CN115124645B - Polyolefin material with crystalline alternating structure and preparation method thereof - Google Patents
Polyolefin material with crystalline alternating structure and preparation method thereof Download PDFInfo
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Abstract
The invention provides a polyolefin material with a crystalline alternating structure and a preparation method thereof, belonging to the technical field of functional polymer materials. The alternating structure polyolefin material is a series of alternating structure polymers and di/tri/tetra/penta block/random-alternating structure polymers with crystallization performance, which are obtained by respectively copolymerizing 1, 1-diphenylethylene derivatives after being initiated by alkyl lithium with cyclopropyl styrene (CPVB), cyclobutylstyrene (CBVB), 2-phenyl-1, 3-butadiene (2-PB), 1-cyclopropyl-1-phenyl-1, 3-butadiene (CPBB) and 1-cyclobutyl-1-phenyl-1, 3-butadiene (CBBB). Because the framework structure and microstructure of the repeating units of the alternating structure can be controlled, the crystallization capability of the polyolefin material with the alternating structure prepared by the invention can be regulated and controlled gradually. The series of alternating structure polyolefin materials provided by the invention overcomes the defect that the polyolefin materials with crystallization capability are difficult to synthesize by using the traditional anionic polymerization.
Description
Technical Field
The invention belongs to the technical field of functional polymer materials, and particularly relates to a polyolefin material with a crystalline alternating structure and a preparation method thereof.
Background
The crystalline state is one of the most important aggregation state structures of the polymer, and can directly control the usability of the polymer material in the process of processing and forming. The high molecular crystallization is a process of orderly arranging and folding molecular chains into a crystal lattice, and has a microstructure different from common ceramics, glass oxides, metals and the like, and the microstructure is a structure of mutually staggered crystallization and amorphous phase on the scale of tens of nanometers. The polymer material having a crystalline property is composed of a crystalline phase and an amorphous phase, and the crystallinity thereof cannot reach 100%, and is therefore called a semicrystalline polymer. It imparts the necessary strength and hardness to the polymeric material for the crystalline phase and provides the thermoplastic elastomer with physical cross-linking points. The molecular chain in the amorphous phase can be twisted in a large scale, so that the necessary flexibility of the high polymer material is provided. The interaction of the crystalline phase with the amorphous phase thus results in the polymeric material exhibiting tough properties.
In general, the preparation of polyolefin materials having crystallization properties requires the regulation of the tacticity and arrangement of monomer units in the chain, such as ethylene, propylene, styrene, etc., through specific catalysts to synthesize polyolefin materials having crystallization properties. In the Terpolymerization of ethylene and two different methoxyaryl substituted propylenes by scandium catalyst makes tough and fast self-healing elastomers literature, the authors report that the elastomeric chain synthesized by terpolymerization contains crystalline chains of polyethylene, which serve as stress crosslinking points to give the elastomer good mechanical properties and self-healing properties. The polymer synthesized by the traditional anionic polymerization method is mostly in a random configuration, and usually depends on the preparation of polybutadiene with a high content of 1,4 structures, and then the crystalline polymer similar to polyethylene can be obtained by hydrogenation after treatment, so that the direct preparation of crystalline high molecular materials by using anionic polymerization is difficult. In the "Synthesis, structure, and photophysical and electrochemical properties of a pi-supported polymer" literature, the authors report that the crystalline polymer is synthesized directly from Dibenzofuran (DBF) as a monomer for the first time by an anionic polymerization method, but the molecular weight of the product can only reach 3000g/mol at most due to the high crystallinity, so that the crystalline polymer is only remained in academic research and is difficult to be widely applied industrially. Therefore, how to break through the traditional thinking formula and apply anionic polymerization to prepare a polyolefin material with main chain crystallinity and adjustable crystallinity is a problem to be solved in the field of polymer materials at present.
Disclosure of Invention
The invention solves the dilemma that the traditional anionic polymerization is difficult to directly synthesize the crystalline polymer, and designs and synthesizes a polymer with an alternate structure and crystallinity.
The invention adopts the technical scheme that:
the polyolefin material with crystalline alternating structure is an alternating structure polymer obtained by copolymerizing cyclopropyl styrene (CPVB), cyclobutyl styrene (CBVB), 2-phenyl-1, 3-butadiene (2-PB), 1-cyclopropyl-1-phenyl-1, 3-butadiene (CPBB) and 1-cyclobutyl-1-phenyl-1, 3-butadiene (CBBB) with 1,1 diphenylethylene Derivatives (DPEs) respectively, and the crystallization capability of the product is controlled by polymerization solvent and additive types. The alternating structures are CPVB, CBVB and 2-PB, CPBB, CBBB which are respectively and alternately arranged with the DPEs units. Total 48, no. 1: CPVB/DPEs alternating copolymer; no. 2: CBVB/DPEs alternating copolymer; no. 3: 2-PB/DPEs alternating copolymer; no. 4: CPBB/DPEs alternating copolymer; no. 5: CBBB/DPEs alternating copolymers; no. 6: CPVB/DPEs-block-CBVB/DPEs two-block alternating copolymer; no. 7: CPVB/DPEs-block-2-PB/DPEs two-block alternating copolymer; no. 8: CPVB/DPEs-block-CPBB/DPEs two-block alternating copolymer; no. 9: CPVB/DPEs-block-CBBB/DPEs two-block alternating copolymer; number 10: CBVB/DPEs-block-2-PB/DPEs two-block alternating copolymer; no. 11: CBVB/DPEs-block-CPBB/DPEs two-block alternating copolymer; no. 12: CBVB/DPEs-block-CBBB/DPEs two-block alternating copolymer; no. 13: 2-PB/DPEs-block-CPBB/DPEs two-block alternating copolymer; no. 14: 2-PB/DPEs-block-CBBB/DPEs two-block alternating copolymer; no. 15: CPBB/DPEs-block-CBBB/DPEs two-block alternating copolymer; number 16: CPVB/DPEs-block-CBVB/DPEs-block-2-PB/DPEs triblock copolymer; no. 17: CPVB/DPEs-block-CBVB/DPEs-block-CPBB/DPEs triblock copolymer; no. 18: CPVB/DPEs-block-CBVB/DPEs-block-CBBB/DPEs triblock copolymer; 19: CPVB/DPEs-block-2-PB/DPEs-block-CPBB/DPEs triblock copolymer; number 20: CPVB/DPEs-block-2-PB/DPEs-block-CBBB/DPEs triblock copolymer; no. 21: CBVB/DPEs-block-2-PB/DPEs-block-CPBB/DPEs triblock copolymer; no. 22: CBVB/DPEs-block-2-PB/DPEs-block-CBBB/DPEs triblock copolymer; no. 23: 2-PB/DPEs-block-CPBB/DPEs-block-CBBB/DPEs triblock copolymer; no. 24: CPVB/DPEs-block-CBVB/DPEs-block-2-PB/DPEs-block-CPBB/DPEs tetrablock copolymers; 25: CPVB/DPEs-block-CBVB/DPEs-block-2-PB/DPEs-block-CBBB/DPEs tetrablock copolymers; no. 26: CBVB/DPEs-block-2-PB/DPEs-block-CPBB/DPEs-block-CBBB/DPEs tetrablock copolymers; no. 27: CPVB/DPEs-block-CBVB/DPEs-block-2-PB/DPEs-block-CPBB/DPEs-block-CBBB/DPEs pentablock copolymer; no. 28: CPVB/DPEs/CBVB random alternating copolymer; 29: CPVB/DPEs/2-PB random alternating copolymer; no. 30: CPVB/DPEs/CPBB random alternating copolymer; no. 31: CPVB/DPEs/CBBB random alternating copolymer; no. 32: CBVB/DPEs/2-PB random alternating copolymer; 33: CBVB/DPEs/CPBB random alternating copolymer; 34 # 3: CBVB/DPEs/CBBB random alternating copolymer; no. 35: 2-PB/DPEs/CPBB random alternating copolymer; no. 36: 2-PB/DPEs/CBBB random alternating copolymer; no. 37: CPBB/DPEs/CBBB random alternating copolymer; no. 38: CPVB/DPEs/CBVB random alternating copolymer; 39: CPVB/DPEs/CBVB/2-PB random alternating copolymer; number 40: CPVB/DPEs/CBVB/CPBB random alternating copolymer; no. 41: CPVB/DPEs/CBVB/CBBB random alternating copolymer; no. 42: CBVB/DPEs/2-PB/CPBB random alternating copolymer; 43 # s: CBVB/DPEs/2-PB/CBBB random alternating copolymer; number 44: 2-PB/DPEs/CPBB/CBBB random alternating copolymer; no. 45: CPVB/DPEs/2-PB/CBVB/CPBB random alternating polymer; 46: CPVB/DPEs/2-PB/CBVB/CBBB random alternating polymer; no. 47: CBVB/DPEs/2-PB/CPVB/CBBB random alternating polymer; no. 48: CPVB/DPEs/2-PB/CBVB/CPBB/CBBB random alternating copolymer.
