EP2753653A1 - Procédé de préparation de dicarboxylate de zinc - Google Patents

Procédé de préparation de dicarboxylate de zinc

Info

Publication number
EP2753653A1
EP2753653A1 EP12751534.4A EP12751534A EP2753653A1 EP 2753653 A1 EP2753653 A1 EP 2753653A1 EP 12751534 A EP12751534 A EP 12751534A EP 2753653 A1 EP2753653 A1 EP 2753653A1
Authority
EP
European Patent Office
Prior art keywords
zinc
oxide
dicarboxylic acid
dicarboxylate
zinc dicarboxylate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP12751534.4A
Other languages
German (de)
English (en)
Inventor
Anna Katharina Brym
Jürgen ZUBILLER
Gerrit Luinstra
Revaz KORASHVILI
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Priority to EP12751534.4A priority Critical patent/EP2753653A1/fr
Publication of EP2753653A1 publication Critical patent/EP2753653A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
    • C07F3/06—Zinc 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
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/32—General preparatory processes using carbon dioxide
    • C08G64/34—General preparatory processes using carbon dioxide and cyclic ethers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/41—Preparation of salts of carboxylic acids
    • C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part

Definitions

  • the invention relates to a process for the preparation of a zinc dicarboxylate from a zinc compound and a C 4 -C 10 -dicarboxylic acid in the presence of a cationic emulsifier and a solvent.
  • the invention also relates to zinc dicarboxylates obtainable by the above-mentioned process and having a BET surface area of from 50 to 750 m 2 / g.
  • the invention further relates to a process for the preparation of polyalkylene carbonates by polymerization of carbon dioxide with at least one epoxide selected from ethylene oxide, propylene oxide, butene oxide, cyclopentene oxide and cyclohexene oxide, in the presence of a zinc salt of a C4-Cio-dicarboxylic acid (zinc dicarboxylate), characterized in that the zinc dicarboxylate is prepared from a zinc compound, a C4-Cio-dicarboxylic acid in the presence of a cationic emulsifier and a solvent.
  • a zinc salt of a C4-Cio-dicarboxylic acid characterized in that the zinc dicarboxylate is prepared from a zinc compound, a C4-Cio-dicarboxylic acid in the presence of a cationic emulsifier and a solvent.
  • Polyalkylene carbonates such as polypropylene carbonate are obtained by alternating copolymerization of carbon dioxide and alkylene oxide such as propylene oxide.
  • alkylene oxide such as propylene oxide.
  • Zinc glutarates are used in particular as heterogeneous catalysts.
  • WO 03/029325 describes processes for preparing aliphatic polycarbonates. Besides multimetal cyanide compounds, it is also possible to use zinc dicarboxylates, in particular zinc glutarate or zinc adipate.
  • the zinc glutarate catalyst is prepared by reacting triturated zinc oxide with glutaric acid in toluene. After the reaction, the reaction water is distilled off azeotropically. Then the solvent toluene is distilled off, and the residue is dried under high vacuum.
  • the catalyst activity depends on the moisture content of the catalyst.
  • Zinc glutarate shows no or only a very low polymerization activity when completely dried. Only by addition of water or absorption of air humidity, the maximum activity is reached.
  • the zinc glutarate catalyst powder tends to clump and can thus be difficult to dose especially after prolonged storage.
  • the object of the present invention is to provide improved polymerization catalysts for the preparation of polyalkylene carbonates which avoid the abovementioned disadvantages of the hitherto known zinc glutarate catalysts and, in particular, show an improved activity.
  • the object is achieved by zinc salts of a C4-Cio-dicarboxylic acid (Zinkdi- carboxylate), which are characterized in that the zinc dicarboxylate is prepared from a zinc compound, a C4-Cio-dicarboxylic acid in the presence of a cationic emulsifier and a solvent.
  • Zinkdi- carboxylate Zinkdi- carboxylate
  • a zinc oxide, zinc nitrate or a zinc acetate is usually used as the zinc source.
  • any other soluble zinc salt is equally suitable.
  • surface-modified zinc oxide particles as described in PCT / EP201 / 053259 and WO 06/092442. There, surface-modified zinc oxide particles are described which are obtainable by treating zinc oxide particles with organosilanes, silazanes and / or polysiloxanes and subsequent heat treatment and / or UV irradiation of the treated zinc oxide particles.
