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WO2016005961A1 - Catalyseur à site unique immobilisé sur un support d'oxyde inorganique et son procédé de préparation - Google Patents

Catalyseur à site unique immobilisé sur un support d'oxyde inorganique et son procédé de préparation Download PDF

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Publication number
WO2016005961A1
WO2016005961A1 PCT/IB2015/055276 IB2015055276W WO2016005961A1 WO 2016005961 A1 WO2016005961 A1 WO 2016005961A1 IB 2015055276 W IB2015055276 W IB 2015055276W WO 2016005961 A1 WO2016005961 A1 WO 2016005961A1
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WO
WIPO (PCT)
Prior art keywords
inorganic oxide
oxide support
catalyst
single site
group
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Application number
PCT/IB2015/055276
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English (en)
Inventor
Yogesh Popatrao PATIL
Mahuya BAGUI
Viralkumar PATEL
Krishna Renganath SARMA
Raksh Vir Jasra
Ajit Behari Mathur
Suketu VAKIL
Original Assignee
Reliance Industries Limited
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.)
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Publication date
Application filed by Reliance Industries Limited filed Critical Reliance Industries Limited
Publication of WO2016005961A1 publication Critical patent/WO2016005961A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene

Definitions

  • the present disclosure relates to catalysts and methods for preparing the same. Particularly, the present disclosure relates to supported polymerization catalysts.
  • Disentangled polyethylene The term 'disentangled' is used to describe ultrahigh molecular weight polyethylene - homo-polymer (s) or copolymer(s) of ethylene having molar mass in the range of 0.3 million to 20 million; crystallinity greater than 75%; heat of fusion greater than 200 J/g and bulk density ranging from 0.01 to 0.3 g/cc, wherein the polyethylene chains have low entanglement or are completely disentangled.
  • Mobil composition of matter No.41 (MCM-41) and Mobil composition of matter No.48 (MCM-48) are the types of mesoporous silica.
  • ultra-high molecular weight polyethylene is prepared by ethylene polymerization catalyzed by metallocene or non-metallocene type homogeneous catalyst compositions.
  • the homogenous catalyst compositions mainly contain transition metal complexes such as complexes of metals including Titanium (Ti), Zirconium (Zr), Hafnium (Hf) and the like.
  • transition metal complexes such as complexes of metals including Titanium (Ti), Zirconium (Zr), Hafnium (Hf) and the like.
  • M is a Group IV transition metal
  • Rj, R3, R4, R5, R6, R7, R9, Rio, Rn, Ri2, Ri 3 are independently a -H or an alkyl group;
  • R 2 is a functionalized inorganic oxide support selected as
  • R 8 and R 14 are t-butyl
  • R 15 is a -CO- or a -SO 3 H- group
  • Xj and X 2 are independently one of F, CI, Br and I.
  • a method for immobilizing a single site catalyst on an inorganic oxide support is functionalized by treating with a reagent to obtain a functionalized inorganic oxide support.
  • the functionalized inorganic oxide support is treated with a hydroxyl group containing aldehyde to obtain an inorganic oxide support with Schiff base imine ligand.
  • the inorganic oxide support with the Schiff base imine ligand is lithiated with a lithiating agent to obtain an inorganic oxide support with a lithiated Schiff base imine ligand; and the inorganic oxide support with the lithiated Schiff base imine ligand is treated with a titanium halide to obtain the immobilized single site catalyst.
  • a method for synthesis of dis-entangled ultrahigh molecular weight polyethylene by employing the immobilized single site heterogeneous catalyst of the present disclosure along with a co-catalyst.
  • Figure 1 illustrates an IR spectrum of 3, 5-diamino benzoic acid
  • Figure 2 illustrates an IR spectrum of the immobilized 3, 5-diamino benzoic acid on silica
  • Figure 3 illustrates an IR spectrum of the immobilized Schiff base imine ligand (3-tert- butyl salicylaldehyde based) on silica;
  • Figure 4 illustrates a thermo gravimetric analysis of the immobilized catalyst prepared in accordance with the present disclosure
  • Figure 5 illustrates the XRD pattern of the polymer obtained using the immobilized catalyst prepared in accordance with the present disclosure
  • Figure 6 illustrates the DSC of the polymer obtained using the immobilized catalyst prepared in accordance with the present disclosure.
  • the present disclosure provides a novel immobilized heterogeneous single site catalyst, immobilized on an inorganic support, by way of functionalizing the support.
  • a heterogeneous single site catalyst immobilized on an inor anic oxide support represented by Formula I is herein disclosed:
  • M is a Group IV transition metal
  • Rj, R 3 , R 4 , R 5 , R 6 , R 7 , R 9 , R 10 , Rn, R 1 2, R13 are independently a -H or an alkyl group;
  • R 2 is a functionalized inorganic oxide support selected as
  • R 8 and R 14 are t-butyl
  • R 15 is a -CO- or a -SO 3 H- group
  • Xj and X 2 are independently F, CI, Br or I.
  • a non-limiting example of the inorganic oxide support is at least one of silica, typically mesoporous silica MCM-41 and MCM-48.
  • a synthetic method for immobilizing a single site catalyst on an inorganic oxide support surface that comprises the following steps: a. functionalizing the support by treating with a reagent to obtain a functionalized inorganic oxide support;