Further, the number average molecular weight of the polymer is in the range of 1X 10 4 －100×10 4 g/mol。
Further, the microstructure of the polymer has a trans-structure content of 8% -90%.
Further, the 1, 1-diphenylethylene Derivatives (DPEs) are one or more functional monomers selected from substituent nitrogen atom groups, siloxane groups, hydroxyl groups, hydrosilyl groups, alkynyl groups, mercapto groups, fluorine atom groups, chlorine atom groups and bromine atom groups of the 1, 1-diphenylethylene.
The preparation method of the polyolefin material with the crystalline alternating structure comprises the following steps:
for polyolefin materials of alternating structure having crystallinity No. 1-5:
s1, under the protection of nitrogen or argon, firstly adding an organic solvent, a 1, 1-diphenylethylene derivative, a polarity regulator (a polarity additive/Li=0-100 equivalent) and alkyl lithium into a polymerization reactor, and initiating to be a chain end monomer 1, 1-diphenylethylene derivative active species solution for 10-30 min to obtain DPEs-Li.
S2, heating the reaction solution in the polymerization reactor to the polymerization temperature of 30-80 ℃, and rapidly adding one of CPVB, CBVB and 2-PB, CPBB, CBBB monomers (the combination of five monomers is called CS), so as to carry out DPEs and the monomer to carry out alternating copolymerization for 2-8h;
S3, injecting isopropanol into the reaction liquid to terminate polymerization, depositing glue, and drying in a vacuum drying oven to constant weight.
For the polyolefin materials of the two-block alternating structure having crystallinity of No. 6 to 15:
s1, under the protection of nitrogen or argon, firstly adding an organic solvent, a 1, 1-diphenylethylene derivative, a polarity regulator (a polarity additive/Li=0-100 equivalent) and alkyl lithium into a polymerization reactor, and initiating to obtain a chain end nitrogen/silicon oxygen-containing monomer 1, 1-diphenylethylene derivative active species solution for 10min-30min to obtain DPEs-Li.
S2, heating the reaction liquid in the polymerization reactor to the polymerization temperature of 30-80 ℃, rapidly adding one of CPVB, CBVB and 2-PB, CPBB, CBBB monomers, and carrying out alternating copolymerization on DPEs and the monomers for 2-8h to obtain DPEs-alt-CS1-Li;
s3, rapidly adding one of CPVB, CBVB and 2-PB, CPBB, CBBB monomers, and copolymerizing for 2-8 hours to obtain DPEs-alt-CS1-block-DPEs-alt-CS2-Li;
s4, injecting isopropanol into the reaction liquid to terminate polymerization, depositing glue, and drying in a vacuum drying oven to constant weight.
For the triblock alternating structure polyolefin material having crystallinity of No. 16-23:
s1, under the protection of nitrogen or argon, firstly adding an organic solvent, a 1, 1-diphenylethylene derivative, a polarity regulator (a polarity additive/Li=0-100 equivalent) and alkyl lithium into a polymerization reactor, and initiating to obtain a chain end nitrogen/silicon oxygen-containing monomer 1, 1-diphenylethylene derivative active species solution for 10min-30min to obtain DPEs-Li.
S2, heating the reaction liquid in the polymerization reactor to the polymerization temperature of 30-80 ℃, rapidly adding one of CPVB, CBVB and 2-PB, CPBB, CBBB monomers, and carrying out alternating copolymerization on DPEs and the monomers for 2-8h to obtain DPEs-alt-CS1-Li;
s3, rapidly adding one of CPVB, CBVB and 2-PB, CPBB, CBBB monomers, and copolymerizing for 2-8 hours to obtain DPEs-alt-CS1-block-DPEs-alt-CS2-Li;
s4, rapidly adding one of CPVB, CBVB and 2-PB, CPBB, CBBB monomers, and copolymerizing for 2-8 hours to obtain DPEs-alt-CS1-block-DPEs-alt-CS2-block-DPEs-alt-CS3-Li;
s5, injecting isopropanol into the reaction liquid to terminate polymerization, depositing glue, and drying in a vacuum drying oven to constant weight.
For the tetrablock alternating structure polyolefin materials having crystallinity of No. 24 to 26:
s1, under the protection of nitrogen or argon, firstly adding an organic solvent, a 1, 1-diphenylethylene derivative, a polarity regulator (a polarity additive/Li=0-100 equivalent) and alkyl lithium into a polymerization reactor, and initiating to obtain a chain end nitrogen/silicon oxygen-containing monomer 1, 1-diphenylethylene derivative active species solution for 10min-30min to obtain DPEs-Li.
S2, heating the reaction liquid in the polymerization reactor to the polymerization temperature of 30-80 ℃, rapidly adding one of CPVB, CBVB and 2-PB, CPBB, CBBB monomers, and carrying out alternating copolymerization on DPEs and the monomers for 2-8h to obtain DPEs-alt-CS1-Li;
S3, rapidly adding one of CPVB, CBVB and 2-PB, CPBB, CBBB monomers, and copolymerizing for 2-8 hours to obtain DPEs-alt-CS1-block-DPEs-alt-CS2-Li;
s4, rapidly adding one of CPVB, CBVB and 2-PB, CPBB, CBBB monomers, and copolymerizing for 2-8 hours to obtain DPEs-alt-CS1-block-DPEs-alt-CS2-block-DPEs-alt-CS3-Li;
s5, rapidly adding one of CPVB, CBVB and 2-PB, CPBB, CBBB monomers, and copolymerizing for 2-8 hours to obtain DPEs-alt-CS1-block-DPEs-alt-CS2-block-DPEs-alt-CS3-block-DPEs-alt-CS4-Li;
s6, injecting isopropanol into the reaction liquid to terminate polymerization, depositing glue, and drying in a vacuum drying oven to constant weight.
For the pentablock alternating structure polyolefin material having crystallinity No. 27:
s1, under the protection of nitrogen or argon, firstly adding an organic solvent, a 1, 1-diphenylethylene derivative, a polarity regulator (a polarity additive/Li=0-100 equivalent) and alkyl lithium into a polymerization reactor, and initiating to obtain a chain end nitrogen/silicon oxygen-containing monomer 1, 1-diphenylethylene derivative active species solution for 10min-30min to obtain DPEs-Li.
S2, heating the reaction liquid in the polymerization reactor to the polymerization temperature of 30-80 ℃, rapidly adding one of CPVB, CBVB and 2-PB, CPBB, CBBB monomers, and carrying out alternating copolymerization on DPEs and the monomers for 2-8h to obtain DPEs-alt-CS1-Li;
S3, rapidly adding one of CPVB, CBVB and 2-PB, CPBB, CBBB monomers, and copolymerizing for 2-8 hours to obtain DPEs-alt-CS1-block-DPEs-alt-CS2-Li;
s4, rapidly adding one of CPVB, CBVB and 2-PB, CPBB, CBBB monomers, and copolymerizing for 2-8 hours to obtain DPEs-alt-CS1-block-DPEs-alt-CS2-block-DPEs-alt-CS3-Li;
s5, rapidly adding one of CPVB, CBVB and 2-PB, CPBB, CBBB monomers, and copolymerizing for 2-8 hours to obtain DPEs-alt-CS1-block-DPEs-alt-CS2-block-DPEs-alt-CS3-block-DPEs-alt-CS4-Li;
s6, rapidly adding one of CPVB, CBVB and 2-PB, CPBB, CBBB monomers, and copolymerizing for 2-8 hours to obtain DPEs-alt-CS1-block-DPEs-alt-CS2-block-DPEs-alt-CS3-block-DPEs-alt-CS4-block-DPEs-alt-CS5-Li;
and S7, injecting isopropanol into the reaction liquid to terminate polymerization, depositing the gel, and drying in a vacuum drying oven to constant weight.
For polyolefin materials of random alternating structure having crystallinity No. 28-48:
s1, under the protection of nitrogen or argon, firstly adding an organic solvent, a 1, 1-diphenylethylene derivative, a polarity regulator (a polarity additive/Li=0-100 equivalent) and alkyl lithium into a polymerization reactor, and initiating to be a chain end monomer 1, 1-diphenylethylene derivative active species solution for 10-30 min to obtain DPEs-Li.
