WO2012114357A1 - Process for preparing hyperbranched polyestersfield of the invention - Google Patents
Process for preparing hyperbranched polyestersfield of the invention Download PDFInfo
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- WO2012114357A1 WO2012114357A1 PCT/IN2012/000125 IN2012000125W WO2012114357A1 WO 2012114357 A1 WO2012114357 A1 WO 2012114357A1 IN 2012000125 W IN2012000125 W IN 2012000125W WO 2012114357 A1 WO2012114357 A1 WO 2012114357A1
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- Prior art keywords
- catalyst
- range
- acid
- reaction
- double
- Prior art date
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 96
- 229910052751 metal Inorganic materials 0.000 claims abstract description 38
- 239000002184 metal Substances 0.000 claims abstract description 38
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000002253 acid Substances 0.000 claims abstract description 24
- 229920005862 polyol Polymers 0.000 claims abstract description 24
- 150000003077 polyols Chemical class 0.000 claims abstract description 22
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 67
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 40
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 229920000728 polyester Polymers 0.000 claims description 33
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 22
- 239000011541 reaction mixture Substances 0.000 claims description 21
- 239000001384 succinic acid Substances 0.000 claims description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 15
- 239000001361 adipic acid Substances 0.000 claims description 11
- 235000011037 adipic acid Nutrition 0.000 claims description 11
- -1 Zn2+ ions Chemical class 0.000 claims description 7
- 239000011949 solid catalyst Substances 0.000 claims description 7
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 5
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 5
- 239000000600 sorbitol Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 4
- 239000002841 Lewis acid Substances 0.000 claims description 3
- 150000007517 lewis acids Chemical class 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- 229930195725 Mannitol Natural products 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 230000002209 hydrophobic effect Effects 0.000 claims description 2
- 239000000594 mannitol Substances 0.000 claims description 2
- 235000010355 mannitol Nutrition 0.000 claims description 2
- 239000012454 non-polar solvent Substances 0.000 claims description 2
- 239000002798 polar solvent Substances 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 2
- 229920006150 hyperbranched polyester Polymers 0.000 abstract description 32
- 230000035484 reaction time Effects 0.000 abstract description 6
- 239000000047 product Substances 0.000 description 21
- 238000002360 preparation method Methods 0.000 description 17
- 229920000642 polymer Polymers 0.000 description 16
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 12
- 238000005119 centrifugation Methods 0.000 description 12
- 238000001816 cooling Methods 0.000 description 12
- 239000011521 glass Substances 0.000 description 12
- 239000007788 liquid Substances 0.000 description 12
- 238000001879 gelation Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 150000007513 acids Chemical class 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 4
- 239000003377 acid catalyst Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- 229920005906 polyester polyol Polymers 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 150000002924 oxiranes Chemical class 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 235000015112 vegetable and seed oil Nutrition 0.000 description 3
- 239000008158 vegetable oil Substances 0.000 description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 229940035437 1,3-propanediol Drugs 0.000 description 2
- 229910020521 Co—Zn Inorganic materials 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 229920000463 Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) Polymers 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000412 dendrimer Substances 0.000 description 2
- 229920000736 dendritic polymer Polymers 0.000 description 2
- 239000012154 double-distilled water Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 2
- 229920000587 hyperbranched polymer Polymers 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000003930 superacid Substances 0.000 description 2
- 235000019871 vegetable fat Nutrition 0.000 description 2
- 229940043375 1,5-pentanediol Drugs 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 1
- LNPQMDSMIGLHSR-UHFFFAOYSA-N 2-oxaspiro[3.5]non-5-ene-1,3-dione Chemical compound O=C1OC(=O)C11C=CCCC1 LNPQMDSMIGLHSR-UHFFFAOYSA-N 0.000 description 1
- 235000019737 Animal fat Nutrition 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HSSJULAPNNGXFW-UHFFFAOYSA-N [Co].[Zn] Chemical compound [Co].[Zn] HSSJULAPNNGXFW-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229920000229 biodegradable polyester Polymers 0.000 description 1
- 239000004622 biodegradable polyester Substances 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 1
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 229940124447 delivery agent Drugs 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical class OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 239000006254 rheological additive Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 239000012970 tertiary amine catalyst Substances 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof
-
- 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
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/87—Non-metals or inter-compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
- B01J27/26—Cyanides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Definitions
- the present invention relates to a process for preparing hyperbranched polyesters in the presence of a solid-acid catalyst.
