阅读说明：本技术 一种共轭二烯与极性烯烃单体共聚物的可控制备方法 (Controllable preparation method of conjugated diene and polar olefin monomer copolymer ) 是由 王庆刚 朱广乾 王亮 周丽 匡佳 于 2020-12-31 设计创作，主要内容包括：一种共轭二烯与极性烯烃单体共聚物的可控制备方法。本发明属于自由基聚合领域。本发明为解决现有传统共轭二烯与极性单体的共聚方法工艺复杂难控制,产物分离繁杂以及所得聚合产物分子量小、分子量分布宽、有乳化剂残留和微观结构调控困难的技术问题。本发明的制备方法：在氩气氛围下,将自由基引发剂、极性烯烃单体、共轭二烯和溶剂按任意顺序加至反应体系中,形成均相溶液,于50～100℃聚合反应2h～48h,得到共轭二烯与极性烯烃单体共聚物；所述自由基引发剂为偶氮类自由基引发剂或过氧类自由基引发剂。本发明方法聚合工艺简单,普适性强,可实现多种共轭二烯与极性单体的任意共聚,所得的聚合物分子量较高,分子量分布较窄,无其他杂质残留。(A controllable preparation method of a conjugated diene and polar olefin monomer copolymer. The present invention belongs to the field of free radical polymerization. The invention aims to solve the technical problems that the conventional copolymerization method of the conjugated diene and the polar monomer is complex in process and difficult to control, the product is complicated to separate, and the obtained polymerization product has small molecular weight, wide molecular weight distribution, residual emulsifier and difficult microstructure regulation. The preparation method comprises the following steps: adding a free radical initiator, a polar olefin monomer, conjugated diene and a solvent into a reaction system in any order under an argon atmosphere to form a homogeneous solution, and carrying out polymerization reaction for 2-48 h at 50-100 ℃ to obtain a conjugated diene and polar olefin monomer copolymer; the free radical initiator is an azo free radical initiator or a peroxy free radical initiator. The method has simple polymerization process and strong universality, can realize the random copolymerization of various conjugated dienes and polar monomers, and the obtained polymer has higher molecular weight, narrower molecular weight distribution and no other impurity residues.)

1. A controllable preparation method of a conjugated diene and polar olefin monomer copolymer is characterized by comprising the following steps:

adding a free radical initiator, a polar olefin monomer, conjugated diene and a solvent into a reaction system in any order under an argon atmosphere to form a homogeneous solution, and carrying out polymerization reaction for 2-48 h at 50-100 ℃ to obtain a conjugated diene and polar olefin monomer copolymer; the free radical initiator is an azo free radical initiator or a peroxy free radical initiator.

2. The controllable preparation method of the conjugated diene and polar olefin monomer copolymer according to claim 1, wherein the polar olefin monomer is methyl methacrylate, methyl acrylate, tert-butyl acrylate, acrylonitrile or ethyl sorbate.

3. The controllable preparation method of the conjugated diene and polar olefin monomer copolymer according to claim 1, wherein the conjugated diene is isoprene, butadiene, β -myrcene or β -farnesene.

4. The controllable preparation method of the conjugated diene and polar olefin monomer copolymer according to claim 1, wherein the solvent is one or more of toluene, ethylbenzene, xylene, chlorobenzene, trifluorotoluene, hexane and cyclohexane.

5. The method of claim 1, wherein the azo radical initiator is azobisisobutyronitrile, and the peroxy radical initiator is dibenzoyl peroxide.

6. The controllable preparation method of the conjugated diene and polar olefin monomer copolymer according to claim 1, wherein the molar ratio of the conjugated diene to the polar olefin monomer is (1-9): (9-1).

7. The controllable preparation method of the conjugated diene/polar olefin monomer copolymer according to claim 1, wherein the molar ratio of the conjugated diene to the radical initiator is (100-10000): 1.

8. the controllable preparation method of the conjugated diene and polar olefin monomer copolymer according to claim 1, wherein the ratio of the total volume of the conjugated diene and polar olefin monomer to the volume of the solvent is (1-5): (5-1).

