CN108659182B - Conjugated diene-polar monomer block copolymer and preparation method thereof - Google Patents

Conjugated diene-polar monomer block copolymer and preparation method thereof Download PDF

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CN108659182B
CN108659182B CN201810494481.4A CN201810494481A CN108659182B CN 108659182 B CN108659182 B CN 108659182B CN 201810494481 A CN201810494481 A CN 201810494481A CN 108659182 B CN108659182 B CN 108659182B
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conjugated diene
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CN108659182A (en
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张学全
庄锐
胡雁鸣
郑文洁
刘恒
毕吉福
张春雨
于琦周
那丽华
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Changchun Institute of Applied Chemistry of CAS
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/06—Butadiene
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    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/58—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with silicon, germanium, tin, lead, antimony, bismuth or compounds thereof

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Abstract

The invention provides a preparation method and application of a conjugated diene-polar monomer block copolymer, wherein the method comprises the following steps: polymerizing first conjugated diene in a solvent under the action of a catalyst to obtain a polymer a solution; the catalyst is prepared by the reaction of an alkoxy rare earth compound, a hydrogen alkyl aluminum compound, a chloride and second conjugated diene; mixing the polymer a solution and a blocking agent, reacting, and terminating the reaction by a terminator to obtain a polymer b; and (3) reacting the polymer b, a free radical initiator, tetrabutylammonium bromide and a polar monomer, and terminating the reaction to obtain the conjugated diene-polar monomer segmented copolymer. The method has mild reaction conditions, controllable molecular weight of the block copolymer, narrow molecular weight distribution and adjustable chain segment length and proportion of two blocks; the catalyst has high catalytic activity and good stability; the selectivity is good, so that the tacticity of polydiene chain segments in the copolymer is higher. The compatibility of the copolymer with polar additives, white carbon black and other polar polymers is improved.

Description

Conjugated diene-polar monomer block copolymer and preparation method thereof
Technical Field
The invention relates to the technical field of synthesis, in particular to a conjugated diene-polar monomer block copolymer and a preparation method thereof.
Background
Synthetic rubber is an extremely important synthetic material, and the important position in the economic and social development cannot be replaced. The conjugated diene polymer is one of the most important varieties of synthetic rubber, and has poor compatibility with polar additives, white carbon black and other polar polymers in the processing process due to the non-polarity of a macromolecular chain. And a polar group or a polar molecular chain segment is introduced into the nonpolar rubber for functionalization, so that the compatibility and the adhesive force between the nonpolar rubber and a polar high polymer material can be effectively improved, and the colorability, the antistatic property and the like of the nonpolar rubber can be improved.
The currently reported methods for preparing the block copolymer of the conjugated diene and the polar monomer mainly comprise methods of anion polymerization, ring-opening metathesis polymerization, coordination polymerization and ring-opening polymerization, and the like. Yu et al (Macromolecules 1996,29, 2738-; fontaine et al (Macromolecules 1996,29, 6090-; cui, Zhang and the like (Organometallics 2011,30, 757-; li Yang et al (Polymer. Bull.2010, 46-51; Acta polymeric ica Sinica 2013, 216-223.) adopt a method of combining anion polymerization and Atom Transfer Radical Polymerization (ATRP) to prepare PMMA-b-PB-b-PMMA and star PB-g-PMMA copolymer, the composition of the copolymer obtained by the method is adjustable, the structure is clear, the defect is that the stereoselectivity of a polybutadiene section is poor, and meanwhile, when a macromolecular initiator is synthesized, the bromine functionalization degree is 90%, and the polybutadiene needs to be separated.
The method for block copolymerization of conjugated diene and polar monomer reported in the prior art has harsh reaction conditions, and a method with mild reaction conditions needs to be developed to enrich the field of copolymers of conjugated diene blocks and polar monomers.
Disclosure of Invention
In view of the above, the present invention aims to provide a conjugated diene-polar monomer block copolymer and a preparation method thereof, wherein the reaction conditions of the method are mild, and the prepared conjugated diene-polar monomer block copolymer has controllable molecular weight and narrow molecular weight distribution.
The invention provides a preparation method of a conjugated diene-polar monomer block copolymer, which comprises the following steps:
1) polymerizing first conjugated diene in a solvent under the action of a catalyst to obtain a polymer a solution; the catalyst is prepared by reacting an alkoxy rare earth compound, a hydrogen alkyl aluminum compound, a chloride and second conjugated diene;
2) mixing the solution of the polymer a with a terminating agent, reacting, and terminating the reaction by a terminating agent to obtain a polymer b;
3) and reacting the polymer b, a free radical initiator, tetrabutylammonium iodide and a polar monomer, and terminating the reaction to obtain the conjugated diene-polar monomer block copolymer.
