-OH), amino (-NR2), halogen, allyl, epoxy, alkoxy (-OR), S-alkyl, S-aryl, silyl, groups having a hydrophilic or ionic character such as the alkali salts of carboxylic acids, the alkali salts of sulfonic acid, the polyalkylene oxide chains
• the transfer agent of formula (I) is a dithiocarbonate chosen from the compounds of formulas (IA), (IB) and (IC) below:
• R2 and R2 ' represent an (i) alkyl, acyl, aryl, alkene or alkyne group, or a ring
• R1 and R1 ' represent an (i) alkyl, acyl, aryl, alkene or alkyne group optionally substituted, or a carbon (ii) saturated or unsaturated, optionally substituted or aromatic ring, or a heterocycle (iii), saturated or unsaturated, optionally substituted, a polymer chain,.
• p is between 2 and 10.
• a first block of the polymer is synthesized of hydrophilic or hydrophobic nature depending on the nature and the amount of the monomers used.
• step 2 the other block of the polymer is synthesized.
• the ethylenically unsaturated monomers are chosen from hydrophilic and hydrophobic monomers in the proportions suitable for obtaining a surfactant block copolymer whose blocks have the characteristics of the invention. According to this process, if all the successive polymerizations are carried out in the same reactor, it is generally preferable that all the monomers used during a stage have been consumed before the polymerization of the following stage begins, therefore before the new monomers are not introduced. However, it may happen that the hydrophobic or hydrophilic monomers of the previous step are still present in the reactor during the polymerization of the next block.
• these monomers generally do not represent more than 5 mol% of all the monomers and they participate in the following polymerization by helping to introduce hydrophobic or hydrophilic units into the next block.
• the block surfactant copolymers prepared according to this polymerization process can be simply diblock with a hydrophobic block and a hydrophilic block or alternatively also triblock with either a hydrophilic block surrounded by two hydrophobic blocks or else a hydrophobic block surrounded by two blocks hydrophilic.
• the block surfactant copolymer can be obtained by using, as hydrophilic monomer with a view to preparing the hydrophilic block, at least one ethylenically unsaturated monomer chosen from:
• the mono-alkyl esters of dicarboxylic acids of the type mentioned with the alkanols preferably having 1 to 4 carbon atoms and their N-substituted derivatives, such as, for example, 2-hydroxyethyl acrylate or methacrylate,
• ethylenic monomers comprising a sulfonic acid group and its alkali or ammonium salts, for example vinylsulfonic acid, vinyl-benzene sulfonic acid, alpha-acrylamido methylpropane-sulfonic acid, 2-sulfoethylene-methacrylate,
• hydrophilic monomers are acrylic acid (AA), acrylamide (AM), 2-acrylamido-2-methyl-propanesulfonic acid (AMPS), and styrene sulfonate (SS).
• hydrophobic monomers which can be used to prepare the hydrophobic block, mention may be made in particular of (meth) acrylic esters, vinyl esters and vinyl nitriles.
• (meth) acrylic esters is meant the esters of acrylic acid and methacrylic acid with hydrogenated or fluorinated C-
• the preferred monomers are the acrylic acid esters with linear or branched CJ-C4 alcohols such as methyl, ethyl, propyl and butyl acrylate.
• Vinyl nitriles more particularly include those having 3 to 12 carbon atoms, such as in particular acrylonitrile and methacrylonitrile.
• the other ethylenically unsaturated monomers which can be used alone or as a mixture, or which can be copolymerized with the above monomers are in particular:
• the unsaturated ethylenic monomers comprising a secondary, tertiary or quaternary amino group, or a heterocyclic group containing nitrogen such as for example vinyipyridines, vinylimidazole, aminoalkyl (meth) acrylates and (meth) acrylamides) aminoalkyl such as dimethylaminoethyl acrylate or -methacrylate, ditertiobutylaminoethyl acrylate or -methacrylate, dimethylamino methyl-acrylamide or -methacrylamide.
