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WO1996002588A1 - Procede de preparation de dendrimeres - Google Patents

Procede de preparation de dendrimeres Download PDF

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Publication number
WO1996002588A1
WO1996002588A1 PCT/NL1995/000249 NL9500249W WO9602588A1 WO 1996002588 A1 WO1996002588 A1 WO 1996002588A1 NL 9500249 W NL9500249 W NL 9500249W WO 9602588 A1 WO9602588 A1 WO 9602588A1
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WO
WIPO (PCT)
Prior art keywords
excess
process according
extraction
reaction product
reactant
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.)
Ceased
Application number
PCT/NL1995/000249
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English (en)
Inventor
Ellen Marleen Monique De Brabander-Van Den Berg
Andre Banier De Haan
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Koninklijke DSM NV
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DSM NV
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Filing date
Publication date
Application filed by DSM NV filed Critical DSM NV
Publication of WO1996002588A1 publication Critical patent/WO1996002588A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/002—Dendritic macromolecules
    • C08G83/003—Dendrimers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/22—Separation; Purification; Stabilisation; Use of additives
    • C07C231/24—Separation; Purification
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/32—Separation; Purification; Stabilisation; Use of additives
    • C07C253/34—Separation; Purification
    • 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
    • C08G73/0206—Polyalkylene(poly)amines
    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G85/00—General processes for preparing compounds provided for in this subclass
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Definitions

