WO1993018079A1 - Polyester hyper-ramifie et son procede de preparation - Google Patents

Polyester hyper-ramifie et son procede de preparation Download PDF

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Publication number
WO1993018079A1
WO1993018079A1 PCT/NL1993/000051 NL9300051W WO9318079A1 WO 1993018079 A1 WO1993018079 A1 WO 1993018079A1 NL 9300051 W NL9300051 W NL 9300051W WO 9318079 A1 WO9318079 A1 WO 9318079A1
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WO
WIPO (PCT)
Prior art keywords
generation
compound containing
group
hydroxyl
hyperbranched polymer
Prior art date
Application number
PCT/NL1993/000051
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English (en)
Inventor
Gerard Hardeman
Tosko Alexander Misev
Albert Heyenk
Original Assignee
Dsm N.V.
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 Dsm N.V. filed Critical Dsm N.V.
Priority to AU39065/93A priority Critical patent/AU3906593A/en
Publication of WO1993018079A1 publication Critical patent/WO1993018079A1/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
    • C08G83/005—Hyperbranched macromolecules
    • 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
    • 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
    • C08G63/42—Cyclic ethers; Cyclic carbonates; Cyclic sulfites; Cyclic orthoesters
    • 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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on 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
    • 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
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/005—Dendritic macromolecules