• the block copolymers can include in the composition of the block copolymers a certain proportion of hydrophobic monomers in the hydrophilic block and a certain proportion of hydrophilic monomers in the hydrophobic block, as soon as the surfactant properties and the limits of the number molecular mass, the glass transition temperature of the hydrophobic group and the surface tension, remain verified.
• the polymerization of the copolymer can be carried out in an aqueous medium and / or organic solvent such as tetrahydrofuran or an aliphatic alcohol in cyclic or branched d-Cslinear such as methanol, ethanol, or cyclohexanol, or a diol such than ethylene glycol.
• hydrophilic monomers are acrylic acid (AA), acrylamide (AM), 2-acrylamido-2-methyl-propanesulfonic acid (AMPS), and styrene sulfonate (SS) and hydrophobic monomers are n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, t-butyl acrylate.
• the transfer agent located at one of the chain ends of the block surfactant polymer can be rendered inert if desired for the end use of the copolymer.
• the nature of the polymerization reaction medium is sufficient in itself to inactivate the transfer agent at the end of polymerization. It is also possible that the medium to be treated during the final use of the copolymer inherently inactivates or neutralizes the transfer agent. It is recommended, if necessary for certain applications, to mask the active chemical functions of said agent by means of a suitable chemical masking agent, or destroying the transfer agent by a reaction of hydrolysis, oxidation by metallic catalysis or by the use of primary radicals.
• xanthate as transfer agent, it is recommended to make it inert, if necessary, by a treatment of the copolymer formed by means of a heat treatment for example in the temperature range 80 to 180 ° C in the presence of an alkanolamine such as triethanolamine.
• the present invention also relates to the production of block copolymers which, in addition to their surfactant properties and aqueous emulsion stabilizers, lower the surface tension of water, resulting in the formation of micelles and / or small vesicles in suspension in water inside which a chemical reaction can be implemented or else an active ingredient can be encapsulated.
• the invention also relates to the use of the preceding block copolymers as adhesion promoters.
• the polymers can also be used as wetting agents or hydrophylizing agents for coating more or less hydrophobic surfaces with a residual effect after rinsing.
• the polymers can be used in an amount generally between 0.1% and 10% by weight relative to the aqueous medium.
• the block copolymers according to the invention have the particular advantage of improving the adhesion of paints to hydrophobic substrates such as plastic substrates and of increasing the adhesion of fibers and plastic supports with compounds derived from aqueous dispersions (cement, mastics).
• cement, mastics aqueous dispersions
• block copolymers according to the invention are also promoters of conventional detergents such as benzenes alkyl sulfonates when they are used in combination with the latter at a dose preferably of between 0.5 and 5% by weight relative to the weight of the detergent.
• p (BA) -bp (AA) a polybutylacrylate / polyacrylic acrylic block copolymer denoted p (BA) -bp (AA)
• the following range of properties is obtained by varying the mass ratios p (BA) / p (AA) as follows: surfactant and aqueous emulsion stabilizer properties: p (BA) / p (AA) between 10/90 and 40/60; vesicle formation: p (BA) / p (AA) between 70/30 and 80/20; and adhesion promoters and wetting agents: p (BA) / p (AA) between 70/30 and 40/60;
• the transfer agent located at one of the chain ends of the block surfactant polymer can be made chemically inert by any suitable means.
