CN111499857B - Conjugated diene and epoxy compound block copolymer and preparation method thereof - Google Patents

Conjugated diene and epoxy compound block copolymer and preparation method thereof Download PDF

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CN111499857B
CN111499857B CN202010483063.2A CN202010483063A CN111499857B CN 111499857 B CN111499857 B CN 111499857B CN 202010483063 A CN202010483063 A CN 202010483063A CN 111499857 B CN111499857 B CN 111499857B
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CN111499857A (en
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王凤
张铭铭
吴广峰
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Changchun University of Technology
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    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
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Abstract

The invention provides a conjugated diene and epoxy compound block copolymer and a preparation method thereof, belonging to the field of copolymer synthesis. Firstly, reacting a reaction monomer with a solvent under the action of a catalyst to obtain a solution A; then adding an epoxy compound monomer into the solution A to react to obtain a reaction solution B; and finally, adding an ethanol solution into the solution B, and settling to obtain the block copolymer of the conjugated diene and the epoxy compound monomer. The obtained block copolymer of the conjugated diene and the epoxy compound monomer has low molecular weight and narrow molecular weight distribution; the experimental results show that: the yield of the synthesized conjugated diene and epoxy compound block copolymer is 70-99 percent, and the number average molecular weight is 7.24 multiplied by 10 3 ～15.1×10 3 The molecular weight distribution is 1.41-1.87.

Description

Conjugated diene and epoxy compound block copolymer and preparation method thereof
Technical Field
The invention belongs to the field of copolymer synthesis, and particularly relates to a conjugated diene and epoxy compound block copolymer and a preparation method thereof.
Background
In modern times with a high level of technology, high molecular materials have already been a very important part of industrial and agricultural production and human daily life. Rubber is an important branch of polymer materials, and is one of important materials indispensable to national economy and daily life. The synthetic rubber is a high-elasticity polymer which is artificially synthesized, is cheap and easily available, has various varieties, can be synthesized into various rubbers with special properties (such as heat resistance, cold resistance, wear resistance, oil resistance, corrosion resistance and the like) according to the requirements of industry and public transport, and has larger industrial production requirements.
The polymerization of diolefin is an important method for preparing synthetic rubber, wherein high cis-polybutadiene rubber and high cis-polyisoprene rubber have excellent mechanical properties, fatigue resistance, low temperature resistance and the like, and are key rubber species in the field of synthetic rubber. However, although the chain structure and the stereoregularity are similar to those of natural rubber, since natural rubber contains a small amount of polar non-rubber groups, these polar groups can improve the kneading uniformity with carbon black and the interaction with rubber filler, and can induce rubber elongation crystallization, and polybutadiene or polyisoprene, which are non-polar polymers, are hardly compatible with natural rubberIts polar material is blended and hybridized, and its application in printing dye property, conductivity and antistatic property is limited (Li Guilian, dong is Ren, jiang Liang, zhang Xuequan. "homogeneous phase Nd (vers) 3 /Al(i-Bu) 2 H/Al(i-Bu) 2 Cl catalyzed polymerization of isoprene ", synthetic rubber industry, 2006. Therefore, polar groups are introduced into the high cis-diolefin polymer, and the polarity of the diolefin polymer is increased on the basis of keeping the excellent performance of the original polymer, so that the inherent defects of diolefin polymer materials can be effectively compensated, the diolefin polymer alloy materials can be designed and synthesized, even new and special functions (such as conductivity, antistatic property, magnetism, flame retardance, degradability and the like) can be endowed, the application field is even expanded to the fields of catalyst carriers, medicines, optoelectronic materials, biomedical materials, photographic equipment, environmental protection and the like, and the method has extremely important theoretical significance and good application prospect.
In recent years, considerable progress has been made in the rare earth catalyst catalysis of the copolymerization of the conjugated diene and the polar monomer. Cui and the like realize the copolymerization of isoprene and an oxygen-containing monomer 2- (4-methoxyphenyl) -1,3-butadiene by using a rare earth complex containing an electron-donating beta-diketone diimine ligand to obtain a polymer with high cis-selectivity (Liu, D.; wang, M.; wang, Z.; wu, C.; pan, Y.; cui, D.Angew.chem., int.Ed.2017,56,2714.). Stefan packing et al have studied the stereoselective copolymerization of butadiene and functionalized 1,3-butadiene using neodymium neodecanoate, neodymium isopropoxide systems to catalyze butadiene with Ar 2 Copolymerization of N-, phS-functionalized butadiene derivatives gives copolymers based on the cis-1,4 structure (Schuster, N.; runzi, T.; mecking, S.macromolecules,2016,49,1172.).
Although the scope of diolefins as functional monomers has been gradually expanded with the development of new high-efficiency catalysts, the polar monomers reported in the literature have many disadvantages, such as: the copolymerizable monomer has few kinds, low insertion rate when copolymerized with diolefin, and easy coordination of hetero atom in the monomer with the active center of transition metal catalyst or rare earth catalyst to deactivate the catalyst.
Disclosure of Invention
The invention aims to provide a conjugated diene and epoxy compound block copolymer and a preparation method thereof, and the obtained block copolymer of the conjugated diene and the epoxy compound monomer has low molecular weight and narrow molecular weight distribution.
The invention provides a preparation method of a block copolymer of conjugated diene and epoxy compound monomer, which comprises the following steps:
the method comprises the following steps: reacting a reaction monomer with a solvent under the action of a catalyst to obtain a solution A;
the reaction monomer is butadiene, isoprene or piperylene;
the catalyst comprises neodymium octyldecanoate (Nd), isoprene (IP), diisobutylaluminum hydride (Al) and dichlorodimethylsilane;
step two: adding an epoxy compound monomer into the solution A to react to obtain a reaction solution B;
step three: and adding an ethanol solution into the solution B, and settling to obtain the block copolymer of the conjugated diene and the epoxy compound monomer.
