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Cost-Effective and Up-Scale Synthesis of p-[CH2=C（H）C6H4CH2CH2CH2]2Zn and [iPrN{P（C6H4-p-SiR3）2}2CrCl2]+[B（C6F5）4]−

  • 박주용 (아주대학교 일반대학원)

초록/요약

This paper covers cost-effective and up-scale synthesis of functional organozinc reagents and chromium catalysts for industrial specialty products. The compounds we designed were aimed at developing both economical synthetic routes and scale- up for commercialization. Chapter 1 reviews background information of polyolefin elastomer and α-olefin market and technology trends. In addition, we will cover general information regarding p-[CH2=C（H）C6H4CH2CH2CH2]2Zn and [iPrN{P（C6H4-p- SiR3）2}2CrCl2] +[B（C6F5）4] − developed for market penetration. Chapter 2 addresses large scale of synthesis R2Zn compound which was used for chain transfer agent in coordinative chain transfer polymerization （CCTP）. R2Zn compounds prepared by the conventional method （reaction of 2 eq RMgCl with ZnCl2 in Et2O, followed by filtration to remove MgCl2） are often unsuitable for certain organic and polymer syntheses—particularly CCTP—due to residual impurities. Herein, we disclose a convenient, safe, scalable, and cost-effective method for the preparation of high-purity R2Zn that perform effectively in CCTP. In this approach, RMgCl, generated in Et2O or the less hazardous （CH3O）2CH2, are reacted with ZnCl2. Subsequent removal of the ether solvent affords a residue containing both the desired R2Zn product and dried MgCl2 byproduct. The dried MgCl2 acts as an impurity scrubber during the hexane extraction step, enabling isolation of highly pure R2Zn compounds. Using this method, [CH2=C（R）C6H4（CH2）x]2Zn [1 （x = 3, R = H）; 2 （x = 3, R = Me）; 3 （x = 2, R = H）; 4 （x = 2, R = Me）] were efficiently synthesized. These reagents enabled the formation of high yields of CH2=C（R）C6H4（CH2）x-[（CH（R）CH2）]n-Zn-[（CH2CH（R）]n- （CH2）xC6H4C（R）=CH2 in CCTP. GPC, 1H NMR, and rotational rheology analyses of the resulting polymers indicate that a fraction of the styrenic units in 1 and 3 is incorporated into the polymer backbone, leading to higher-molecular-weight materials with long-chain branching. Chapter 3 discuss the method for synthesizing PNP ligands, a key component of Cr catalysts, in large quantities. The Cr-catalyst-based industrial production of 1-octene via selective ethylene tetramerization, which requires both economic viability and high catalytic performance. 1-Octene is a raw material used to make polyolefin elastomers and can be applied to solar encapsulation materials. It is also known that there are currently no domestic companies capable of producing 1-octene in-house. In this study, we established a novel and cost-effective synthetic platform for PNP ligands—key components in Cr catalysts—by utilizing a key intermediate, iPrN（PCl2）2, derived directly from inexpensive PCl3. We reduced the existing synthesis steps and were able to lower unit costs. Also, PNP ligand-based Cr catalyst showed a similar level of activity to the previous one. Notably, this catalyst maintained full activity for over six months in solution. Ultimately, the industrial feasibility was demonstrated by the successful 100 g scale production of the final chromium catalyst, bridging the gap between cost-efficient ligand synthesis and high-performance, large-scale catalysis. Chapter 4 discuss the method for synthesizing Chromium borate, a key precursor of Cr catalysts, in large quantities. And the method for removing protic ligands from various metal halides will be discussed. Many chemical reactions generate alcohol or water as byproducts under equilibrium conditions. For complete conversion, it is necessary to remove these protic byproducts entirely from the equilibrium system, which can often be challenging. To address this issue, we developed a ＂simultaneous back-and-forth dual reflux apparatus＂ consisting of two reactors （Reactor A and B）, each connected to a separate condenser （Condenser A and B）. The key feature of this design is that the liquid condensed in Condenser A is returned to Reactor B, while the liquid condensed in Condenser B is returned to Reactor A. Using this apparatus, [Cr（EtOH）4Cl2][B（C6F5）4] was efficiently converted on a large scale to [CrCl2][B（C6F5）4]·6.5（CH3CN）. In this reaction, the EtOH formed in Reactor A was transferred, along with CH3CN serving as both solvent and reactant, via Condenser A to Reactor B containing （iBu）3Al in CH3CN, where the transferred EtOH was decomposed.The versatility of this apparatus was demonstrated in the conversion of various hydrated metal complexes, such as [Ni（H2O）6][ClO4]2, CrCl3·6（H2O）, CeCl3·7（H2O）, and NiBr3·3（H2O）, into their corresponding aprotic donor congeners: Ni（ClO4）2·5.8（CH3CN）, CrCl3·3.0（THF）, CeCl3·1.5（THF） （or CeCl3·2LiCl in THF solution）, and NiBr2·1.0（DME）, respectively. Additionally, the apparatus proved effective in imine formation reactions, where water is produced as a byproduct under equilibrium conditions. Keywords: Cost-effective, large-scale, Cr catalysts, R2Zn compounds, polyolefin elastomer

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목차

CHAPTER 1 1
1.1 Introduction 2
1.2 Polyolefin materials and α-olefin 2
1.2.1 Polyolefin materials market and technology trends 2
1.2.2 α-Olefin market and technology trends 4
1.3 Organozinc reagents and chromium catalysts. 6
1.3.1 The need for industrial specialty products 6
1.3.2 Organozinc reagents: key elements of Coordinative Chain Transfer Polymerization (CCTP) 7
1.3.3 Chromium catalysts for 1-octene production 9
CHAPTER 2 12
2.1 Introduction 13
2.2 RESULTS AND DISCUSSION 16
2.2.1 Straightforward synthesis of R2Zn for use in CCTP 16
2.2.2 Cost-effective synthesis of 1 and its analogues 21
2.2.3 CCTP studies 24
2.3 Experiment section 28
2.4 Conclusions 40
CHAPTER 3 41
3.1 Introduction 42
3.2 Result and discussion 44
3.2.1 Large scale synthesis of [1-CrCl2][B(C6F5)4] 44
3.2.2 Synthesis of Derivatives 46
3.3 Experiment Section 49
3.4 Conclusion 52
CHAPTER 4 53
4.1 Introduction 54
4.2 Results and discussion 56
4.2.1 Designing simultaneous back-and-forth dual reflux appartus 56
4.2.2. Converting [Cr(EtOH)4Cl2][B(C6F5)4 to [CrCl2][B(C6F5)4]·6.5(CH3CN) 57
4.2.3 Converting [CrCl3]·6H2O to CrCl3·3.0(THF) 57
4.2.4 Converting CeCl3·7H2O to CeCl3·0.84(THF), CeCl3·1.5(THF) and CeCl3·LiCl 62
4.2.5 Converting NiBr2·3H2O to NiBr2·1.0(DME) 64
4.2.6 Imine formation 65
4.3 Experiment Section 65
4.4 Conclusion 73
Reference 75
Chapter 1 76
Chapter 2 82
Chapter 3 88
Chapter 4 93
Supporting Information 97
Chapter 2 98
Chapter 3 118
Chapter 4 122

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