Preferably, the first and second conjugated dienes are independently selected from 1, 3-butadiene or isoprene;
the polar monomer is selected from one or more of methyl methacrylate, methyl acrylate, ethyl acrylate, butyl methacrylate, butyl acrylate, acrylamide and N-isopropyl acrylamide.
Preferably, the alkoxy rare earth compound in the step 1) is selected from one or more of n-propoxyl neodymium, isopropoxy neodymium, ethoxy neodymium, isopropoxy lanthanum, isobutoxy lanthanum, isopropoxy samarium and isobutoxy samarium;
the hydrogen alkyl aluminum compound is selected from one or more of dimethyl aluminum hydride, diethyl aluminum hydride, diisopropyl aluminum hydride, diisobutyl aluminum hydride, di-n-butyl aluminum hydride, dicyclohexyl aluminum hydride, di-n-octyl aluminum hydride and diisooctyl aluminum hydride;
the chloride is selected from one or more of carbon tetrachloride, dichloromethane, tert-butyl chloride, dichlorodimethylsilane, trichloromethylsilane and silicon tetrachloride.
Preferably, the polymerization temperature in the step 1) is 25-60 ℃, and the polymerization time is 3-6 h.
Preferably, the reaction temperature in the step 2) is 25-60 ℃, and the reaction time is 3-20 h.
Preferably, the reaction temperature in the step 3) is 50-100 ℃, and the reaction time is 1-5 h.
Preferably, the capping agent in step 2) is selected from elemental iodine, iodine chloride or N-iodosuccinimide.
Preferably, the radical initiator in step 3) is selected from azobisisobutyronitrile, azobisisoheptonitrile or benzoyl peroxide.
Preferably, the amount ratio of the polar monomer to the first conjugated diene in the step 3) is 0.5-3: 1;
the mass ratio of the first conjugated diene to the catalyst is 500-2000: 1.
The invention provides an application of the conjugated diene-polar monomer block copolymer in rubber.
The invention provides a preparation method of a conjugated diene-polar monomer block copolymer, which comprises the following steps: 1) in the presence of a catalyst, a first conjugated dienePolymerizing in a solvent to obtain a polymer a solution; the catalyst is prepared by reacting an alkoxy rare earth compound, a hydrogen alkyl aluminum compound, a chloride and second conjugated diene; 2) mixing the solution of the polymer a with a terminating agent, reacting, and terminating the reaction by a terminating agent to obtain a polymer b; 3) and reacting the polymer b, a free radical initiator, tetrabutylammonium iodide and a polar monomer, and terminating the reaction to obtain the conjugated diene-polar monomer block copolymer. The method has mild reaction conditions, controllable molecular weight of the conjugated diene-polar monomer block copolymer, narrow molecular weight distribution, and adjustable chain segment length and proportion of two blocks in the copolymer. The catalyst adopted by the method is a homogeneous rare earth catalytic system, and the catalyst has high catalytic activity, good stability, low cost and easy preparation; the selectivity is good, so that the tacticity of polydiene chain segments in the block copolymer is higher. The compatibility of the block copolymer with polar additives, white carbon black and other polar polymers is improved. The experimental results show that: the number average molecular weight of the conjugated diene-polar monomer block copolymer is 1X 104～5×104g/mol, the molecular weight distribution is between 1.4 and 2.0; the nonpolar block of the block copolymer has a 1, 4-structural unit content of about 98%, and a number average molecular weight of 7X 103g/mol, and the molecular weight distribution is about 1.65; the contact angle of a polybutadiene water drop was 91.1 °, and the contact angle of a block copolymer water drop was 73.4 °.
Drawings
FIG. 1 is a GPC chart of polymers prepared in examples 1 and 8 of the present invention;
FIG. 2 shows NMR spectra of polymers prepared in example 1 and example 8 of the present invention;
FIG. 3 is a graph showing the results of a contact angle test of a polymer prepared in example 1 of the present invention;
FIG. 4 is a graph showing the results of a contact angle test of a polymer prepared in example 8 of the present invention.
Detailed Description
The invention provides a preparation method of a conjugated diene-polar monomer block copolymer, which comprises the following steps:
1) polymerizing first conjugated diene in a solvent under the action of a catalyst to obtain a polymer a solution; the catalyst is prepared by reacting an alkoxy rare earth compound, a hydrogen alkyl aluminum compound, a chloride and second conjugated diene;
2) mixing the solution of the polymer a with a terminating agent, reacting, and terminating the reaction by a terminating agent to obtain a polymer b;
3) and reacting the polymer b, a free radical initiator, tetrabutylammonium iodide and a polar monomer, and terminating the reaction to obtain the conjugated diene-polar monomer block copolymer.