Preferably, the molar ratio of the reaction monomers and the neodymium octyldecanoate in the catalyst in the first step is 500.
Preferably, the reaction temperature of the first step is 20-60 ℃, and the reaction time is 3-5 h.
Preferably, the step one catalyst preparation comprises: neodymium octyldecanoate (Nd), isoprene (IP), diisobutylaluminum hydride (Al) and dichlorodimethylsilane are mixed and react for 15 to 60 minutes at the temperature of between 20 and 60 ℃ to obtain the catalyst.
Preferably, the molar ratio of the neodymium octyldecanoate (Nd), the Isoprene (IP), the diisobutylaluminum hydride (Al) and the dichlorodimethylsilane is 1.
Preferably, the molar ratio of the epoxy compound monomer in the second step to the neodymium octyldecanoate in the catalyst is 200-800.
Preferably, the epoxy compound monomer in the second step is cyclohexene oxide, epichlorohydrin, ethylene oxide or propylene oxide.
Preferably, the reaction temperature of the second step is preferably 20 to 60 ℃, and the reaction time is preferably 1 to 3 hours.
Preferably, the third step further comprises adding an ethanol solution of hydrochloric acid to the solution B.
The invention also provides a block copolymer of conjugated diene and epoxy compound monomer obtained by the preparation method, the number average molecular weight of the block copolymer is 7.24 multiplied by 10 3 ～15.1×10 3 The molecular weight distribution is 1.41-1.87.
The invention has the advantages of
The invention provides a conjugated diene and polar monomer block copolymer and a preparation method thereof, and the invention adopts a traditional rare earth Ziegler-Natta type homogeneous rare earth catalyst to discover that the copolymer can catalyze the polymerization of conjugated diene and the ring-opening polymerization of epoxy compounds. The method utilizes the activity characteristic of the catalytic system to synthesize the block copolymer containing polar end groups or polar polymer chain segments. The chain segment length of the nonpolar segment and the epoxy compound segment in the copolymer can be accurately regulated and controlled by regulating the molar ratio of the epoxy compound monomer to the catalyst, and in addition, as the added epoxy compound belongs to a polar monomer, the glass transition temperature and the polarity of the block copolymer can be directly influenced by the change of the chain segment length of the conjugated diene and the epoxy compound. The obtained block copolymer of the conjugated diene and the epoxy compound monomer has low molecular weight and narrow molecular weight distribution; the experimental results show that: the yield of the synthesized conjugated diene and epoxy compound block copolymer is 70-99 percent, and the number average molecular weight is 7.24 multiplied by 10 3 ～15.1×10 3 The molecular weight distribution is 1.41-1.87.
Drawings
FIG. 1 is a GPC chart of a butadiene and epoxycyclohexane block copolymer of example 3 of the present invention, the number average molecular weight of the copolymer being M n ＝8.71×10 3 The molecular weight distribution index was 1.41.
FIG. 2 is a nuclear magnetic spectrum of a butadiene and epoxycyclohexane block copolymer of example 3 of the present invention, obtained by 1 H-NMR calculationThe molar ratio of polybutadiene block to poly (cyclohexene oxide) block in the copolymer obtained is 1/1.01.
FIG. 3 is an IR spectrum of a block copolymer of butadiene and cyclohexene oxide of example 3 of the present invention.
FIG. 4 is a TEM photograph of a butadiene and epoxycyclohexane block copolymer compatibilized PBD/PCHO blend system of example 5 of the present invention.
FIG. 5 is a photograph showing contact angles of butadiene and a block copolymer in example 5 of the present invention.
Detailed Description
The invention provides a preparation method of a block copolymer of conjugated diene and epoxy compound monomer, which comprises the following steps:
the method comprises the following steps: reacting a reaction monomer with a solvent under the action of a catalyst to obtain a solution A;
the reaction monomer is butadiene, isoprene or piperylene; the molar concentration of the reaction monomer is preferably 1 mol/L-5 mol/L; the solvent is preferably an alkane solvent, and the alkane solvent is preferably toluene; the reaction temperature in the first step is preferably 20-60 ℃, more preferably 50 ℃, and the reaction time is preferably 3-5 h, more preferably 4h; the molar ratio of the reaction monomers to neodymium octyldecanoate in the catalyst is preferably 500.
According to the invention, the catalyst comprises neodymium octyldecanoate (Nd), isoprene (IP), diisobutylaluminum hydride (Al) and dichlorodimethylsilane; the preparation of the catalyst preferably comprises:
neodymium octyldecanoate (Nd), isoprene (IP), diisobutylaluminum hydride (Al) and dichlorodimethylsilane are mixed and react for 15 to 60 minutes at the temperature of between 20 and 60 ℃ to obtain the catalyst. The molar ratio of the neodymium octyldecanoate (Nd), the Isoprene (IP), the diisobutylaluminum hydride (Al) and the dichlorodimethylsilane is preferably 1.
Step two: adding an epoxy compound monomer into the solution A to react to obtain a reaction solution B; the molar ratio of the epoxy compound monomer to neodymium octyldecanoate in the catalyst is preferably 200 to 800, more preferably 500:1; the reaction temperature is preferably 20-60 ℃, more preferably 50 ℃, and the reaction time is preferably 1-3 h, more preferably 1h;
the epoxy compound monomer is preferably cyclohexene oxide, epichlorohydrin, ethylene oxide or propylene oxide, more preferably cyclohexene oxide, and the structural formula is shown in formula (1):
Figure BDA0002517983010000051
the polar epoxy cyclohexane chain segment is introduced into the nonpolar poly-conjugated diene chain segment, so that the compatibility of the non-polar epoxy cyclohexane chain segment with other high polymer materials can be improved, and the surface adhesion, the solvent resistance and the like of the non-polar poly-conjugated diene chain segment are improved.