- the present invention relates to an efficient, eco-friendly, solvent-free process for preparing hyperbranched polyesters comprising contacting polyols with polycarboxylic acids in the presence of a solid, acidic, crystalline, micro-mesoporous double- metal cyanide catalyst.
- Hyperbranched polyesters belong to the family of dendrimers bearing large number of functional groups on their periphery. Despite their high polydispersities and low degree of branching, their chemical performances are quite similar to their dendrimer analogues. Topological specifics of hyperbranched polymers like high level of solubility and compatibility, low viscosity of solutions, resistance to aggregate even in concentrated solutions, ability to function as nanocontainers for substances sorbed inside, weak dependence of hydrodynamic volume on molecular weight and lump of free ends of chains with functional groups on their periphery open a new window for their diverse industrial use.
- Hyperbranched polymers find wide applicability as cosmetics, food additives, surfactants, lubricants, plasticizers, drug delivery agents, azeotropic phase separators, in orthopaedic and ophthalmic fields, building blocks for preparing poly-addition or poly-condensation polymers, additives in paints, coverings, adhesive promoters, sealants, casting elastomers, as rheology modifiers and as surface or interface modifiers.
- Discovery of unique properties of hyperbranched polyesters has expedited a rapid development in this area of materials. Hyperbranched polyesters derived from renewables broaden their applicability as novel, environmental-friendly materials for various applications.
- Polyesters are conventionally synthesized by polycondensation of di- or polycarboxylic acids with polyols.
- aromatic polyesters i.e., polyesters from aromatic dicarboxylic acids such as phthalic acid or terephthalic acid and alcohols such as 1,2-ethane diol, 1,2- or 1,3-propane diol or 1,4-butane diol, are more significant.
- polyesters derived from parent molecules like succinic acid, glutaric acid or adipic acid and alcohols such as 1,2-ethane diol, 1,2- or 1,3-propane diol, 1,3- or 1,4-butane diol, 1,5-pentane diol or 1,6-hexane diol are making these polymers more attractive in recent years.
- US 6,441,126 and US 20100048813 describes a process for producing cross-linked, branched, aliphatic polyesters for gum base from glycerol and adipic acid at 150-200°C without any catalyst under solvent-free conditions.
- EP 0799279 discloses the synthesis from an ethoxylated pentaerythritol and 2,2-dimethylol propanoic acid using conventional homogenous mineral acid catalyst, H 2 S0 4 , at 140°C.
- H 2 S0 4 homogenous mineral acid catalyst
- prior arts disclose synthesis of polyesters from different reactants employing different catalysts, in solvent-free conditions or in the presence of solvent.
- Enzymatic and microbial catalysed processes also form part of prior art in this area. The results of such prior art processes are polyesters that donot possess the characteristics of low viscosity at a high degree of branching and with controlled gelation.
- a solid catalyst-based process has several engineering, environmental and economic advantages.
- the solid catalyst can be easily separated and reused in subsequent recycles. It is therefore desirable to develop an efficient solid catalyst-based process for producing hyperbranched polyesters of low-viscosity and high degree of branching with controlled gelation to achieve polyesters for speciality applications.
- Double-metal cyanides were used as catalysts for the preparation of polyether polyols (WO 2009055436; US 6624286; Chen et al., J Polym Sci A Polym Chem., Year 2004, Vol. 42, pp.6519), alternative copolymerization of epoxides and C0 2 (US Patent Nos. 6,359,101, 6,953,765 and 6,852,663) and biodiesel and biolubricants manufacture by transesterification/esterification of vegetable oils or animal fat (monohydric carboxylic acid) with monohydric alcohols (US Patent Nos. 7,754,643, 7,482,480 and 7,842,653; EP 1 733 788; Sreeprasanth et al., Appl. Catal. A: Gen., Year 2006, Vol. 314, pp. 148).
- their application for the preparation of hyperbranched polyesters is not disclosed so far.
- Double metal cyanide catalysts of different crystallite structures (monoclinic) and amorphous nature have been used for the preparation of polyesters and other hybrid polymers as described in the following prior arts.
