Classifications

• • 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
  • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
  • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
  • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
• • 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
  • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
• • 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
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/02—Polyamines
  • C08G73/028—Polyamidoamines
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of 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
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/02—Polyamines

Definitions

• the present invention relates to supramolecular polymers.
• Supramolecular polymers are polymers in which the units are low-mass monomers or prepolymers which are linked together by hydrogen bonds ("H bridges" or "H bonds") whereas in a conventional polymer the units are linked between them by covalent bonds.
• H bridges or "H bonds”
• H bonds hydrogen bonds
• An advantage of these supramolecular polymers is that these hydrogen bonds are reversible.
• the prepolymer units in the present invention contain imidazolidone groups which form hydrogen bonds according to the following scheme:
• prepolymer units can be very easily prepared by reacting urea with polyalkyleneimines, polyamines or polyamides.
• Patent 6320018 describes supramolecular polymers based on units having ureido-pyrimidone groups.
• Patent application EP 1031589 describes supramolecular polymers based on units with isocyanate functions or their derivatives.
• Patent application EP 1136506 describes supramolecular polymers based on units with glutarimide functions.
• Patent application WO 01 07396 describes supramolecular polymers based on of units having hydroxyl functions and carboxylic acid functions carried by aromatic rings.
• Supramolecular polymers have now been found in which the units are monomers or prepolymers which can be produced in a very simple manner, much simpler than in the prior art. It suffices, for example, to react urea on a product having NH 2 or NH functions separated by 2 or 3 carbon atoms. In addition, some of these monomers or prepolymers are new products in themselves.
• the present invention relates to a supramolecular polymer comprising units linked by hydrogen bonds, these units being monomers or prepolymers comprising at least one function chosen from functions (1) and (3) and a second function chosen from functions (1 ) to (5) below:
• A denotes oxygen, sulfur or NH and X any unit; the hydrogen bonds in the supramolecular polymer taking place between two identical or different functions chosen from functions (1) to (5).
• the carbon atoms in formulas (1) to (4) may be substituted.
• the monomers or prepolymers comprising at least one of the functions (1) to (4) can be obtained by reaction of a product of formula (6) below:
• the function (1) is obtained by reaction of the product (6) on a monomer or a prepolymer containing the following sequences (1 '):
• the function (2) is obtained by reaction of the product (6) on a monomer or a prepolymer containing the following sequences (2 '):
• the function (3) is obtained by reaction of the product (6) on a monomer or a prepolymer containing the following sequences (3 '):
• the function (4) is obtained by reaction of the product (6) on a monomer or a prepolymer containing the following sequences (4 '):
• the carbon atoms which are between the nitrogen can be substituted.
• the polymers of the invention can be used alone, that is to say in the form of a composition consisting essentially of these polymers and optionally of stabilizers, antioxidants, etc., either in the form of a mixture with other polymers or other products.
• the polymers of the invention are particularly useful as: - rheology modifiers for paints or coatings, additives for varying the fluidity of epoxy paints with temperature and in particular in powder paints, additives in the use of thermoplastics for reversible crosslinking, - additives to facilitate recycling of thermoplastic materials by destruction of the hydrogen bonds by a specific solvent, additives in coatings to then facilitate their pickling by a specific solvent for the hydrogen bonds, additives for the shock modification of polyamides , - additives in hot-melts (hot-melt adhesives), hot-melts, additives in lubricants.
• the present invention also relates to the uses mentioned above as well as the compositions comprising the supramolecular polymers of the invention. [Detailed description of the invention]
• the monomers or prepolymers comprising at least one function chosen from functions (1) and (3) and a second function chosen from functions (1) to (5) advantageously "A" denotes an oxygen atom.
• the monomers or prepolymers containing one or more of the functions (1) to (4) can be obtained by reaction of a product of formula (6) with monomers or prepolymers carrying the corresponding precursors (1 ') to (4') as well that it is explained above.
• These monomers or prepolymers comprising at least one of the functions (1) to (4) can also be manufactured by fixing these functions on a product to transform it into a monomer or prepolymer carrying these functions (1) to (4).
• a polyamine is reacted with urea, that is to say the product of formula (6) in which A is an oxygen atom, then this polyamine carrying functions (1) and a function -NH- reacts with an alkyl halide to form a monomer or prepolymer carrying the functions (1).
• urea that is to say the product of formula (6) in which A is an oxygen atom
• this polyamine carrying functions (1) and a function -NH- reacts with an alkyl halide to form a monomer or prepolymer carrying the functions (1).
• urea is reacted with diethylene triamine, one obtains: which is then reacted on a monomer or a prepolymer carrying at least one carboxylic acid function to obtain a monomer carrying the functions (1) and (5).
• the monomers and the prepolymers which constitute it may contain other monomers or prepolymers which cause a molecular disorder preventing crystallization.
• monomers or prepolymers containing -NH2 and -NH- or -NH- and -NH- functions separated by 2 or 3 carbon atoms mention may be made of polyamines such as diethylene triamine (DETA), triethylene tetramine ( TETA), and tetraethylene pentamine (TEPA). Illustrated below are examples of monomers or prepolymers carrying functions (1) and (2) in which A is an oxygen atom. Mention may also be made of the diamines derived from acid dimers, the formation of the functions (1) in which A is an oxygen atom is illustrated below:
• polyamide-type prepolymers resulting from the condensation of polyamines such as DETA, TETA and TEPA mentioned above with diacids.
• these diacids are fatty acids.
• these diacids contain traces of acid trimers. This is illustrated by the following diagram in which the product of formula (5) is urea.
• x% starlike oligomers designates star oligomers produced by the presence of the acid trimers “x% acid trimer”.
• Ethylene-bis-diimidazolidone contains 2 functions (1) is very pure so it crystallizes.
• This aqueous solution contains the monomer of the invention comprising the functions (1).
• This fraction does not crystallize due to a molecular disorder caused by impurities in triethylene tetramine. Analysis shows that this fraction is mainly composed of ethylene-bis-diimidazolidone (A), N- piperazinoethyl-imidazolidone (B), Bis AEP: N, N'-bis- (2-aminoethyl) -piperazine (C), Branched TETA: tris- (2-aminoethyl) amine (D). "industrial" amine
• TETA N, N'-bis (2- aminoethyl) -1,2-ethanediamine
• Bis AEP N, N'-bis- (2-aminoethyl-piperazine
• PEEDA N - [(2-aminoethyl) -2- aminoethyl] piperazine
• Branched TETA tris- (2- aminoethyl) amine.
• the glass transition temperatures (Tg), measured by differential enthalpy analysis (AED) are recorded in the following table:
• PEEDA Bis AEP BPE The procedure (dropwise addition of 34 mmol of dibromoethane and then reflux for 3 hours) is repeated until the contents of TETA and PEEDA are approximately equal in the mixture.
• Example 4 After evaporation of the solvent and other volatile materials under vacuum and cooling, 2.4 g (40 mmol) of urea are added. The mixture is then treated according to the indications in Example 1. At the end of the reaction, the reaction mixture does not crystallize but forms a glassy mass soluble in water. The mixture obtained, combined with polyacrylic acid, makes it possible to form films according to the indications in Example 2.
• Example 4
• Crayamid 115 is a polyamide (Mw -2000-4000 g / mol), condensation product of a TOFA type acid dimer (Anglo-Swedish abbreviation of Tall Oil Fatty Acid or fatty acid from pine) and triethylene tetramine.
• Example 5 50g of Crayamid 140 (• Note 4) and 15g of urea are treated according to the indications in Example 5.
• the mother solution obtained (with 13% of dry extract) is washed with 2x100 ml of salted water, dried over magnesium sulfate and filtered through 4g of silica gel.
• the films prepared from this solution according to the indications of Example 6 are transparent, flexible and non-sticky. The thickness in the center is 0.70 mm. These films can be cut precisely with a cookie cutter or using cutting tools. The objects thus obtained retain their dimensional characteristics.
• Crayamid 140 is a polyamide (Mw -2000-4000 g / mol), condensation product of a TOFA type acid dimer (Anglo-Swedish abbreviation of Tall Oil Fatty Acid or fatty acid from pine) and triethylene tetramine.
• Example 9