Step three: adding an ethanol solution containing a small amount of hydrochloric acid into the solution B to coagulate a product, and repeatedly washing the product with ethanol to obtain a white solid product of the conjugated diene and epoxy compound monomer block copolymer; the product was dried in a vacuum oven for more than 48 hours to obtain a dried block copolymer of conjugated diene and epoxy monomer.
The invention also provides a block copolymer of conjugated diene and epoxy compound monomer obtained by the preparation method, wherein the number average molecular weight of the block copolymer is 7.24 multiplied by 10 3 ～15.1×10 3 The molecular weight distribution is 1.41-1.87.
The microstructure, molecular weight and molecular weight distribution of the conjugated diene and epoxy compound block copolymer prepared by the invention are measured by the following methods:
the molecular weight and molecular weight distribution of the copolymer (including examples) were determined by gel permeation chromatography using four chromatographic columns (HMW 7, HMW6 E.times.2, HMW2) with tetrahydrofuran as the mobile phase, at a test temperature of 30 ℃, a flow rate of 1.0mL/min and a solution concentration of 0.2 to 0.3mg/10mL, filtered through a 0.45 μm filter and injected. The number average molecular weight (M) of the polymer was calculated using polystyrene as an internal standard n ) And weight average molecular weight (M) w ) And using M in combination w /M n To characterize the molecular weight distribution index of the polymer.
The microstructure of the copolymer, including the examples, was determined by carbon disulphide coating on a Bruker Vertex-70FTIR type infrared spectrometer. The molar ratio of the poly (conjugated diene) blocks to the poly (cyclohexene oxide) blocks in the block copolymer, including the examples, was determined by means of a Unity-400 NMR spectrometer, manufactured by Virian corporation, using deuterated chloroform as the solvent. The microscopic phase (including examples) of the block copolymer was observed with a transmission electron microscope (TEM, JEM-1011, JEOL, japan) at an acceleration voltage of 100kV. The surface polarity of the block copolymers (including the examples) was characterized by contact angle measurements.
Glass transition temperature (T) of block copolymer of conjugated diene and epoxy compound g ) (including examples) measured using a Q100DSC differential scanning calorimeter from TA corporation, a helium atmosphere and a gas flux of 50ml/min, the temperature increase and decrease rates were all 10 ℃/min.
The preferred embodiments of the present invention are described in further detail below with reference to specific examples. It is to be understood that such description is merely illustrative of the features and advantages of the present invention and is not intended to limit the invention to the claims.
Example 1
Neodymium octyldecanoate (Nd), isoprene (IP), diisobutylaluminum hydride (Al) and dichlorodimethylsilane (Cl) are sequentially added into a 10mL catalyst reaction bottle which is vacuumized, baked and filled with nitrogen for reaction in a constant-temperature water bath at 50 ℃ for 60min to obtain a homogeneous rare earth catalyst, wherein the molar ratio of [ Nd ]/[ IP ] [ Al ]/[ Cl ] in the catalyst is 1/10/20/3.
Toluene, butadiene and the homogeneous rare earth catalyst are sequentially added into a 40mL ampoule bottle which is vacuumized, baked and dried and is filled with nitrogen for treatment, the concentration of the butadiene is 1.85mol/L, and the molar ratio of the butadiene to [ BD ]/[ Nd ] of neodymium octyldecanoate in the rare earth catalyst is 500/1. Carrying out polymerization in a constant-temperature water bath at 50 ℃, and carrying out polymerization reaction for 4 hours to obtain a solution A;
adding epoxy Cyclohexane (CHO) monomer into the solution A, wherein the molar ratio of epoxy cyclohexane to neodymium octyldecanoate in a rare earth catalyst is [ CHO ]/[ Nd ] =200/1, after the polymerization reaction is carried out for 1h at 50 ℃, adding ethanol solution and dilute hydrochloric acid to terminate the polymerization reaction, introducing the reaction solution into ethanol for settling, and washing by using the ethanol to obtain a white product of the conjugated diene and polar monomer block copolymer; the white product was dried in a vacuum oven for 48 hours to obtain a dried block copolymer of a conjugated diene and a polar monomer.
The yield of the polymer obtained was 86.37%, and the number-average molecular weight of the polybutadiene block in the copolymer was M n ＝8.02×10 3 Molecular weight distribution of M w /M n =1.39, number average molecular weight of copolymer, M n ＝8.63×10 3 Molecular weight distribution index of M w /M n =1.79. By passing 1 The molar ratio of polybutadiene blocks to poly (cyclohexene oxide) blocks in the copolymer was 1/0.49 as calculated by H NMR. The glass transition temperature (T) of the butadiene block was measured by DSC g ) At-101.6 deg.C, very low polar segment content and no T g 。
Example 2
As described in example 1, the other conditions and preparation methods were identical, and the molar ratio of the polar monomer to the catalytic system was changed only during the polymerization, and the molar ratio of cyclohexene oxide to neodymium octyldecanoate in the homogeneous rare earth catalyst was [ CHO ]]/[Nd]=400/1, the yield of the polymer obtained is 77.18%, and the number average molecular weight of the polybutadiene block in the copolymer is M n ＝8.97×10 3 Molecular weight distribution of M w /M n =1.38, number average molecular weight of copolymer, M n ＝10.3×10 3 Molecular weight distribution index of M w /M n =1.84. By passing 1 H NMR calculated as the molar ratio of polybutadiene blocks to poly (cyclohexene oxide) blocks in the copolymer was 1/1.13. The glass transition temperature (T) of the butadiene block was measured by DSC g ) It was-101.9 ℃ and the glass transition temperature of the copolymer was 49.9 ℃.
