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WO2003064502A1 - Dendrimeres de polyester, procede de fabrication de ces dendrimeres et utilisation correspondante - Google Patents

Dendrimeres de polyester, procede de fabrication de ces dendrimeres et utilisation correspondante Download PDF

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Publication number
WO2003064502A1
WO2003064502A1 PCT/FI2003/000074 FI0300074W WO03064502A1 WO 2003064502 A1 WO2003064502 A1 WO 2003064502A1 FI 0300074 W FI0300074 W FI 0300074W WO 03064502 A1 WO03064502 A1 WO 03064502A1
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WO
WIPO (PCT)
Prior art keywords
group
groups
alkali metal
dendrimers
polyester
Prior art date
Application number
PCT/FI2003/000074
Other languages
English (en)
Inventor
Kari Rissanen
Jarmo Ropponen
Kalle NÄTTINEN
Original Assignee
University Of Jyväskylä
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by University Of Jyväskylä filed Critical University Of Jyväskylä
Publication of WO2003064502A1 publication Critical patent/WO2003064502A1/fr

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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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/246—Intercrosslinking of at least two polymers
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • 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
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/002—Dendritic macromolecules
    • C08G83/003—Dendrimers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/005—Dendritic macromolecules
    • 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
    • C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
    • 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
    • C08J2389/00—Characterised by the use of proteins; Derivatives thereof