S2, heating the reaction liquid in the polymerization reactor to the polymerization temperature of 30-80 ℃, and rapidly adding CPVB, CBVB and 2-PB, CPBB, CBBB monomers according to a specific proportion to carry out random and alternating copolymerization of DPEs and the monomers for 2-8 hours;
s3, injecting isopropanol into the reaction liquid to terminate polymerization, depositing glue, and drying in a vacuum drying oven to constant weight.
Preferably, after the polymerization reaction is finished, the polymer glue solution is subjected to post-treatment by adopting a traditional method, and the structure and the performance of the product are analyzed after drying.
Preferably, the alkyl lithium initiator is selected from monofunctional alkyl lithium initiators; the monofunctional lithium initiator is any initiator or a mixture of initiators disclosed in the prior art as being useful in anionic polymerization reactions and is generally selected from the group consisting of: one or a mixture of a plurality of monofunctional lithium initiators in RLi and TRLi, wherein R is a hydrocarbon group with 2-20 carbon atoms, R can be an alkane group or an arene group, T is a metal atom or a nitrogen atom, and metal elements such as tin Sn, silicon Si, lead Pb, titanium Ti, germanium Ge and the like are generally selected from the following materials: ethyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, tin-containing or nitrogen atom-containing monofunctional lithium initiators, and the like.
Preferably, the organic solvent is selected from one hydrocarbon solvent or a mixture of several hydrocarbon solvents in nonpolar aromatic hydrocarbon and nonpolar aliphatic hydrocarbon, and is generally selected from: pentane, hexane, heptane, octane, cyclohexane, n-hexane, cyclopentane, mixed aromatics (e.g. mixed xylenes), mixed aliphatic hydrocarbons (e.g. raffinate oil), preferably from: benzene, toluene, hexane, n-hexane, cyclohexane, cyclopentane or a mixture of several kinds.
Preferably, the polar additive is selected from one or a mixture of several compounds of oxygen-containing, nitrogen-containing, sulfur-containing, phosphorus-containing polar compounds and metal alkoxides, such as: (1) an oxygenate, generally selected from: diethyl ether, tetrahydrofuran (THF), R 1 OCH 2 CH 2 OR 2 (wherein: R 1 、R 2 Is alkyl having 1 to 6 carbon atoms, R 1 、R 2 May be the same or different, with R 1 、R 2 Different are preferred, such as: ethylene glycol dimethyl ether, ethylene glycol diethyl ether), R 1 OCH 2 CH 2 OCH 2 CH 2 OR 2 (wherein: R 1 、R 2 Is alkyl having 1 to 6 carbon atoms, R 1 、R 2 May be the same or different, with R 1 、R 2 Different are preferred, such as: diethylene glycol dimethyl ether, diethylene glycol dibutyl ether), crown ethers; (2) a nitrogen-containing compound, generally selected from: triethylamine, tetramethyl ethylenediamine (TMEDA), dipiperidine ethane (DPE); (3) Phosphorus-containing compounds, generally selected from hexamethylphosphoric triamide (HMPA); (4) the metal alkoxide compound is generally selected from ROM, wherein: r is an alkyl group having 1 to 6 carbon atoms, O is an oxygen atom, and M is metallic sodium Na or potassium K, preferably selected from the group consisting of: potassium tert-butoxide, potassium tert-pentyloxy, sodium 2, 3-dimethyl-3-pentanol (NaODP).
Compared with the prior polyolefin material synthesized by anionic polymerization, the invention has the following beneficial effects:
the majority of polyolefin materials with crystallization properties are synthesized at present through coordination polymerization, and the crystallization capability of the polyolefin is difficult to control through external means in the traditional coordination polymerization. While researchers have developed catalysts of various structures that can control the crystallization properties of the products during polymerization, these catalysts are cumbersome and expensive to synthesize and are difficult to apply to industrial production. The conventional polyolefin materials synthesized by anionic polymerization are all in random configuration, and it is difficult to impart crystallization properties to the polyolefin materials, thus greatly limiting the application range of the polyolefin materials synthesized by anionic polymerization. The invention uses traditional anion polymerization, and obtains a series of alternating structure polymers, binary block/random-alternating structure polymers, ternary block/random-alternating structure polymers, quaternary block/random-alternating structure polymers and five-membered block/random-alternating structure polymers with crystallization property through CPVB, CBVB and 2-PB, CPBB, CBBB respectively and alternating copolymerization with DPEs. In addition, the crystallization property of the polymer with the alternating structure can be simply controlled by polar additives, polymerization temperature, polymerization solvent and the like added in the polymerization process.
Drawings
FIG. 1 is an X-ray diffraction pattern of an alternating copolymer of 1, 1-diphenylethylene and cyclopropylstyrene.
Detailed Description
The following examples are presented as further illustrations of the invention and are not intended to limit the scope of the invention as claimed. The copolymer composition sequence distribution was analyzed by nuclear magnetic resonance spectroscopy, and the molecular weight and molecular weight distribution index (ratio of weight average molecular weight to number average molecular weight) of the copolymer were analyzed by gel permeation chromatography.
Example 1 (No. 1)
Under the protection of argon, 12.5g of 1, 1-diphenylethylene derivative was first introduced into the polymerization reactor (without solvent), and n-butyllithium initiator was added at a designed molecular weight of 10kg/mol, without regulator (regulator/li=0 equivalent). The reaction solution in the polymerization reactor was heated to a polymerization temperature of 30℃and 10g of Cyclopropylstyrene (CPVB) was rapidly added to initiate polymerization for 8 hours. The polymerization was terminated by adding degassed isopropanol, the reaction solution was precipitated in excess absolute ethanol, and the resulting polymer was dried in a vacuum oven to constant weight. The product structure analysis results are as follows: the polymer is in an alternating structure; the number average molecular weight is 10kg/mol, and the molecular weight distribution is 1.06; the first graph shows the X-ray diffraction pattern of the obtained alternating polymer, which clearly contains crystallization peaks in the vicinity of 8-30 degrees in addition to amorphous peaks, and the crystallinity was calculated to be 32%.
Example 2 (No. 2)
Under the protection of argon, 400ml of cyclohexane is firstly added into a polymerization reactor, n-butyllithium as an initiator is added according to the designed molecular weight of 200kg/mol, 1-diphenylethylene derivative is added to initiate the reaction for 10min, and 5g of tetramethyl ethylenediamine TMEDA (TMEDA/Li=30 equivalent) is added. The reaction solution in the polymerization reactor was heated to a polymerization temperature of 40℃and 20g of Cyclobutylstyrene (CBVB) was rapidly added to initiate polymerization for 7 hours. The polymerization was terminated by adding degassed isopropanol, the reaction solution was precipitated in excess absolute ethanol, and the resulting polymer was dried in a vacuum oven to constant weight. The product structure analysis results are as follows: the polymer is in an alternating structure; a number average molecular weight of 201kg/mol and a molecular weight distribution of 1.10; the crystallinity was 20%.
Example 3 (No. 3)
Under the protection of argon, 400ml of cyclohexane is firstly added into a polymerization reactor, sec-butyllithium as an initiator is added according to the designed molecular weight of 500kg/mol, 1-diphenylethylene derivative is added to initiate the reaction for 10min, and 8g of crown ether (crown ether/Li=50 equivalent) is added. The reaction solution in the polymerization reactor was heated to a polymerization temperature of 50℃and 20g of 2-phenyl-1, 3-butadiene (2-PB) was rapidly added to initiate polymerization for 6 hours. The polymerization was terminated by adding degassed isopropanol, the reaction solution was precipitated in excess absolute ethanol, and the resulting polymer was dried in a vacuum oven to constant weight. The product structure analysis results are as follows: the polymer is in an alternating structure; a number average molecular weight of 506kg/mol and a molecular weight distribution of 1.05; the crystallinity was 26%.
Example 4 (No. 4)
Under the protection of argon, 800ml of heptane was first added to the polymerization reactor, sec-butyllithium as initiator was added according to the designed molecular weight of 800kg/mol, 1-diphenylethylene derivative was added to initiate the reaction for 10min, and then 10 g of tetrahydrofuran THF (THF/li=80 eq) was added. The reaction solution in the polymerization reactor was heated to a polymerization temperature of 70℃and 40g of 1-cyclopropyl-1-phenyl-1, 3-butadiene (CPBB) was rapidly added to initiate polymerization for 4 hours. The polymerization was terminated by adding degassed isopropanol, the reaction solution was precipitated in excess absolute ethanol, and the resulting polymer was dried in a vacuum oven to constant weight. The product structure analysis results are as follows: the polymer is in an alternating structure; the number average molecular weight was 810kg/mol and the molecular weight distribution was 1.08; the crystallinity was 28%.