Example 3
As described in example 1, the other conditions and preparation methods were identical, and the molar ratio of the polar monomer to the catalytic system was changed only during the polymerization, and the molar ratio of cyclohexene oxide to neodymium octyldecanoate in the homogeneous rare earth catalyst was [ CHO ]]/[Nd]=500/1, yield of polymer obtained 71.47%, number average molecular weight of polybutadiene block in copolymer M n ＝7.97×10 3 Having a molecular weight distribution ofM w /M n =1.38, number average molecular weight of copolymer, M n ＝8.71×10 3 Molecular weight distribution index of M w /M n =1.41 (as shown in the GPC diagram of fig. 1). By passing 1 The molar ratio of polybutadiene block to poly (cyclohexene oxide) block in the copolymer was 1/1.01 as calculated by H NMR, as shown in FIG. 2, and the IR spectrum of the butadiene and cyclohexene oxide block copolymer as shown in FIG. 3,
the glass transition temperature (T) of the butadiene block was measured by DSC g ) At-101.8 ℃ and a copolymer glass transition temperature of 44.3 ℃.
Example 4
As described in example 1, the other conditions and the preparation process were identical, the molar ratio of the polar monomer to the catalytic system was varied only during the polymerization, the molar ratio of cyclohexene oxide to neodymium octyldecanoate in the homogeneous rare earth catalyst was [ CHO]/[Nd]=600/1, the yield of the polymer obtained is 81.17%, and the number average molecular weight of the polybutadiene block in the copolymer is M n ＝8.97×10 3 Molecular weight distribution of M w /M n =1.38, number average molecular weight of copolymer, M n ＝10.7×10 3 Molecular weight distribution index of M w /M n =1.84. By passing 1 The molar ratio of polybutadiene blocks to poly (cyclohexene oxide) blocks in the copolymer was 1/1.09 by H NMR calculation. The glass transition temperature (T) of the butadiene block was measured by DSC g ) It was-102.8 ℃ and the glass transition temperature of the copolymer was 39.1 ℃.
Example 5
As described in example 1, the other conditions and preparation methods were identical, and the molar ratio of the polar monomer to the catalytic system was changed only during the polymerization, and the molar ratio of cyclohexene oxide to neodymium octyldecanoate in the homogeneous rare earth catalyst was [ CHO ]]/[Nd]=800/1, yield of polymer obtained was 70.01%, number average molecular weight of polybutadiene block in copolymer was M n ＝13.9×10 3 Molecular weight distribution of M w /M n =1.44, number average molecular weight of copolymer, M n ＝15.1×10 3 Molecular weight distribution index of M w /M n =1.70. By passing 1 Calculation of copolymerization by H NMRThe molar ratio of polybutadiene block to poly (cyclohexene oxide) block in the polymer is 1/1.31. The glass transition temperature (T) of the butadiene block was measured by DSC g ) It was-101.3 ℃ and the glass transition temperature of the copolymer was 38.7 ℃.
FIG. 4 is a TEM photograph of a butadiene and epoxycyclohexane block copolymer compatibilized PBD/PCHO blend system of example 5 of the present invention. As can be seen from FIG. 4, the PB/PCHO blend has significant phase separation (panel a) and poor compatibility. After the PBD-b-PCHO block copolymer is added into a blending system (b picture), the appearance is remarkably changed, and the phase separation size becomes very small, which shows that the block copolymer synthesized by the method can effectively compatibilize the PBD/PCHO blending system.
FIG. 5 is a photograph showing contact angles of butadiene and a block copolymer in example 5 of the present invention. Wherein a is the deionized water is dropped on the PBD surface, and the contact angle is 98.8 ℃; and b, the diagram shows that deionized water is dripped on the PBD-b-PCHO surface, and the contact angle is 84.6 ℃. It can be seen from fig. 5 that after the introduction of the epoxy monomer segment, deionized water spreads on the surface of the copolymer and the contact angle decreases, which indicates that the block copolymer synthesized by us has good hydrophilicity.
Comparative example 1
As described in example 1, the other conditions and preparation methods were identical, and the molar ratio of the polar monomer to the catalytic system was changed only during the polymerization, and the molar ratio of cyclohexene oxide to neodymium octyldecanoate in the homogeneous rare earth catalyst was [ CHO ]]/[Nd]=50/1, yield of polymer obtained 98.44%, number average molecular weight of polybutadiene block in copolymer M n ＝8.07×10 3 Molecular weight distribution of M w /M n =1.39, number average molecular weight of copolymer M n ＝7.62×10 3 Molecular weight distribution index of M w /M n =1.51. By passing 1 The molar ratio of polybutadiene blocks to poly (cyclohexene oxide) blocks in the copolymer was 1/0.03 as calculated by H NMR. The glass transition temperature (T) of the butadiene block was measured by DSC g ) At-102.6 deg.C, very low polar segment content and no T g 。
Comparative example 2
As described in example 1, the other conditions and preparation process were identical, except that polymerization was carried outThe molar ratio of the polar monomer to the catalytic system is changed in time, and the molar ratio of the epoxy cyclohexane to the neodymium octyldecanoate in the homogeneous rare earth catalyst is [ CHO]/[Nd]=100/1, the yield of the polymer obtained is 84.24%, and the number average molecular weight of the polybutadiene block in the copolymer is M n ＝7.87×10 3 Molecular weight distribution of M w /M n =1.41, number average molecular weight of copolymer, M n ＝8.01×10 3 Molecular weight distribution index of M w /M n =1.39. By passing 1 The molar ratio of polybutadiene blocks to poly (cyclohexene oxide) blocks in the copolymer was 1/0.05 calculated by H-NMR. The glass transition temperature (T) of the butadiene block was measured by DSC g ) At-102.3 deg.C, low polar segment content and no T g 。
Comparative example 3
As described in example 1, the other conditions and preparation methods were identical, and the molar ratio of the polar monomer to the catalytic system was changed only during the polymerization, and the molar ratio of cyclohexene oxide to neodymium octyldecanoate in the homogeneous rare earth catalyst was [ CHO ]]/[Nd]=1000/1, the yield of the polymer obtained is 90.29%, and the number average molecular weight of the polybutadiene block in the copolymer is M n ＝14.7×10 3 Molecular weight distribution of M w /M n =1.35, number average molecular weight of copolymer, M n ＝25.8×10 3 Molecular weight distribution index of M w /M n =2.02. By passing 1 H NMR calculated molar ratio of polybutadiene block to poly (cyclohexene oxide) block in the copolymer was 1/1.36. The glass transition temperature (T) of the butadiene block was measured by DSC g ) It was-97.2 ℃ and the glass transition temperature of the copolymer was 40.2 ℃.