The method has mild reaction conditions, controllable molecular weight of the conjugated diene-polar monomer block copolymer, narrow molecular weight distribution, and adjustable chain segment length and proportion of two blocks in the copolymer. The catalyst adopted by the method is a homogeneous rare earth catalytic system, and the catalyst has high catalytic activity, good stability, low cost and easy preparation.
In the presence of a catalyst, the first conjugated diene is polymerized in a solvent to obtain a polymer a solution.
In the invention, the catalyst is prepared by reacting an alkoxy rare earth compound, a hydrogen alkyl aluminum compound, a chloride and second conjugated diene. The alkoxy rare earth compound is preferably selected from one or more of n-propoxyl neodymium, isopropoxy neodymium, ethoxy neodymium, isopropoxy lanthanum, isobutoxy lanthanum, isopropoxy samarium and isobutoxy samarium; more preferably one or more selected from neodymium isopropoxide, lanthanum isopropoxide and samarium isobutoxide; most preferably from neodymium isopropoxide. In the embodiment of the invention, the neodymium isopropoxide is preferably a hexane solution of neodymium isopropoxide.
The hydroalkylaluminum compound is preferably selected from one or more of dimethylaluminum hydride, diethylaluminum hydride, diisopropylaluminum hydride, diisobutylaluminum hydride, di-n-butylaluminum hydride, dicyclohexylaluminum hydride, di-n-octylaluminum hydride and diisooctylaluminum hydride; more preferably one or more selected from dimethylaluminum hydride, diisobutylaluminum hydride, di-n-octylaluminum hydride and diisooctylaluminum hydride; most preferably from diisobutylaluminum hydride.
The chloride is preferably selected from one or more of carbon tetrachloride, dichloromethane, tert-butyl chloride, dichlorodimethylsilane, trichloromethylsilane and silicon tetrachloride; more preferably one or more selected from the group consisting of dichloromethane, dichlorodimethylsilane and silicon tetrachloride; most preferably selected from dichlorodimethylsilane.
The invention preferably mixes and reacts the alkoxy rare earth compound, the hydrogen alkyl aluminum compound and the second conjugated diene, and then mixes and reacts with chloride; the alkoxy rare earth compound, the hydrogen alkyl aluminum compound and the second conjugated diene are firstly reacted at 45-55 ℃ for 8-12 min, and more preferably at 50 ℃ for 10 min. And then mixed with chloride for reaction for 35-45 min at 45-55 ℃, and more preferably for reaction for 40min at 50 ℃. In the invention, the mass ratio of the alkoxy rare earth compound, the hydroalkylaluminum compound, the chloride and the second conjugated diene is preferably 0.5-2: 10-30: 1-4: 5 to 20.
In the invention, the reaction temperature of the alkoxy rare earth compound, the hydroalkylaluminum compound, the chloride and the second conjugated diene is preferably 20-60 ℃, and more preferably 40-55 ℃; in a specific embodiment of the invention, the temperature for reacting the alkoxy rare earth compound, the hydroalkylaluminum compound, the chloride and the second conjugated diene is 50 ℃; the reaction time of the alkoxy rare earth compound, the hydroalkylaluminum compound, the chloride and the second conjugated diene is preferably 20-60 min, and more preferably 30-55 min; in a specific embodiment of the present invention, the time for the reaction of the alkoxy rare earth compound, the hydroalkylaluminum compound, the chloride and the second conjugated diene is 40 min.
In the present invention, the first conjugated diene and the second conjugated diene are independently preferably selected from 1, 3-butadiene or isoprene. The solvent selected for the environment in which the first conjugated diene is reacted preferably comprises toluene, hexane or cyclohexane. In the invention, the molar concentration of the first conjugated diene is preferably 1-5 mol/L. The mass ratio of the first conjugated diene to the catalyst is preferably 500-2000: 1.
The polymerization of the first conjugated diene is preferably carried out in a water bath according to the present invention; the polymerization temperature is preferably 25-60 ℃, more preferably 40-55 ℃, and most preferably 50 ℃; the polymerization time is preferably 3 to 6 hours, more preferably 4 to 5.5 hours, and most preferably 5 hours.
After obtaining the polymer a solution, the invention mixes the polymer a solution and the end-capping reagent for reaction, and the terminator terminates the reaction to obtain the polymer b.
The invention preferably adds an end-capping agent to the polymer a solution. In the present invention, the capping agent is preferably selected from elemental iodine, iodine chloride or N-iodosuccinimide. The mass ratio of the blocking agent to the catalyst is preferably 100-400: 1.
