A method of preparing a functionalized polymer from a commercial olefin precursor and a functionalized polymer

Abstract

The application discloses a method for preparing photoelectric dual-response sensing polymer materials with self-repairing performance by using commercial olefin precursors and functionalized polymers based on the method; the method directly copolymerizes flexible comonomers and vinyl aromatic hydrocarbon monomers, and under suitable polymerization conditions, the two monomers are polymerized in a random copolymerization manner to generate functional polymers with micro-phase separation characteristics; the above method provided by the application can upgrade the commercial olefin monomers to obtain self-repairing performance, optical and electrical sensing performance, the conversion efficiency is high, the process is simple, the functionalization upgrading of the olefin polymers lacking of functions can be fully realized, the cost can be significantly reduced, the environmental pollution and resource waste can be reduced, and the application range of the olefin materials is widened.

Description

Technical Field

[0001] This invention relates to the field of upgrading commercial polyolefins, and particularly to upgrading commercial polyolefins into functionalized polymers with self-healing properties and dual photoelectric recognition responses. Background Technology

[0002] Polyolefins are widely used in substrates, packaging, electronics, and machinery due to their low price, high transparency, lightweight, and good mechanical strength and processing properties. Total polyolefin production capacity is projected to reach 41.53 million tons by 2025, with over 20 million tons of new capacity planned for the coming years. However, most polyolefins are single-use consumer products and are only used as basic materials, lacking functional applications. Most waste polyolefin products are disposed of in landfills, and their inherently simple saturated carbon chain structure significantly limits their application scope.

[0003] Functional upgrades of polyolefin materials can significantly improve their optical properties, electrical conductivity, gas barrier properties, and mechanical properties, expanding their applications in cutting-edge fields such as new energy and aerospace, and creating greater economic benefits. Functionalized polyolefins can also reduce environmental pollution by optimizing recyclability and biodegradability. For example, introducing biodegradable segments or improving the reprocessability of waste materials can enhance the rational utilization of resources.

[0004] This invention addresses the aforementioned problems in the prior art by proposing a method for preparing functionalized polymers from commercial olefin precursors, as well as the functionalized polymers themselves. The aim is to improve the technical problem of limited commercial value of existing commercial olefin precursors and to provide a simple technical means for preparing functionalized polymers. Summary of the Invention

[0005] To address the problems existing in the prior art, firstly, the main objective of this invention is to provide a method for preparing functionalized polymers from commercial olefin precursors, comprising the following steps: Copolymerizing flexible comonomers with vinyl aromatic hydrocarbon monomers; The copolymer is formed by reacting alkyl lithium and rare earth metal catalysts to form a polymer; The flexible comonomer is at least one of ethylene, 1,3-butadiene, isoprene, myrcene, and farnesene, and the vinyl aromatic hydrocarbon monomer includes at least one of vinylnaphthalene, vinylanthracene, vinylphenanthrene, and vinylpyrene.

[0006] Preferably, the initiator is an alkyllithium initiator with the general chemical formula RLi, wherein R is a straight-chain or branched alkyl, cycloalkyl, or aryl group, preferably one or more of lithium methyl, lithium ethyl, lithium propyl, lithium isopropyl, lithium n-butyl, lithium sec-butyl, lithium tert-butyl, lithium pentyl, lithium hexyl, lithium cyclohexyl, lithium tert-octyl, lithium n-eicosyl, lithium phenyl, lithium methylphenyl, lithium butylphenyl, lithium naphthyl, lithium butylcyclohexyl, and lithium hexyl.

[0007] Preferably, the catalyst comprises titanium tetrachloride and / or a rare earth metal catalyst, wherein the rare earth metal catalyst has a semi-sandwich structure in part or all of its components. or or .

[0008] Preferably, the flexible comonomer and the vinyl aromatic monomer undergo anionic polymerization under the initiation of the initiator, and the flexible comonomer and the vinyl aromatic monomer undergo cationic polymerization and metal coordination polymerization under the catalysis of the catalyst.

[0009] Preferably, the functionalized polymer is either a block polymer or a random polymer.

[0010] Preferably, the molar ratio of the flexible comonomer to the vinyl aromatic monomer is 60-99: 1-40.

[0011] Preferably, the amount of the initiator and / or catalyst is 0.04% to 10% of the molar ratio of the flexible comonomer to the vinyl aromatic monomer.

[0012] Preferably, the copolymerization reaction temperature is 30±5℃ and the reaction time is 1~24h.