- DE 10 2008 004 343 Al discloses a process for preparing polyester alcohol useful to prepare polyurethane foams and thermoplastic polyurethane elastomers, comprising catalytic conversion of at least a difunctional carboxylic acid with at least a difunctional alcohol, where at least a part of the reaction is carried out in the presence of a polymetal cyanide or a double metal cyanide catalyst usually in an amount up to 1% by weight of the reaction mixture.
- the polycondensation reaction can be performed both in presence and in absence of a solvent at temperature 160 - 280°C. This disclosure is specific for conversion of dicarboxylic compounds with dihydroxy compounds.
- WO 2011/137011 Al tells a process for preparing a hybrid polyester-polyether polyols comprising reacting a carboxyl group-containing component and an epoxide, optionally in the presence of one or more double metal cyanide catalyst, a superacid catalyst, a metal salt of a superacid catalyst and/or a tertiary amine catalyst, under conditions such that a hybrid polyester-polyether polyol is formed. Further, the said reaction is carried out in presence of solvent such as toluene.
- the process results in products having narrow polydispersity, a low acid number and unsaturation and reduced byproducts formation, particularly when the metal cyande catalyst is employed.
- the product is a hybrid polyester-polyether-polyol, different from that of the present invention.
- US 7842653 describes a process for preparing lubricants wherein the said process comprises contacting a monocarboyxlic vegetable oil or fat with a monohydric C6 - C8 alcohol in the presence of a double-metal cyanide catalyst wherein the vegetable oil/fat to alcohol molar ratio being 1 : 6, reaction temperature being in the range 150 - 200°C and reaction time being in the range 3 - 6 hrs.
- the product is a monoester.
- WO 2011/075343 Al discloses a process to convert a secondary hydroxyl-capped polyol to a primary hydroxyl-capped polyol comprises reacting a polyether polyol, a polyester polyol, polyether-ester polyol or a polyether-polyester polyol with a cyclic anhydride of a polycarboxylic acid to form a half acid ester, followed by the reacting the half acid ester with ethylene oxide, to form a polyester polyol or a polyether-polyester polyol. Both steps are carried out in the presence of an amine catalyst and a double metal cyande catalyst.
- the latter catalyst useful for polymerization of epoxides generally may include an organic complex agent such a diglyme.
- CN101570595 discloses a terpolymer containing polyester chain links and polycarbonate chain links and a synthetic method thereof, which comprises the mixing of zinc-cobalt double metal cyanide complex catalyst, cyclohexene oxide and dicarboxylic anhydride in a solvent.
- the double metal cyanide catalyst used in the present invention is unique and thereby shows efficient catalytic activity for the preparation of hyperbranched polyesters.
- the unusual surface hydrophobicity of the catalyst facilitates the adsorption of polycarboxylic acids and polyols but not the water formed as by-product in the esterification reaction and micro- mesoporous architecture controls the gelation and degree of branching.
- the main object of present invention is to provide a process for preparing hyperbranched polyesters of low viscosity, high degree of branching and controlled gelation making use of an efficient, reusable, heterogeneous acid catalyst.
- Another object of present invention is to provide an efficient, eco-friendly process for the synthesis of hyperbranched polyesters from renewables in presence of a solid, reusable, acid catalyst.
- Yet another objective is to describe a process for providing hyperbranched polyesters at moderate temperatures, short period of reaction time and solvent-free conditions.
- the present invention provides an efficient, eco-friendly, solvent-free a process for preparing hyper branched polyesters having degree of branching in range 45 - 90% and inherent viscosity in the range 0.02 - 0.1 dL/g and the said process comprising the steps of:
- step (b) subjecting the reaction mixture as obtained in step (a) at temperature in the range
- polyesters 160 to 200°C and for a reaction period of 0.5 - 2 h to obtain polyesters;
- step (c) dissolving the reaction mixture obtained in step (b) in a polar solvent like
- step (d) adding a non-polar solvent like heptane to the reaction mixture obtained from step (c) to precipitate out and isolate the hyper branched polyesters.
- step (a) the chemical formula of double metal cyanide Catalyst used in step (a) is :
- R is tertiary-butyl
- M is a transition metal ion selected from the group consisting of Fe and Co
- x varies from 0 to 0.5
- y varies from 3 - 5
- n is 10 or 12.
