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WO1999000440A1 - Synthese d'un polyalcool dendritique - Google Patents

Synthese d'un polyalcool dendritique Download PDF

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Publication number
WO1999000440A1
WO1999000440A1 PCT/SE1998/001229 SE9801229W WO9900440A1 WO 1999000440 A1 WO1999000440 A1 WO 1999000440A1 SE 9801229 W SE9801229 W SE 9801229W WO 9900440 A1 WO9900440 A1 WO 9900440A1
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WO
WIPO (PCT)
Prior art keywords
process according
hydroxyl groups
protected
branching
chain extender
Prior art date
Application number
PCT/SE1998/001229
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English (en)
Inventor
Henrik Ihre
Anders Hult
Original Assignee
Perstorp Ab
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 Perstorp Ab filed Critical Perstorp Ab
Priority to AU79510/98A priority Critical patent/AU7951098A/en
Publication of WO1999000440A1 publication Critical patent/WO1999000440A1/fr

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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
    • 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
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • 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
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/40—Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds, other than from esters thereof

Definitions

  • the present invention relates to a process for a double stage convergent synthesis of a polymeric polyalcohol (polyol) substantially and preferably built up from polyester units, optionally in combination with ether or polyether units
  • the polymeric polyalcohol is a hyperbranched dendritic polyester alcohol having reactive or protected terminal hydroxyl groups
  • the polyester alcohol is synthesized by repeated addition of ketal protected chain extenders, producing a dendron, followed by addition of said dendron to a core
  • the core has n reactive unprotected hydroxyl or epoxide groups to which n branches each consisting of g branching generations are added, whereby n and g are integers and at least 1
  • the branching generations comprises at least one polymeric or monomeric branching chain extender having three reactive groups of which two are hydroxyl groups
  • Hyperbranched and dendritic macromolecules normally consist of an initiator or core having one or more reactive sites and a number of branching layers and optionally a layer of chain terminating molecules. Continued replication of branching layers normally yields increased branch multiplicity and, where applicable or desired, increased number of terminal groups.
  • the layers are usually called generations and the branches dendrons, which are designations herein used.
  • EP 0 1 15 771 claims a dense star polymer having at least three symmetrical core branches, each core branch having at least one terminal group, and a ratio terminal groups to core branches being greater than 2 1
  • the properties of claimed polymer is specified through a comparative relation to an unspecified and allegedly known star polymer Claim 1 can due to inoperable teaching of terminal groups and unspecified comparison not be interpreted
  • EP 0 1 15 771 also relates to a process, which process substantially also is disclosed in US 4,410,688, for synthesis of a symmetrical dense star polymer The process teaches a repeated and alternately addition of alkyl acrylate and alkylene diamine to a core consisting of ammonia
  • SE 468 771 discloses a hyperbranched dendritic macromolecule substantially built up from polyester units and a process for synthesis of said macromolecule
  • the macromolecule is composed of an initiator, having at least one hydroxyl group, to which initiator at least one branching generation comprising at least one chain extender, having at least one carboxyl group and at least two hydroxyl groups, is added
  • the macromolecule is optionally chain terminated
  • the process for synthesis of said macromolecule teaches a co-esterification of the initiator and the chain extender, optionally followed by a chain termination
  • WO 93/18075 teaches a hyperbranched polymer having at least six terminal hydroxyl or carboxyl groups and a process for its synthesis
  • the hyperbranched polymer is synthesized by repeated and alternately addition of a compound having at least one anhydride group followed by a compound having at least one epoxide group to a core having at least one hydroxyl group
  • EP 0 575 596 discloses a dendritic macromolecule comprising a core having 1 - 10 functional groups and branches synthesized from vinyl cyanide units as well as a process for synthesis thereof The process involves three repeated steps beginning with a reaction between the core and monomeric vinyl cyanide units followed by reduction of incorporated nitrile groups to amine groups In a third step said amine groups are reacted with monomeric vinyl cyanide units
  • SE 503 342 discloses a hyperbranched dendritic macromolecule of polyester type and a process for synthesis of said macromolecule
  • the macromolecule is substantially composed of a core, having at least one epoxide group, to which core at least one branching generation comprising at least one chain extender, having at least three reactive functions of which at least one is a carboxyl or epoxide group and at least one is a hydroxyl group, is added.
  • the macromolecule is optionally chain terminated.