  • the reagents used for functionalizing the inorganic oxide support are at least one selected from the group consisting of a diamino carboxylic acid and a diamino sulphonic acid, the non-limiting examples of which include amino substituted carboxylic acids like 3,5- dianino benzoic acid, amino substituted sulphonic acids of benzene, naphthalene like 3,5- dianino benzene- 1- sulphonic acid.
  • the functionalizing agent used is 3, 5-diamino benzoic acid.
  • Functionalizing the inorganic oxide support is a critical method step.
  • the idea is to enable reaction between the free -OH groups in the inorganic oxide supports with suitable groups like carboxylic acid or sulphonic acid as in anthranilic acid, benzene/naphthalene sulphonic acids etc. in the amino containing reagents so as to generate an "amino functionalized inorganic oxide support".
  • the amino group containing the functionalized silica is then subsequently reacted with a substituted salicylaldehyde, the non-limiting examples of which include 3-tert-butyl salicylaldehyde, 3,5-ditertiary butyl salicylaldehyde, 5-fluoro-3-methyl salicylaldehyde, un-substituted salicylaldehyde and 2-hydroxy-l naphthaldehyde to generate the Schiff base imine ligand on the functionalized inorganic oxide support.
  • a substituted salicylaldehyde the non-limiting examples of which include 3-tert-butyl salicylaldehyde, 3,5-ditertiary butyl salicylaldehyde, 5-fluoro-3-methyl salicylaldehyde, un-substituted salicylaldehyde and 2-hydroxy-l naphthaldehyde to generate the Schiff base imine ligand on the functionalized
  • immobilized Schiff base imine ligands are subsequently lithiated using a lithiating agent, the non-limiting examples of which include alkyl lithiums, aryl lithiums and lithium hydride.
  • n-butyl lithium is used as the lithiating agent. It converts the -OH group in the substituted salicylaldehyde to O " Li + .
  • the immobilized heterogeneous single site titanium catalyst is then prepared by treating the immobilized lithiated Schiff base imine ligand with a titanium halide compound, a non-limiting example of which is titanium tetrachloride.
  • One of the most advantageous aspects of the immobilized single site heterogeneous catalysts of the present disclosure is that unlike the prior art catalysts they are not physically anchored over inorganic oxide supports. Therefore, these catalysts do not get deactivated quickly.
  • the polymerization catalyst of the present disclosure also enhances the bulk density of the resultant UHMWPE by capitalizing on the diverse physico-chemical properties like surface area, porosity, average particle size, and particle size distribution, etc., of the support.
  • the selection of a suitable support along with process conditions can produce a diverse range of polymers with varied characteristics by controlling the polymerization activity in a much better way.
  • a method for synthesis of dis-entangled ultra-high molecular weight polyethylene (UHMWPE) by employing the immobilized single site heterogeneous catalyst of the present disclosure along with a co- catalyst is as described below.
  • the non-limiting examples of which are hexane, varsol (a mixture of hydrocarbons having boiling point in the range of 140-170 °C.) and toluene, is added a specific amount of a co-catalyst, the non-limiting examples of which are P-MAO (poly methylaluminoxane) and an alkyl aluminium, followed by the immobilized Ti containing catalyst of the present disclosure in such quantity so that the Al/Ti molar ratio as derived from the co-catalyst and catalyst is in the range of 15 to 300.
  • a co-catalyst the non-limiting examples of which are P-MAO (poly methylaluminoxane) and an alkyl aluminium
  • This mixture is charged into a reactor, a non-limiting example of which is a Buchi polyclave reactor, under an inert atmosphere such as nitrogen or argon, and subsequently agitated for different optimized time intervals under different optimized ethylene pressures ranging from atmospheric to 8 bar, preferably higher pressures.
  • the polymerization temperature is also optimized and ranged between 30 to 75 °C.
  • the polymer obtained during the run is filtered, washed with hexane and dried under vacuum for further characterization.
  • the single site catalyst prepared in accordance with the present disclosure is used for ethylene polymerization using an alkyl aluminium as a co-catalyst under different conditions.
  • Poly methylaluminoxane (P-MAO) as a co-catalyst is found to be very effective for synthesizing disentangled polyethylene with ultra-high molecular weight (3 - 7 million g/mole) as assessed by polymer characteristics including low bulk density, physical appearance (morphology), crystallinity and the like.
  • the catalyst prepared in accordance with the present disclosure is required in comparatively smaller quantity and hence, prevents fouling of the reactor by not generating and depositing polymer lumps on the reactor walls and the stirrer shaft/paddle assembly.
  • 3 5-diamino benzoic acid is reacted with dry silica to form a mixture.
  • the mixture is then refluxed in dry toluene to a temperature in the range of 115 to 120°C for a time period in the range of 6 to 12 hours to form ester linkage between the hydroxyl group in the silica and the carboxylic acid group in 3, 5- diamino benzoic acid, resulting in synthesis of an esterified and immobilized metaphenylene diamino benzene containing moiety as depicted in reaction-I.