9. The process of claim 1, wherein the addition sequence is one of four: adding a free radical initiator and a solvent in sequence, and adding a polar olefin monomer and conjugated diene after completely dissolving; adding polar olefin monomer, conjugated diene and solvent in sequence, mixing uniformly, and then adding a free radical initiator; adding polar olefin monomer, free radical initiator and solvent successively and adding conjugated diene; and fourthly, adding the conjugated diene, the free radical initiator and the solvent in sequence, and then adding the polar olefin monomer.

10. The controllable preparation method of the conjugated diene and polar olefin monomer copolymer as claimed in claim 1, wherein the obtained conjugated diene and polar olefin monomer copolymer is elastomer or jelly with number average molecular weight M_n10000 g/mol-200000 g/mol, 1.5-3.0 molecular weight distribution PDI, 15% -45% polar monomer insertion rate.

Technical Field

The invention belongs to the field of free radical polymerization, and particularly relates to a controllable preparation method of a conjugated diene and polar olefin monomer copolymer.

Background

The polymer obtained by polymerizing the conjugated diene as the monomer is one of the main materials of synthetic rubber, and is widely applied to the fields of aviation, automobile tires, medical treatment and health and daily life according to the characteristics of excellent stereoselectivity, mechanical property, thermal stability, processability and the like. However, the polyolefin obtained has poor printability and poor compatibility with other materials due to the non-polar chain, which results in a greatly limited range of applications of the poly-conjugated diene material. The introduction of polar groups or polar polymer chains well solves the problem, improves the surface wettability, the colorability, the oil resistance, the heat resistance, the adhesion and the like of the material, and improves the compatibility of the poly-conjugated diene and other high polymer materials and the vulcanization property of rubber.

The traditional method for copolymerizing the conjugated diene and the polar monomer is to functionalize the side chain or the end group of the poly-conjugated diene, and the method is difficult to control the degree of functionalization, so that the microstructure of the polymer is difficult to regulate and control; examples of copolymerization of conjugated diene and polar monomer by coordination polymerization have been developed, but the conditions are harsh, and the problems of poisoning effect of the polar monomer on the metal complex and catalyst cost limit large-scale industrial application thereof; in comparison, free radical polymerization has good universality on conjugated dienes and polar monomers, and various copolymerization applications are realized in a free radical emulsion polymerization mode, but emulsion polymerization generally needs to form emulsion by the aid of a monomer through an emulsifier, and then a polymerization reaction is initiated through an initiator, so that the defects that a polymerization process is complex and difficult to control, a product separation and precipitation process is complicated and the like exist, and the performance of the product is influenced by the problems of small molecular weight, wide molecular weight distribution, residual emulsifier and the like of the obtained product.

Disclosure of Invention

The invention provides a controllable preparation method of a conjugated diene and polar olefin monomer copolymer, aiming at solving the technical problems of complex and difficult control of the conventional copolymerization method of the conjugated diene and the polar monomer, complex product separation, small molecular weight of the obtained polymerization product, wide molecular weight distribution, residual emulsifier and difficult microstructure regulation.

The controllable preparation method of the conjugated diene and polar olefin monomer copolymer is carried out according to the following steps:

adding a free radical initiator, a polar olefin monomer, conjugated diene and a solvent into a reaction system in any order under an argon atmosphere to form a homogeneous solution, and carrying out polymerization reaction for 2-48 h at 50-100 ℃ to obtain a conjugated diene and polar olefin monomer copolymer; the free radical initiator is an azo free radical initiator or a peroxy free radical initiator.

Further defined, the polar olefin monomer is methyl methacrylate, methyl acrylate, t-butyl acrylate, acrylonitrile, or ethyl sorbate.

Further defined, the conjugated diene is isoprene, butadiene, beta-myrcene, or beta-farnesene.