  • the process teaches self condensation of the chain extender molecules yielding a dendron (a core branch), which dendron in a second step is added to the core.
  • the process also comprises an optionally further chain extension by addition of spacing or branching chain extenders and/or an optional chain termination.
  • the process yields inexpensive polydisperse hyperbranched dendritic macromolecules.
  • US 5,561 ,214 relates to highly asymmetrical hyperbranched polydisperse polyaspartate esters and a process for their synthesis.
  • the process comprises self condensation, via transesterification, of at least a portion of the hydroxyl or ester groups of a hydroxyaspartate.
  • the dendrimers are synthesized in the convergent fashion, whereby dendrons (core branches) first are synthesized from acylated 2,2-Bis(hydroxymethyl)propanoic acid and then coupled to a polyfunctional phenolic core molecule.
  • dendrons core branches
  • a further disclosure of recent developments is "Hyperbranched Aliphatic Polyesters - Synthesis, Characterization and Applications” by Eva Malmstr ⁇ m, Royal Institute of Technology, Sweden 1996, wherein hyperbranched dendritic polyesters of the type disclosed in SE 468 771 are studied and discussed.
  • Hyperbranched dendritic including dendrimers, polyalcohols substantially built up from polyester units give, due to the symmetrical or near symmetrical highly branched structure, in comparison to ordinary polyalcohols and randomly branched, polydisperse, polyester polyalcohols great advantages.
  • Said hyperbranched dendritic polyalcohols exhibit a low polydispersity and can, due to the structure, be formulated to give a very high molecular weight yet exhibiting a very low viscosity
  • Hyperbranched dendritic, including dendrimers, polyester polyalcohols can advantageously be used for further processing, such as chain termination and/or functionalization, thus yielding dendritic products having for instance a fatty acid chain termination, alkenyl groups, such as allyl, vinyl or acryl, primary or secondary epoxide groups, isocyanate groups and/or undergo similar conversion of or reaction involving the hydroxyl groups of said polyalcohol.
  • the inexpensive, readily available and easy to handle material used in the process of the present invention provide quite unexpectedly possibility to formulate an easy, reliable and reproducible process for the synthesis of monodisperse or substantially monodisperse polyester alcohols, that is dendritic polyesters having terminal unprotected or protected hydroxyl groups.
  • the process of the present invention is easily and conveniently adjusted to desired processing conditions and desired final structure and properties of yielded dendritic polyalcohol.
  • the present invention relates to a process for a double stage convergent synthesis of a polymeric polyalcohol having reactive or protected terminal hydroxyl groups, which polymeric polyalcohol is composed of a monomeric or polymeric core having n reactive hydroxyl or epoxide groups (A), to which n dendritic branches (dendrons), each consisting of g branching generations, are coupled by addition, whereby n and g are integers and at least 1 .
  • the dendrons are first synthesized and then coupled/added to said core.
  • the branching generations of said dendron comprise at least one polymeric or monomeric branching chain extender having three functional groups of which two are reactive hydroxyl groups (B) and one is a reactive carboxyl group (C).
  • the two hydroxyl groups of the branching chain extender are ketal protected during addition. Ketals are yielded together with water from a reaction between an alcohol, having at least two hydroxyl groups and a ketone, such as acetone
  • the process of the present invention employs two types a monomeric or polymeric branching chain extenders, one wherein said two hydroxyl groups (B) are two ketal protected hydroxyl groups (B') and one wherein said carboxyl group is a protected, preferably ester protected, carboxyl group (C).
  • Ketal protection - Step (i) - is obtained by reaction between said two hydroxyl groups (B) and a ketone, yielding a branching chain extender having two ketal protected hydroxyl groups (B') and one reactive carboxyl group (C).
  • Protection, ester protection, of the carboxyl group - Step (ii) - is obtained by reacting said carboxyl group with a carboxyl protective compound, such as an alkyl or arylhalide, preferably benzyl chloride, benzyl bromide, allyl chloride, allyl bromide or combinations thereof or by reaction with an alcohol, such as allyl or benzyl alcohol, yielding a branching chain extender having two reactive hydroxyl groups (B) and one protected carboxyl group (C).
  • a carboxyl protective compound such as an alkyl or arylhalide, preferably benzyl chloride, benzyl bromide, allyl chloride, allyl bromide or combinations thereof
  • an alcohol such as allyl or benzyl alcohol
  • the branching chain extenders yielded in said Steps (i) and (ii) are in a Step (iii) reacted at a molar ratio reactive carboxyl groups (C) to reactive hydroxyl groups (B) of at least 1 : 1 , yielding a polymer having four ketal protected hydroxyl groups (B') and one protected carboxyl group (C).
  • the protected hydroxyl groups (B 1 ) of a polymer yielded according to Step (iii) is in a fourth step - Step (iv) - deprotected yielding a polymer having four reactive hydroxyl groups (B) and one protected carboxyl group (C).