• Making the transfer agent inert can be advantageous for some applications. It is therefore recommended to mask the active chemical functions of said agent by means of an appropriate chemical masking agent, or to destroy the transfer agent by a reaction of hydrolysis, of oxidation by metallic catalysis or by the use of primary radicals. .
• Mn represents the number-average molecular mass Mn of the polymers, Mn is expressed in polystyrene equivalents (g / mol),
• Example 1 Preparation of a 50/50 diblock polymer by weight p (BA) -b-p (AA) (polybutylacrylate-acrylic acid) comprising a reactive end of the xanthate type
• AIBN azo bis-isobutyronitrile
• the temperature is then lowered to 65 ° C by the addition of 560g of acetone. While maintaining the temperature at 65 ° C., 140 g of butyl acrylate (BA) are gradually added over 3 hours. 0.40 g of AIBN is added at the start of the BA addition. The reaction is allowed to continue for another 3 hours. The reaction mixture is allowed to cool and the solvents are practically completely removed using a rotary evaporator (rotary evaporator). The residue obtained is dispersed in water and lyophilized. The polymers are analyzed by nuclear magnetic resonance of carbon 13 and by the measurement of their acid content. The number-average molecular mass of the copolymer is 15,000. The glass transition temperature of the hydrophobic block is -54 ° C. The surface tension is 55 mN / m at 10 "4 mole / l.
• Example 3 Preparation of a 60/40 diblock polymer by weight p (BA) -bp (AA) comprising a reactive end of the xanthate type: The following are introduced into a reactor fitted with a magnetic stirrer and a reflux column, and comprising 160 g of acetone, the following mixture:
• the temperature is then lowered to 65 ° C by adding 280 g of acetone. While maintaining the temperature at 65 ° C., 60 g of butyl acrylate (BA) are gradually added over 3 hours. 0.20 g of AIBN are added at the start of the BA addition. The nitrogen purge is stopped and the reaction is allowed to continue for another 12 hours. The reaction mixture is allowed to cool and the solvents are practically completely removed using a rotary evaporator (rotary evaporator). The residue obtained is dispersed in water and lyophilized. The polymers are analyzed by nuclear magnetic resonance of carbon 13 and by the measurement of their acid content. The molecular weight of the number copolymer is 15,000.
• the glass transition temperature of the hydrophobic PBA block is -54 ° C and 105 ° C for the PAA block.
• Example 4 Preparation of a 80/20 Diblock Polymer by Weight p (BA) -bp (AA) (Polybutylacrylate-Polyacid Acrylic Acid) comprising a reactive end of the xanthate type and a reflux column, and comprising 60 g of acetone, the following mixture:
• the temperature is then lowered to 65 ° C by adding 112 g of acetone. While maintaining the temperature at 65 ° C., 32 g of butyl acrylate (BA) are gradually added over 3 hours. 0.08 g of AIBN is added at the start of the BA addition. The nitrogen purge is stopped and the reaction is allowed to continue for another 12 hours. The reaction mixture is allowed to cool and the solvents are practically completely removed using a rotary evaporator (rotary evaporator). The residue obtained is dispersed in water and lyophilized. The polymers are analyzed by nuclear magnetic resonance of carbon 13 and by the measurement of their acid content. The molecular weight of the number copolymer is 15,000.
• the glass transition temperature of the hydrophobic PBA block is -54 ° C and 105 ° C for the PAA block.
• Example 5 Preparation of a 55/45 diblock polymer by weight p (BA) -b-p (AA) (polybutylacrylate-acrylic acid) comprising a reactive end of the xanthate type:
• AIBN azo bis-isobutyronitrile