[0013] Preferably, the solvent for the copolymerization reaction is any one of toluene, cyclohexane, tetrahydrofuran, and dichloromethane, and the amount of solvent used is 200% to 500% of the total mass of the flexible comonomer and the vinyl aromatic hydrocarbon monomer.

[0014] Secondly, the present invention also provides a flexible optoelectronic functionalized polymer with self-healing properties, which is prepared according to the commercial olefin precursor described in the first aspect.

[0015] Preferably, the self-healing flexible optoelectronic functionalized polymer has self-healing properties and is prepared by a one-pot method to obtain a flexible optoelectronic dual recognition sensing functional polymer that can completely self-heal within 48 hours at room temperature, has a luminescence quantum yield of over 98%, and retains charge for more than 30 days.

[0016] Compared with the prior art, the beneficial effects of the present invention are as follows: (1) The present invention directly mixes flexible comonomers and vinyl aromatic hydrocarbons, and prepares flexible photoelectric dual recognition sensing polymers that can completely self-heal within 48 h at room temperature, have a luminescence quantum yield of more than 98%, and retain charge for more than 30 days by one-pot method under the conditions of initiator or catalyst. The reaction pathway provided by this invention, through ingenious molecular and reaction design, enables two monomers to form random polymer segments with similar polymerization rates under the catalysis of an initiator. By controlling the molar ratio of the two monomers, a suitable and uniform phase separation is formed in the microstructure. The macroscopic properties of the material are controlled from the microstructure, significantly improving the material's performance and expanding its functions. The synthesis method of this type of material is simple and easy to implement, with a yield of over 90% and good mechanical properties. Currently, it is difficult to achieve both quantum yield and solid-state flexibility in flexible optical polymers. For example, although polystyrene-vinylpyrene-di(ethylene glycol)diacrylate can achieve a high quantum yield, its poor mechanical properties mean that it can only be used in liquid dispersion. Although poly4-[2-(1-pyrenyl)styrene]-ethylene-propylene has good mechanical properties, its solid-state quantum yield is only 40%, which limits its great commercial application value.

[0017] (2) This invention uses commercially available ethylene monomers to prepare high-value-added elastomer polymers. Compared with thermosetting olefin polymers, this material is easier to recycle and reuse, solving its recycling problem. It is of great significance for solving environmental pollution and reusing resources.

[0018] (3) In the functional upgrade utilization method of the present invention, the mechanical properties, heat resistance, self-healing properties, optical properties and electret properties of the obtained functional polymer can be easily controlled by selecting different types of monomers and adjusting the molar ratio of the monomers.

[0019] (4) The polymer synthesis method of the present invention can be carried out directly using existing polyolefin production equipment, with low equipment requirements, which is conducive to the rapid promotion of the process. Attached Figure Description

[0020] Figure 1 Poly(1-vinylnaphthalene-isoprene) of Example 1 1 H NMR spectrum; Figure 2 Poly(1-vinylanthracene-isoprene) of Example 2 1 H NMR spectrum; Figure 3 Poly(1-vinylpyrene-isoprene) of Example 3 1 H NMR spectrum; Figure 4For example 4, poly(1-vinylanthracene-myrcene) 1 H spectrum; Figure 5 Tensile strength and elongation at break of poly(1-vinylnaphthalene-isoprene) with different naphthalene contents; Figure 6 Self-healing test of poly(1-vinylnaphthalene-isoprene) in Example 1; Figure 7 Microscopic morphology images of poly(1-vinylnaphthalene-isoprene) with different naphthalene contents; Figure 8 The fluorescence excitation and emission spectra of poly(1-vinylnaphthalene-isoprene) from Example 1 are shown. Figure 9 The luminescence quantum yield diagrams are for poly(1-vinylnaphthalene-isoprene) with different naphthalene contents and polyisoprene (PIP) with different naphthalene monomer contents uniformly dispersed. Figure 10 Electret performance test diagrams for poly(1-vinylnaphthalene-isoprene) with different naphthalene contents and self-healing electret performance test diagrams. Detailed Implementation

[0021] To better understand the present invention, the following embodiments are further illustrations of the present invention, but the content of the present invention is not limited to the following embodiments.

[0022] In this embodiment of the invention, all reactions are carried out in an inert gas (nitrogen, argon). Example 1

[0023] Synthesis of poly(1-vinylnaphthalene-isoprene): The polymerization method for poly(1-vinylnaphthalene-isoprene) disclosed in Example 1 includes the following steps: Add 1.3 × 10 to a 50 mL round-bottom flask -2 A mixture of 9.36 mmol of vinylnaphthalene and 23.4 mmol of isoprene was slowly added dropwise after thoroughly mixing 1 mmol of sec-butyllithium initiator and 20 mL of cyclohexane solvent. The reaction was carried out at room temperature and pressure. After 24 h of reaction, the reaction was terminated with methanol and the polymer was washed with methanol. Then, it was vacuum dried overnight at 60 °C in a vacuum oven. The product obtained was poly(1-vinylnaphthalene-isoprene).