  • the protected carboxyl group of a Step (iii) polymer is in an optional Step (v) deprotected yielding a polymer having ketal protected hydroxyl groups (B') and one reactive carboxyl group (C).
  • a sixth step - Step (vi) - of the present process include reacting, in a number of Steps yielding g branching generations, the product yielded in Step (iv) or a hydroxyl deprotected product yielded in present Step (vi) with the product yielded in Step (i) or Step (v) at a molar ratio reactive hydroxyl groups (B) to reactive carboxyl groups (C) of at least 1 : 1 , yielding a product having ketal protected hydroxyl groups (B') and one reactive carboxyl group (C) or one protected carboxyl group (C).
  • Step (vii) the step that results in generation g, yielded dendron or the dendron yielded in Step (iii) is now in a Step (vii), after deprotection of the optionally protected carboxyl group (C), added to the core at a molar ratio core to said Step (vi) product of 1 : 1 to ⁇ :n, yielding a dendritic polymer having at least one dendritic branch emanating from said core.
  • An optional Step (viii) include deprotection of the ketal protected hydroxyl groups (B') of the hyperbranched dendritic polyalcohol obtained in Step (vii), yielding terminal reactive hydroxyl groups (B).
  • Each additions of a branching generation - Step (iii) or Steps (vi) - to the initially synthesized dendron can according to various embodiments individually employ a ketal protected branching chain extender being a reaction product of the same or a different branching chain extender and/or the same or a different ketone as well as employ a protected branching chain extender being a reaction product between the same or a different branching chain extender and/or the same or a different carboxyl protective compound, such as said alkyl or aryl halide
  • n is in preferred embodiments between 1 and 20, preferably between 2 and 12 and most preferably between 2 and 8 and the integer value of g is in likewise preferred embodiments between 1 and 50, preferably between 2 and 20 and most preferably between 2 and 8.
  • the polymeric polyalcohol yielded from the process according to the present invention has in its preferred embodiments n identical and/or symmetrical dendritic branches, whereby n is an integer and at least 2.
  • Dendrons having continued branching chain extension yields in these embodiments polymeric polyalcohols having increased branching density and increased number of reactive hydroxyl groups (B) or ketal protected hydroxyl groups (B 1 ).
  • Addition of branching generations and addition of said dendron, for instance the product obtained in Step (iii) or Step (vi), to said core are preferably performed at a temperature of -30- 150°C, such as - 10-80°C or 10-50°C.
  • Especi ally preferred embodiments of the present invention employ ketal protected branching chain extenders selected from the group consisting of dihydroxyfunctional monocarboxylic acids or adducts between dihydroxyfunctional monocarboxylic acids and at least one alkylene oxide, which adduct has two hydroxyl groups and one carboxyl group.
  • Preferred alkylene oxides are ethylene oxide, propylene oxide, butylene oxide, phenylethylene oxide and mixtures thereof.
  • the branching chain extender used to produce the ketal protected branching chain extender is in the most preferred embodiments of the present invention a dihydroxyfunctional monocarboxylic acid, such as 2,2-bis(hydroxy- methyl)propanoic acid, 2,2-bis(hydroxymethyl)butanoic acid, 2,2-bis(hydroxy- methyl)pentanoic acid or 2,3-dihydroxypropanoic acid.
  • a dihydroxyfunctional monocarboxylic acid such as 2,2-bis(hydroxy- methyl)propanoic acid, 2,2-bis(hydroxymethyl)butanoic acid, 2,2-bis(hydroxy- methyl)pentanoic acid or 2,3-dihydroxypropanoic acid.
  • Ester protection such benzyl ester protection can suitable be obtained by first forming an alkali metal salt and in a second step reacting the salt with for instance benzyl bromide or by reaction with for instance benzyl alcohol.
  • the benzyl ester group can be removed selectively in very high yield by catalytic hydrogenolysis without affecting the ester bonds formed in the synthesized dendritic polymer.
  • Deprotection can for instance be performed at atmospheric pressure using a catalyst, such as a palladium catalyst on activated carbon (Pd/C).
  • a catalyst such as a palladium catalyst on activated carbon (Pd/C).
  • Pd/C palladium catalyst on activated carbon
  • Activation (for esterification) of carboxyfunctional chain extenders include activation as (a) anhydride, formed in situ, for instance aided by dicyclohexylcarbodiimide, or prefabricated; (b) acid chloride, for instance from oxalyl chloride, (c) mixed anhydride, for instance carboxylic acid and trifluoroacetic anhydride, or (d) as imidazolide
  • the acylation is preferably performed in the presence of a solvent or solvent combination, such as methylene chloride, ethylene chloride, chloroform, pyridine, toluene, dimethoxyethane, diethyl ether, dipropyl ether, triethylamine, nitrobenzene, chlorobenzene and/or acetonitrile Esterification is advantageously performed in for instance dichloromethane through a dicyclohexylcarbodiimi
  • Deprotection of the two ketal protected hydroxyl groups of the monomeric or polymeric branching chain extender is suitably performed by a mild solvolytic decomposition, such as a methanolysis, under acidic conditions. Decomposition of built up dendrimers and dendritic structures is thus highly unlikely and not observed during deprotection.