  • the invention relates to a process for the preparation of dendrimers wherein a starting compound successively in different reaction steps is reacted with a reactant, the reactant being different from one step to the next and the reactant being applied in excess in at least one of the steps.
  • the supercritical state of an extraction agent is understood to mean the state in which the temperature is higher than or equal to 0.9 times the critical temperature and the pressure is higher than or equal to 0.9 times the critical pressure of the extraction agent.
  • the process according to the invention offers the advantage that undesirable substances present in the reaction mixture can be removed fast and simply down to a low level and that the preparation of dendrimers can be carried out in an economical way on a commercially attractive scale.
  • one extraction agent or a mixture of two or more extraction agents can be used.
  • Application of a mixture of extraction agents offers the advantage that both the extraction capacity and the extraction selectivity can be further increased.
  • 'Extraction capacity' according to the invention is understood to be the volume of a substance that can be extracted per volume unit of extraction agent.
  • 'Extraction selectivity' according to the invention is understood to be the volume of a certain substance that is extracted relative to the total volume of extracted substances.
  • the extraction agents are mostly selected in such a way that the degradation temperature of the dendrimer is higher than 0.9 times the critical temperature of the extraction agent.
  • the extraction agents according to the invention have a high affinity to the substances to be removed, for instance reactants and/or solvents.
  • Suitable extraction agents are for instance NH 3 , C0 2 , CO, NO, N0 2 , N 2 0, N 2 , S0 2 , Ci-C j alkanes or alkenes, such as for instance methane, ethane, propane, pentane, ethene and propene, halogenated hydrocarbons having 1 or 2 carbon atoms, for instance dichloromethane, halogenated sulphur compounds for instance sulphur hexafluoride and ethers such as for instance dimethyl ether.
  • ethane, ethene or C0 2 are preferably used as extraction agent.
  • Such extraction agents offer the advantage of possessing a high extraction selectivity.
  • the extraction agent according to the invention will be selected depending on, among other things, the polarity of the substance to be extracted, the solubility of the substance to be extracted in the extraction agent, the selectivity of the extraction agent towards the substance to be extracted, and the thermal stability of the dendrimer.
  • the superc itical extraction agent is selected so that it does not react with the substances to be extracted, nor with the dendrimer.
  • polar extraction agents may be used, while for the extraction of apolar substances, mostly apolar extraction agents will be used.
  • apolar extraction agents are mostly used.
  • the supercritical extraction is mostly carried out at a reduced extraction temperature between 0.9 and 2.
  • the supercritical extraction temperature applied according to the invention depends on, among other factors, the critical temperature of the extraction agent applied.
  • the supercritical extraction temperature will mostly be chosen as high as possible in order to realize the highest possible volatility of the substance(s) to be extracted.
  • the extraction temperature applied also depends on other factors, for instance the thermal stability of the dendrimer and the substance to be extracted and the safety requirements in relation with the reaction conditions.
  • a supercritical extraction temperature between 0 and 300°C is applied, in particular between 10 and 200°C, preferably between 20 and 150°C.
  • the process according to the invention is mostly carried out at a reduced pressure of between 0.9 and 10.
  • 'reduced pressure' is understood the ratio between the absolute pressure applied and the critical pressure of the extraction agent.
  • other pressures may be applied, taking into account the extraction temperature and the safety requirements.
  • the pressure is chosen in such a way that the separating effect and the extraction selectivity of the extraction agent are as high as possible.
  • a pressure between 10 and 1500 bar is applied, preferably between 50 and 800 bar, more preferably between 50 and 350 bar.
  • the extraction temperature and pressure are chosen in such a way that there is always a two-phase system present.
  • Such a two-phase system comprises a first phase which contains the dendrimer, optionally still provided with the substances to be extracted, and a second phase which contains the extraction agent, optionally already provided with the substances to be extracted.
  • the mass ratio of the amount of extraction agent applied relative to the amount of dendrimer is mostly chosen between 1 and 1000.
  • a frequently applied ratio according to the invention is between 1 and 500, preferably between 1 and 100. It has been found that with such ratios the undesirable substances present in the dendrimer can be extracted to a residual content ⁇ 1 wt.%, often between 100 and 1 ppm or lower than 1 ppm, i.e. down to the detection limit of the substance concerned, even if a 100-fold excess of the substance to be removed is present in the reaction mixture that is subjected to the supercritical extraction.
  • a suitable filling degree of the reactor used in the supercritical extraction according to the invention is mostly between 10 and 80%.
  • the reactor filling degree according to the invention is understood to mean the ratio of the volume occupied by the dendrimer to the reactor volume. With such a filling degree a suitable retention time and a good mass transfer can be realized, resulting in a high extraction capacity and selectivity, within periods of time that are economically attractive for the process. Frequently applied filling degrees are between 20 and 75%. Such filling degrees offer the additional advantage that the extraction is well reproducible. If lower filling ratios are applied, the retention time of the extraction agent in the dendrimer phase may become too short and result in a less good mass transfer during the supercritical extraction, as well as less good reproducibility of the supercritical extraction.
  • entrainers are for instance water, alcohols, N 2 0, ethene, ethers, for instance dimethyl ether and tetrahydrofuran, volatile low- molecular ketones for instance acetone and volatile low- molecular esters.
  • an alcohol more preferably methanol, is used as entrainer.
  • the entrainers used according to the invention in particular may be substances that are applied in a possible subsequent reaction step in the process for the preparation of the dendrimers.
  • the use of these particular entrainers offers the advantage that there is no need to remove these entrainers in a separate purification step.
  • the extraction temperature is mostly chosen in such a way that the entrainer does not react or reacts as little as possible, for instance with the substances to be extracted and/or the dendrimer.
  • the amount of entrainers applied is mostly 2-30 wt.%, preferably 5-15 wt.%, relative to the weight of extraction agent applied.
  • the supercritical extraction according to the invention may be carried out batchwise as well as continuously.
  • Dendrimers according to the invention are understood to be dendrimers as described in Angew. Chem. Int. Engl. 29 (1990) pp. 138-175, WO-A-9314147, WO-A- 9502008, EP-A-115771, US-A-5041516, WO-A-9214543, US-A- 4410668 and US-A-4289872.
  • the starting compound preferably is a core molecule.