[0024] The poly(1-vinylnaphthalene-isoprene) corresponding to Example 1 1 H NMR spectrum as shown Figure 1 As shown. Example 2

[0025] Synthesis of poly(1-vinylanthracene-isoprene): The method for synthesizing poly(1-vinylanthracene-isoprene) disclosed in Example 2 includes the following steps: 0.01 mmol of Sc-TMS catalyst and 5 mL of toluene were added to a 50 mL round-bottom flask. After the catalyst was fully dissolved, 0.01 mmol of [Ph3C][(C6F5)4B] was added to 1 mL of toluene and fully dissolved, and then slowly added dropwise to the Sc-TMS catalyst dispersion. 1 mmol of 1-vinylanthracene and 24 mmol of isoprene were added to 10 mL of toluene and fully dissolved. Then, the monomer mixture was slowly added dropwise to the catalyst dispersion. The reaction was carried out under ambient temperature and pressure. After 24 h of reaction, the reaction was terminated with methanol and the polymer was washed with methanol. Then, it was vacuum dried overnight at 60 °C in a vacuum oven. The obtained product was poly(1-vinylanthracene-isoprene).

[0026] Example 2 corresponds to poly(1-vinylanthracene-isoprene) 1 H NMR spectrum as shown Figure 2 As shown. Example 3

[0027] Synthesis of poly(1-vinylpyrene-isoprene): The method for synthesizing poly(1-vinylpyrene-isoprene) disclosed in Example 3 includes the following steps: Add 1.3 × 10 to a 50 mL round-bottom flask -2 A mixture of 1 mmol sec-butyllithium initiator and 20 mL cyclohexane solvent was thoroughly mixed, and then a mixture of 5.2 mmol vinylpyrene and 27.3 mmol isoprene was slowly added dropwise. The reaction was carried out under normal temperature and pressure conditions. After 24 h of reaction, the reaction was terminated with methanol and the polymer was washed with methanol. Then, it was vacuum dried overnight at 60 °C in a vacuum oven. The product obtained was poly(1-vinylpyrene-isoprene).

[0028] Example 3 corresponds to poly(1-vinylpyrene-isoprene) 1 H NMR spectrum as shown Figure 3 As shown. Example 4

[0029] Synthesis of poly(1-vinylnaphthalene-myrcene): The method for synthesizing poly(1-vinylanthracene-myrcene) disclosed in Example 4 includes the following steps: Add 1.3 × 10 to a 50 mL round-bottom flask -2A mixture of 1 mmol titanium tetrachloride catalyst and 20 mL dichloromethane solvent was thoroughly mixed, and then a mixture of 5.2 mmol vinylanthracene and 27.3 mmol myrcene was slowly added. The reaction was carried out at a low temperature of -85 °C and a normal pressure. After 24 h of reaction, the reaction was terminated with methanol and the polymer was washed with methanol. Then, it was vacuum dried overnight at 60 °C in a vacuum oven. The product obtained was poly(1-vinylanthracene-myrcene).

[0030] Example 4 corresponds to poly(1-vinylanthracene-myrcene) 1 H NMR spectrum as shown Figure 4 As shown. Performance testing

[0031] Mechanical property test 1: Poly(1-vinylnaphthalene-isoprene) was injection molded into corresponding test strips according to a standardized process. The tensile strength and elongation at break of the samples were measured according to the measurement method specified in ISO 527-2, Test Method for Tensile Properties of Plastics (tensile rate of 300 mm / min). The test results are as follows. Figure 5 As shown.

[0032] Self-healing test: Poly(1-vinylnaphthalene-isoprene) P3 from Example 1 was injection molded into corresponding test strips according to a uniform process. Different test strips were completely cut and spliced ​​together, and allowed to self-heal at room temperature without any intervention. At different time intervals (30 minutes, 1 day, 2 days), the spliced ​​strips were measured for tensile strength and elongation at break according to the measurement method specified in ISO 527-2, Test Method for Tensile Properties of Plastics (tensile rate 300 mm / min). The test results are as follows. Figure 6 As shown.

[0033] Microstructure analysis: Poly(1-vinylnaphthalene-isoprene) with different monomer ratios (10% 1-vinylnaphthalene (10% VN), 30% VN, 50% VN) was analyzed using transmission electron microscopy. The results are as follows. Figure 7 As shown.