  • the esterified and immobilized metaphenylene diamino benzene containing support is then washed with dry hexane and dried under nitrogen.
  • the dried, esterified and immobilized metaphenylene diamino benzene containing moiety is then reacted with an either 3-tert-butyl salicylaldehyde, or 3,5-ditert-butyl salicylaldehyde or any other substituted salicylaldehydes by refluxing in dry toluene to a temperature in the range of 115 to 120°C for a time period in the range of 6 to 12 hours in the presence of catalytic quantity of paratoluene sulphonic acid to obtain the corresponding immobilized Schiff base imine ligands as depicted in reaction-II.
  • the immobilized Schiff base imine ligands are then lithiated using rc-butyl lithium in dry ether to a temperature in the range of -70°C to -75°C for a time period in the range of 1 hour to 4 hours to form a reaction mixture and convert the hydroxyl group to 0 " Li + using dry ice and acetone. Temperature of lithiation is further increased to a temperature in the range of 25 to 30°C for a time period in the range of 2 hours to 6 hours. After lithiation, temperature of the reaction mixture is cooled to a temperature in the range of -78 °C to - 85°C to obtain a cooled reaction mixture. The cooled reaction mixture is reacted with TiCl 4 at a room temperature for a time period in the range of 6 hours to 8 hours followed by stirring to generate an immobilized transition metal single site catalyst as depicted below in reaction-Ill.
  • the titanium content of the so-prepared immobilized [bis-(N-3-tert-butylsalicylidene)-3, 5-diamino benzoyl] -titanium (IV) dichloride is determined by UV-Vis spectroscopy and the titanium present in the single site catalyst prepared in accordance with the present disclosure is 6.22%.
  • the single site catalyst prepared in accordance with the present disclosure is used for ethylene polymerization using different co-catalysts. The polymerization is studied under different conditions and the polymer obtained is characterized for its viscosity, molecular weight and bulk density.
  • the esterified and immobilized metaphenylene diamino benzene containing support was washed with dry hexane for 30 minutes and dried under nitrogen for 1 hour.
  • the dried, esterified and immobilized metaphenylene diamino benzene containing moiety was then reacted with 3,5-ditert-butyl salicylaldehyde by refluxing in dry toluene at 115°C in the presence of catalytic quantity of paratoluene sulphonic acid for 6 hours to obtain the corresponding immobilized Schiff base imine ligands.
  • the immobilized Schiff base imine ligands was lithiated using 1.6 moles of rc-butyl lithium in dry ether at -78°C for 1 hour using dry ice and acetone to form a reaction mixture and convert the hydroxyl group to 0 " Li + . Temperature of lithiation was further raised to 25°C for 2 hours. After lithiation, temperature of the reaction mixture was cooled to -78°C to form a cooled reaction mixture. The cooled reaction mixture was then reacted with 2 mmol of TiCl 4 at a room temperature for 5 hours followed by stirring to generate an immobilized transition metal single site catalyst.
  • the catalyst of the present disclosure was used in the polymerization of ethylene.
  • the product of reaction III, as represented by Formula - II below was used as the catalyst for the polymerization.
  • Table 1 summarizes the ethylene polymerization carried out under different conditions.
  • Thermo gravimetric analysis of the prepared single site catalyst shows that the catalyst contains around 49.39% volatile content or organic content (from the organic Schiff base imine ligand) and 50.61% residue or inorganic content (from the silica and titanium) as depicted in figure 4.
  • the catalyst contains one titanium and 2 chlorine moieties immobilized on the silica support.
  • the polymer obtained during polymerization using the single site catalyst of the present disclosure is further characterized using X-Ray Diffraction (XRD). It is seen that the crystallinity of the resulting polymer is in the range of 95-99% which is higher than normal UHMWPE (60-65% crystallinity) as depicted in figure 5.
  • XRD X-Ray Diffraction
  • Differential scanning calorimetry (DSC) of the synthesized polymer is carried out to ascertain the melting and crystallization temperature of the polymer.
  • the melting temperature of polymers synthesized are observed to be around 138 - 139 °C on first heating and on second heating it got reduced to 134 - 137 °C as depicted in figure 6.
  • the crystallization temperature was also observed to be around 118-120 °C.
  • the obtained polymers also exhibited high enthalpy of melting, ranging from 189-190 J/g, compared to normal UHMWPE (enthalpy of melting - 140 J/g) indicating a high degree of chain disentanglement in the polymer obtained using the single site catalyst of the present disclosure.
  • the present disclosure provides an immobilized single site catalyst on an inorganic oxide support.
  • the present disclosure also provides a method for preparation of single site catalyst on an inorganic oxide support.
  • the polyethylene obtained using the single site catalyst of the present disclosure has a high molecular weight and thus can be classified as UHMWPE.
  • the catalyst of the present disclosure prevents fouling of the reactor as it is used in a comparatively smaller quantity.