Definitions

  • the invention relates to a hyperbranched polymer and a process for the preparation of a hyperbranched poly- mer.
  • Hyperbranched polymers are often referred to as "dendrimers" in the literature (see, for example, Encyclopedia of Polymer Science and Engineering, Index Volume,.1990, pp. 46-92).
  • Hyperbranched polymers are three-dimensional, highly ordered oligomeric and polymeric molecules with a good defined chemical structure. These dendrimers differ from classical oligomers and polymers by their extraordinary symmetry, high branching and maximized terminal functionality density. They are formed from a functional core (nucleus) surrounded by a plurality of layers of branched structural units. The plurality of layer around the nucleus are called generations and in each generation the functionality of the macromolecule multiplie with the degree of branching of the structural units used.
  • the resulting dendrimers have a tree-like structure (Greek: "dendrites”) within ball-shaped macromolecules having a ver high functionality and a very narrow molecular weight dis ⁇ tribution.
  • Such highly branched and highly functional macromolecules cannot be prepared by the conventional processes for making normal branched polymers because they would result in broad molecular weight distributions and in macroscopic gelling of the system.
  • Hawker et al. describe a synthesis of hyperbranche polyesters starting from dihydroxybenzoicacid which is reacted with trimethylsilyl chloride and thionyl chloride to give di-trimethylsiloxybenzoyl chloride, after which the hyperbranched polyester is formed by means of a one-step synthesis.
  • the Hawker process has many disadvantages.
  • the process cannot be used on an industrial scale because of the reactants used, such as, for example, trimethylsilyl chloride, thionyl chloride and benzoyl chloride, and because of the process stages such as the solvent process and the purification step.
  • the large quantities of solvent which have to be distilled off make the process unattractive.
  • Another disadvantage of the Hawker process is the limited freedom of choice in the composition of the monomers to be used. This process consequently leads only to purely aromatic polyesters.
  • the starting materials such as aromatic and (cyclo)alipha- tic monomers.
  • An object of the invention is to provide hyper ⁇ branched polymers. Another objective of the invention is to provide an industrially readily useable process for the preparation of these hyperbranched polymers, which avoids the disadvantages and problems of conventional processes described above. A further objective of the invention is to provide a coating composition containing the hyperbranched polymers.
  • the hyperbranched polymer according to the invention is characterized in that it comprises a nucleus and polyol and polycarboxy residues the hyperbranched polymer having at least 6 terminal hydroxyl- or carboxyl groups and a Carothers gelpoint lower than 1.
  • the hyperbranched polymer has at least 8 terminal hydroxyl- or carboxyl groups; more preferably at least 10.
  • the gelpoint according to the Carothers equation being the theoretical conversion factor at which the polyme tends to gelate, preferably is lower than 0.95; more preferably lower than 0.90.
  • the Carothers equation has been disclosed by G. Odian, Principles of polymerization, J. Wiley & Sons (1981), p. 113-116. Surprisingly, it has been found, that - although all the addition reactions almost have a conversion factor of 1 - no gelation takes place.
  • the hyperbranced polymers according the invention have in general a relatively low polydispersity.
  • the polydispersity of linear polyesters is about 2.
  • Branched polyesters -made via direct and transesterification methods in general have very much higher polydispersities.
  • the polymers according the invention in general have a low polydispersity although it may steadily increase with (very) high branching.
  • the nucleus has a polydispersity of 1, than the polydispersity of the polymer can be dipicted by the following formula:
  • the hyperbranched polymer is obtainable by startin with a nucleus compound containing at least one hydroxyl group and reacting it with a compound containing at least one anhydride group, after which the resulting first-generation acid-terminated addition product is reacte with a compound containing at least one epoxy group; the resulting first-generation hydroxyl-terminated addition product thereafter is reacted, in the second generation, with a compound containing at least one anhydride group, after which the resulting second-generation acid-terminated addition product is reacted with a compound containing at least one epoxy group, resulting in a second-generation hydroxyl-terminated addition product whereby in at least on generation monomers are used that have at least one functional group besides the anhydride group or epoxy group Both the addition reactions are repeated
  • reaction mechanisms in the subsequent generations are identical with those in the second generation.
  • the abovementioned nucleus with hydroxyl groups is regarded for the sole purpose of definition as being of generation zero; the first acid-terminated and hydroxyl-terminated addition products are of generation one; the second acid-terminated and hydroxyl-terminated addition products are of generation two, etc.
  • the obtained hyperbranched polymer has 1-20 generations; preferably 2 or more generations and very preferably 3-10 generations.
  • the nucleus which can be a monomeric, oligomeric or polymeric compound, contains at least one hydroxyl group.