- the polyol used in step (a) has atlest two alcoholic groups.
- the polyols is selected from the group consisting of glycerol, sorbitol, mannitol, glucose and sucrose .
- polycarboxylic acid used in step (a) contains at least two carboxylic groups.
- polycarboxylic acid used in step (a) is selected from the group consisting of succinic acid and adipic acid.
- the solid catalyst is reusable.
- the isolated yield of polyester is in the range 50 - 90 wt%.
- the double-metal cyanide catalyst was prepared as per the US patent 7,754,643 and has the characteristics as described therein.
- the catalyst of the present invention possesses micro-mesoporous architecture as shown in Fig. 2 (high-resolution transmission electron micrograph) and an average pore diameter of 2.5 nanometers as revealed the the N 2 adsorption-desorption isotherm data (Fig. 3).
- the catalyst is hydrophobic at reaction conditions and contains Lewis acid centers (Fig. 4; Pyridine-IR spectrum) due to tetra- coordinated Zn 2+ ions in the crystalline framework with the total acidity of the catalyst being in the range 1.5 - 2.2 mmol/g.
- the degree of branching of the polyester is in the range 45 - 90%. In still another embodiment of the present invention, the viscosity of the polyester is in the range 0.02 - 0.1 dL/g.
- Figure 2 High-resolution transmission electron micrographs of micro-mesoporous Fe-Zn double-metal cyanide catalyst.
- FIG. 3 Nitrogen adsorption-desorption isotherms of Fe-Zn double metal cyanide catalyst. Inset shows pore size distribution.
- the M-Zn double-metal cyanide catalysts with micro-mesoporous architecture are highly efficient and could be easily separated from the products for further reuse.
- the prior art catalysts, mineral acid, organometallic compounds and enzymes needed additional process steps and efforts for catalyst separation. Moreover those catalysts cannot be recycled.
- double-metal cyanide catalysts have been used in several acid catalyzed reactions, their application for the polycondensation of polycarboxylic acids with polyols resulting hyperbranched polyesters with low viscosity and high degree of branching and controlled gelation is disclosed in this invention.
- An easily separable catalyst system e.g., the catalyst of the present invention is more advantageous.
- the solid catalyst of the present invention is not only efficient but avoids the tedious process of catalyst recovery characteristic of the prior art processes.
- the catalyst of the present invention yields hyperbranched polyesters of low viscosity, high degree of branching and controlled gelation from renewable feedstock at moderate temperatures, short period of reaction time and solvent-free conditions. It is a feature of the process of present invention that the catalyst is a solid and the reaction takes place in a heterogeneous condition. The solid catalyst can be easily separated from products by centrifugation-filtration/decantation for further reuse. It is another feature of the process of present invention that the process is eco-friendly, economical and generates no waste products unlike in the prior art processes in the process steps of catalyst separation /removal.
- the catalyst of present invention It is the unique feature of the catalyst of present invention that its unusual surface hydrophobicity (that facilitates the adsorption of polycarboxylic acids and polyols but not the water formed as by-product in the polyesterification reaction) and micro-/mesoporous architecture (that controls the gelation and degree of branching).
- the polyesterification reaction is conducted in the absence of a solvent.
- the polyester is prepared from bio-derived polyol feedstocks and it is biodegradable.
- the polyester has low viscosity unlike that in the prior art processes which produce gel.
- Still another feature is that the reaction completes in a short period of times ca., 0.5 - 2 h. Still another feature of the present invention is that the number average molecular weight of the polymer can be tuned to be in the range 1000 - 6000 depending on reaction temperature and reaction time.
- Example 1 The present invention is illustrated herein below with examples, which are illustrative only and should not be construed to limit the scope of the present invention in any manner.
- Example 1
- Poly(ethylene glycol)-block-poly(propylene glycol)- block-poly(ethylene glycol) (15 g) was separately dissolved in 2 ml of distilled water and 40 ml of tertiary-butanol (Solution- 3).
- Solution-2 was added to solution-1 over 60 min at 50°C with vigorous stirring. White precipitation occurred during the addition.
- solution-3 was added to the above reaction mixture over a period of 5 min and stirring was continued for further 1 h.