Example 5 (No. 5)
Under the protection of argon, 600ml of octane is firstly added into a polymerization reactor, an initiator ethyl lithium is added according to the designed molecular weight of 1000kg/mol, 1-diphenylethylene derivative is added to initiate reaction for 10min, and 15g of dipiperidine ethane (dipiperidine ethane/Li=100 equivalent) is added. The reaction solution in the polymerization reactor was heated to a polymerization temperature of 80℃and 30g of 1-cyclobutyl-1-phenyl-1, 3-butadiene (CBBB) was rapidly added to initiate polymerization for 2 hours. The polymerization was terminated by adding degassed isopropanol, the reaction solution was precipitated in excess absolute ethanol, and the resulting polymer was dried in a vacuum oven to constant weight. The product structure analysis results are as follows: the polymer is in an alternating structure; the number average molecular weight is 1000kg/mol, and the molecular weight distribution is 1.08; the crystallinity was 30%.
Example 6 (No. 6)
Under the protection of argon, 900ml of cyclopentane is added into a polymerization reactor, benzyl lithium as an initiator is added according to the design molecular weight of 10kg/mol, and 1, 1-diphenylethylene derivative is added to initiate the reaction for 10min, and no regulator (regulator/Li=0 equivalent) is added. The reaction solution in the polymerization reactor was heated to a polymerization temperature of 30℃and 30g of Cyclopropylstyrene (CPVB) was rapidly added to initiate polymerization for 8 hours. 32.9g of Cyclobutylstyrene (CBVB) was added rapidly and the polymerization was continued for 8h. The polymerization was terminated by adding degassed isopropanol, the reaction solution was precipitated in excess absolute ethanol, and the resulting polymer was dried in a vacuum oven to constant weight. The product structure analysis results are as follows: the polymer is of a two-block alternating structure; a number average molecular weight of 10kg/mol and a molecular weight distribution of 1.03; the crystallinity was 24%.
Example 7 (No. 8)
Under the protection of argon, 900ml of cyclopentane is added into a polymerization reactor, benzyl lithium as an initiator is added according to the designed molecular weight of 200kg/mol, and 1, 1-diphenylethylene derivative is added to initiate the reaction for 10min, and 5g of tetramethyl ethylenediamine TMEDA (TMEDA/Li=30 equivalent). The reaction solution in the polymerization reactor was heated to a polymerization temperature of 40℃and 30g of Cyclopropylstyrene (CPVB) was rapidly added to initiate polymerization for 7 hours. 40g of 1-cyclopropyl-1-phenyl-1, 3-butadiene (CPBB) was added rapidly and polymerization was continued for 7h. The polymerization was terminated by adding degassed isopropanol, the reaction solution was precipitated in excess absolute ethanol, and the resulting polymer was dried in a vacuum oven to constant weight. The product structure analysis results are as follows: the polymer is of a two-block alternating structure; a number average molecular weight of 201kg/mol and a molecular weight distribution of 1.03; the crystallinity was 28%.
Example 8 (No. 10)
Under the protection of argon, 900ml of cyclohexane was added to the polymerization reactor, n-butyllithium as an initiator was added according to a designed molecular weight of 500kg/mol, and 1, 1-diphenylethylene derivative was added to initiate the reaction for 10min, followed by 8g of crown ether (TMEDA/Li=60 equivalent). The reaction solution in the polymerization reactor was heated to a polymerization temperature of 50℃and 30g of Cyclobutylstyrene (CBVB) was rapidly added to initiate polymerization for 6 hours. 40g of 2-phenyl-1, 3-butadiene (2-PB) was added rapidly and polymerization was continued for 6h. The polymerization was terminated by adding degassed isopropanol, the reaction solution was precipitated in excess absolute ethanol, and the resulting polymer was dried in a vacuum oven to constant weight. The product structure analysis results are as follows: the polymer is of a two-block alternating structure; a number average molecular weight of 501kg/mol and a molecular weight distribution of 1.05; the crystallinity was 12%.
Example 9 (No. 15)
Under the protection of argon, 900ml of n-hexane was added to the polymerization reactor, n-butyllithium as an initiator was added according to a designed molecular weight of 1000kg/mol, and 1, 1-diphenylethylene derivative was added to initiate the reaction for 10 minutes, and 15g of dipiperidine ethane (dipiperidine ethane/li=100 equivalents). The reaction solution in the polymerization reactor was heated to a polymerization temperature of 80℃and 30g of Cyclobutylstyrene (CBVB) was rapidly added to initiate polymerization for 2 hours. 40g of 2-phenyl-1, 3-butadiene (CBBB) was rapidly added and polymerization was continued for 2h. The polymerization was terminated by adding degassed isopropanol, the reaction solution was precipitated in excess absolute ethanol, and the resulting polymer was dried in a vacuum oven to constant weight. The product structure analysis results are as follows: the polymer is of a two-block alternating structure; the number average molecular weight is 1000kg/mol, and the molecular weight distribution is 1.06; the crystallinity was 22%.
Example 10 (No. 16)
Under the protection of argon, 900ml of cyclopentane is added into a polymerization reactor, benzyl lithium as an initiator is added according to the design molecular weight of 10kg/mol, and 1, 1-diphenylethylene derivative is added to initiate the reaction for 10min, and no regulator (regulator/Li=0 equivalent) is added. The reaction solution in the polymerization reactor was heated to a polymerization temperature of 30℃and 15g of Cyclopropylstyrene (CPVB) was rapidly added to initiate polymerization for 8 hours. 16.5g of Cyclobutylstyrene (CBVB) was added rapidly and the polymerization was continued for 8h. 13.5g of 2-phenyl-1, 3-butadiene (2-PB) was added and polymerization was continued for 8h. The polymerization was terminated by adding degassed isopropanol, the reaction solution was precipitated in excess absolute ethanol, and the resulting polymer was dried in a vacuum oven to constant weight. The product structure analysis results are as follows: the polymer is in a triblock alternating structure; the number average molecular weight is 16kg/mol, and the molecular weight distribution is 1.03; the crystallinity was 35%.
Example 11 (No. 20)
900ml of raffinate oil was charged into a polymerization reactor under argon protection, sec-butyllithium initiator was added according to a designed molecular weight of 500kg/mol, 1-diphenylethylene derivative was added to initiate the reaction for 10min, and 8g of crown ether (crown ether/li=50 eq) was added. The reaction solution in the polymerization reactor was heated to a polymerization temperature of 50℃and 15g of Cyclopropylstyrene (CPVB) was rapidly added to initiate polymerization for 6 hours. 16.5g of Cyclobutylstyrene (CBVB) was added rapidly and the polymerization was continued for 6h. 13.5g of 2-phenyl-1, 3-butadiene (2-PB) was added and polymerization was continued for 6h. The polymerization was terminated by adding degassed isopropanol, the reaction solution was precipitated in excess absolute ethanol, and the resulting polymer was dried in a vacuum oven to constant weight. The product structure analysis results are as follows: the polymer is in a triblock alternating structure; a number average molecular weight of 516kg/mol and a molecular weight distribution of 1.03; the crystallinity was 35%.
Example 12 (number 23)
900ml of raffinate oil was fed into the polymerization reactor under argon protection, sec-butyllithium initiator was added according to the designed molecular weight of 1000kg/mol, 1-diphenylethylene derivative was added to initiate the reaction for 10min, and 15g of dipiperidine ethane (dipiperidine ethane/li=100 eq) was added. The reaction solution in the polymerization reactor was heated to a polymerization temperature of 50℃and 15g of Cyclopropylstyrene (CPVB) was rapidly added to initiate polymerization for 6 hours. 16.5g of 1-cyclopropyl-1-phenyl-1, 3-butadiene (CPBB) was added rapidly and polymerization was continued for 6h. 13.5g of 1-cyclobutyl-1-phenyl-1, 3-butadiene (CBBB) was added and the polymerization was continued for 6h. The polymerization was terminated by adding degassed isopropanol, the reaction solution was precipitated in excess absolute ethanol, and the resulting polymer was dried in a vacuum oven to constant weight. The product structure analysis results are as follows: the polymer is in a triblock alternating structure; a number average molecular weight of 1001kg/mol and a molecular weight distribution of 1.03; the crystallinity was 30%.