  • Acetonide protected hydroxyl groups can for instance smoothly be removed by stirring the acetonide derivative in methanol in the presence of for instance a Dowex H resin.
  • the core is preferably selected from the group consisting of aliphatic, cycloaliphatic or aromatic mono, di, tri or polyalcohols and adducts thereof, such as hydroxysubstituted allyl ethers, formals and alkoxylates, or from the group consisting of glycidyl ethers, glycidyl esters, epoxides of unsaturated carboxylic acids and triglycerides, aliphatic, cycloaliphatic or aromatic epoxy polymers and epoxidized polyolefines.
  • Suitable cores are for instance 4-hydroxymethyl- - 1 ,3-dioxolane, 5-methyl-5-hydroxymethyl- l ,3-dioxane, 5-ethyl-5-hydroxymethyl- - 1 ,3-dioxane, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, neopentyl glycol, dimethylolpropane, 5,5-dihydroxymethyl- l ,3-dioxane, glycerol, trimethylolethane, trimethylolpropane, pentaerythritol, ditrimethylol- ethane, ditrimethylolpropane, anhydroennea-heptitol, dipentaerythritol, sorbitol and mannitol; hydroxysubstituted allyl ethers,
  • Alkoxylates are adducts between an alcohol and an alkylene oxide, such as ethylene oxide, propylene oxide, butylene oxide and/or phenylethylene oxide, and can suitably be exemplified by glycerol propoxylates, trimethylolethane ethoxylates, trimethylolethane propoxylates, trimethylolpropane ethoxylates, trimethylolpropane propoxylates, pentaerythritol ethoxylates and pentaerythritol propoxylates as well as ethoxylates or propoxylates of hydroxysubstituted allyl ethers, such as trimethylolpropane diallyl ether.
  • glycerol propoxylates trimethylolethane ethoxylates, trimethylolethane propoxylates, trimethylolpropane ethoxylates, trimethylolpropane propoxylates, penta
  • phenolic alcohols such as xylyLene alcohols, hydroxyphenylalkanes and hydroxybenzenes.
  • cores are advantageously exemplified by xylylene glycol, l , l , l -(trishydroxyphenyl)ethane, dihydroxybenzene and trihydroxybenzene.
  • Core molecules such as 1 ,3-dioxane and 1 ,3-dioxolane alcohols, which are formals having two protected hydroxyl groups, can after completed addition of branching chain extenders be deprotected yielding hydroxyl groups according to methods disclosed in for instance "Protective Groups in Organic Synthesis” by Theodora W. Greene and Peter G.M. Wuts, Chapter 2 "Protection for the Hydroxyl Group” - John Wiley & Sons Inc., New York 1991 .
  • Epoxyfunctional cores can be exemplified by glycidyl ethers, such as 3-allyloxy- l ,2-epoxypropane, l ,2-epoxy-3-phenoxypropane and l -glycidyloxy-2- -ethylhexane; glycidyl ethers of phenols or reaction products thereof, such as condensation products between at least one phenol and at least one aldehyde or ketone; mono, di or triglycidyl substituted isocyanurates; and glycidyl esters, such
  • Cardura compounds which compounds are glycidyl esters of a highly branched saturated synthetic monocarboxylic acid named Versatic acid (Cardura and Versatic are trademarks of Shell Chemicals).
  • ketal protected acylating agents such as acetonide protected dihydroxyfunctional monocarboxylic acids
  • chain extenders and branching fragments in the construction of dendrimers and hyperbranched dendritic structures.
  • Hydroxyfunctional carboxylic acids protected with other groups such as acetate or benzyl do not show the same high reactivity, thus construction of dendrimers from such molecules is highly complicated and of no practical importance.
  • Embodiment Examples 1 discloses synthesis of a ketal protected branching chain extender and Example 2 discloses synthesis of an ester protected branching chain extender, both employed in embodiments of the present invention.
  • Examples 3-7 disclose various steps in the synthesis of a hyperbranched dendron and Examples 8 and 9 disclose synthesis of a tridendron hyperbranched dendritic polyalcohol. All Examples are in accordance with one preferred embodiment of the process of the present invention.
  • Examples 1 -9 were reported protected branching chain extenders (Example 1 -2), dendrons having reported number of branching generations and terminal protected or reactive hydroxyl groups (Example 3-7) and a hyperbranched dendritic polyester polyalcohol having reported number of dendritic branches of substantially identical and symmetrical structure and reported number of protected or reactive hydroxyl groups (Example 8 and 9).
  • Example 6 8.28 g of the product of Example 6 was dissolved in 120 ml of ethyl acetate and 0.83 g of Pd/C(10%) was added. Deprotection of the ester protected carboxyl group was performed in accordance with Example 4 yielding as a colourless viscous oil 7.44 g of a fourth generation dendron having sixteen ketal protected hydroxyl groups and one reactive carboxyl group. Yield: 97%.
  • the crude product was purified by liquid chromatography on silica gel eluating with hexane ⁇ gradually increasing to 100% ethyl acetate to yield as a colourless viscous oil 5.30 g of a hyperbranched dendritic polyalcohol having 48 ketal protected hydroxyl groups on three dendrons each having four generations and 16 ketal protected hydroxyl groups. Yield: 85%.
  • Example 8 4.50 g of the product of Example 8 was dissolved in 100 ml of methanol and the ketal protected hydroxyl groups were deprotected according to the procedure of Example 5 yielding after 48 hours of reaction 3.60 g as a white glass of a hyperbranched dendritic polyalcohol having 48 reactive hydroxyl groups on three dendrons each having four generations and 16 reactive hydroxyl groups. Yield: 92%.