  • C4-Cio-dicarboxylic acids are succinic acid, glutaric acid, adipic acid, pimelic acid, succinic acid, azelaic acid (nonanedioic acid) and sebacic acid. Glutaric acid and adipic acid are particularly preferred.
  • Cationic emulsifiers are generally to be understood as meaning long-chain amines, preferably primary amines and particularly preferably primary C 10 -C 30 -alkylamines. In particular, they can form micelles in polar solvents.
  • the amines can be used directly or in the form of their salts. Preferably, the amines are used directly (in free form). At least a portion of the amine should be used in free form to obtain good yields of zinc dicarboxylates.
  • the active catalysts are isolated after removal of the surfactant, preferably by washing with a liquid or by drying.
  • the drying temperature is essential in the activation of zinc carboxylates.
  • the test series listed in Table 4 shows that the activity of the obtained catalyst can be increased by the proper drying temperature.
  • the removal of the hexadecylamine is carried out in vacuo at a temperature of 100 ° C to 250 ° C, preferably 130 ° C to 170 ° C and a pressure of
  • the cationic emulsifier is usually used in a molar ratio (in mol%) of 100: 1 to 1: 100, preferably 10: 1 to 1: 2 and particularly preferably 4: 1 to 1: 1 with respect to the zinc salt.
  • n-hexadecylamine is particularly preferred. Amines with shorter chains (eg lower Cio) lead to lower catalyst activities. N-octadecylamine also gives zinc glutarates with very high catalyst activities, but octadecylamine is already more difficult to remove. Even when distilled off under vacuum, this amine can already partially decompose and it comes to browning of the catalyst.
  • the zinc dicarboxylates are prepared in the presence of a solvent.
  • a solvent Preference is given to using a polar and especially preferably a polar, protic solvent.
  • a polar, protic solvent In particular water and particularly preferably alcohols such as, for example, ethanol, propanol, butanol, hexanol or octanol or mixtures of water and alcohols have proven to be polar, protic solvents.
  • the higher alcohols may be primary, secondary or tertiary alcohols.
  • Ethanol is particularly suitable as a solvent because the cationic emulsifier can be easily recycled and re-isolated.
  • the synthesis can also be carried out without a solvent.
  • the zinc carboxylate prepared with cationic surfactants may have different morphologies, as a crystallite or as a nearly amorphous phase.
  • it may be formed as thin platelets, much like zinc carboxylates which are crystallized in water or toluene [Zheng, Y.-Q .; Lin, J.-L .; Zhang, H.-L. Journal of Crystallography - New Crystal Structures (2000), 215 (4), 535-536], but with a multiple (3-1 Ox) of the surface.
  • one of the dimensions of the crystallites is considerably smaller and the surface appears possibly curved or straight.
  • the zinc carboxylate can crystallize as a rod.
  • These rods may be nanoscale, ie the longest dimension is in the range of 30 to 1000 nm, the smallest in the range of 5 to 100 nm. Preferably, these rods are less than 500 nm long and 50 nm wide.
  • These rods are catalytically highly active and are still present in the polypropylene propylene carbonate (PPC) after a catalytic copolymerization of propylene oxide and carbon dioxide. Due to the nanoscale dimensions of the catalyst, the catalyst-containing polypropylene carbonate appears transparent. Further morphologies or mixed phases of platelets or rods of the catalyst can be obtained by the method.
  • the zinc dicaroxylates and in particular zinc glutarates prepared by the abovementioned process generally have a BET surface area of 50 to 750 m 2 / g and preferably 100 m 2 / g to 500, measured by the method described under the examples (analysis).
  • the zinc dicaroxylates and, in particular, zinc glutarates prepared by the abovementioned process have a residual nitrogen content of from 0.4 to 5% by weight, preferably from 1 to 2% by weight, based on the zinc salt, after working up and, in particular, drying. Examples 1. catalyst Preparation
  • Residual hexadecylamine was removed at 170 ° C in an oil pump vacuum (6 X 10-2 bar) (about 4 to 6 hours).