The invention preferably adopts 0.1 percent of ethanol solution of 2, 6-ditert-butyl-p-cresol as a terminator to terminate the reaction. The amount of the terminator used in the present invention is not particularly limited, and any amount of the terminator known to those skilled in the art may be used.
In the invention, the reaction temperature of the polymer a solution and the end-capping reagent is preferably 25-60 ℃; the reaction time is preferably 3-20 h.
After the termination reaction, the present invention preferably washes and dries the termination reaction product; the present invention preferably employs ethanol for washing. In the present invention, the polymer b is an iodine-terminated polymer.
In the invention, the content of the 1, 4-structural unit in the polymer b is more than 98 percent; the number average molecular weight of the polymer b is preferably 7.1X 103～7.6×103g/mol; the molecular weight distribution index MWD of the polymer b is 1.64-1.69.
After the polymer b is obtained, the polymer b, a free radical initiator, tetrabutylammonium iodide and a polar monomer are reacted, and the reaction is terminated to obtain the conjugated diene-polar monomer block copolymer. In the present invention, the radical initiator is preferably selected from azobisisobutyronitrile, azobisisoheptonitrile or benzoyl peroxide.
In the present invention, the polar monomer is preferably selected from one or more of methyl methacrylate, methyl acrylate, ethyl acrylate, butyl methacrylate, butyl acrylate, acrylamide and N-isopropylacrylamide, and more preferably from one or more of methyl methacrylate, butyl methacrylate and methyl acrylate. In the present invention, the amount ratio of the polar monomer to the first conjugated diene is preferably 0.5 to 3: 1.
In the present invention, the polymer b, the radical initiator, tetrabutylammonium iodide and the polar monomer are preferably reacted in a solvent; the solvent is preferably selected from hexane, cyclohexane or toluene. The reaction of polymer b, free radical initiator, tetrabutylammonium iodide and polar monomers is preferably terminated with ethanol according to the invention.
In the present invention, the ratio of the mass of the polymer b, the amount of the substance of the radical initiator, the amount of the substance of tetrabutylammonium iodide and the amount of the substance of the polar monomer is preferably (0.05 × 10)5～0.2×105) g: (0.5-2) mol: (0.05-2) mol: (200-2000) mol. In a specific embodiment of the invention, the ratio of the mass of the polymer b, the amount of substance of the radical initiator, the amount of substance of tetrabutylammonium iodide and the amount of substance of the polar monomer is specifically 0.1X 105g: 1.1 mol: 0.11 mol: 1100 mol; or 0.1X 105g: 1.1 mol: 0.22 mol: 1100 mol; or 0.1X 105g: 1.1 mol: 0.55 mol: 1100 mol; or 0.1X 105g: 1.1 mol: 1.1 mol: 1100 mol; or 0.1X 105g: 1.1 mol: 2.2 mol: 1100 mol; or 0.1X 105g: 1.1 mol: 0.11 mol: 220 mol; or 0.1X 105g: 1.1 mol: 0.11 mol: 550 mol; or 0.1X 105g： 1.1mol：0.11mol：880mol。
In the invention, the reaction temperature of the polymer b, the free radical initiator, the tetrabutylammonium iodide and the polar monomer is preferably 50-100 ℃, and the reaction time is preferably 1-5 h. In a specific embodiment of the present invention, the temperature for the reaction of the polymer b, the radical initiator, tetrabutylammonium iodide and the polar monomer is specifically 80 ℃; the time is 10h and 7 h.
After the termination reaction is finished, the reaction mixture is preferably put into ethanol for precipitation, and then filtered, washed and dried to obtain the conjugated diene-polar monomer block copolymer.
The conjugated diene-polar monomer block copolymer obtained by the invention is characterized by the following method:
the microstructure of the poly-conjugated diene block in the conjugated diene-polar monomer block copolymer is measured by a carbon disulfide coating method on a Vertex-70 FTIR type spectrometer of Bruker company. The molar ratio of the two blocks in the block copolymer was determined by means of a Unity-400 NMR spectrometer, manufactured by Virian corporation, the solvent being deuterated chloroform. The relative molecular weight and the distribution of the conjugated diene-polar monomer block copolymer are measured by a gel permeation chromatograph (515 type HPLC pump and 2414 type refractive index detector), four chromatographic columns (HMW7, HMW6E X2 and HMW2) are adopted, the mobile phase is tetrahydrofuran, the test temperature is 30 ℃, the flow rate is 1.0mL/min, the solution concentration is 0.1-0.3 mg/mL, and a filter head with the thickness of 0.45 mu m is adopted. The relative number average molecular weight and weight average molecular weight and molecular weight distribution of the conjugated diene-polar monomer block copolymer are calculated by taking polystyrene as an internal standard.