- the solid cake formed was filtered, washed with distilled water (500 ml) and dried at 25°C for 2 days. This material was activated at 180°C for 4 h prior to using it in the reactions.
- This example describes the preparation of hyperbranched polyester derived from bio-glycerol and succinic acid over Fe-Zn double-metal cyanide catalyst at 180°C.
- Glycerol (1 mol), succinic acid (1 mol), catalyst (3 wt% of reaction mixture) were taken in a glass round-bottom flask. The temperature was raised to 180°C. The reaction was carried out for 1 h at atmospheric pressure. After cooling to 25°C, about 10 ml of dry-acetone was to the contents of the flask. Catalyst was separated by centrifugation followed by filtration. The polymer was reprecipitated by adding 20 ml of n-heptane. The product polyester is a clear liquid. 13 C NMR spectroscopy was used to analyze the degree of branching and viscosity (in dry- tetrahydrofuran solvent) was determined using a Ubbelhode viscometer.
- This example describes the preparation of hyperbranched polyester by reacting bio-glycerol with succinic acid at 180°C for 1.5 h over Fe-Zn double-metal cyanide catalyst.
- Glycerol (1 mol), succinic acid (1 mol), catalyst (3 wt% of reaction mixture) were taken in a glass round- bottom flask. The temperature was raised to 180°C. The reaction was carried out for 1.5 h at atmospheric pressure. After cooling to 25°C, about 10 ml of dry-acetone was to the contents of the flask. Catalyst was separated by centrifugation followed by filtration. The polymer was reprecipitated by adding 20 ml of n-heptane. The product polyester is a clear liquid. 13 C NMR spectroscopy was used to analyze the degree of branching and viscosity (in dry- tetrahydrofuran solvent) was determined using a Ubbelhode viscometer.
- This example describes the preparation of hyperbranched polyester by reacting bio-glycerol with succinic acid at 180°C for 2 h over Fe-Zn double-metal cyanide catalyst.
- Glycerol (1 mol), succinic acid (1 mol), catalyst (3 wt% of reaction mixture) were taken in a glass round- bottom flask. The temperature was raised to 180°C. The reaction was carried out for 2 h at atmospheric pressure. After cooling to 25°C, about 10 ml of dry-acetone was to the contents of the flask. Catalyst was separated by centrifugation followed by filtration. The polymer was reprecipitated by adding 20 ml of n-heptane. The product polyester is a clear liquid. 13 C NMR spectroscopy was used to analyze the degree of branching and viscosity (in dry- tetrahydrofuran solvent) was determined using a Ubbelhode viscometer.
- This example describes the preparation of hyperbranched polyester by reacting glycerol with succinic acid at 190°C for 1.5 h over Fe-Zn double-metal cyanide catalyst.
- Glycerol (1 mol), succinic acid (1 mol), catalyst (3 wt% of reaction mixture) were taken in a glass round-bottom flask. The temperature was raised to 190°C. The reaction was carried out for 1.5 h at atmospheric pressure. After cooling to 25°C, about 10 ml of dry-acetone was to the contents of the flask. Catalyst was separated by centrifugation followed by filtration. The polymer was reprecipitated by adding 20 ml of n-heptane. The product polyester is a clear liquid. 13 C NMR spectroscopy was used to analyze the degree of branching and viscosity (in dry- tetrahydrofuran solvent) was determined using a Ubbelhode viscometer.
- This example describes the preparation of hyperbranched polyester by reacting glycerol with succinic acid in the molar ratio of 1 : 1.5 at 180°C for 1.5 h over Fe-Zn double-metal cyanide catalyst.
- Glycerol (1 mol), succinic acid (1.5 mol), catalyst (3 wt% of reaction mixture) were taken in a glass round-bottom flask. The temperature was raised to 180°C. The reaction was carried out for 1.5 h at atmospheric pressure. After cooling to 25°C, about 10 ml of dry- acetone was to the contents of the flask. Catalyst was separated by centrifugation followed by filtration. The polymer was reprecipitated by adding 20 ml of n-heptane. The product polyester is a clear liquid. 13 C NMR spectroscopy was used to analyze the degree of branching and viscosity (in dry-tetrahydrofuran solvent) was determined using a Ubbelhode viscometer.