  • the resulting catalyst (100% yield) was ground again before use and heated at 200 ° C under vacuum (0.1 mbar) for at least 3 hours.
  • Example 3 30 g of zinc nitrate hexahydrate and 12.6 g of glutaric acid were dissolved in 1500 ml of ethanol in a 3 l HWS stirred vessel. With stirring, 50 g of hexadecylamine was added to the zinc nitrate solution. The mixture was stirred at room temperature for 12 h and the viscous mass was filtered through a glass frit D3. The precipitate was then washed three times with 500 ml_ ethanol and dried at 70-100 ° C in a drying oven. Furthermore, the product was dried in vacuo for 5-10 hours under protective gas flow (argon or nitrogen).
  • protective gas flow argon or nitrogen
  • Pressure of about 0.5 mbar and a temperature of 160 ° C were in a 10 L steel reactor with stirring (near the wall) from this after about 50 hours about 1, 95 kg hexadecylamine separated and 1, 18 kg of zinc glutarate as a nanoscopic catalyst receive.
  • Example 5 (Use of Other Dicarboxylic Acids) The method of synthesis of Example 1 was changed only to the extent that other dicarboxylic acids were used instead of glutaric acid (succinic acid, adipic acid, pimelic acid and azelaic acid (nonanedioic acid)). In general, the zinc dicarboxylates of Example 5 were less active in the synthesis of polypropylene carbonate than zinc glutarate. Table 1
  • Emulsifiers used Activities Temperature ° C Pressure (bar) PO
  • Example 7 BET surface area of various zinc glutarates
  • Example 7 was carried out as Example 1 only with different molar ratio (molar ratio) of zinc salt / amine (emulsifier). These experiments show that zinc glutarates with higher surface areas and more active sites are obtained by the process according to the invention. Table 3
  • Example 7 (Drying Temperature and Catalytic Action) Example 7 was carried out as Example 1 except that it was dried at different temperatures: In Table 4, the drying temperatures and nitrogen content of zinc glutarates with the respective activity and productivity of the catalyst are PPC synthesis in 4 hours specified. The highest activity was at the lowest temperature of 140 ° C be achieved. To determine the activities, polymerizations were carried out for 4 hours at 60 ° C under 20 bar CO2 pressure with 0.20 g of catalyst and 30 ml_ of propylene oxide. These examples show how drying can influence the catalytic effect.
  • polypropylene carbonate was prepared analogously to WO 03/029325.
  • the nitrogen physisorption measurements were carried out on a Quadrasorb S1 instrument from Quantachrome Instruments. The samples were previously activated a Degasser station of the company Quantachrome. The measurements were carried out at 77.35 K. The measured data were evaluated with the program Quadra Win Version 3.0.
  • Zinc glutarate PO cat. PO conversion g polymer / M n [g / mol],% carbonate,
  • the molecular weights were determined by GPC, with THF as solvent and polystyrene as standard;
  • cPC cyclic propylene carbonate
  • carbonate portions the remainder being 100 units of ether
  • 1 H-NMR spectra solvent CDC, 400 MHz, here the average carbonate methylene group at 1.35 ppm with the cPC methylene group at 1, 48-1, 50 ppm and ether carbonate and carbonate ether methylene group at 1, 1 - 1, 3 ppm related.
  • Example 1 94 4 25 60 ° C 0.2 30 380 5% 90% 1 18000
  • the results of Tables 3 and 4 show that the zinc glutarate prepared by the process according to the invention is about twice to three times as active as the zinc glutarate prepared according to WO03 / 029325 or WO06 / 092442. As a result, fewer wash cycles are needed to achieve a residual level of 10 ppm zinc. Furthermore, when working up the polymer solutions, about 50% less acid, e.g. Citric acid. In addition, less by-product is formed, such as cyclic carbonate.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de préparation d'un dicarboxylate de zinc à partir d'un composé du zinc et d'un acide dicarboxylique en C4-C10 en présence d'un émulsifiant cationique et d'un solvant. L'invention concerne également des dicarboxylates de zinc qui peuvent être obtenus à l'aide du procédé susmentionné et présentent une surface BET de 50 à 750 m2/g.
EP12751534.4A 2011-09-09 2012-08-31 Procédé de préparation de dicarboxylate de zinc Withdrawn EP2753653A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP12751534.4A EP2753653A1 (fr) 2011-09-09 2012-08-31 Procédé de préparation de dicarboxylate de zinc