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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)
  • Polyesters Or Polycarbonates (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne un procédé de synthèse convergente en deux temps d'un polyalcool élaboré sensiblement et, de préférence, à partir de motifs polyester et composé d'un noyau monomère ou polymère auquel est ajouté au moins un dendron (branche dendritique hyperramifiée) consistant en un certain nombre de générations de ramifications. Les générations de ramifications comprennent un allongeur de chaîne à ramification polymère ou monomère présentant trois fonctions réactives dont deux sont des groupes hydroxyle et une un groupe carboxyle. Les groupes hydroxyle de l'allongeur de chaîne à ramification sont, dans un premier temps, protégés par du cétal par réaction de ces deux groupes hydroxyle avec un cétal. Dans un deuxième temps, ce procédé consiste à protéger le groupe carboxyle dudit allongeur de chaîne à ramification. L'allongeur de chaîne à ramification protégé par le cétal et l'allongeur de chaîne protégé par le carboxyle sont ensuite employés par additions répétées, en plusieurs opérations, pour produire un nombre déterminé de générations de ramifications. Le dendron ainsi synthétisé est finalement ajouté au noyau présentant des groupes époxide ou hydroxyle réactifs, les groupes hydroxyle protégés par du cétal étant éventuellement déprotégés.
PCT/SE1998/001229 1997-06-26 1998-06-24 Synthese d'un polyalcool dendritique WO1999000440A1 (fr)