  • the nucleus contains 1-10 hydroxyl groups; more preferably this is 2-8.
  • the nucleus can be formed by the addition reaction of a compound containing at least one carboxyl group and a compound containing at least one epoxy group, resulting in a hydroxyl-terminated addition product.
  • a hydroxyl functional nucleus can be made -in case of oligomers or polymers- by well known esterification methods, urethane oligo- and polymerisation, radical polymerisation and the like.
  • the quantities of the added reactants are chosen in such a way, that substantially all terminal hydroxyl groups or acid groups of the nucleus or the respective addition products can react. Therefore, the reactants are added in at least about an equimolar amount.
  • the molar ratio between the terminal hydroxyl groups and the anhydride group containing compounds or between the terminal acid groups and the epoxy group containing compounds in all the reactions mentioned are about 1.1:0.9 to 0.9:100? preferably 1.1:0.09 to 0.9:10; more preferably 1.1:0.9 to 0.9:1.1. Most preferably the molar ratios are about 1:1, since at that moment extra purification steps a avoided.
  • the reaction temperatures can be chosen in a broa range.
  • the reaction in all steps is usually carried out below 200°C, preferably below 180°C to avoid side reaction
  • the reactions preferably are carried out at temperatures of between 80°C and 160°C.
  • Suitable compounds containing at least one hydrox group useful for being comprised in the nucleus are, for example: glycols, for example 2,2,4-trimethyl-l,3- pentanediol, cyclo-hexane dimethanol, dipropyleneglycol, neopentyl glycol, 1,4-butanediol, 1,3-butanediol, 1,6- hexanediol or 1,8-octanediol; triols, for example glycerol, trimethylolethane and trimethylolpropane; polyols, for example ditrimethylolpropane, pentaerythritol, di-pentaerythritol or sorbitol; and low molecular polyeste or polyurethanes having a molecular weight of, for example, about 3000.
  • glycols for example 2,2,4-trimethyl-l,3- pentanedio
  • oligomers are e.g. polyethyleneglycol, polypropyleneglycol, monoalkylethers o polyethylene- or polypropyleneglycol, and alkoxylated bisphenol-A, such as with 2-12 units ethoxylated or propoxylated bisphenol, and the corresponding hydrogenated compounds.
  • low molecular weight polyols are use as the compound containing hydroxyl groups.
  • Suitable compounds containing at least one epoxy group are, for example: monoepoxides, for example: monocarboxylicacidglycidylester (Cardura E10 R ; Shell), ethylene oxide, propylene oxide or phenyl glycidyl ether; hydroxyepoxides such as the glycidylester of hydroxypivali acid, of hydroxybutyric acid, or of hydroxystearic acid; diepoxides, for example diglycidylterephthalate, bisphenol A based epoxyresins; diglycidyl ethers, for example: 1,6- hexanediol diglycidyl ether; or triepoxides, for example: trimethylolpropane triglycidyl ether, triglycidylisocyanurate, trimethylolethane triglycidyl ether, the polyglycidyl
  • polyepoxides are used in the addition reactions of the generations building, it is preferred to have, after the addition reaction, a reaction that opens the remaining epoxy groups, e.g. a reaction with water.
  • a reaction that opens the remaining epoxy groups e.g. a reaction with water.
  • monoepoxides are used in the generation building, more preferably, Cardura E10 R and/or propylene oxide are used.
  • Suitable compounds containing at least one carboxyl group are, for example, acid-terminated polyesters polyethers or polyurethanes, dicarboxylic acids, for example isophthalicacid, terephthalicacid, adipicacid and for example trimelliticacid.
  • Suitable compounds containing at least one anhydride group are, for example, trimelliticacidanhydride, succinicacidanhydride, pyromelliticacidanhydride, maleic- acidanhydride, succinicacidanhydride, phthalicacidanhydride, tetrahydrophthalicacidanhydride, hexahydrophthalicacid- anhydride, butanesuccinicacidanhydride, glutaricacid- anhydride and itaconicacidanhydride.
  • trimelliticacidanhydride succinicacidanhydride, pyromelliticacidanhydride, maleic- acidanhydride, succinicacidanhydride, phthalicacidanhydride, tetrahydrophthalicacidanhydride, hexahydrophthalicacid- anhydride, butanesuccinicacidanhydride, glutaricacid- anhydride and itaconicacidanhydride.
  • a reaction that opens the remaining anhydride groups e.g. a
  • trimelliticacidanhydride is used as the compound containing anhydride groups for the generation building.
  • Suitable solvents are, for example, toluene, benzene, aceton, ethyleneglycolmonobutyletheracetate, n-methylpyrrolidine, methylisobutylketone, methylethylketone, xylene and propyleneglycolmonomethyl- etheracetate. If required, a mixture of solvents can be used. Preferably, methylisobutylketone is used as the solvent.
  • Suitable catalysts in the preparation of the hyperbranched polymer are, for example, tertiary amines, phosphonium salts and metal tin compounds. Suitable tertiar amines are e.g.
  • Suitable phosphonium salts are e.g. trifenylethylphosphoniumbromide and trifenylmethylphosphoniumchloride.
  • Suitable metal tin compounds are e.g. dibutyltinoxide, dibutyltinlaureate and dibutylhydroxytinchloride. If required the addition reactions can be carried out without adding a catalyst. Of course, it is possible to have urethane groups built in via chain lengthening reactions, or by the use of oligourethanes with anhydride or epoxy functionality.
  • the process can be readily used industrially and has the further advantage that there is large freedom in t choice of the monomeric composition for the hyperbranched polymer.