Definitions

  • Polyester dendrimers method for the manufacture thereof, and their use
  • the invention is related to new polyester dendrimers prepared via a two-step process from a polyol and a haloacetyl halide (step 1) and subsequent reaction with an alkali metal enolate (step 2). Further, the invention is directed to the use of said dendrimers as cross linkers in polymers and gels, active components in glues and coatings, matrix material in inorganic or organic or bio-composites as well as ionselective complexation agents for analytical and catalysis applications.
  • Dendrimers have a very compact spherical structure and their surface can contain from a few to hundreds of functional groups depending on the nature and size of the dendrimer.
  • the low intrinsic viscosity of dendrimers versus molecular weight and possibility to multi- functionality on the surface of the dendrimer are properties, which are either com- pletely absent or very difficult to achieve with linear polymers.
  • Dendrimers with a very branched structure can be used in many applications, such as catalysts, parts of pharmaceuticals, carriers or transporters, imaging agents in medicine, in improving viscosity or gen- eral properties of cosmetics, as glues and coating agents, matrix material for inorganic or organic or bio-composites, lubricants, anti-corrosion agents, pesticides or agricultural chemicals and polyfunctional cross linkers in polymer production, medical and dentistry preparates, dentures and prosthesis.
  • the polyester dendrimers according to the invention are polyester dendrimers of a polyol with 2 - 64 reactive hydroxyl groups, wherein the surface of the dendrimer is formed using an alternating sequence of haloacetyl halide and an alkali metal enolate.
  • the polyester dendrimers according to the invention are polyester dendrimers of a polyol with 2 - 64 reactive hydroxyl groups wherein the surface of the dendrimer is formed using an alternating sequence of haloacetyl halide and an alkali metal enolate, and preferably said dendrimers are surface functionalized by bis- or tris- methyl and ethyl esters.
  • the polyester dendrimers according to the invention are pure single crystal forming crystalline compounds or liquid compounds.
  • the polyester dendrimers are manufactured by reacting a bisfunctionalized chemical, a haloacetyl halide, with a core molecule that contains hydroxyl groups, such as a polyol with 2 - 64 reactive hydroxyl groups. This reaction produces an easily separable reactive dendritic polyester polyhalide, which readily reacts subsequently with a third chemical, an alkali metal enolate, producing the desired polyester dendrimer.
  • ⁇ -haloacetyl anhydride or ⁇ -haloacetic acid with some condensing agent, such as cyclohexylcar- bodiimide.
  • condensing agent such as cyclohexylcar- bodiimide.
  • haloacetyl halides are prefened.
  • the obtained polyester polyhalide (III) is allowed to react with an alkali metal enolate (IVa), or bis- or tris(carbonyl)methane derivative (IVb) together with an alkali metal base, in a solvent or a mixture of solvents and preferably at an elevated temperature. Then a suitable solvent is added to the reaction mixture, the reaction mixture is washed with water, with concentrated alkali metal hydrogen carbonate and again with water. The solvent layer is dried and the solvent is evaporated, preferably under vacuum.
  • an alkali metal enolate (IVa), or bis- or tris(carbonyl)methane derivative (IVb) together with an alkali metal base
  • Groups R 2 , R 3 and R 4 are selected, independently from each other, so that a bis(carbonyl)methane or tris(carbonyl)methane derivative is obtained. This selection is done from a group consisting of H, COH, CSH, COOR 5 , COSR 5 , CSOR 5 , CSSR 5 , COR 5 , CSR 5 , CO ⁇ R 5 R 6 , CSNR 5 R 6 . Preferable ones are methoxycar- bonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl and hexyloxycarbonyl groups and aryloxycarbonyl groups.
  • Suitable aryl groups, (hetero) aromatic groups and aliphatic groups, which contain oxygen, sulfur, nitrogen or phosphorous atoms are 3-hydroxymethylpyridine, 2- hydroxymethyltiophene, 2-hydroxymethylfurane, 2-hydroxymethylpynole and hydroxymethyldiethyl phosphonate groups.
  • step 2 the intermediate (III) obtained from step 1 is reacted with an alkali metal enolate (INa), or bis- or tris(carbonyl)methane compound (IVb) together with an alkali metal base, in an inert aprotic solvent or a mixture of inert aprotic solvents, preferably DMF, at a temperature of 20-120 °C, preferably at 60-100 °C.
  • the reaction mixture is then agitated at a temperature of 20-120 °C, preferably 80-100 °C, for approximately 20 hours and it is then cooled to room temperature.
  • a non- polar solvent or a mixture of non-polar solvents is added to the reaction mixture, and the obtained mixture is then washed with water, then with saturated alkaline earth metal hydrogen carbonate, dried and the solvent is evaporated, preferably under vacuum.
  • a polar solvent or a mixture of polar sol- vents such as an alcohol like ethanol is added and the obtained final product dendrimer (V) is separated, hi the case it is a crystalline product, it is preferable filtered and dried and if it is a liquid, it may be distilled under vacuum.
  • the novel polyester dendrimers according to the invention have several advantages.
  • the products are very pure, no or very little undesired side-products or mixtures ofproducts are formed. This results in that the cureability of polyester prod- ucts made from these dendrimers is good as no or very little impurities interfere in the curing reaction. Additionally, due to the unique and true crystalline stmcture and crystallinity of many of the products, and because of the reaction conditions, the obtained dendrimers contain no or very little detectable amounts of solvents.
  • These polyester dendrimers, many of which are first truly crystalline polyester dendrimers, are easy to handle, they are stable for long storage periods and they are non- hygroscopic. Because said dendrimers are chemically polyesters, they also are at least partially biodegradable and relatively non-toxic.
  • the method according to the invention has several advantages.
  • the yields are good, very pure final products can be obtained, the starting materials are cheap and usually commercially available substances, and almost all materials used in the process may be recirculated.
  • polyester dendrimers according to the invention may be used in many applications, such as catalysts, parts of pharmaceuticals, carriers, transporters, imaging agents in medicine, in improving viscosity or general properties of cosmetics, as glues and coating agents, matrix material for inorganic or organic or bio- composites, lubricants, anti-conosion agents, pesticides or agricultural chemicals and polyfunctional cross linkers in polymer and gel production, medical and dentistry preparates, dentures and prosthesis as well as ionselective complexation agents for analytical and catalysis applications, like the commercially available dendrimers are used.
  • polyester dendrimers according to the invention can be used in similar application fields as what is disclosed in US 5,834,118, WO 96/07688, WO 93/17060, WO 96/12754, WO 96/13558 and WO 96/19537 for dendrimers according to the state of the art.
  • Pentaerythritol (3.08 g, 22.6 mmol) was refluxed with chloroacetyl chloride (15.3 g, 136 mmol) for 45 minutes. Excess of acid chloride was removed in vacuo. The residue solidified on cooling and it was recrystalhzed twice from ethanol to give white flakes. The yield of ten"alds-(2-chloro-acetoxymethyl)-methane was 8.3 g (83 %).
  • Dipentaerythritol (7.13 g, 28.0 mmol) was refluxed with chloroacetyl chloride (25.5 g, 252 mmol) for 2 hours. Excess of acid chloride was removed in vacuo. The residue solidified on cooling and it was recrystalhzed twice from ethanol to give white flakes. The yield of 2,2,2-tris-(2-chloro-acetoxymethyl)-ethoxymethyl- tris-(2-chloro-acetoxymethyl)methane was 14.2 g (71 %).
  • Tetrakis-(2-chloro-acetoxymethyl)-methane obtained in example 1 (1.27 g, 2.88 mmol) was added to a stined solution of NaC(CO 2 Me) 3 (2.70 g, 12.7 mmol) in DMF (40 ml) at 90 °C. After 20 hours, the solution was cooled down to RT and CHC1 3 (75 ml) was added. The solution was washed with water (3*30ml), saturated NaHCO 3 (3*30 ml), water (3*30ml), and dried over anhydrous MgSO 4 . The solution was concentrated in vacuo, then ethanol was added. The product was crystallized as white flakes. The yield of tetrakis-(2,2,2-tris-(methoxycarbonyl)- acetoxymethyl)-methane was 2.8 g (93 %).
  • Tetralds-(2-chloro-acetoxymethyl)-methane obtained in example 1 (1.44 g, 3.26 mmol) was added to a stined solution of NaC(CO 2 Et) 3 (3.33 g, 13.1 mmol) in DMF (40 ml) at 90 °C. After 20 hours, the solution was cooled down to RT and CHC1 3 (75 ml) was added. The solution was washed with water (3*30ml), saturated NaHCO 3 (3*30 ml), water (3*3Qm ⁇ ), and dried over anhydrous MgSO 4 . The solution was concentrated in vacuo, then ethanol was added. The product crystallized as white flakes.
  • Tetrakis-(2-chloro-acetoxymethyl)-methane obtained in example 1 (1.78 g, 4.03 mmol) was added to a stined solution of NaC(CO 2 Hex) 3 (6.83 g, 16.1 mmol) in DMF (40 ml) at 90 °C. After 20 hours, the solution was cooled down to RT and CHC1 3 (75 ml) was added. The solution was washed with water (3*30ml), saturated NaHCO 3 (3*30 ml), water (3*30ml), and dried over anhydrous MgSO 4 . The solution was concentrated in vacuo. The product dodecahexyl polyester dendrimer was dark oil. Yield 4.03 g (13 %).