As can be seen from examples 1-5 and comparative examples 1-3, by changing the molar ratio of the epoxy compound monomer to neodymium octyldecanoate in the catalytic system, the lengths of the nonpolar segment and the polar segment in the block copolymer can be adjusted, and the molecular weight, distribution and surface energy (polarity) of the copolymer can be further influenced. When the molar ratio of the epoxy compound monomer to neodymium octyldecanoate in the homogeneous rare earth catalyst is [ TMC ]/[ Nd ] =50/1 and 100/1, and the content of the epoxy compound monomer is too low, the access rate of the second section in the block copolymer is very small, so that the influence on the related performance of the copolymer is small; when the molar ratio of the epoxy compound monomer to neodymium octyldecanoate in the homogeneous rare earth catalyst is [ TMC ]/[ Nd ] =1000/1, the molecular weight distribution and the surface energy of the block copolymer can be directly influenced along with the degradation of the epoxy compound monomer. From the data, the addition of epoxy monomer has a great influence on the glass transition temperature of the block copolymer, and the monomer feed ratio and the ratio of butadiene segment to epoxy segment in the copolymer are close to each other, which indicates that the polymerization efficiency is high.
Example 6
Neodymium octyldecanoate (Nd), isoprene (IP), diisobutylaluminum hydride (Al) and dichlorodimethylsilane (Cl) are sequentially added into a 10mL catalyst reaction bottle which is vacuumized, baked and filled with nitrogen for reaction in a thermostatic waterbath at 50 ℃ for 60min to obtain a homogeneous rare earth catalyst, wherein the molar ratio of [ Nd ]/[ IP ] [ Al ]/[ Cl ] in the catalyst is 1/10/30/3.
Sequentially adding toluene, butadiene and the homogeneous rare earth catalyst into a 40mL ampoule bottle which is vacuumized, baked and dried and is filled with nitrogen for treatment, wherein the concentration of the butadiene is 1.85mol/L, the molar ratio of the butadiene to [ BD ]/[ Nd ] of neodymium octyldecanoate in the rare earth catalyst is 500/1, polymerizing in a constant-temperature water bath at 50 ℃, and carrying out polymerization reaction for 4 hours to obtain a solution A;
adding epoxy Cyclohexane (CHO) monomer into the solution A, wherein the molar ratio of epoxy cyclohexane to neodymium octyldecanoate in a rare earth catalyst is [ CHO ]/[ Nd ] =200/1, after the polymerization reaction is carried out for 1h at 50 ℃, adding ethanol solution and dilute hydrochloric acid to terminate the polymerization reaction, introducing the reaction solution into ethanol for settling, and washing by using the ethanol to obtain a white product of the conjugated diene and polar monomer block copolymer; the white product was dried in a vacuum oven for 48 hours to obtain a dried block copolymer of a conjugated diene and a polar monomer.
The yield of the polymer obtained was 84.36%, and the number-average molecular weight of the polybutadiene block in the copolymer was M n ＝5.37×10 3 Molecular weight distribution of M w /M n =1.44, number average molecular weight of copolymer, M n ＝7.46×10 3 Molecular weight distribution index of M w /M n =1.87. By passing 1 H NMR calculated as the molar ratio of polybutadiene blocks to poly (cyclohexene oxide) blocks in the copolymer was 1/0.33. The glass transition temperature (T) of the butadiene block was measured by DSC g ) At-100.9 deg.C, low polar segment content and no T g 。
Example 7
As described in example 6, the other conditions and preparation methods were identical, and the molar ratio of the polar monomer to the catalytic system was changed only during the polymerization, and the molar ratio of cyclohexene oxide to neodymium octyldecanoate in the homogeneous rare earth catalyst was [ CHO ]]/[Nd]=500/1, yield of polymer obtained 87.25%, number average molecular weight of polybutadiene block in copolymer is M n ＝4.88×10 3 Molecular weight distribution of M w /M n =1.47, number average molecular weight of copolymer, M n ＝9.65×10 3 Molecular weight distribution index of M w /M n =1.73. By passing 1 The molar ratio of polybutadiene blocks to poly (cyclohexene oxide) blocks in the copolymer was 1/0.82 as calculated by H NMR. The glass transition temperature (T) of the butadiene block was measured by DSC g ) At-101.2 ℃ and a copolymer glass transition temperature of 40.5 ℃.
Example 8
As described in example 6, the other conditions and the preparation process were identical, the molar ratio of the polar monomer to the catalytic system was varied only during the polymerization, the molar ratio of cyclohexene oxide to neodymium octyldecanoate in the homogeneous rare earth catalyst was [ CHO]/[Nd]=600/1, yield of polymer 89.76%, number average molecular weight of polybutadiene block in copolymer M n ＝5.31×10 3 Molecular weight distribution of M w /M n =1.49, number average molecular weight of copolymer, M n ＝9.77×10 3 Molecular weight distribution index of M w /M n =1.68. By passing 1 The molar ratio of polybutadiene blocks to poly (cyclohexene oxide) blocks in the copolymer was 1/1.37 as calculated by H NMR. The glass transition temperature (T) of the butadiene block was measured by DSC g ) It was-102.3 ℃ and the glass transition temperature of the copolymer was 41.6 ℃.