  • Suitable core molecules may be chosen for instance from the group comprising ammonia, water, methanol, polymethylene diamines, for instance hexamethylene diamine, ethylene diamine, 1,4-diamino- butane, polyalkylene polyamines, for instance diethylene - triamine, triethylene tetramine, tetraethylene pentamine, linear and branched polyethylene imines, primary amines, for instance methyl amine, hydroxyethyl amine, octadecyl amine, polyamino alkylarenes, for instance 1,3,5-tris(aminomethyl)benzene, tris(aminoalkyl)amines, for instance tris(aminoethyl)amine, heterocyclic amines, for instance imidazolines and piperidines, other amines for instance hydroxyethyl aminoethyl amine, mercaptoethyl amine, morpholine, piperazine, pentaery
  • a core is used that is chosen from the group comprising ammonia, polymethylene diamines, glycols and tris(1,3,5-aminomethyl)benzene. More preferably, ammonia or 1,4-diaminobutane is applied as core molecule.
  • suitable core molecules according to the invention are for example (co)polymers containing one or more functional groups for example an amine, alcohol or thiol group.
  • suitable core molecules are for example (co)polymers containing one or more functional groups for example an amine, alcohol or thiol group.
  • suitable core molecules are for example (co)polymers containing one or more functional groups for example an amine, alcohol or thiol group.
  • suitable core molecules are for example (co)polymers containing one or more functional groups for example an amine, alcohol or thiol group.
  • suitable core molecules according to the invention are for example (co)polymers containing one or more functional groups for example an amine, alcohol or thiol group.
  • suitable core molecules according to the invention are for example (co)polymers containing one or more functional groups for example an amine, alcohol or thiol group.
  • suitable core molecules according to the invention are for example (co)polymers containing one or more functional groups for example an amine, alcohol or
  • suitable core molecules according to the invention are for example low-generation dendrimers, for instance dendrimers of the 1st, 2nd and/or 3rd generation, as described in US-A-4507466 and F. Vogtle et al., Synthesis, February 1978, pp. 155-158.
  • the reactant according to the invention is mostly chosen from the series of saturated and unsaturated nitriles, halogen cyanides with 3-50 carbon atoms which contain one or more cyanide groups -for instance mono- and polycyanides of n-propyl chloride, n-butyl chloride, isobutyl chloride, hexyl chloride, heptyl chloride, n- propyl bromide, isobutyl bromide, hexyl bromide, heptyl bromide- ⁇ , ⁇ -ethylenically unsaturated amides or esters, polyols, ethylenically unsaturated sulphides, alkylene polyamides and polyalkene polyamines, for instance ethylene diamine, diethylene triamine, triethylene tetramine, ⁇ , ⁇ -ethylenically unsaturated esters, acids and nitriles containing an acrylyl group, for instance methyl acrylate,
  • R 2 - H, -CH 3 or a hydrocarbon compound with 2- 18 carbon atoms which contains at least one double bond, conjugated with the double bond of formula 1, for instance
  • the reactant according to the invention preferably belongs to the group of acrylonitrile, methacrylate and ethylene diamine.
  • solvents and/or reactants that can be removed with the process according to the invention are, inter alia, acid anhydrides for example maleic anhydride; esters, for instance C ⁇ -C ⁇ i alkylesters of various polycarboxylic acids, for instance benzene tricarboxylic acid, acrylic acid and methacrylic acid and the corresponding acrylate and methacrylate esters of which the alkyl group contains 1 to 4 carbon atoms, for instance methyl acrylate, ethyl acrylate, methyl methacrylate, methyl itaconate; vinyl cyanides that correspond to formula 1, for instance acrylonitrile, methacrylonitrile, ethacrylonitrile; halogen cyanides with 3-50 catbon atoms which contain one or more cyanide groups, for instance mono- and polycyanides of n-propyl chloride, n
  • the process according to the invention is particularly suitable for the preparation of dendrimers as described in WO-A-9314147 and WO-A-9502008.
  • a core molecule for instance 1 , 4-diaminobutane
  • a vinyl cyanide for instance acrylonitrile
  • the excess acrylonitrile is removed down to ppm level through a supercritical extraction with C0 2 as extraction agent.
  • the nitrile groups of the resulting reaction product are hydrogenated in the presence of hydrogen whereby an amine terminated reaction product is obtained whereby water is used as a solvent. Thereafter, the amine terminated reaction product is again reacted with an excess of acrylonitrile.
  • the supercritical extraction procedure can be repeated a number of times, for example after every Michael addition reaction in case dendrimers of higher generations are prepared.
  • the process according to the invention is also suitable for the preparation of polyamidoamine dendrimers as described in Angew. Chem. Int. Engl. 29 (1990) pp. 138- 175.
  • the following reaction steps are repeated alternately until a dendrimer of the desired generation or the desired molecular weight is obtained: for instance an amount of ammonia is reacted in a Michael reaction with an excess of methacrylate in methanol as solvent, so that every ammonia molecule reacts with three molecules of methylacrylate whereby an ester terminated reaction product is obtained.
  • the excess of methylacrylate is removed from the reaction mixture down to ppm level, for instance by means of a supercritical extraction whereby C0 2 is used as extraction agent.
  • the resulting ester terminated reaction product is subsequently reacted in an amidation reaction with an excess of ethylene diamine, whereby methanol is used as solvent and whereby an amine terminated reaction product is obtained.
  • the molar excess of ethylene diamine relative to methacrylate groups is between 4:1 and 50:1.
  • the excess of ethylene diamine is removed from the reaction mixture for instance by means of a supercritical extraction in an apolar extraction agent, for instance ethane to which 5 wt.% of methanol is added as entrainer.
  • the Michael reaction, the amidation reaction and the intermediate supercritical extractions may be repeated the required number of times.
  • the invention will be further elucidated in the following examples, without however being restricted thereto.
  • Example I To an autoclave with a volume of 50 cm 3 20 g of a second-generation polypropylamine dendrimer, 8- cascade:1,4-diaminobutane[4] : (1-azabutylidene) 4 : azabutylidene) :propionitrile containing 1 wt.% of acrylonitrile, was added. To remove the acrylonitrile from the polypropylamine dendrimer, a supercritical extraction was carried out, by passing a flow of 400 g of C0 2 through the dendrimer for 45 minutes, at a pressure of 180 bar and a temperature of 313 K. The residual acrylonitrile content of the dendrimer, as determined by gas chromatography, was less than 0.01 wt.%.
  • a supercritical extraction is carried out by passing a flow of 100 g of ethane to which 5 wt.% methanol is added through the dendrimer phase for 60 minutes, at a pressure of 180 bar and a temperature of 333 K.
  • the residual ethylene diamine content of the dendrimer determined by gas chromatography is ⁇ 0.05 wt.%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Procédé de préparation de dendrimères, selon lequel on fait réagir successivement dans des étapes de réaction différentes un composé initial et un réactif dans chacune des étapes successives différentes, le réactif étant différent d'une étape à l'autre, et mis en oeuvre en quantité excédentaire dans l'une au moins de ces étapes, tandis que dans l'une au moins desdites étapes, l'excédent de réactif est extrait au moyen d'un agent d'extraction à l'état surcritique. L'agent d'extraction peut également renfermer un agent entraînant.
PCT/NL1995/000249 1994-07-18 1995-07-17 Procede de preparation de dendrimeres Ceased WO1996002588A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL9401179A NL9401179A (nl) 1994-07-18 1994-07-18 Werkwijze voor de bereiding van dendrimeren.
NL9401179 1994-07-18