- This example describes the preparation of hyperbranched polyester by reacting glycerol with succinic acid in the molar ratio of 1 : 2 at 180°C for 1.5 h over Fe-Zn double-metal cyanide catalyst.
- Glycerol (1 mol), succinic acid (2 mol), catalyst (3 wt% of reaction mixture) were taken in a glass round-bottom flask. The temperature was raised to 180°C. The reaction was carried out for 1.5 h at atmospheric pressure. After cooling to 25°C, about 10 ml of dry- acetone was to the contents of the flask. Catalyst was separated by centrifugation followed by filtration. The polymer was reprecipitated by adding 20 ml of n-heptane. The product polyester is a clear liquid. 13 C NMR spectroscopy was used to analyze the degree of branching and viscosity (in dry-tetrahydrofuran solvent) was determined using a Ubbelhode viscometer.
- This example describes the preparation of hyperbranched polyester by reacting bio-glycerol with adipic acid at 180°C for 2 h over Fe-Zn double-metal cyanide catalyst.
- Glycerol (1 mol), adipic acid (1 mol), catalyst (3 wt% of reaction mixture) were taken in a glass round-bottom flask. The temperature was raised to 180°C. The reaction was carried out for 2 h at atmospheric pressure. After cooling to 25°C, about 10 ml of dry-acetone was to the contents of the flask. Catalyst was separated by centrifugation followed by filtration. The polymer was reprecipitated by adding 20 ml of n-heptane. The product polyester is a clear liquid. 13 C NMR spectroscopy was used to analyze the degree of branching and viscosity (in dry- tetrahydrofuran solvent) was determined using a Ubbelhode viscometer.
- This example describes the preparation of hyperbranched polyester by reacting glycerol with adipic acid at 190°C for 1.5 h over Fe-Zn double-metal cyanide catalyst.
- Glycerol (1 mol), adipic acid (1 mol), catalyst (3 wt% of reaction mixture) were taken in a glass round-bottom flask. The temperature was raised to 190°C. The reaction was carried out for 1.5 h at atmospheric pressure. After cooling to 25°C, about 10 ml of dry-acetone was to the contents of the flask. Catalyst was separated by centrifugation followed by filtration. The polymer was reprecipitated by adding 20 ml of n-heptane. The product polyester is a clear liquid. 13 C NMR spectroscopy was used to analyze the degree of branching and viscosity (in dry- tetrahydrofuran solvent) was determined using a Ubbelhode viscometer.
- This example describes the preparation of hyperbranched polyester by reacting glycerol with adipic acid at a molar ratio of 1 : 2 at 180°C for 1.5 h over Fe-Zn double-metal cyanide catalyst.
- Glycerol (1 mol), adipic acid (2 mol), catalyst (3 wt% of reaction mixture) were taken in a glass round-bottom flask. The temperature was raised to 180°C. The reaction was carried out for 1.5 h at atmospheric pressure. After cooling to 25°C, about 10 ml of dry- acetone was to the contents of the flask. Catalyst was separated by centrifugation followed by filtration. The polymer was reprecipitated by adding 20 ml of n-heptane. The product polyester is a clear liquid. 13 C NMR spectroscopy was used to analyze the degree of branching and viscosity (in dry-tetrahydrofuran solvent) was determined using a Ubbelhode viscometer.
- This example describes the preparation of hyperbranched polyester derived from sorbitol and succinic acid over Fe-Zn double-metal cyanide catalyst at 180°C.
- Sorbitol (1 mol), succinic acid (1 mol), catalyst (3 wt% of reaction mixture) were taken in a glass round-bottom flask. The temperature was raised to 180°C. The reaction was carried out for 1 h at atmospheric pressure. After cooling to 25°C, about 10 ml of dry-acetone was to the contents of the flask. Catalyst was separated by centrifugation followed by filtration. The polymer was reprecipitated by adding 20 ml of n-heptane. The product polyester is a clear liquid. 13 C NMR spectroscopy was used to analyze the degree of branching and viscosity (in dry- tetrahydrofuran solvent) was determined using a Ubbelhode viscometer.
- This example illustrated the reusability of the catalyst recovered from example 3.