In order to further illustrate the present invention, the conjugated diene-polar monomer block copolymer and the preparation method thereof provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Under nitrogen, 5.0X 10 catalyst metering tanks were charged sequentially to a dry 20mL catalyst metering tank-5mol of Neodymium isopropoxide in hexane, 5X 10-4mol of isoprene, 1.0X 10-3mol diisobutylaluminum hydride, aged in a 50 ℃ water bath for 10 minutes, then added with 1.5X 10-4mol dichlorodimethylsilane, prepared to a neodymium atom concentration of 2.0X 10-5The mol/mL catalyst solution was aged for 40 minutes at 50 ℃ until use.
To a dry 40 ml ampoule, 10 ml of a 1.85 mol/L solution of butadiene in toluene and 0.925 ml of the above catalyst solution were added in this order under nitrogen. After 5 hours of polymerization in a thermostatic water bath at 50 ℃ to obtain a polymer solution, 5.0X 10 was added-3Stirring the toluene solution of the iodine simple substance for 3 hours, and using the toluene solution containing 0.1 percent of 2, 6-ditertbutyl-p-cresol after the reaction is finishedThe reaction was terminated with an ethanol solution. Washing with ethanol, and drying to constant weight to obtain iodine-terminated Polybutadiene (PBD). The number average molecular weight of the polymer is 7.1 × 103g/mol, a molecular weight distribution index MWD of 1.69 and a 1, 4-structural unit content of 98.3%.
GPC measurements were made on iodine-terminated polybutadiene prepared in example 1 of the present invention, see FIG. 1, and FIG. 1 is a GPC chart of polymers prepared in examples 1 and 8 of the present invention.
The NMR hydrogen spectra of the iodine-terminated polybutadiene obtained in example 1 of the present invention were measured, and the results are shown in FIG. 2, and FIG. 2 is an NMR hydrogen spectrum of the polymer obtained in example 1 and example 8 of the present invention.
The present inventors dropped deionized water on the surface of the iodine-terminated polybutadiene prepared in example 1 and tested the contact angle of the water drop. FIG. 3 is a graph showing the results of a contact angle test of a polymer prepared in example 1 of the present invention; as can be seen from fig. 3, the water droplet contact angle of the iodine-terminated polybutadiene prepared in example 1 was 91.1 °.
Example 2
0.1g of the iodine-terminated polybutadiene prepared in example 1, 1.1X 10 in that order, under nitrogen protection, are placed in a 40 ml ampoule with a magnetic stirrer-5mol benzoyl peroxide, 1.1X 10-6mol of tetrabutylammonium iodide, 1.1X 10-2mol of methyl methacrylate and 3 ml of toluene, and then heated to 80 ℃ for polymerization for 10 hours. And after the reaction is finished, pouring the reaction mixed solution into a large amount of ethanol, filtering and washing the polymer precipitate with ethanol, and drying the polymer precipitate in vacuum at 30 ℃ to constant weight to obtain the conjugated diene-polar monomer block copolymer. The conversion of methyl methacrylate was 66.2%, the molecular weight distribution index MWD of the polymer was 1.78, the molecular weight was 3.7X 104g/mol。
Example 3
0.1g of the iodine-terminated polybutadiene prepared in example 1, 1.1X 10 in that order, under nitrogen protection, are placed in a 40 ml ampoule with a magnetic stirrer-5mol of azobisisobutyronitrile, 1.1X 10-6mol of tetrabutylammonium iodide, 1.1X 10-2mol of methyl methacrylate, 3 ml of methylBenzene was then heated to 80 ℃ and polymerized for 10 hours. And after the reaction is finished, pouring the reaction mixed solution into a large amount of ethanol, filtering and washing the polymer precipitate with ethanol, and drying the polymer precipitate in vacuum at 30 ℃ to constant weight to obtain the conjugated diene-polar monomer block copolymer. The conversion of methyl methacrylate was 74.3%, the molecular weight distribution index MWD of the polymer was 1.95, the molecular weight was 3.8X 104g/mol。
Example 4
0.1g of the iodine-terminated polybutadiene prepared in example 1, 1.1X 10 in that order, under nitrogen protection, are placed in a 40 ml ampoule with a magnetic stirrer-5mol of azobisisobutyronitrile, 2.2X 10-6mol of tetrabutylammonium iodide, 1.1X 10-2mol of methyl methacrylate and 3 ml of toluene, and then heated to 80 ℃ for polymerization for 10 hours. And after the reaction is finished, pouring the reaction mixed solution into a large amount of ethanol, filtering and washing the polymer precipitate with ethanol, and drying the polymer precipitate in vacuum at 30 ℃ to constant weight to obtain the conjugated diene-polar monomer block copolymer. The conversion of methyl methacrylate was 68.7%, the molecular weight distribution index MWD of the polymer was 1.73, the molecular weight was 4.2X 104g/mol。