  • the successive generations can be built up from t same monomeric building-blocks in each generation, but -if required- it is also possible to use various monomeric building-blocks in distinct successive generations.
  • Using this process has the advantage of a large freedom in choosing these building blocks.
  • aromatic compounds such as, for example, trimelliticacidanhydride and phenyl glycidyl ether
  • aliphatic and aromatic compounds in the outermost genera ⁇ tions, as a result of which a macromolecule with a hard cor and a soft shell results.
  • This principle can also be employed in reverse. This results in a hyperbranched polymer, such as, for example, a hyperbranched polyester, having a core-shell structure.
  • the hyperbranched polyester as a rule has at least 6 branches, and hence, at least 6 functional groups.
  • the polymer has at least 10 branches or 10 functional groups.
  • the initial functional groups are either hydroxy or carboxy.
  • These groups may be modified (if required, only partly) by methods known per se, as long as the temperature applied during these reactions does not allow substantial transesterification. Hence, as a rule, the temperature should remain below 180°C.
  • acid groups may be neutralised with amines, metal hydroxides, yielding a water dispersable hyperbranched polymer. Also the acid groups can be reacted with a (large) excess of diepoxy as to make an epoxy functional hyperbranched polymer.
  • a hydroxy-functional polymer may be modified e.g.
  • an isocyanate functional dendrimer may e.g. be modified with hydroxyethyl(meth)acrylate to make UV curable coatings.
  • hyperbranched polyesters have a very high molecular weight coupled with a very low viscosity. As a result, they are very suitable for use in coating compositions in order to increase the solids contents.
  • Example IV (4th generation) In a 3-litre reaction flask having a mechanical stirrer and a thermometer, 621 grams of the product (0.035 mol of solid resin) obtained in generation 3, 161 grams of trimelliticacidanhydride (0.840 mol) and 122 grams of propyleneglycolmonomethyletheracetate were warmed to 150°C under a constant stream of nitrogen, after which the temperature was kept at 150°C for 30 minutes. After cooling to 120°C, 420 grams of monocarboxylicacidglycidylester (Cardura E10 R from Shell) (1.680 mol) and 0.1% by weight of triphenylethylphosphoniumbromide were added, with the temperature being kept below 155°C. After the acid number had fallen to less than 3 mg of KOH/gram of resin, the resin was cooled.
  • monocarboxylicacidglycidylester Cardura E10 R from Shell
  • Viscosity according to the falling ball method 44 dPa.s (65% solid in propyleneglycolmonomethylether acetate, 23°C).
  • the viscosity (in dPa.s) was determined (at 23°C) according to the falling ball method (Noury-v.d. Lande).
  • Viscosity according to the falling ball method 11 dPa.s (65% solid in propyleneglycolmonomethyletheracetate, 23°C).
  • Viscosity according to the falling ball method 27 dPa.s (65% solid in propyleneglycolmonomethyletheracetate, 23°C).
  • Example VIII (4th generation) In a 1.5-litre glass pressure reactor having a mechanical stirrer and a thermometer, 549 grams of the product (0.057 mol of solid resin) obtained in generation 3, 263 grams of trimelliticacidanhydride (1.37 mol) and 142 grams of propyleneglycolmonomethyletheracetate were warmed to 135°C, after which the temperature was kept at 135°C for 30 minutes. After cooling to 120°C, 0.2% by weight of dimethylbenzylamine was added, after which 175 grams of propyleneoxide (2.74 mol + 10% excess) were metered in, with the temperature being kept below 125°C. After the acid number had fallen to below 4 mg of KOH/gram of resin, 55 grams of propyleneglycolmonomethyletheracetate were added and the resin was cooled.
  • Viscosity according to the falling ball method 104 dPa.s (65% solid in propyleneglycolmonomethylether- acetate, 23°C).
  • the viscosity (in dPa.s) was determined, at 23°C, according to the falling ball method.
  • The- acid number (mg of KOH/gram of resin) was determined by titration with an ethanolic potassiumhydroxid solution.
  • Cardura E10TM (0.35 mol) and 0.1 gram dimethylaminopyridine were warmed to 150°C in a nitrogen atmosphere. The temperature was kept at 150°C during 2 hours, while the loss of MIBK was destilled off. At the moment the acid-number was lower than 3 mg KOH/gram the product (D) was cooled and th MIBK was added again. The hydroxy-number of the obtained second generation product (D) was determined: 116 mg
  • the obtained coating compositions were mixed with propyleneglycolmonomethyletheracetate until a solid content of 62% was reached.
  • a 100 ⁇ m film was made of these polymer compositions using an Erichsen filmforming apparatus (type 360, width 60 mm) on a glass or steel surface. A curing cycle of 5 minutes at 200°C was used.
  • the mechanical properties of the films obtained are given in the following table III:
  • the elasticity is determined according to DIN 53156.
  • the reverse impact is determined according to ASTM-D-2794.
  • a composition was made using: 27.01 parts by weight of the product obtained in Example
  • Uralac XP 970 SH solid resin, high molecular weight polyester, Mn 15000
  • a composition was made using: 11.49 parts by weight of the product obtained in Example
  • Uralac XP 970 SH solid resin, high molecular weight polyester, Mn 15000
  • the elasticity is determined according to DIN 53156.
  • the reverse impact is determined according to ASTM-D-2794.
  • the K ⁇ nig hardness is determined according to DIN 53157.