Example 13 (No. 24)
Under the protection of argon, 1000ml of cyclohexane was added to the polymerization reactor, n-butyllithium as an initiator was added according to a designed molecular weight of 10kg/mol, and 1, 1-diphenylethylene derivative was added to initiate the reaction for 10min without regulator (regulator/li=0 equivalent). The reaction solution in the polymerization reactor was heated to a polymerization temperature of 30℃and 15g of Cyclopropylstyrene (CPVB) was rapidly added to initiate polymerization for 8 hours. 16.5g of Cyclobutylstyrene (CBVB) was added rapidly and the polymerization was continued for 8h. The polymerization was continued for 8 hours with the addition of 2-phenyl-1, 3-butadiene (2-PB). 17.7g of 1-cyclopropyl-1-phenyl-1, 3-butadiene (CPBB) was further added and polymerization was continued for 8 hours. The polymerization was terminated by adding degassed isopropanol, the reaction solution was precipitated in excess absolute ethanol, and the resulting polymer was dried in a vacuum oven to constant weight. The product structure analysis results are as follows: the polymer is in a tetrablock alternating structure; a number average molecular weight of 12kg/mol and a molecular weight distribution of 1.03; the crystallinity was 29%.
Example 14 (No. 25)
1000ml of cyclopentane was charged into a polymerization reactor under argon protection, sec-butyllithium as an initiator was added at a designed molecular weight of 500kg/mol, 1-diphenylethylene derivative was added to initiate the reaction for 10min, and 8g of crown ether (crown ether/li=50 eq) was added. The reaction solution in the polymerization reactor was heated to a polymerization temperature of 50℃and 15g of Cyclopropylstyrene (CPVB) was rapidly added to initiate polymerization for 6 hours. 16.5g of Cyclobutylstyrene (CBVB) was added rapidly and the polymerization was continued for 6h. The polymerization was continued for 6 hours with the addition of 2-phenyl-1, 3-butadiene (2-PB). 20g of 1-cyclobutyl-1-phenyl-1, 3-butadiene (CBBB) was further added and the polymerization was continued for 6 hours. The polymerization was terminated by adding degassed isopropanol, the reaction solution was precipitated in excess absolute ethanol, and the resulting polymer was dried in a vacuum oven to constant weight. The product structure analysis results are as follows: the polymer is in a tetrablock alternating structure; a number average molecular weight of 501kg/mol and a molecular weight distribution of 1.09; the crystallinity was 32%.
Example 15 (No. 26)
Under the protection of argon, 1000ml of octane is added into a polymerization reactor, sec-butyllithium as an initiator is added according to the designed molecular weight of 1000kg/mol, 1-diphenylethylene derivative is added to initiate the reaction for 10min, and 15g of dipiperidine ethane (dipiperidine ethane/Li=100 eq) is added. The reaction solution in the polymerization reactor was heated to a polymerization temperature of 80℃and 15g of Cyclobutylstyrene (CBVB) was rapidly added to initiate polymerization for 2 hours. 16.5g of 2-phenyl-1, 3-butadiene (2-PB) was added rapidly and the polymerization was continued for 2h. The polymerization was continued for 2h with the addition of 1-cyclopropyl-1-phenyl-1, 3-butadiene (CPBB). 20g of 1-cyclobutyl-1-phenyl-1, 3-butadiene (CBBB) was further added and the polymerization was continued for 2 hours. The polymerization was terminated by adding degassed isopropanol, the reaction solution was precipitated in excess absolute ethanol, and the resulting polymer was dried in a vacuum oven to constant weight. The product structure analysis results are as follows: the polymer is in a tetrablock alternating structure; the number average molecular weight was 1011kg/mol and the molecular weight distribution was 1.02; the crystallinity was 39%.
Example 16 (number 27)
Under the protection of argon, 1200ml of raffinate oil is added into a polymerization reactor, n-butyllithium initiator is added according to the designed molecular weight of 10kg/mol, and 1, 1-diphenylethylene derivative is added to initiate reaction for 10min, and no regulator (regulator/Li=0 equivalent) is adopted. The reaction solution in the polymerization reactor was heated to a polymerization temperature of 30℃and 15g of Cyclopropylstyrene (CPVB) was rapidly added to initiate polymerization for 8 hours. 16.5g of Cyclobutylstyrene (CBVB) was added rapidly and the polymerization was continued for 8h. The polymerization was continued for 8 hours with the addition of 2-phenyl-1, 3-butadiene (2-PB). 17.7g of 1-cyclopropyl-1-phenyl-1, 3-butadiene (CPBB) was further added and polymerization was continued for 8 hours. 19.2g of 1-cyclobutyl-1-phenyl-1, 3-butadiene (CBBB) was further added and the polymerization was continued for 8 hours. The polymerization was terminated by adding degassed isopropanol, the reaction solution was precipitated in excess absolute ethanol, and the resulting polymer was dried in a vacuum oven to constant weight. The product structure analysis results are as follows: the polymer is in a pentablock alternating structure; a number average molecular weight of 10kg/mol and a molecular weight distribution of 1.05; the crystallinity was 25%.
Example 17 (No. 27)
Under the protection of argon, 1200ml of raffinate oil is added into a polymerization reactor, n-butyllithium as an initiator is added according to the designed molecular weight of 500kg/mol, 1-diphenylethylene derivative is added to initiate reaction for 10min, and 10g of tetramethyl ethylenediamine (TMEDA) is added (TMEDA/Li=50 equivalent). The reaction solution in the polymerization reactor was heated to a polymerization temperature of 50℃and 15g of Cyclopropylstyrene (CPVB) was rapidly added to initiate polymerization for 6 hours. 16.5g of Cyclobutylstyrene (CBVB) was added rapidly and the polymerization was continued for 6h. The polymerization was continued for 6 hours with the addition of 2-phenyl-1, 3-butadiene (2-PB). 17.7g of 1-cyclopropyl-1-phenyl-1, 3-butadiene (CPBB) was further added and polymerization was continued for 6 hours. 19.2g of 1-cyclobutyl-1-phenyl-1, 3-butadiene (CBBB) was further added and the polymerization was continued for 6 hours. The polymerization was terminated by adding degassed isopropanol, the reaction solution was precipitated in excess absolute ethanol, and the resulting polymer was dried in a vacuum oven to constant weight. The product structure analysis results are as follows: the polymer is in a pentablock alternating structure; a number average molecular weight of 520kg/mol and a molecular weight distribution of 1.06; the crystallinity was 26%.
Example 18 (No. 27)
Under the protection of argon, 1200ml of octane is added into a polymerization reactor, n-butyllithium as an initiator is added according to the designed molecular weight of 1000kg/mol, 1-diphenylethylene derivative is added to initiate the reaction for 10min, and 15g of dipiperidine ethane (dipiperidine ethane/Li=100 equivalent) is added. The reaction solution in the polymerization reactor was heated to a polymerization temperature of 80℃and 15g of Cyclopropylstyrene (CPVB) was rapidly added to initiate polymerization for 2 hours. 16.5g of Cyclobutylstyrene (CBVB) was added rapidly and the polymerization was continued for 2h. The polymerization was continued for 2 hours with the addition of 2-phenyl-1, 3-butadiene (2-PB). 17.7g of 1-cyclopropyl-1-phenyl-1, 3-butadiene (CPBB) was further added and polymerization was continued for 2 hours. 19.2g of 1-cyclobutyl-1-phenyl-1, 3-butadiene (CBBB) was further added and the polymerization was continued for 2 hours. The polymerization was terminated by adding degassed isopropanol, the reaction solution was precipitated in excess absolute ethanol, and the resulting polymer was dried in a vacuum oven to constant weight. The product structure analysis results are as follows: the polymer is in a pentablock alternating structure; the number average molecular weight is 1020kg/mol, and the molecular weight distribution is 1.06; the crystallinity was 32%.
Example 19 (number 28)
Under the protection of argon, 1200ml of cyclohexane is added into a polymerization reactor, n-butyllithium as an initiator is added according to the designed molecular weight of 10kg/mol, and 1, 1-diphenylethylene derivative is added to initiate the reaction for 10min, without regulator (regulator/Li=0 equivalent). The reaction solution in the polymerization reactor was heated to a polymerization temperature of 30℃and 30g of Cyclopropylstyrene (CPVB) and 32.9g of Cyclobutylstyrene (CBVB) were rapidly added to initiate polymerization for 8 hours. The polymerization was terminated by adding degassed isopropanol, the reaction solution was precipitated in excess absolute ethanol, and the resulting polymer was dried in a vacuum oven to constant weight. The product structure analysis results are as follows: the polymer is in a random alternating structure; a number average molecular weight of 10kg/mol and a molecular weight distribution of 1.09; the crystallinity was 19%.