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP11180727 2011-09-09
EP12751534.4A EP2753653A1 (fr) 2011-09-09 2012-08-31 Procédé de préparation de dicarboxylate de zinc
PCT/EP2012/066930 WO2013034489A1 (fr) 2011-09-09 2012-08-31 Procédé de préparation de dicarboxylate de zinc

Publications (1)

Publication Number Publication Date
EP2753653A1 true EP2753653A1 (fr) 2014-07-16

Family

ID=46755016

Family Applications (1)

Application Number Title Priority Date Filing Date
EP12751534.4A Withdrawn EP2753653A1 (fr) 2011-09-09 2012-08-31 Procédé de préparation de dicarboxylate de zinc

Country Status (5)

Country Link
US (1) US20140200328A1 (fr)
EP (1) EP2753653A1 (fr)
KR (1) KR20140062130A (fr)
CN (1) CN103781817A (fr)
WO (1) WO2013034489A1 (fr)

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Publication number Priority date Publication date Assignee Title
KR101729300B1 (ko) * 2014-06-13 2017-04-21 주식회사 엘지화학 유기 아연 촉매, 이의 제조 방법 및 상기 촉매를 이용한 폴리알킬렌 카보네이트 수지의 제조 방법
US10047032B2 (en) 2014-06-13 2018-08-14 Lg Chem, Ltd. Preparation method of organic zinc catalyst and poly(alkylene carbonate) resin
KR101747399B1 (ko) 2014-06-13 2017-06-14 주식회사 엘지화학 유기 아연 촉매의 제조 방법 및 폴리알킬렌 카보네이트 수지의 제조 방법
WO2015190874A1 (fr) * 2014-06-13 2015-12-17 주식회사 엘지화학 Catalyseur de zinc organique, procédé de fabrication de ce dernier et procédé de préparation d'une résine de carbonate de polyalkylène à l'aide d'un catalyseur de zinc organique
KR101767310B1 (ko) 2015-07-10 2017-08-10 국민대학교산학협력단 전자끄는기를 포함하는 에폭사이드, 이산화탄소 및 전자끄는기를 포함하지 않는 에폭사이드의 삼원중합체 제조방법
KR102088505B1 (ko) * 2015-07-13 2020-03-12 주식회사 엘지화학 아연계 촉매의 제조방법 및 이를 이용한 폴리알킬렌카보네이트의 제조방법
KR102109788B1 (ko) 2016-03-09 2020-05-12 주식회사 엘지화학 유기 아연 촉매, 이의 제조 방법 및 상기 촉매를 이용한 폴리알킬렌 카보네이트 수지의 제조 방법
KR102000129B1 (ko) * 2016-03-24 2019-07-15 주식회사 엘지화학 유기 아연 담지 촉매, 이의 제조 방법, 및 상기 촉매를 이용한 폴리알킬렌 카보네이트 수지의 제조 방법
CN110382114A (zh) 2017-08-28 2019-10-25 Lg化学株式会社 制备有机锌催化剂的方法，通过该方法制备的有机锌催化剂以及采用该催化剂制备聚碳酸亚烷基酯树脂的方法
WO2019045418A1 (fr) * 2017-08-28 2019-03-07 주식회사 엘지화학 Procédé de production d'un catalyseur de zinc organique et catalyseur de zinc organique produit par ce procédé, et procédé de préparation de résine de carbonate de polyalkylène utilisant ce catalyseur
CA3099972A1 (fr) 2018-12-20 2020-06-25 Lg Chem, Ltd. Procede de preparation d'un catalyseur au zinc organique et procede de preparation d'une resine au carbonate-polyalkylene a l'aide du catalyseur au zinc organique ainsi prepare
JPWO2021140869A1 (fr) * 2020-01-08 2021-07-15
IT202000029237A1 (it) * 2020-12-01 2022-06-01 Epox Co2 S R L Processo per la preparazione di zinco dicarbossilato e il suo uso come catalizzatore nella sintesi di polialchilene carbonato a partire da co2 tramite catalisi eterogenea
CN115028845B (zh) * 2022-05-11 2023-05-12 烟台大学 一种锌配位聚合物催化剂及其制备方法和应用
KR102576776B1 (ko) * 2022-10-28 2023-09-07 아주대학교산학협력단 이산화탄소-에폭사이드 반응 촉매, 이의 제조 방법 및 이를 이용한 폴리머 합성 방법

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Also Published As

Publication number Publication date
CN103781817A (zh) 2014-05-07
KR20140062130A (ko) 2014-05-22
WO2013034489A1 (fr) 2013-03-14
US20140200328A1 (en) 2014-07-17

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