Example 9
Other conditions and preparation were all the same as described in example 6Meanwhile, the molar ratio of the polar monomer to the catalytic system is changed only during polymerization, and the molar ratio of the cyclohexene oxide to neodymium octyldecanoate in the homogeneous rare earth catalyst is [ CHO [ ]]/[Nd]=800/1, the yield of the polymer obtained is 76.29%, and the number-average molecular weight of the polybutadiene block in the copolymer is M n ＝5.19×10 3 Molecular weight distribution of M w /M n =1.53, number average molecular weight of copolymer, M n ＝9.74×10 3 Molecular weight distribution index of M w /M n =1.76. By passing 1 The molar ratio of polybutadiene blocks to poly (cyclohexene oxide) blocks in the copolymer was 1/1.42 as calculated by H NMR. The glass transition temperature (T) of the butadiene block was measured by DSC g ) It was-100.1 ℃ and the glass transition temperature of the copolymer was 39.62 ℃.
Comparative example 4
As described in example 6, the other conditions and preparation methods were identical, and the molar ratio of the polar monomer to the catalytic system was changed only during the polymerization, and the molar ratio of cyclohexene oxide to neodymium octyldecanoate in the homogeneous rare earth catalyst was [ CHO ]]/[Nd]=50/1, yield of polymer obtained 92.46%, number average molecular weight of polybutadiene block in copolymer is M n ＝4.98×10 3 Molecular weight distribution of M w /M n =1.49, number average molecular weight of copolymer M n ＝7.21×10 3 Molecular weight distribution index of M w /M n =1.98. By passing 1 H NMR calculated as the molar ratio of polybutadiene blocks to poly (cyclohexene oxide) blocks in the copolymer was 1/0.11. The glass transition temperature (T) of the butadiene block was measured by DSC g ) At-101.5 deg.C, very low polar segment content and no T g 。
Comparative example 5
As described in example 6, the other conditions and preparation methods were identical, and the molar ratio of the polar monomer to the catalytic system was changed only during the polymerization, and the molar ratio of cyclohexene oxide to neodymium octyldecanoate in the homogeneous rare earth catalyst was [ CHO ]]/[Nd]=100/1, yield of polymer obtained is 93.25%, number average molecular weight of polybutadiene block in copolymer is M n ＝5.17×10 3 Molecular weight distribution of M w /M n =1.43, number average molecule of copolymerAn amount of M n ＝9.25×10 3 Molecular weight distribution index of M w /M n =1.95. By passing 1 H NMR calculated molar ratio of polybutadiene block to poly (cyclohexene oxide) block in the copolymer was 1/0.15. The glass transition temperature (T) of the butadiene block was measured by DSC g ) At-102.7 deg.C, very low polar segment content and no T g 。
Comparative example 6
As described in example 6, the other conditions and preparation methods were identical, and the molar ratio of the polar monomer to the catalytic system was changed only during the polymerization, and the molar ratio of cyclohexene oxide to neodymium octyldecanoate in the homogeneous rare earth catalyst was [ CHO ]]/[Nd]=1000/1, yield of polymer obtained was 90.15%, number average molecular weight of polybutadiene block in copolymer was M n ＝5.23×10 3 Molecular weight distribution of M w /M n =1.50, number average molecular weight of copolymer, M n ＝10.12×10 3 Molecular weight distribution index of M w /M n =2.12. By passing 1 H NMR calculated molar ratio of polybutadiene block to poly (cyclohexene oxide) block in the copolymer was 1/1.19. The glass transition temperature (T) of the butadiene block was measured by DSC g ) It was-97.58 ℃ and the glass transition temperature of the copolymer was 38.26 ℃.
As can be seen from examples 6-9 and comparative examples 4-6, by changing the molar ratio of the epoxy monomer to neodymium octyldecanoate in the catalyst system, the lengths of the nonpolar segment and the polar segment in the block copolymer can be adjusted, and the molecular weight, distribution and surface energy (polarity) of the copolymer can be further influenced. When the molar ratio of the epoxy compound monomer to neodymium octyldecanoate in the homogeneous rare earth catalyst is [ TMC ]/[ Nd ] =50/1 and 100/1, and the content of the epoxy compound monomer is too low, the access rate of the second section in the block copolymer is very small, so that the influence on the related performance of the copolymer is small; when the molar ratio of the epoxy monomer to neodymium octyldecanoate in the homogeneous rare earth catalyst is [ TMC ]/[ Nd ] =1000/1, the molecular weight distribution and the surface energy of the block copolymer are directly influenced along with the degradation of the epoxy monomer.
Example 10
Neodymium octyldecanoate (Nd), isoprene (IP), diisobutylaluminum hydride (Al) and dichlorodimethylsilane (Cl) are sequentially added into a 10mL catalyst reaction bottle which is vacuumized, baked and filled with nitrogen for reaction in a constant-temperature water bath at 50 ℃ for 60min to obtain a homogeneous rare earth catalyst, wherein the molar ratio of [ Nd ]/[ IP ] [ Al ]/[ Cl ] in the catalyst is 1/10/40/3.
Sequentially adding toluene, butadiene and the homogeneous rare earth catalyst into a 40mL ampoule bottle which is subjected to vacuumizing, baking and drying and is filled with nitrogen for treatment, wherein the concentration of the butadiene is 1.85mol/L, the molar ratio of [ BD ]/[ Nd ] of neodymium octyldecanoate in the butadiene and rare earth catalyst is 500/1, polymerizing in a constant-temperature water bath at 50 ℃, and performing polymerization reaction for 4 hours to obtain a solution A;
adding epoxy Cyclohexane (CHO) monomer into the solution A, wherein the molar ratio of epoxy cyclohexane to neodymium octyldecanoate in a rare earth catalyst is [ CHO ]/[ Nd ] =200/1, after the polymerization reaction is carried out for 1h at 50 ℃, adding ethanol solution and dilute hydrochloric acid to terminate the polymerization reaction, introducing the reaction solution into ethanol for settling, and washing by using the ethanol to obtain a white product of the conjugated diene and polar monomer block copolymer; the white product was dried in a vacuum oven for 48 hours to obtain a dried block copolymer of a conjugated diene and a polar monomer.