Example 20 (No. 41)
Under the protection of nitrogen, 1600ml of octane is added into a polymerization reactor, n-butyllithium as an initiator is added according to the designed molecular weight of 500kg/mol, 1-diphenylethylene derivative is added to initiate the reaction for 10min, and then 10g of tetrahydrofuran THF (THF/Li=50 equivalent) is added. The reaction solution in the polymerization reactor was heated to a polymerization temperature of 50℃and 30g of Cyclopropylstyrene (CPVB), 32.9g of Cyclobutylstyrene (CBVB) and 20g of 1-cyclobutyl-1-phenyl-1, 3-butadiene (CBBB) were rapidly added to initiate polymerization for 6 hours. The polymerization was terminated by adding degassed isopropanol, the reaction solution was precipitated in excess absolute ethanol, and the resulting polymer was dried in a vacuum oven to constant weight. The product structure analysis results are as follows: the polymer is in a random alternating structure; the number average molecular weight was 490kg/mol and the molecular weight distribution was 1.09; the crystallinity was 26%.
Example 21 (number 48)
Under the protection of nitrogen, 1600ml of cyclohexane is added into a polymerization reactor, an initiator n-butyllithium is added according to the designed molecular weight of 1000kg/mol, 1-diphenylethylene derivative is added to initiate the reaction for 10min, and 20g of triethylamine (triethylamine/Li=100 equivalent) is added. The reaction solution in the polymerization reactor was heated to a polymerization temperature of 80℃and 15g of Cyclopropylstyrene (CPVB), 16.4g of Cyclobutylstyrene (CBVB), 13.5g of 2-phenyl-1, 3-butadiene (2-PB), 18.1g of 1-cyclopropyl-1-phenyl-1, 3-butadiene (CPBB) and 19.1g of 1-cyclobutyl-1-phenyl-1, 3-butadiene (CBBB) were rapidly added to initiate polymerization for 2 hours. The polymerization was terminated by adding degassed isopropanol, the reaction solution was precipitated in excess absolute ethanol, and the resulting polymer was dried in a vacuum oven to constant weight. The product structure analysis results are as follows: the polymer is in a random alternating structure; the number average molecular weight is 1020kg/mol, and the molecular weight distribution is 1.10; the crystallinity was 42%.
Comparative example 1
Under the protection of argon, 400ml of cyclohexane is firstly added into a polymerization reactor, an initiator n-butyllithium is added according to the designed molecular weight of 50kg/mol, and 1, 1-diphenylethylene derivative is added to initiate the reaction for 10min, and no regulator (regulator/Li=0 equivalent) is adopted. The reaction solution in the polymerization reactor was heated to a polymerization temperature of 30℃and 13.1g of styrene was rapidly added to initiate polymerization for 8 hours. The polymerization was terminated by adding degassed isopropanol, the reaction solution was precipitated in excess absolute ethanol, and the resulting polymer was dried in a vacuum oven to constant weight. The product structure analysis results are as follows: the polymer is in an alternating structure; the number average molecular weight is 11kg/mol, and the molecular weight distribution is 1.10; no crystallization ability.
The alternating structure polymer of 1, 1-diphenylethylene derivative and styrene was used as comparative example 1 while controlling the molecular weight of the polymer product and its distribution to be similar to that of the alternating structure polymer of 1, 1-diphenylethylene derivative and cyclobutylstyrene synthesized in example 2. The alternating structure polymers synthesized separately in example 2 and comparative example 1 were examined for the crystallization ability of other alternating structure polyolefins than the alternating structure polyolefin proposed in the present invention under the same test conditions. The test shows that the alternating structure polymer of the 1, 1-diphenylethylene derivative and the styrene has no crystallization capability, and the alternating structure polymer of the 1, 1-diphenylethylene derivative and the cyclobutylstyrene prepared by the technical scheme of the invention has crystallization capability.
The examples described above represent only embodiments of the invention and are not to be understood as limiting the scope of the patent of the invention, it being pointed out that several variants and modifications may be made by those skilled in the art without departing from the concept of the invention, which fall within the scope of protection of the invention.
Claims (6)
1. A polymer having an alternating structure of crystallinity, characterized by the preparation method comprising:
under the protection of argon, cyclohexane 400 ml is firstly added into a polymerization reactor, an initiator sec-butyllithium is added according to the designed molecular weight of 500 kg/mol, a 1, 1-diphenylethylene derivative is added to initiate the reaction for 10 min, and then crown ether 8 g is added, wherein the crown ether/Li=50 equivalent; heating the reaction liquid in the polymerization reactor to the polymerization temperature of 50 ℃, rapidly adding 2-phenyl-1, 3-butadiene (2-PB) 20 and g, and initiating polymerization for 6 hours; adding degassed isopropanol to terminate polymerization, precipitating the reaction solution in excessive absolute ethyl alcohol, and drying the obtained polymer in a vacuum oven to constant weight; the product structure analysis results are as follows: the polymer is in an alternating structure; a number average molecular weight of 506 kg/mol and a molecular weight distribution of 1.05; crystallinity 26%;
Or under the protection of argon, firstly adding heptane 800 ml into a polymerization reactor, adding an initiator sec-butyllithium according to the designed molecular weight of 800 kg/mol, adding a 1, 1-diphenylethylene derivative to initiate reaction for 10 min, and then adding tetrahydrofuran THF10 g, wherein THF/Li=80 equivalent; heating the reaction liquid in the polymerization reactor to the polymerization temperature of 70 ℃, rapidly adding 1-cyclopropyl-1-phenyl-1, 3-butadiene (CPBB) 40 g, and initiating polymerization for 4 hours; adding degassed isopropanol to terminate polymerization, precipitating the reaction solution in excessive absolute ethyl alcohol, and drying the obtained polymer in a vacuum oven to constant weight; the product structure analysis results are as follows: the polymer is in an alternating structure; the number average molecular weight was 810kg/mol and the molecular weight distribution was 1.08; crystallinity 28%;
under the protection of argon, firstly adding octane 600 ml into a polymerization reactor, adding an initiator ethyl lithium according to the designed molecular weight of 1000kg/mol, adding a 1, 1-diphenylethylene derivative to initiate reaction for 10 min, and then adding dipiperidine ethane 15 g, wherein dipiperidine ethane/Li=100 equivalent; heating the reaction liquid in the polymerization reactor to the polymerization temperature of 80 ℃, and rapidly adding 1-cyclobutyl-1-phenyl-1, 3-butadiene (CBBB) 30 g to initiate polymerization for 2h; adding degassed isopropanol to terminate polymerization, precipitating the reaction solution in excessive absolute ethyl alcohol, and drying the obtained polymer in a vacuum oven to constant weight; the product structure analysis results are as follows: the polymer is in an alternating structure; the number average molecular weight is 1000kg/mol, and the molecular weight distribution is 1.08; crystallinity of 30%;
The 1, 1-diphenylethylene derivative DPEs is one or more functional monomers selected from nitrogen atom groups, siloxane groups, hydroxyl groups, hydrosilylation groups, alkynyl groups, mercapto groups, fluorine atom groups, chlorine atom groups and bromine atom groups of substituents of 1, 1-diphenylethylene.