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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)
  • Catalysts (AREA)

Abstract

La présente invention concerne un catalyseur à site unique hétérogène immobilisé sur un support d'oxyde inorganique et son procédé de synthèse faisant appel à une étape de génération d'un ligand imine utilisé comme base de Schiff sur le support d'oxyde inorganique suivie par une étape de lithiation et de titanation. L'utilisation du catalyseur à site unique de la présente invention est destinée à la polymérisation de l'éthylène pour obtenir un polyéthylène de masse moléculaire ultra-élevée qui est démêlé.
PCT/IB2015/055276 2014-07-11 2015-07-13 Catalyseur à site unique immobilisé sur un support d'oxyde inorganique et son procédé de préparation WO2016005961A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016207909A1 (fr) 2015-06-22 2016-12-29 Council Of Scientific & Industrial Research Catalyseurs pour la préparation de polyéthylène à ultra-haut poids moléculaire (pe-uhmw) et leur procédé de préparation
CN108699088A (zh) * 2016-01-25 2018-10-23 瑞来斯实业公司 过渡金属席夫碱亚胺配体络合物制备工艺
WO2021101457A1 (fr) * 2019-11-20 2021-05-27 Scg Chemicals Co., Ltd. Polyéthylène à ultra haut poids moléculaire

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6875718B2 (en) * 1997-04-25 2005-04-05 Mitsui Chemicals, Inc. Olefin polymerization catalysts, transition metal compounds, processes for olefin polymerization, and α-olefin/conjugated diene copolymers
WO2013118140A2 (fr) * 2012-02-08 2013-08-15 Reliance Industries Ltd Immobilisation de catalyseur monosite sur support d'oxyde inorganique pour la préparation de polyéthylène de très haute masse moléculaire

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6875718B2 (en) * 1997-04-25 2005-04-05 Mitsui Chemicals, Inc. Olefin polymerization catalysts, transition metal compounds, processes for olefin polymerization, and α-olefin/conjugated diene copolymers
WO2013118140A2 (fr) * 2012-02-08 2013-08-15 Reliance Industries Ltd Immobilisation de catalyseur monosite sur support d'oxyde inorganique pour la préparation de polyéthylène de très haute masse moléculaire

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DAL SANTO ET AL.: "Design and Use of Nanostructured Single-Site Heterogeneous Catalysts for the Selective Transformation of Fine Chemicals", MOLECULES, vol. 15, 26 May 2010 (2010-05-26), pages 3829 - 3856, ISSN: 1420-3049 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016207909A1 (fr) 2015-06-22 2016-12-29 Council Of Scientific & Industrial Research Catalyseurs pour la préparation de polyéthylène à ultra-haut poids moléculaire (pe-uhmw) et leur procédé de préparation
CN108699088A (zh) * 2016-01-25 2018-10-23 瑞来斯实业公司 过渡金属席夫碱亚胺配体络合物制备工艺
CN108699088B (zh) * 2016-01-25 2021-07-23 瑞来斯实业公司 过渡金属席夫碱亚胺配体络合物制备工艺
WO2021101457A1 (fr) * 2019-11-20 2021-05-27 Scg Chemicals Co., Ltd. Polyéthylène à ultra haut poids moléculaire

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