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Application Number Priority Date Filing Date Title
AU79510/98A AU7951098A (en) 1997-06-26 1998-06-24 Synthesis of a dendritic polyalcohol

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SE9702447-5 1997-06-26
SE9702447A SE510088C2 (sv) 1997-06-26 1997-06-26 Syntetisering av en dendritisk polyalkohol

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Cited By (8)

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US6444758B2 (en) 2000-02-09 2002-09-03 Ciba Specialty Chemicals Corporation Hyperbranched amphiphilic polymeric additives and polymer compositions with increased surface energy
US7544746B2 (en) 2002-05-29 2009-06-09 Tate & Lyle Public Limited Company Hyperbranched polymers
WO2009115580A2 (fr) * 2008-03-20 2009-09-24 National University Of Ireland, Galway Dendrimères et applications de dendrimères
WO2009156400A1 (fr) 2008-06-23 2009-12-30 Sicpa Holding Sa Encre pour l'impression intaglio comprenant des dendrimères
US7642320B2 (en) 2001-05-17 2010-01-05 Ciba Specialty Chemicals Corporation Polymer additives with improved permanence and surface affinity
US20100113709A1 (en) * 2006-09-27 2010-05-06 Huiguang Kou Polyethylene imine based dendritic dispersant
CN114805783A (zh) * 2021-01-18 2022-07-29 万华化学集团股份有限公司 一种亲水扩链剂的制备方法及扩链剂在水性聚氨酯中的应用
CN114989364A (zh) * 2021-03-01 2022-09-02 中国石油化工股份有限公司 一种聚胺酯类树枝状聚合物及其制备方法和应用

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6617397B2 (en) 2000-02-09 2003-09-09 Ciba Specialty Chemicals Corporation Hyperbranched amphiphilic polymeric additives and polymer compositions with increased surface energy
US6444758B2 (en) 2000-02-09 2002-09-03 Ciba Specialty Chemicals Corporation Hyperbranched amphiphilic polymeric additives and polymer compositions with increased surface energy
US7642320B2 (en) 2001-05-17 2010-01-05 Ciba Specialty Chemicals Corporation Polymer additives with improved permanence and surface affinity
US7544746B2 (en) 2002-05-29 2009-06-09 Tate & Lyle Public Limited Company Hyperbranched polymers
US20100113709A1 (en) * 2006-09-27 2010-05-06 Huiguang Kou Polyethylene imine based dendritic dispersant
US9381481B2 (en) * 2006-09-27 2016-07-05 Basf Se Polyethylene imine based dendritic dispersant
WO2009115580A2 (fr) * 2008-03-20 2009-09-24 National University Of Ireland, Galway Dendrimères et applications de dendrimères
WO2009115580A3 (fr) * 2008-03-20 2010-03-18 National University Of Ireland, Galway Dendrimères et applications de dendrimères
US8540813B2 (en) 2008-06-23 2013-09-24 Sicpa Holding Sa Intaglio printing ink comprising dendrimers
WO2009156400A1 (fr) 2008-06-23 2009-12-30 Sicpa Holding Sa Encre pour l'impression intaglio comprenant des dendrimères
CN114805783A (zh) * 2021-01-18 2022-07-29 万华化学集团股份有限公司 一种亲水扩链剂的制备方法及扩链剂在水性聚氨酯中的应用
CN114805783B (zh) * 2021-01-18 2023-05-26 万华化学集团股份有限公司 一种亲水扩链剂的制备方法及扩链剂在水性聚氨酯中的应用
CN114989364A (zh) * 2021-03-01 2022-09-02 中国石油化工股份有限公司 一种聚胺酯类树枝状聚合物及其制备方法和应用
CN114989364B (zh) * 2021-03-01 2023-07-25 中国石油化工股份有限公司 一种聚胺酯类树枝状聚合物及其制备方法和应用

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AU7951098A (en) 1999-01-19
SE9702447L (sv) 1998-12-27
SE510088C2 (sv) 1999-04-19

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