2. A two-block polymer having an alternating structure of crystallinity, characterized in that the preparation method comprises the steps of:
under the protection of argon, cyclopentane 900 ml is added into a polymerization reactor, an initiator benzyl lithium is added according to the designed molecular weight of 200 kg/mol, a 1, 1-diphenylethylene derivative is added to initiate reaction for 10 min, and tetramethyl ethylenediamine TMEDA5g, wherein TMEDA/Li=30 equivalent; heating the reaction liquid in the polymerization reactor to the polymerization temperature of 40 ℃, rapidly adding 30 g of cyclopropyl styrene (CPVB), and initiating polymerization for 7h; rapidly adding 1-cyclopropyl-1-phenyl-1, 3-butadiene (CPBB) 40 g, and continuing to polymerize for 7h; adding degassed isopropanol to terminate polymerization, precipitating the reaction solution in excessive absolute ethyl alcohol, and drying the obtained polymer in a vacuum oven to constant weight; the product structure analysis results are as follows: the polymer is of a two-block alternating structure; a number average molecular weight of 201kg/mol and a molecular weight distribution of 1.03; crystallinity 28%;
Or under the protection of argon, cyclohexane 900 ml is added into a polymerization reactor, initiator n-butyllithium is added according to the designed molecular weight of 500 kg/mol, 1-diphenylethylene derivative is added to initiate reaction for 10 min, crown ether 8g, wherein TMEDA/Li=60 equivalent; heating the reaction liquid in the polymerization reactor to the polymerization temperature of 50 ℃, and rapidly adding cyclobutyl styrene (CBVB) 30 g to initiate polymerization for 6h; 2-phenyl-1, 3-butadiene (2-PB) 40 g was added rapidly and polymerization was continued for 6h; adding degassed isopropanol to terminate polymerization, precipitating the reaction solution in excessive absolute ethyl alcohol, and drying the obtained polymer in a vacuum oven to constant weight; the product structure analysis results are as follows: the polymer is of a two-block alternating structure; a number average molecular weight of 501kg/mol and a molecular weight distribution of 1.05; crystallinity of 12%;
or under the protection of argon, adding n-hexane 900 and ml into a polymerization reactor, adding an initiator n-butyllithium according to the designed molecular weight of 1000kg/mol, and adding a 1, 1-diphenylethylene derivative to initiate the reaction for 10 min, wherein the ratio of dipiperidine ethane to Li=100 equivalents; heating the reaction liquid in the polymerization reactor to the polymerization temperature of 80 ℃, and rapidly adding cyclobutyl styrene (CBVB) 30 g to initiate polymerization for 2h; 2-phenyl-1, 3-butadiene (CBBB) 40 g was added rapidly and polymerization was continued for 2h; adding degassed isopropanol to terminate polymerization, precipitating the reaction solution in excessive absolute ethyl alcohol, and drying the obtained polymer in a vacuum oven to constant weight; the product structure analysis results are as follows: the polymer is of a two-block alternating structure; the number average molecular weight is 1000kg/mol, and the molecular weight distribution is 1.06; crystallinity of 22%;
The 1, 1-diphenylethylene derivative DPEs is one or more functional monomers selected from nitrogen atom groups, siloxane groups, hydroxyl groups, hydrosilylation groups, alkynyl groups, mercapto groups, fluorine atom groups, chlorine atom groups and bromine atom groups of substituents of 1, 1-diphenylethylene.
3. A triblock polymer having an alternating structure of crystallinity, characterized in that the preparation method comprises the steps of:
under the protection of argon, cyclopentane 900 ml is added into a polymerization reactor, an initiator benzyl lithium is added according to the designed molecular weight of 10 kg/mol, and a 1, 1-diphenylethylene derivative is added to initiate reaction for 10 min without a regulator, wherein the regulator/Li=0 equivalent; heating the reaction liquid in the polymerization reactor to the polymerization temperature of 30 ℃, and rapidly adding Cyclopropylstyrene (CPVB) 15 g to initiate polymerization 8h; 16.5g of Cyclobutylstyrene (CBVB) was added rapidly and polymerization was continued for 8h; 13.5g of 2-phenyl-1, 3-butadiene (2-PB) was added and polymerization was continued for 8h; adding degassed isopropanol to terminate polymerization, precipitating the reaction solution in excessive absolute ethyl alcohol, and drying the obtained polymer in a vacuum oven to constant weight; the product structure analysis results are as follows: the polymer is in a triblock alternating structure; the number average molecular weight is 16kg/mol, and the molecular weight distribution is 1.03; crystallinity of 35%;
Or under the protection of argon, adding raffinate oil 900 ml into a polymerization reactor, adding initiator sec-butyllithium according to the designed molecular weight of 500 kg/mol, adding 1, 1-diphenylethylene derivative to initiate reaction for 10 min, and adding crown ether 8 g, wherein crown ether/Li=50 equivalent; heating the reaction liquid in the polymerization reactor to the polymerization temperature of 50 ℃, rapidly adding Cyclopropylstyrene (CPVB) 15 g, and initiating polymerization for 6 hours; 16.5g of Cyclobutylstyrene (CBVB) was added rapidly and polymerization was continued for 6h; 13.5g of 2-phenyl-1, 3-butadiene (2-PB) was added and polymerization was continued for 6h; adding degassed isopropanol to terminate polymerization, precipitating the reaction solution in excessive absolute ethyl alcohol, and drying the obtained polymer in a vacuum oven to constant weight; the product structure analysis results are as follows: the polymer is in a triblock alternating structure; a number average molecular weight of 516kg/mol and a molecular weight distribution of 1.03; crystallinity of 35%;
under the protection of argon, adding raffinate oil 900 ml into a polymerization reactor, adding an initiator sec-butyllithium according to the designed molecular weight of 1000 kg/mol, adding a 1, 1-diphenylethylene derivative to initiate reaction for 10 min, and then adding dipiperidine ethane 15 g, wherein dipiperidine ethane/Li=100 equivalent; heating the reaction liquid in the polymerization reactor to the polymerization temperature of 50 ℃, rapidly adding Cyclopropylstyrene (CPVB) 15 g, and initiating polymerization for 6 hours; 16.5g of 1-cyclopropyl-1-phenyl-1, 3-butadiene (CPBB) was added rapidly and polymerization was continued for 6h; 13.5g of 1-cyclobutyl-1-phenyl-1, 3-butadiene (CBBB) was further added and polymerization was continued for 6 hours; adding degassed isopropanol to terminate polymerization, precipitating the reaction solution in excessive absolute ethyl alcohol, and drying the obtained polymer in a vacuum oven to constant weight; the product structure analysis results are as follows: the polymer is in a triblock alternating structure; a number average molecular weight of 1001kg/mol and a molecular weight distribution of 1.03; crystallinity of 30%
The 1, 1-diphenylethylene derivative DPEs is one or more functional monomers selected from nitrogen atom groups, siloxane groups, hydroxyl groups, hydrosilylation groups, alkynyl groups, mercapto groups, fluorine atom groups, chlorine atom groups and bromine atom groups of substituents of 1, 1-diphenylethylene.
4. A tetrablock polymer having an alternating structure of crystallinity, characterized by the process of preparation comprising:
under the protection of argon, cyclohexane 1000 ml is added into a polymerization reactor, initiator n-butyllithium is added according to the designed molecular weight of 10 kg/mol, and 1, 1-diphenylethylene derivative is added to initiate reaction for 10 min without regulator, wherein the regulator/Li=0 equivalent; heating the reaction liquid in the polymerization reactor to the polymerization temperature of 30 ℃, rapidly adding Cyclopropylstyrene (CPVB) 15 g, and initiating polymerization for 8 hours; 16.5g of Cyclobutylstyrene (CBVB) was added rapidly and polymerization was continued for 8h; continuing to add 2-phenyl-1, 3-butadiene (2-PB) and continuing to polymerize 8h; continuing to add 1-cyclopropyl-1-phenyl-1, 3-butadiene (CPBB) 17.7, g, continuing to polymerize 8, h; adding degassed isopropanol to terminate polymerization, precipitating the reaction solution in excessive absolute ethyl alcohol, and drying the obtained polymer in a vacuum oven to constant weight; the product structure analysis results are as follows: the polymer is in a tetrablock alternating structure; a number average molecular weight of 12kg/mol and a molecular weight distribution of 1.03; crystallinity of 29%;
Or under the protection of argon, adding cyclopentane 1000 ml into a polymerization reactor, adding an initiator sec-butyllithium according to the designed molecular weight of 500 kg/mol, adding a 1, 1-diphenylethylene derivative to initiate reaction for 10 min, and adding crown ether 8g, wherein crown ether/Li=50 equivalent; heating the reaction liquid in the polymerization reactor to the polymerization temperature of 50 ℃, rapidly adding Cyclopropylstyrene (CPVB) 15 g, and initiating polymerization for 6 hours; 16.5g of Cyclobutylstyrene (CBVB) was added rapidly and polymerization was continued for 6h; continuously adding 2-phenyl-1, 3-butadiene (2-PB) and continuously polymerizing for 6h; continuously adding 1-cyclobutyl-1-phenyl-1, 3-butadiene (CBBB) 20 and g, and continuously polymerizing for 6h; adding degassed isopropanol to terminate polymerization, precipitating the reaction solution in excessive absolute ethyl alcohol, and drying the obtained polymer in a vacuum oven to constant weight; the product structure analysis results are as follows: the polymer is in a tetrablock alternating structure; a number average molecular weight of 501kg/mol and a molecular weight distribution of 1.09; crystallinity of 32%;
or under the protection of argon, adding octane 1000 ml into a polymerization reactor, adding an initiator sec-butyllithium according to the designed molecular weight of 1000 kg/mol, adding a 1, 1-diphenylethylene derivative to initiate reaction for 10 min, and then adding dipiperidine ethane 15 g, wherein dipiperidine ethane/Li=100 equivalent; heating the reaction liquid in the polymerization reactor to the polymerization temperature of 80 ℃, and rapidly adding cyclobutyl styrene (CBVB) 15 g to initiate polymerization for 2h; 16.5g of 2-phenyl-1, 3-butadiene (2-PB) was added rapidly and polymerization was continued for 2h; continuing to add 1-cyclopropyl-1-phenyl-1, 3-butadiene (CPBB) for polymerization for 2 hours; continuously adding 1-cyclobutyl-1-phenyl-1, 3-butadiene (CBBB) 20 and g, and continuously polymerizing for 2h; adding degassed isopropanol to terminate polymerization, precipitating the reaction solution in excessive absolute ethyl alcohol, and drying the obtained polymer in a vacuum oven to constant weight; the product structure analysis results are as follows: the polymer is in a tetrablock alternating structure; the number average molecular weight was 1011kg/mol and the molecular weight distribution was 1.02; crystallinity of 39%;
The 1, 1-diphenylethylene derivative DPEs is one or more functional monomers selected from nitrogen atom groups, siloxane groups, hydroxyl groups, hydrosilylation groups, alkynyl groups, mercapto groups, fluorine atom groups, chlorine atom groups and bromine atom groups of substituents of 1, 1-diphenylethylene.