• the temperature is then lowered to 65 ° C by adding 112 g of acetone. While maintaining the temperature at 65 ° C., 22 g of butyl acrylate (BA) are gradually added over 3 hours. 0.08 g of AIBN is added at the start of the BA addition. The nitrogen purge is stopped and the reaction is allowed to continue for another 12 hours. The reaction mixture is allowed to cool and the solvents are practically completely removed using a rotary evaporator (rotary evaporator). The residue obtained is dispersed in water and lyophilized. The polymers are analyzed by nuclear magnetic resonance of carbon 13 and by the measurement of their acid content. The molecular weight of the number copolymer is 15,000. The glass transition temperature of the hydrophobic PBA block is -54 ° C and 105 ° C for the PAA block. The surface tension is 58.0 mN / m at 10 "4 mole / l.
• Example 6 Preparation of a Diblock Polymer with Weight Ratio p (BA) / p (AM): 60/40 p (BA ⁇ nrrb-p (AM (polybutylacrylate-polvacrylamide) comprising a reactive end of the xanthate type: 1 )
• Step 1 Synthesis of the monoblock p (BA) 300 oX (X ⁇ xanthate) Composition of the reaction mixture:
• AIBN Azo-bis-isobutyronitrile
• the above ingredients are loaded into a 250 ml polymerization reactor fitted with a magnetic stirrer.
• the reaction is carried out under an atmosphere of dry nitrogen for 20 minutes, the reaction mixture is then heated to 60 ° C. and maintained at this temperature for 20 hours. Small amounts of polymer samples are taken from time to time to check the conversion.
• the solid content is 28.09%.
• Step 2 Synthesis of the diblock p (BA ) 3 ooo-bp (AM) ? 0 oo - X Composition of the reaction mixture:
• AIBN Azo-bis-isobutyronitrile
• the reaction mixture is allowed to cool and the solvents are practically completely removed using a rotary evaporator (rotary evaporator).
• the number-average molecular mass of the copolymer is 5,000.
• the glass transition temperature of the hydrophobic PBA block is: -54 ° C and 165 ° C for the PAM block.
• the surface tension is 58 mN / m.
• Example 7 Preparation of a Diblock Polymer with Weight Ratio p (BA) / p (AA): 80/20 p (BA) 4nnn-bp (AA) 10 oo (polybutylacrylate-acrylic acid) comprising a reactive end of the xanthate type in ethanol: 1) Step 1: Synthesis of the monoblock p (BA) 40 oo (Composition of the reaction mixture:
• AIBN Azo-bis-isobutyronitrile
• the above ingredients are loaded into a 250 ml polymerization reactor fitted with a magnetic stirrer.
• the reaction is carried out under an atmosphere of dry nitrogen for 20 minutes, the reaction mixture is then heated to 60 ° C. and maintained at this temperature for 20 hours. Small amounts of polymer samples are taken from time to time to check the conversion.
• the solid content is 30.04%.
• Step 2 Synthesis of the diblock p (BA) 4 ooo-bp (AA) 100 o - X Composition of the reaction mixture:
• AIBN Azo-bis-isobutyronitrile
• the above ingredients are loaded into a dry container under a dry nitrogen atmosphere for 20 minutes, then transferred to the polymerization reactor using a 2-tip syringe. At the end of the transfer, the reaction mixture is then heated to 60 ° C. and kept at this temperature for 20 hours. Small quantities Polymer samples are taken from time to time to check the conversion. The solid content is 30%.
• the reaction mixture is allowed to cool and the solvents are practically completely removed using a rotary evaporator (rotary evaporator).
• the number-average molecular mass of the copolymer is 5,000.
• the glass transition temperature of the hydrophobic pBA block is -54 ° C and 105 ° C for the pAA block.
• Example 8 Synthesis of the diblock p (BA) 75 oo-bp (AA) 75 oo - X with weight ratio P (BAVP (AA): (50/50)
• Step 1 Synthesis of the monoblock p (BA) 750 o ⁇ X Composition of the reaction mixture:
• AIBN Azo-bis-isobutyronitrile
• the above ingredients are loaded into a 250 ml polymerization reactor fitted with a magnetic stirrer.
• the reaction is carried out under an atmosphere of dry nitrogen for 20 minutes, the reaction mixture is then heated to 60 ° C. and maintained at this temperature for 20 hours. Small amounts of polymer samples are taken from time to time to check the conversion.