Example 5
0.1g of the iodine-terminated polybutadiene prepared in example 1, 1.1X 10 in that order, under nitrogen protection, are placed in a 40 ml ampoule with a magnetic stirrer-5mol of azobisisobutyronitrile, 5.5X 10-6mol of tetrabutylammonium iodide, 1.1X 10-2mol of methyl methacrylate and 3 ml of toluene, and then heated to 80 ℃ for polymerization for 10 hours. And after the reaction is finished, pouring the reaction mixed solution into a large amount of ethanol, filtering and washing the polymer precipitate with ethanol, and drying the polymer precipitate in vacuum at 30 ℃ to constant weight to obtain the conjugated diene-polar monomer block copolymer. The conversion of methyl methacrylate was 66.4%, the molecular weight distribution index MWD of the polymer was 1.68, the molecular weight was 4.3X 104g/mol。
Example 6
Under nitrogen, 0.1g of the example is added in succession to a 40 ml ampoule with a magnetic stirrer1 iodine-terminated polybutadiene, 1.1X 10-5mol of azobisisobutyronitrile, 1.1X 10-5mol of tetrabutylammonium iodide, 1.1X 10-2mol of methyl methacrylate and 3 ml of toluene, and then heated to 80 ℃ for polymerization for 10 hours. And after the reaction is finished, pouring the reaction mixed solution into a large amount of ethanol, filtering and washing the polymer precipitate with ethanol, and drying the polymer precipitate in vacuum at 30 ℃ to constant weight to obtain the conjugated diene-polar monomer block copolymer. The conversion of methyl methacrylate was 53.9%, the molecular weight distribution index MWD of the polymer was 1.71, the molecular weight was 4.4X 104g/mol。
Example 7
0.1g of the iodine-terminated polybutadiene prepared in example 1, 1.1X 10 in that order, under nitrogen protection, are placed in a 40 ml ampoule with a magnetic stirrer-5mol of azobisisobutyronitrile, 2.2X 10-5mol of tetrabutylammonium iodide, 1.1X 10-2mol of methyl methacrylate and 3 ml of toluene, and then heated to 80 ℃ for polymerization for 10 hours. And after the reaction is finished, pouring the reaction mixed solution into a large amount of ethanol, filtering and washing the polymer precipitate with ethanol, and drying the polymer precipitate in vacuum at 30 ℃ to constant weight to obtain the conjugated diene-polar monomer block copolymer. The conversion of methyl methacrylate was 58.8%, the molecular weight distribution index MWD of the polymer was 1.66, the molecular weight was 4.3X 104g/mol。
Example 8
0.1g of the iodine-terminated polybutadiene prepared in example 1, 1.1X 10 in that order, under nitrogen protection, are placed in a 40 ml ampoule with a magnetic stirrer-5mol of azobisisobutyronitrile, 1.1X 10-6mol tetrabutylammonium iodide, 2.2X 10-3mol of methyl methacrylate and 3 ml of toluene, and then heated to 80 ℃ for polymerization for 10 hours. After the reaction is finished, pouring the reaction mixed solution into a large amount of ethanol, filtering and washing the polymer precipitate with ethanol, and drying the polymer precipitate in vacuum at 30 ℃ to constant weight to obtain the conjugated diene-polar monomer block copolymer (PBD-b-PMMA). The conversion of methyl methacrylate was 79.5%, the molecular weight distribution index MWD of the polymer was 1.40, the molecular weight was 1.6×104g/mol。
The conjugated diene-polar monomer block copolymer prepared in example 8 was subjected to GPC measurement by the present invention, and shown in FIG. 1.
The hydrogen nuclear magnetic resonance spectroscopy test of the conjugated diene-polar monomer block copolymer prepared in example 8 was carried out, and the results are shown in FIG. 2.
The present invention dropped deionized water on the surface of the conjugated diene-polar monomer block copolymer prepared in example 8, and tested the contact angle of the water drop. Fig. 4 is a graph showing the contact angle test result of the polymer prepared in example 8 of the present invention, and it can be seen from fig. 4 that the contact angle of the water drop of the polymer prepared in example 8 is 73.4 °.