Publications (1)

Publication Number Publication Date
WO1996002588A1 true WO1996002588A1 (fr) 1996-02-01

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PCT/NL1995/000249 Ceased WO1996002588A1 (fr) 1994-07-18 1995-07-17 Procede de preparation de dendrimeres

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WO (1) WO1996002588A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004048442A1 (fr) * 2002-11-26 2004-06-10 Centro Nacional De Investigaciones Cientificas (Cnic) Procede de preparation de dendrons et de dendrimeres a partir de sous-structures heterocycliques d'iminoethers et de derives par des voies non classiques et sous micro-ondes
WO2005007726A1 (fr) * 2003-07-11 2005-01-27 Basf Aktiengesellschaft Procede de fabrication de polymeres hyperramifies
WO2015050916A1 (fr) 2013-10-04 2015-04-09 The Procter & Gamble Company Compositions comprenant des substances de parfum compatibles avec des polymères de polyamine à modification hydrophobique
WO2015050915A1 (fr) 2013-10-04 2015-04-09 The Procter & Gamble Company Compositions comprenant des matières de parfum compatibles avec des polymères de polyamine
CN113337007A (zh) * 2021-04-28 2021-09-03 佳化化学（抚顺）新材料有限公司 液体阻燃剂、阻燃硅橡胶及其制备方法和应用
CN116082228A (zh) * 2023-01-06 2023-05-09 南通立洋化学有限公司 一种2-氰基吡啶的超临界萃取工艺

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01272601A (ja) * 1988-04-25 1989-10-31 Asahi Denka Kogyo Kk 塩素化樹脂の溶媒除去方法

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01272601A (ja) * 1988-04-25 1989-10-31 Asahi Denka Kogyo Kk 塩素化樹脂の溶媒除去方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 14, no. 37 (C - 680) 24 January 1990 (1990-01-24) *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004048442A1 (fr) * 2002-11-26 2004-06-10 Centro Nacional De Investigaciones Cientificas (Cnic) Procede de preparation de dendrons et de dendrimeres a partir de sous-structures heterocycliques d'iminoethers et de derives par des voies non classiques et sous micro-ondes
WO2005007726A1 (fr) * 2003-07-11 2005-01-27 Basf Aktiengesellschaft Procede de fabrication de polymeres hyperramifies
CN100447180C (zh) * 2003-07-11 2008-12-31 巴斯福股份公司 超支化聚合物的制备
WO2015050916A1 (fr) 2013-10-04 2015-04-09 The Procter & Gamble Company Compositions comprenant des substances de parfum compatibles avec des polymères de polyamine à modification hydrophobique
WO2015050915A1 (fr) 2013-10-04 2015-04-09 The Procter & Gamble Company Compositions comprenant des matières de parfum compatibles avec des polymères de polyamine
CN113337007A (zh) * 2021-04-28 2021-09-03 佳化化学（抚顺）新材料有限公司 液体阻燃剂、阻燃硅橡胶及其制备方法和应用
CN116082228A (zh) * 2023-01-06 2023-05-09 南通立洋化学有限公司 一种2-氰基吡啶的超临界萃取工艺

Also Published As

Publication number Publication date
NL9401179A (nl) 1996-03-01

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