Abstract

Polymère hyper-ramifié comportant un noyau et des restes de polyol et de polycarboxy, possédant au moins 6 groupes hydroxyle ou carboxyle terminaux, et présentant un point de gélification de Carothers inférieur à 1. On peut obtenir ledit polymère hyper-ramifié possédant au moins 6 groupes hydroxyle ou carboxyle terminaux à partir d'un composé de noyau contenant au moins un groupe hydroxyle à titre de noyau, en mettant ce composé en réaction avec au moins un groupe anhydride, et en mettant en réaction avec un composé contenant au moins un groupe époxy le produit d'addition à terminaison acide de première génération ainsi obtenu. Ensuite, on met en réaction, dans la seconde génération et avec un composé contenant au moins un groupe anhydride, le produit d'addition à terminaison hydroxyle de première génération ainsi obtenu, puis on met en réaction avec un composé contenant au moins un groupe époxy le produit d'addition à terminaison acide de seconde génération ainsi obtenu, de manière à obtenir un produit d'addition à terminaison hydroxyle de seconde génération. Dans au moins une génération, on utilise des monomères possédant, outre le groupe anhydride ou le groupe époxy, au moins un groupe fonctionnel.
PCT/NL1993/000051 1992-03-06 1993-03-05 Polyester hyper-ramifie et son procede de preparation WO1993018079A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU39065/93A AU3906593A (en) 1992-03-06 1993-03-05 Hyperbranched polyester and a process for its preparation

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL9200416 1992-03-06
NL9200416A NL9200416A (nl) 1992-03-06 1992-03-06 Hypervertakte polymeren en een werkwijze voor de bereiding van hypervertakte polymeren.

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WO1993018079A1 true WO1993018079A1 (fr) 1993-09-16

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WO1996007688A1 (fr) * 1994-09-08 1996-03-14 Neste Oy Resines durcissables par rayonnement, a polyesters hyperramifies
WO1996012754A1 (fr) * 1994-10-24 1996-05-02 Perstorp Ab Macromolecule a ramification importante du type polyester
WO1996013558A1 (fr) * 1994-10-27 1996-05-09 Perstorp Ab Composition de liant insature
WO1996019537A1 (fr) * 1994-12-21 1996-06-27 Perstorp Ab Produit thermodurcissable
WO1998024831A1 (fr) * 1996-12-04 1998-06-11 Dentsply International Inc. Dendrimeres d'epoxyde-amine, leur preparation et leur utilisation
US6093777A (en) * 1994-12-21 2000-07-25 Perstorp Ab Dendritic polyester macromolecule in thermosetting resin matrix
EP1070748A1 (fr) * 1999-07-20 2001-01-24 E.I. Du Pont De Nemours And Company Compositions de revêtement en poudre, méthode de préparation et utilisation
US6326237B1 (en) * 1997-12-30 2001-12-04 International Business Machines Corporation Reworkable thermoplastic hyper-branched encapsulant
US6812266B2 (en) 2001-08-10 2004-11-02 Dentsply Detrey Gmbh Hydrolysis stable one-part self-etching, self-priming dental adhesive
EP1571189A1 (fr) * 2004-03-04 2005-09-07 Basf Corporation Résine polyester, méthode pour sa préparation, et composition d'enduction à base de cette résine
US7354969B2 (en) 2001-02-06 2008-04-08 Stick Tech Oy Dental and medical polymer composites and compositions
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
EP2113010A1 (fr) * 2007-02-22 2009-11-04 M-Il.L.C., Polyesters hydroxy et utilisations en tant que désémulsifiants
WO2018046334A1 (fr) * 2016-09-08 2018-03-15 Basf Coatings Gmbh Revêtements contenant des polymères hyper-ramifiés durcissables par rayonnement
WO2018046335A1 (fr) * 2016-09-08 2018-03-15 Basf Coatings Gmbh Polymères hyper-ramifiés durcissables par rayonnement ayant un cœur comportant un acide dicarboxylique
US20190185701A1 (en) * 2017-12-20 2019-06-20 Ppg Industries Ohio, Inc. Ultradurable coating composition

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CN1070878C (zh) * 1994-09-08 2001-09-12 奈斯特化学公司 含高度分支聚酯的可辐射固化树脂
WO1996007688A1 (fr) * 1994-09-08 1996-03-14 Neste Oy Resines durcissables par rayonnement, a polyesters hyperramifies
US5834118A (en) * 1994-09-08 1998-11-10 Neste Oy Of Keilaniemi Radiation curable resins comprising hyperbranched polyesters
WO1996012754A1 (fr) * 1994-10-24 1996-05-02 Perstorp Ab Macromolecule a ramification importante du type polyester
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CN1076702A (zh) 1993-09-29
NL9200416A (nl) 1993-10-01

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