5. A pentablock polymer having an alternating structure of crystallinity, characterized in that the preparation method comprises:
under the protection of argon, adding raffinate oil 1200 and ml into a polymerization reactor, adding initiator n-butyllithium according to the designed molecular weight of 10kg/mol, and adding 1, 1-diphenylethylene derivative to initiate reaction for 10 min without regulator, wherein the regulator/Li=0 equivalent; heating the reaction liquid in the polymerization reactor to the polymerization temperature of 30 ℃, and rapidly adding Cyclopropylstyrene (CPVB) 15 g to initiate polymerization 8h; 16.5g of Cyclobutylstyrene (CBVB) was added rapidly and polymerization was continued for 8h; continuously adding 2-phenyl-1, 3-butadiene (2-PB) for continuous polymerization for 8 hours; continuing to add 17.7 of 1-cyclopropyl-1-phenyl-1, 3-butadiene (CPBB) g and continuing to polymerize for 8 hours; continuing to add 1-cyclobutyl-1-phenyl-1, 3-butadiene (CBBB) 19.2-g, and continuing to polymerize for 8h; adding degassed isopropanol to terminate polymerization, precipitating the reaction solution in excessive absolute ethyl alcohol, and drying the obtained polymer in a vacuum oven to constant weight; the product structure analysis results are as follows: the polymer is in a pentablock alternating structure; a number average molecular weight of 10kg/mol and a molecular weight distribution of 1.05; crystallinity 25%;
Or under the protection of argon, adding the raffinate oil 1200 and ml into a polymerization reactor, adding an initiator n-butyllithium according to the designed molecular weight of 500 kg/mol, adding a 1, 1-diphenylethylene derivative to initiate reaction for 10 min, and adding 10g of tetramethyl ethylenediamine (TMEDA), wherein TMEDA/Li=50 equivalent; heating the reaction liquid in the polymerization reactor to the polymerization temperature of 50 ℃, rapidly adding Cyclopropylstyrene (CPVB) 15 g, and initiating polymerization for 6 hours; 16.5g of Cyclobutylstyrene (CBVB) was added rapidly and polymerization was continued for 6h; continuously adding 2-phenyl-1, 3-butadiene (2-PB) and continuously polymerizing for 6h; continuing to add 17.7 of 1-cyclopropyl-1-phenyl-1, 3-butadiene (CPBB) g and continuing to polymerize for 6 hours; continuing to add 1-cyclobutyl-1-phenyl-1, 3-butadiene (CBBB) 19.2-g, and continuing to polymerize for 6h; adding degassed isopropanol to terminate polymerization, precipitating the reaction solution in excessive absolute ethyl alcohol, and drying the obtained polymer in a vacuum oven to constant weight; the product structure analysis results are as follows: the polymer is in a pentablock alternating structure; a number average molecular weight of 520kg/mol and a molecular weight distribution of 1.06; crystallinity 26%;
or under the protection of argon, octane 1200 and ml are added into a polymerization reactor, an initiator n-butyllithium is added according to the designed molecular weight of 1000 kg/mol, a 1, 1-diphenylethylene derivative is added to initiate reaction for 10 min, and dipiperidine ethane 15 and g are added, wherein dipiperidine ethane/Li=100 equivalent; heating the reaction liquid in the polymerization reactor to the polymerization temperature of 80 ℃, rapidly adding Cyclopropylstyrene (CPVB) 15 g, and initiating polymerization for 2h; 16.5g of Cyclobutylstyrene (CBVB) was added rapidly and polymerization was continued for 2h; continuously adding 2-phenyl-1, 3-butadiene (2-PB) for continuous polymerization for 2h; continuing to add 17.7 of 1-cyclopropyl-1-phenyl-1, 3-butadiene (CPBB) g and continuing to polymerize for 2 hours; continuing to add 1-cyclobutyl-1-phenyl-1, 3-butadiene (CBBB) 19.2 g, and continuing to polymerize for 2h; adding degassed isopropanol to terminate polymerization, precipitating the reaction solution in excessive absolute ethyl alcohol, and drying the obtained polymer in a vacuum oven to constant weight; the product structure analysis results are as follows: the polymer is in a pentablock alternating structure; the number average molecular weight is 1020kg/mol, and the molecular weight distribution is 1.06; crystallinity of 32%;
The 1, 1-diphenylethylene derivative DPEs is one or more functional monomers selected from nitrogen atom groups, siloxane groups, hydroxyl groups, hydrosilylation groups, alkynyl groups, mercapto groups, fluorine atom groups, chlorine atom groups and bromine atom groups of substituents of 1, 1-diphenylethylene.
6. A random alternating polymer with a crystalline alternating structure is characterized in that the preparation method comprises the following steps:
under the protection of nitrogen, octane 1600 and ml are added into a polymerization reactor, an initiator n-butyllithium is added according to the designed molecular weight of 500 kg/mol, a 1, 1-diphenylethylene derivative is added to initiate reaction for 10 min, and tetrahydrofuran THF 10 g is added, wherein THF/Li=50 equivalent; heating the reaction liquid in the polymerization reactor to a polymerization temperature of 50 ℃, rapidly adding 30. 30 g g of cyclopropyl styrene (CPVB), 32.9g of cyclobutyl styrene (CBVB) and 20 g g of 1-cyclobutyl-1-phenyl-1, 3-butadiene (CBBB), and initiating polymerization for 6 hours; adding degassed isopropanol to terminate polymerization, precipitating the reaction solution in excessive absolute ethyl alcohol, and drying the obtained polymer in a vacuum oven to constant weight; the product structure analysis results are as follows: the polymer is in a random alternating structure; the number average molecular weight was 490kg/mol and the molecular weight distribution was 1.09; crystallinity 26%;
Or under the protection of nitrogen, cyclohexane 1600 and ml is added into a polymerization reactor, an initiator n-butyllithium is added according to the designed molecular weight of 1000 kg/mol, a 1, 1-diphenylethylene derivative is added to initiate reaction for 10 min, and triethylamine 20 g is added, wherein the triethylamine/Li=100 equivalent; heating the reaction solution in the polymerization reactor to a polymerization temperature of 80 ℃, rapidly adding Cyclopropylstyrene (CPVB) 15 g, cyclobutylstyrene (CBVB) 16.4 g, 2-phenyl-1, 3-butadiene (2-PB) 13.5 g, 1-cyclopropyl-1-phenyl-1, 3-butadiene (CPBB) 18.1g, 1-cyclobutyl-1-phenyl-1, 3-butadiene (CBBB) 19.1 g, and initiating polymerization for 2h; adding degassed isopropanol to terminate polymerization, precipitating the reaction solution in excessive absolute ethyl alcohol, and drying the obtained polymer in a vacuum oven to constant weight; the product structure analysis results are as follows: the polymer is in a random alternating structure; the number average molecular weight is 1020kg/mol, and the molecular weight distribution is 1.10; crystallinity 42%;
the 1, 1-diphenylethylene derivative DPEs is one or more functional monomers selected from nitrogen atom groups, siloxane groups, hydroxyl groups, hydrosilylation groups, alkynyl groups, mercapto groups, fluorine atom groups, chlorine atom groups and bromine atom groups of substituents of 1, 1-diphenylethylene.
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