The yield of the polymer obtained was 81.93% and the number average molecular weight of the polybutadiene block in the copolymer was M n ＝4.07×10 3 Molecular weight distribution of M w /M n =1.62, number average molecular weight of copolymer, M n ＝7.35×10 3 Molecular weight distribution index of M w /M n =1.79. By passing 1 H NMR calculated as the molar ratio of polybutadiene blocks to poly (cyclohexene oxide) blocks in the copolymer was 1/0.69. The glass transition temperature (T) of the butadiene block was measured by DSC g ) At-101.5 deg.C, very low polar segment content and no T g 。
Example 11
As described in example 10, the other conditions and preparation methods were identical, and the molar ratio of the polar monomer to the catalytic system was changed only during the polymerization, and the molar ratio of cyclohexene oxide to neodymium octyldecanoate in the homogeneous rare earth catalyst was [ CHO ]]/[Nd]=500/1, yield of obtained polymer 93.13%, poly in copolymerThe number average molecular weight of the butadiene block is M n ＝3.99×10 3 Molecular weight distribution of M w /M n =1.56, number average molecular weight of copolymer, M n ＝8.02×10 3 Molecular weight distribution index of M w /M n =1.49. By passing 1 H NMR calculated as the molar ratio of polybutadiene blocks to poly (cyclohexene oxide) blocks in the copolymer was 1/0.94. The glass transition temperature (T) of the butadiene block was measured by DSC g ) It was-99.27 ℃ and the glass transition temperature of the copolymer was 39.63 ℃.
Example 12
As described in example 10, the other conditions and preparation methods were identical, and the molar ratio of the polar monomer to the catalytic system was changed only during the polymerization, and the molar ratio of cyclohexene oxide to neodymium octyldecanoate in the homogeneous rare earth catalyst was [ CHO ]]/[Nd]=600/1, yield of polymer obtained is 80.85%, number average molecular weight of polybutadiene block in copolymer is M n ＝4.61×10 3 Molecular weight distribution of M w /M n =1.58, number average molecular weight of copolymer, M n ＝7.24×10 3 Molecular weight distribution index of M w /M n =1.55. By passing 1 H NMR calculated molar ratio of polybutadiene block to poly (cyclohexene oxide) block in the copolymer was 1/1.29. The glass transition temperature (T) of the butadiene block was measured by DSC g ) At-102.7 ℃ and a glass transition temperature of 40.88 ℃.
Example 13
As described in example 10, the other conditions and preparation methods were identical, and the molar ratio of the polar monomer to the catalytic system was changed only during the polymerization, and the molar ratio of cyclohexene oxide to neodymium octyldecanoate in the homogeneous rare earth catalyst was [ CHO ]]/[Nd]=800/1, yield of polymer was 84.33%, number average molecular weight of polybutadiene block in copolymer was M n ＝4.29×10 3 Molecular weight distribution of M w /M n =1.63, number average molecular weight of copolymer, M n ＝7.68×10 3 Molecular weight distribution index of M w /M n =1.70. By passing 1 H NMR calculation of the moles of polybutadiene blocks and poly (cyclohexene oxide) blocks in the copolymerThe ratio was 1/1.44. The glass transition temperature (T) of the butadiene block was measured by DSC g ) At-101.6 ℃ and a glass transition temperature of 41.20 ℃.
Comparative example 7
As described in example 10, the other conditions and the preparation process were identical, the molar ratio of the polar monomer to the catalytic system was varied only during the polymerization, the molar ratio of cyclohexene oxide to neodymium octyldecanoate in the homogeneous rare earth catalyst was [ CHO]/[Nd]=50/1, the yield of the polymer obtained is 98.03%, and the number average molecular weight of the polybutadiene block in the copolymer is M n ＝3.85×10 3 Molecular weight distribution of M w /M n =1.60, number average molecular weight of copolymer is M n ＝7.94×10 3 Molecular weight distribution index of M w /M n =1.47. By passing 1 The molar ratio of polybutadiene blocks to poly (cyclohexene oxide) blocks in the copolymer was 1/0.09 by H NMR calculation. The glass transition temperature (T) of the butadiene block was measured by DSC g ) At-102.3 deg.C, very low polar segment content and no T g 。
Comparative example 8
As described in example 10, the other conditions and preparation methods were identical, and the molar ratio of the polar monomer to the catalytic system was changed only during the polymerization, and the molar ratio of cyclohexene oxide to neodymium octyldecanoate in the homogeneous rare earth catalyst was [ CHO ]]/[Nd]=100/1, yield of polymer 89.35%, number average molecular weight of polybutadiene block in copolymer M n ＝3.76×10 3 Molecular weight distribution of M w /M n =1.59, number average molecular weight of copolymer, M n ＝6.43×10 3 Molecular weight distribution index of M w /M n =1.51. By passing 1 H NMR calculated molar ratio of polybutadiene block to poly (cyclohexene oxide) block in the copolymer was 1/0.17. The glass transition temperature (T) of the butadiene block was measured by DSC g ) At-101.8 deg.C, very low polar segment content and no T g 。
Comparative example 9
As described in example 10, the other conditions and the preparation process were exactly the same, the molar ratio of polar monomer to catalytic system was varied only during the polymerization, cyclohexene oxideThe molar ratio of the rare earth metal and the neodymium octyldecanoate in the homogeneous rare earth catalyst is [ CHO]/[Nd]=1000/1, the yield of the polymer obtained is 90.26%, and the number average molecular weight of the polybutadiene block in the copolymer is M n ＝4.14×10 3 Molecular weight distribution of M w /M n =1.61, number average molecular weight of copolymer, M n ＝8.35×10 3 Molecular weight distribution index of M w /M n =1.51. By passing 1 H NMR calculated molar ratio of polybutadiene block to poly (cyclohexene oxide) block in the copolymer was 1/1.28. The glass transition temperature (T) of the butadiene block was measured by DSC g ) At-98.27 ℃ and a glass transition temperature of 38.44 ℃.