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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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne des dendrimères de polyester d'un polyol renfermant entre 2 et 64 groupes hydroxyle réactifs, les fonctions ester étant assurées par des séquences alternées d'halogénure d'haloacétyle et d'énolate de métal alcalin. Lesdits dendrimères de polyester sont préparés au moyen d'un procédé en deux étapes consistant à utiliser un polyol et un halogénure d'haloacétyle (étape 1), puis à réaliser une réaction avec un énolate de métal alcalin (étape 2). L'invention concerne en outre l'utilisation desdits dendrimères de polyester comme agents de réticulation dans des polymères et des gels, comme constituants actifs dans des colles et des revêtements, comme matériau de base dans des bio-composites inorganiques ou organiques, et comme agents complexants à sélectivité ionique destinés à des applications analytiques et catalytiques.
PCT/FI2003/000074 2002-01-31 2003-01-30 Dendrimeres de polyester, procede de fabrication de ces dendrimeres et utilisation correspondante WO2003064502A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FI20020186 2002-01-31
FI20020186A FI20020186A0 (fi) 2002-01-31 2002-01-31 Toimintakykyiset polyesteridendrimeerit, niiden valmistusmenetelmõ ja kõytt÷

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WO2003064502A1 true WO2003064502A1 (fr) 2003-08-07