• the solid content is 30.2%.
• Step 2 Synthesis of the diblock p (BA) 750 obp (AA) 7500 - X Composition of the reaction mixture: Tetrahydrofuran 47.00 g.
• AIBN Azo-bis-isobutyronitrile
• the above ingredients are loaded into a dry container under a dry nitrogen atmosphere for 20 minutes, then transferred to the polymerization reactor using a 2-tip syringe. At the end of the transfer, the reaction mixture is then heated to 60 ° C. and kept at this temperature for 20 hours. Small amounts of polymer samples are taken from time to time to check the conversion. The solid content is 30%.
• the reaction mixture is allowed to cool and the solvents are practically completely removed using a rotary evaporator (rotary evaporator).
• the number-average molecular mass of the copolymer is 15,000.
• the glass transition temperature of the hydrophobic block p (BA) is -54 ° C and 105 ° C for the block p (AA).
• the surface tension is 55 mN / m.
• Example 9 Synthesis of the p (BA) 1 ooo-bp (AA) 40 oo - X diblock with weight ratio p (BA) / p (AA): (20/80)
• step A) of Example 8 is reproduced exactly, except that the reaction mixture is used:
• AIBN Azo-bis-isobutyronitrile
• Step 2 Synthesis of the diblock p (BA) 1 ooo-bp (AA) 40 oo - X
• step B) of Example 8 is reproduced exactly, except that the reaction mixture is used:
• AIBN Azo-bis-isobutyronitrile
• the reaction mixture is allowed to cool and the solvents are practically completely removed using a rotary evaporator (rotary evaporator).
• the number-average molecular mass of the copolymer is 5,000.
• the glass transition temperature of the hydrophobic pBA block is -54 ° C and 105 ° C for the pAA block.
• the surface tension is 45.11 mN / m.
• Example 10 Synthesis of the diblock p (BA) 7ooo-bp (AM) 3 ooo - X with weight ratio p (BA) / p (AM): (40/60)
• step A) of Example 8 is reproduced exactly, except that the reaction mixture is used:
• AIBN Azo-bis-isobutyronitrile
• Step 2 Synthesis of the diblock p (BA) 2 ooo-bp (AM) ar ⁇ nn - X
• step B) of Example 8 The procedure of step B) of Example 8 is reproduced exactly, except that the reaction mixture is used: Tetrahydrofuran 100.00 g.
• AIBN Azo-bis-isobutyronitrile
• the reaction mixture is allowed to cool and the solvents are practically completely removed using a rotary evaporator (rotary evaporator).
• the number-average molecular mass of the copolymer is 5,000.
• the glass transition temperature of the hydrophobic block p (BA) is -54 ° C and 165 ° C for the block p (AM).
• the surface tension is 52 mN / m.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Polymers & Plastics (AREA)
• Medicinal Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Engineering & Computer Science (AREA)
• Life Sciences & Earth Sciences (AREA)
• Graft Or Block Polymers (AREA)
• Paints Or Removers (AREA)
• Detergent Compositions (AREA)
• Polymerisation Methods In General (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Adhesives Or Adhesive Processes (AREA)

Priority Applications (3)

Applications Claiming Priority (2)

Publications (2)

Family

ID=23108901

Family Applications (1)

Country Status (6)

Cited By (11)

Families Citing this family (16)

Family Cites Families (16)

• 2002
  • 2002-04-19 DE DE60225550T patent/DE60225550T2/de not_active Expired - Lifetime
  • 2002-04-19 JP JP2002587483A patent/JP4744783B2/ja not_active Expired - Lifetime
  • 2002-04-19 WO PCT/FR2002/001349 patent/WO2002090409A2/fr not_active Ceased
  • 2002-04-19 EP EP02727681A patent/EP1397403B1/fr not_active Expired - Lifetime
  • 2002-04-19 AT AT02727681T patent/ATE388970T1/de not_active IP Right Cessation
  • 2002-05-02 US US10/137,945 patent/US20020198347A1/en not_active Abandoned
• 2005
  • 2005-02-01 US US11/047,940 patent/US20050131144A1/en not_active Abandoned

Also Published As

Similar Documents

Legal Events