As can be seen from examples 10-13 and comparative examples 7-9, by changing the molar ratio of the epoxy compound monomer to neodymium octyldecanoate in the catalyst system, the lengths of the nonpolar segment and the polar segment in the block copolymer can be adjusted, and the molecular weight, distribution and surface energy (polarity) of the copolymer can be further influenced. When the molar ratio of the epoxy compound monomer to neodymium octyldecanoate in the homogeneous rare earth catalyst is [ TMC ]/[ Nd ] =50/1 and 100/1, and the content of the epoxy compound monomer is too low, the access rate of the second section in the block copolymer is very small, so that the influence on the related performance of the copolymer is small; when the molar ratio of the epoxy compound monomer to neodymium octyldecanoate in the homogeneous rare earth catalyst is [ TMC ]/[ Nd ] =1000/1, the molecular weight distribution and the surface energy of the block copolymer can be directly influenced along with the degradation of the epoxy compound monomer.
Comparative example 10
In a 10mL catalyst reaction flask which was evacuated and baked and then charged with nitrogen gas, neodymium isopropoxide (Nd) was added in this order i OPr) 3 ) Isoprene (IP), diisobutylaluminum hydride (Al) and dichlorodimethylsilane (Cl) react in a constant-temperature water bath at 50 ℃ for 60min to obtain a homogeneous rare earth catalyst in which [ Nd ] is]/[IP][Al]/[Cl]Is 1/10/20/3.
A block copolymer was synthesized according to the reaction conditions and procedure of example 3, except that neodymium octyldecanoate in the catalyst used was replaced with neodymium isopropoxide (Nd: (R)) i OPr) 3 ) The yield of the obtained polymer was 90.42% based on the copolymerThe number average molecular weight of the polybutadiene block is M n ＝16.4×10 3 Molecular weight distribution of M w /M n =1.85, number average molecular weight of copolymer is M n ＝20.7×10 3 Molecular weight distribution index of M w /M n =4.02. By passing 1 The molar ratio of polybutadiene blocks to poly (cyclohexene oxide) blocks in the copolymer was 3.2 as calculated by H-NMR.
From example 3 and comparative example 10 it can be seen that: when the rare earth compound is neodymium isopropoxide (Nd (Nd) (r)) i OPr) 3 ) The number average molecular weight of the polybutadiene obtained is large and the molecular weight distribution is broad, which also directly affects the molecular weight distribution of the block copolymer and the proportion of polar, non-polar segments in the copolymer.
In summary, examples 1 to 5, 6 to 9, and 10 to 13 show three sets of catalyst preparation ratios, namely, [ Nd ]/[ IP ] [ Al ]/[ Cl ] =1/10/20/3, [ Nd ]/[ IP ] [ Al ]/[ Cl ] =1/10/30/3, [ Nd ]/[ IP ] [ Al ]/[ Cl ] =1/10/40/3, and the ratio of butadiene to cyclohexene oxide was changed during the catalytic polymerization for each set of catalyst system, respectively, and the influence of different monomer addition amounts on the copolymer was investigated. In general, the change of the proportion of the catalytic system has little influence on the block copolymer, and the decisive role for the molecular weight, the distribution and the glass transition temperature of the copolymer is the molar ratio of the conjugated diene to the epoxy compound in the reaction process, and meanwhile, the selection of the neodymium compound in the catalyst also has certain influence on the molecular weight and the molecular weight distribution.

Claims (9)

1. A method for preparing a block copolymer of conjugated diene and epoxy compound monomer is characterized by comprising the following steps:
the method comprises the following steps: reacting a reaction monomer with a solvent under the action of a catalyst to obtain a solution A;
the reaction monomer is butadiene, isoprene or piperylene;
the catalyst comprises neodymium octyldecanoate, isoprene, diisobutylaluminum hydride and dichlorodimethylsilane;
step two: adding an epoxy compound monomer into the solution A to react to obtain a reaction solution B;
step three: and adding an ethanol solution into the solution B, and settling to obtain the block copolymer of the conjugated diene and the epoxy compound monomer.
2. The method for preparing a block copolymer of conjugated diene and epoxy monomer according to claim 1, wherein the molar ratio of neodymium octyldecanoate in the reaction monomer and the catalyst in the first step is 500.
3. The method for preparing a block copolymer of conjugated diene and epoxy monomer as claimed in claim 1, wherein the reaction temperature of the first step is 20-60 ℃ and the reaction time is 3-5 h.
4. The method of claim 1, wherein the step of preparing the catalyst comprises: neodymium octyldecanoate, isoprene, diisobutylaluminum hydride and dichlorodimethylsilane are mixed and react for 15 to 60 minutes at the temperature of between 20 and 60 ℃ to obtain the catalyst.
5. The method for preparing a block copolymer of conjugated diene and epoxy monomer according to claim 1, wherein the molar ratio of neodymium octyldecanoate, isoprene, diisobutylaluminum hydride and dichlorodimethylsilane is 1.
6. The method according to claim 1, wherein the molar ratio of the epoxy compound monomer in the second step to neodymium octyldecanoate in the catalyst is 200 to 800.
7. The method according to claim 1, wherein the epoxy monomer in the second step is cyclohexene oxide, epichlorohydrin, ethylene oxide or propylene oxide.
8. The method for preparing a block copolymer of conjugated diene and epoxy monomer as claimed in claim 1, wherein the reaction temperature of step two is 20-60 ℃ and the reaction time is 1-3 h.
9. The method of claim 1, wherein the third step further comprises adding an ethanol solution of hydrochloric acid to the solution B.
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