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
• Polyamides (AREA)
• Adhesives Or Adhesive Processes (AREA)
• Lubricants (AREA)
• Paints Or Removers (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

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Cited By (26)

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• 2003
  • 2003-01-15 JP JP2003560064A patent/JP2005514498A/ja active Pending
  • 2003-01-15 EP EP03712245A patent/EP1465930B1/fr not_active Expired - Lifetime
  • 2003-01-15 AU AU2003216726A patent/AU2003216726A1/en not_active Abandoned
  • 2003-01-15 WO PCT/FR2003/000114 patent/WO2003059964A2/fr not_active Ceased
  • 2003-01-15 DE DE60304992T patent/DE60304992T2/de not_active Expired - Lifetime
  • 2003-01-15 US US10/503,610 patent/US7250487B2/en not_active Expired - Lifetime
  • 2003-01-15 ES ES03712245T patent/ES2263962T3/es not_active Expired - Lifetime
  • 2003-01-15 AT AT03712245T patent/ATE325140T1/de active
• 2006
  • 2006-11-14 US US11/598,931 patent/US7348397B2/en not_active Expired - Lifetime
• 2008
  • 2008-03-19 US US12/051,278 patent/US7750113B2/en not_active Expired - Fee Related
• 2009
  • 2009-11-27 JP JP2009269623A patent/JP5554549B2/ja not_active Expired - Fee Related
• 2012
  • 2012-12-19 JP JP2012276741A patent/JP2013100512A/ja not_active Withdrawn

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