[0034] Optical Test 1: Poly(1-vinylnaphthalene-isoprene) P3 from Example 1 was injection molded into corresponding test strips according to a uniform process. Fluorescence excitation and emission spectra were obtained using a fluorescence spectrophotometer. The test results are as follows: Figure 8 As shown.

[0035] Optical Test 2: Poly(1-vinylnaphthalene-isoprene) with different naphthalene contents and polyisoprene (PIP) with uniformly dispersed naphthalene monomers were injection molded into corresponding test strips according to a unified process. The photoluminescence quantum yield was measured using a fluorescence spectrophotometer. The test results are as follows. Figure 9 As shown.

[0036] Electret performance testing: Poly(1-vinylnaphthalene-isoprene) with different naphthalene contents (P3: 30%VN, P6: 50%VN, and P7: 10%VN) were injection molded into corresponding test strips according to a unified process. The test strips were then polarized in a charge polarization device and placed in a storage room. Charge tests were conducted at different time intervals (30 minutes to 30 days) to test their charge storage capacity. Furthermore, voltage changes were tested in the original material state, after shearing, and after self-healing. The test results are as follows. Figure 10 As shown.

[0037] It should be noted that, in this document, relational terms such as "first" and "second" are used only to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article, or apparatus.

[0038] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is limited by the appended claims and their equivalents.

Claims

1. A method for preparing functionalized polymers from commercial olefin precursors, characterized in that, Includes the following steps: Copolymerizing flexible comonomers with vinyl aromatic hydrocarbon monomers; The copolymer is formed by reacting alkyl lithium and rare earth metal catalysts to form a polymer; The flexible comonomer is at least one of ethylene, 1,3-butadiene, isoprene, myrcene, and farnesene, and the vinyl aromatic hydrocarbon monomer includes at least one of vinylnaphthalene, vinylanthracene, vinylphenanthrene, and vinylpyrene.

2. The method for preparing functionalized polymers from commercial olefin precursors according to claim 1, characterized in that: The initiator is an alkyllithium initiator with the general chemical formula RLi, wherein R is a straight-chain or branched alkyl, cycloalkyl, or aryl group, preferably one or more of lithium methyl, lithium ethyl, lithium propyl, lithium isopropyl, lithium n-butyl, lithium sec-butyl, lithium tert-butyl, lithium pentyl, lithium hexyl, lithium cyclohexyl, lithium tert-octyl, lithium n-eicosyl, lithium phenyl, lithium methylphenyl, lithium butylphenyl, lithium naphthyl, lithium butylcyclohexyl, and lithium hexyl.

3. The method for preparing functionalized polymers from commercial olefin precursors according to claim 1, characterized in that: The catalyst comprises titanium tetrachloride and / or a rare earth metal catalyst, wherein the rare earth metal catalyst has a semi-sandwich structure in part or all of its components. or or .

4. The method for preparing functionalized polymers from commercial olefin precursors according to any one of claims 1-3, characterized in that, The flexible comonomer and the vinyl aromatic monomer undergo anionic polymerization under the initiation of the initiator, and the flexible comonomer and the vinyl aromatic monomer undergo cationic polymerization and metal coordination polymerization under the catalysis of the catalyst.

5. The method for preparing functionalized polymers from commercial olefin precursors according to any one of claims 1-3, characterized in that, The functionalized polymer can be either a block polymer or a random polymer.

6. The method for preparing functionalized polymers from commercial olefin precursors according to any one of claims 1-3, characterized in that: The molar ratio of the flexible comonomer to the vinyl aromatic monomer is 60–99: 1–40.

7. The method for preparing functionalized polymers from commercial olefin precursors according to any one of claims 1-3, characterized in that, The amount of the initiator and / or catalyst used is 0.04% to 10% of the molar ratio of the flexible comonomer to the vinyl aromatic monomer.

8. The method for preparing functionalized polymers from commercial olefin precursors according to any one of claims 1-3, characterized in that, The copolymerization reaction temperature is 30±5℃, and the reaction time is 1~24h.

9. The method for preparing functionalized polymers from commercial olefin precursors according to any one of claims 1-3, characterized in that, The solvent for the copolymerization reaction is any one or more of toluene, cyclohexane, tetrahydrofuran, and dichloromethane, and the amount of solvent used is 200% to 500% of the total mass of the flexible comonomer and the vinyl aromatic hydrocarbon monomer.

10. A functionalized polymer, characterized in that: The functionalized polymer is prepared by the method for preparing functionalized polymers from commercial olefin precursors according to any one of claims 1-9.

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