Example 9
0.1g of the iodine-terminated polybutadiene prepared in example 1, 1.1X 10 in that order, under nitrogen protection, are placed in a 40 ml ampoule with a magnetic stirrer-5mol of azobisisobutyronitrile, 1.1X 10-6mol tetrabutylammonium iodide, 5.5X 10-3mol of methyl methacrylate and 5 ml of toluene were then heated to 80 ℃ and polymerized for 10 hours. And after the reaction is finished, pouring the reaction mixed solution into a large amount of ethanol, filtering and washing the polymer precipitate with ethanol, and drying the polymer precipitate in vacuum at 30 ℃ to constant weight to obtain the conjugated diene-polar monomer block copolymer. The conversion of methyl methacrylate was 76.5%, the molecular weight distribution index MWD of the polymer was 1.65, the molecular weight was 2.5X 104g/mol。
Example 10
0.1g of the iodine-terminated polybutadiene prepared in example 1, 1.1X 10 in that order, under nitrogen protection, are placed in a 40 ml ampoule with a magnetic stirrer-5mol of azobisisobutyronitrile, 1.1X 10-6mol of tetrabutylammonium iodide, 8.8X 10-3mol of methyl methacrylate and 5 ml of toluene were then heated to 80 ℃ and polymerized for 10 hours. And after the reaction is finished, pouring the reaction mixed solution into a large amount of ethanol, filtering and washing the polymer precipitate with ethanol, and drying the polymer precipitate in vacuum at 30 ℃ to constant weight to obtain the conjugated diene-polar monomer block copolymer. The conversion of butyl methacrylate was 74.8%, the fraction of polymerMolecular weight distribution index MWD of 1.74 and molecular weight of 3.4 × 104g/mol。
Example 11
0.1g of the iodine-terminated polybutadiene prepared in example 1, 1.1X 10 in that order, under nitrogen protection, are placed in a 40 ml ampoule with a magnetic stirrer-5mol of azobisisobutyronitrile, 1.1X 10-6mol of tetrabutylammonium iodide, 1.1X 10-2mol of butyl methacrylate and 3 ml of toluene, and then heated to 80 ℃ for polymerization for 10 hours. And after the reaction is finished, pouring the reaction mixed solution into a large amount of ethanol, filtering and washing the polymer precipitate with ethanol, and drying the polymer precipitate in vacuum at 30 ℃ to constant weight to obtain the conjugated diene-polar monomer block copolymer. The conversion of butyl methacrylate was 69.5%, the molecular weight distribution index MWD of the polymer was 1.91, the molecular weight was 4.5X 104g/mol。
Example 12
0.1g of the iodine-terminated polybutadiene prepared in example 1, 1.1X 10 in that order, under nitrogen protection, are placed in a 40 ml ampoule with a magnetic stirrer-5mol of azobisisobutyronitrile, 1.1X 10-6mol of tetrabutylammonium iodide, 1.1X 10-2mol of methyl acrylate, 3 ml of toluene, then heated to 80 ℃ and polymerized for 10 hours. And after the reaction is finished, pouring the reaction mixed solution into a large amount of ethanol, filtering and washing the polymer precipitate with ethanol, and drying the polymer precipitate in vacuum at 30 ℃ to constant weight to obtain the conjugated diene-polar monomer block copolymer. The conversion of butyl methacrylate was 78.2%, the molecular weight distribution index MWD of the polymer was 1.87, the molecular weight was 4.3X 104g/mol。
Example 13
Iodine as an end-capping agent in example 1 was replaced with iodine chloride under the same conditions as in example 1 to obtain iodine-terminated polybutadiene. The number average molecular weight of the polymer is 7.3X 103g/mol, a molecular weight distribution index MWD of 1.67 and a 1, 4-structural unit content of 98.1%.
Then 0.1g of iodine-terminated polybutadiene, 1.1X 10 are added in succession to a 40 ml ampoule with a magnetic stirrer under nitrogen-5mol of azobisisobutyronitrile, 1.1X 10-6mol of tetrabutylammonium iodide, 1.1X 10-2mol of methyl methacrylate and 3 ml of toluene were heated to 80 ℃ and polymerized for 7 hours. And after the reaction is finished, pouring the reaction mixed solution into a large amount of ethanol, filtering and washing the polymer precipitate with ethanol, and drying the polymer precipitate in vacuum at 30 ℃ to constant weight to obtain the conjugated diene-polar monomer block copolymer. The conversion of methyl methacrylate was 68.5%, the molecular weight distribution index MWD of the polymer was 1.91, the molecular weight was 3.9X 104g/mol。
Example 14
Iodine as the end-capping reagent in example 1 was replaced with N-iodosuccinimide under the same conditions as in example 1 to obtain iodine-terminated polybutadiene. The number average molecular weight of the polymer is 7.6 multiplied by 103g/mol, a molecular weight distribution index MWD of 1.64 and a 1, 4-structural unit content of 98.4%.