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005075563A1 (fr) * 2004-02-04 2005-08-18 Basf Aktiengesellschaft Masses de moulage fluides en polyester
EP1616920A1 (fr) * 2004-07-15 2006-01-18 Agfa-Gevaert Nouveaux initiateurs de polymérisation
EP1616921A1 (fr) * 2004-07-15 2006-01-18 Agfa-Gevaert Nouvelles compositions durcissables par rayonnement
US7507773B2 (en) 2004-07-15 2009-03-24 Agfa Graphics N.V. Radiation curable compositions
US7538144B2 (en) 2004-07-15 2009-05-26 Agfa Graphics, N.V. Photoreactive polymers
WO2009115580A3 (fr) * 2008-03-20 2010-03-18 National University Of Ireland, Galway Dendrimères et applications de dendrimères
US7795324B2 (en) 2004-07-15 2010-09-14 Agfa Graphics, N.V. Radiation curable compositions
US7875698B2 (en) 2004-07-15 2011-01-25 Agfa Graphics Nv Polymeric initiators
US8282959B2 (en) 2006-11-27 2012-10-09 Actamax Surgical Materials, Llc Branched end reactants and polymeric hydrogel tissue adhesives therefrom

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992008749A1 (fr) * 1990-11-19 1992-05-29 Cornell Research Foundation, Inc. Polyamides et polyesters hyper-ramifies
US5418301A (en) * 1992-02-26 1995-05-23 Perstorp Ab Dendritic macromolecule and process for preparation thereof
US5834118A (en) * 1994-09-08 1998-11-10 Neste Oy Of Keilaniemi Radiation curable resins comprising hyperbranched polyesters
EP1006101A1 (fr) * 1997-08-18 2000-06-07 Nippon Steel Chemical Co., Ltd. Dendrimere (meth)acrylate d'ester aromatique et composition de resine capable de durcir
WO2001096291A1 (fr) * 2000-06-02 2001-12-20 National Starch And Chemical Investment Holding Corporation Polymercaptans a multireactivite, polymeres en forme d'etoiles et procedes de preparation

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992008749A1 (fr) * 1990-11-19 1992-05-29 Cornell Research Foundation, Inc. Polyamides et polyesters hyper-ramifies
US5418301A (en) * 1992-02-26 1995-05-23 Perstorp Ab Dendritic macromolecule and process for preparation thereof
US5834118A (en) * 1994-09-08 1998-11-10 Neste Oy Of Keilaniemi Radiation curable resins comprising hyperbranched polyesters
EP1006101A1 (fr) * 1997-08-18 2000-06-07 Nippon Steel Chemical Co., Ltd. Dendrimere (meth)acrylate d'ester aromatique et composition de resine capable de durcir
WO2001096291A1 (fr) * 2000-06-02 2001-12-20 National Starch And Chemical Investment Holding Corporation Polymercaptans a multireactivite, polymeres en forme d'etoiles et procedes de preparation

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005075563A1 (fr) * 2004-02-04 2005-08-18 Basf Aktiengesellschaft Masses de moulage fluides en polyester
CN100455626C (zh) * 2004-02-04 2009-01-28 巴斯福股份公司 可流动的聚酯模塑组合物
AU2005211504B2 (en) * 2004-02-04 2010-08-05 Basf Aktiengesellschaft Fluid polyester moulding masses
EP1616920A1 (fr) * 2004-07-15 2006-01-18 Agfa-Gevaert Nouveaux initiateurs de polymérisation
EP1616921A1 (fr) * 2004-07-15 2006-01-18 Agfa-Gevaert Nouvelles compositions durcissables par rayonnement
US7507773B2 (en) 2004-07-15 2009-03-24 Agfa Graphics N.V. Radiation curable compositions
US7538144B2 (en) 2004-07-15 2009-05-26 Agfa Graphics, N.V. Photoreactive polymers
US7795324B2 (en) 2004-07-15 2010-09-14 Agfa Graphics, N.V. Radiation curable compositions
US7875698B2 (en) 2004-07-15 2011-01-25 Agfa Graphics Nv Polymeric initiators
US8282959B2 (en) 2006-11-27 2012-10-09 Actamax Surgical Materials, Llc Branched end reactants and polymeric hydrogel tissue adhesives therefrom
WO2009115580A3 (fr) * 2008-03-20 2010-03-18 National University Of Ireland, Galway Dendrimères et applications de dendrimères

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Publication number Publication date
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