- glycerol (1 mol), succinic acid (1 mol), recovered Fe-Zn double-metal cyanide catalyst (3 wt% of reaction mixture) were taken in a glass round-bottom flask. The temperature was raised to 180°C. The reaction was carried out for 1 h at atmospheric pressure. After cooling to 25°C, about 10 ml of dry-acetone was to the contents of the flask. Catalyst was separated by centrifugation followed by filtration. The polymer was reprecipitated by adding 20 ml of n-heptane. The product polyester is a clear liquid. 13 C NMR spectroscopy was used to analyze the degree of branching and viscosity (in dry-tetrahydrofuran solvent) was determined using a Ubbelhode viscometer.
- This example describes the preparation of hyperbranched polyester derived from glycerol and succinic acid over Co-Zn double-metal cyanide catalyst at 180°C.
- Glycerol (1 mol), succinic acid (1 mol), catalyst (3 wt% of reaction mixture) were taken in a glass round-bottom flask. The temperature was raised to 180°C. The reaction was carried out for 1 h at atmospheric pressure. After cooling to 25°C, about 10 ml of dry-acetone was added to the contents of the flask. Catalyst was separated by centrifugation followed by filtration. The polymer was reprecipitated by adding 20 ml of n-heptane. The product polyester is a clear liquid.
- aG glycerol
- S sorbitol
- SA succinic acid
- AA adipic acid
- DB degree of branching
- ⁇ inherent viscosity
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Claims
Priority Applications (5)
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EP12715442.5A EP2678370B1 (en) | 2011-02-23 | 2012-02-23 | Process for preparing hyperbranched polyesters |
US14/001,322 US9334361B2 (en) | 2011-02-23 | 2012-02-23 | Process for preparing hyperbranched polyesters |
BR112013021671A BR112013021671A2 (en) | 2011-02-23 | 2012-02-23 | process for preparing a hyperbranched polyester field of the invention |
CN201280018710.6A CN103476824B (en) | 2011-02-23 | 2012-02-23 | Process for preparing hyperbranched polyestersfield |
RU2013142982/04A RU2596831C2 (en) | 2011-02-23 | 2012-02-23 | Method of producing hyperbranched polyesters |
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US (1) | US9334361B2 (en) |
EP (1) | EP2678370B1 (en) |
CN (1) | CN103476824B (en) |
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Cited By (2)
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WO2013175509A1 (en) | 2012-05-22 | 2013-11-28 | Council Of Scientific And Industrial Research | Process for preparing biodegradable lubricant base oils |
CN110922676A (en) * | 2019-10-30 | 2020-03-27 | 中化石化销售有限公司 | Preparation method of foaming agent master batch |
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MY173189A (en) * | 2015-10-07 | 2020-01-03 | Malaysian Palm Oil Board | Metal-incorporated hyperbranched polyester-polyol |
CN109763188B (en) * | 2018-12-13 | 2020-06-12 | 东华大学 | Fiber containing hyperbranched hybrid porous material and preparation method thereof |
CN109706535B (en) * | 2018-12-13 | 2020-08-14 | 东华大学 | Polyacrylonitrile fiber containing hyperbranched polymer and preparation method thereof |
CN114835911B (en) * | 2022-05-18 | 2023-11-03 | 中南民族大学 | Sorbitol type hyperbranched polyester, preparation method, application and polypropylene composite material |
CN115710348B (en) * | 2022-09-28 | 2023-09-12 | 北京工商大学 | Preparation method and application of microcrystalline cellulose grafted hydroxyl-terminated hyperbranched polyester |
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CN110922676A (en) * | 2019-10-30 | 2020-03-27 | 中化石化销售有限公司 | Preparation method of foaming agent master batch |
CN110922676B (en) * | 2019-10-30 | 2022-09-16 | 中化石化销售有限公司 | Preparation method of foaming agent master batch |
Also Published As
Publication number | Publication date |
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CN103476824B (en) | 2015-06-17 |
RU2013142982A (en) | 2015-03-27 |
EP2678370A1 (en) | 2014-01-01 |
RU2596831C2 (en) | 2016-09-10 |
EP2678370B1 (en) | 2016-03-30 |
CN103476824A (en) | 2013-12-25 |
BR112013021671A2 (en) | 2016-11-01 |
WO2012114357A8 (en) | 2013-10-10 |
US9334361B2 (en) | 2016-05-10 |
US20130331542A1 (en) | 2013-12-12 |
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