0.1g of iodine-terminated polybutadiene, 1.1X 10 in this order, are placed in a 40 ml ampoule with a magnetic stirrer under nitrogen-5mol of azobisisobutyronitrile, 1.1X 10-6mol of tetrabutylammonium iodide, 1.1X 10-2mol of methyl methacrylate and 3 ml of toluene were heated to 80 ℃ and polymerized for 7 hours. And after the reaction is finished, pouring the reaction mixed solution into a large amount of ethanol, filtering and washing the polymer precipitate with ethanol, and drying the polymer precipitate in vacuum at 30 ℃ to constant weight to obtain the conjugated diene-polar monomer block copolymer. The conversion of methyl methacrylate was 64.9%, the molecular weight distribution index MWD of the polymer was 2.05, the molecular weight was 4.0X 104g/mol。
From the above examples, it can be seen that the present invention provides a method for preparing a conjugated diene-polar monomer block copolymer, comprising the steps of: 1) polymerizing first conjugated diene in a solvent under the action of a catalyst to obtain a polymer a solution; the catalyst is prepared by reacting an alkoxy rare earth compound, a hydrogen alkyl aluminum compound, a chloride and second conjugated diene; 2) mixing the solution of the polymer a with a terminating agent, reacting, and terminating the reaction by a terminating agent to obtain a polymer b; 3) polymer b, radical initiator and tetrabutylAnd reacting the ammonium iodide with a polar monomer, and terminating the reaction to obtain the conjugated diene-polar monomer segmented copolymer. The method has mild reaction conditions, controllable molecular weight of the conjugated diene-polar monomer block copolymer, narrow molecular weight distribution, and adjustable chain segment length and proportion of two blocks in the copolymer. The catalyst adopted by the method is a homogeneous rare earth catalytic system, and the catalyst has high catalytic activity, good stability, low cost and easy preparation; the selectivity is good, so that the tacticity of polydiene chain segments in the block copolymer is higher. The compatibility of the block copolymer with polar additives, white carbon black and other polar polymers is improved. The experimental results show that: the number average molecular weight of the conjugated diene-polar monomer block copolymer is 1X 104～5×104g/mol, the molecular weight distribution is between 1.4 and 2.0; the nonpolar block of the block copolymer has a 1, 4-structural unit content of about 98%, and a number average molecular weight of 7X 103g/mol, and the molecular weight distribution is about 1.65; the contact angle of a polybutadiene water drop was 91.1 °, and the contact angle of a block copolymer water drop was 73.4 °.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (4)

1. A preparation method of a conjugated diene-polar monomer block copolymer comprises the following steps:
1) polymerizing first conjugated diene in a solvent under the action of a catalyst to obtain a polymer a solution; the catalyst is prepared by reacting neodymium isopropoxide, diisobutyl aluminum hydride, dichlorodimethylsilane and second conjugated diene; the mass ratio of the neodymium isopropoxide, diisobutyl aluminum hydride, dichlorodimethylsilane and second conjugated diene is 0.5-2: 10-30: 1-4: 5-20;
2) mixing the solution of the polymer a with a terminating agent, reacting, and terminating the reaction by a terminating agent to obtain a polymer b; the reaction temperature is 25-60 ℃, and the reaction time is 3-20 h;the end capping agent is selected from elementary iodine, iodine chloride or N-iodosuccinimide; the content of 1, 4-structural units in the polymer b is more than 98 percent; the number average molecular weight of the polymer b is 7.1X 103～7.6×103g/mol; the molecular weight distribution index MWD of the polymer b is 1.64-1.69;
3) reacting the polymer b, a free radical initiator, tetrabutylammonium iodide and a polar monomer, and terminating the reaction to obtain a conjugated diene-polar monomer block copolymer; the reaction temperature is 50-100 ℃, and the reaction time is 1-5 h;
said first and second conjugated dienes are independently selected from 1, 3-butadiene or isoprene;
the polar monomer is selected from one or more of methyl methacrylate, methyl acrylate and butyl methacrylate;
the mass ratio of the polar monomer to the first conjugated diene in the step 3) is 0.5-3: 1;
the mass ratio of the first conjugated diene to the catalyst is 500-2000: 1.
2. The preparation method of claim 1, wherein the polymerization temperature in the step 1) is 25-60 ℃ and the polymerization time is 3-6 h.
3. The method according to claim 1, wherein the radical initiator in step 3) is selected from azobisisobutyronitrile, azobisisoheptonitrile, or benzoyl peroxide.
4. Use of the conjugated diene-polar monomer block copolymer according to any one of claims 1 to 3 in rubber.
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