Further limiting, the solvent is one or a mixture of several of toluene, ethylbenzene, xylene, chlorobenzene, trifluorotoluene, hexane and cyclohexane in any ratio.

Further, the azo-based radical initiator is azobisisobutyronitrile.

Further defined, the peroxy-based free radical initiator is dibenzoyl peroxide.

Further defined, the mole ratio of the conjugated diene to the polar olefin monomer is (1-9): (9-1).

Further defined, the conjugated diene to polar olefin monomer molar ratio is 1: 1.

Further defined, the molar ratio of the conjugated diene to the radical initiator is (100 to 10000): 1.

further defined, the conjugated diene to free radical initiator molar ratio is 200: 1.

further defined, the ratio of the total volume of the conjugated diene and the polar olefin monomer to the volume of the solvent is (1-5): (5-1).

Further defined, the ratio of the total volume of conjugated diene and polar olefin monomers to the volume of solvent is 2: 1.

further limiting, the polymerization reaction is carried out for 24 hours at 70 ℃.

Further limiting, the feeding sequence is one of four: adding a free radical initiator and a solvent in sequence, and adding a polar olefin monomer and conjugated diene after completely dissolving; adding polar olefin monomer, conjugated diene and solvent in sequence, mixing uniformly, and then adding a free radical initiator; adding polar olefin monomer, free radical initiator and solvent successively and adding conjugated diene; and fourthly, adding the conjugated diene, the free radical initiator and the solvent in sequence, and then adding the polar olefin monomer.

Further defined, the resulting copolymer of conjugated diene and polar olefin monomer is an elastomer or gum having a number average molecular weight M_n10000 g/mol-200000 g/mol, molecular weight distribution PDI is 1.5-3.0, and insertion rate of polar monomer is 15% -45%.

Compared with the prior art, the invention has the following remarkable effects:

1) the free radical copolymerization of the conjugated diene and the polar monomer adopts a simple solution polymerization method, compared with an industrial common emulsion polymerization method, the method has the advantages of cheap and easily-obtained catalyst, simple polymerization process and strong universality, can realize the random copolymerization of various conjugated dienes and polar monomers, and can be used for preparing copolymers with different polar monomer contents by using monomers with different proportions. Provides a feasible industrial application way for preparing copolymer materials with different properties.

2) The polymer obtained by the invention has higher molecular weight, narrower molecular weight distribution and no other impurity residue.

Drawings

FIG. 1 is a diagram of a copolymer rubber prepared by free radical solution polymerization of AIBN-toluene system of example 1¹H NMR(,400MHz,CDCl₃298K) spectrum;

FIG. 2 is a diagram of a copolymer rubber prepared by free radical solution polymerization of AIBN-toluene system of example 1¹³C NMR(100MHz,CDCl₃298K) spectrum;

FIG. 3 is a GPC chart of a copolymer rubber prepared by free radical solution polymerization of AIBN-toluene system of example 1.

Detailed Description

Example 1: the controllable preparation method of the conjugated diene and polar olefin monomer copolymer of the embodiment is carried out according to the following steps:

under argon atmosphere, azodiisobutyronitrile (AIBN,3.7mg,23 mu mol,1equiv.) and 2.2mL of toluene solution are sequentially added into a 50mL reaction bottle, methyl acrylate (2.1mL,23mmol,1000equiv.) and isoprene (2.3mL,23mmol,1000equiv.) are added to form a homogeneous solution, the homogeneous solution is polymerized for 24 hours at 70 ℃, quenched by cold methanol, a polymer is separated out, washed twice by methanol and dried in vacuum to constant weight, and a colloidal polymer, namely a conjugated diene and polar olefin monomer copolymer, is obtained.

As a result: the yield was 71%. Characterized therein by NMR: the 1, 4-selectivity content of the polyisoprene chain segment was 96%, and the 3, 4-selectivity content was 4%. The content of polar monomer methyl acrylate is 39 percent; and (3) GPC characterization: m_nIt was 51036g/mol, and the molecular weight distribution PDI was 1.9.

TABLE 1 molecular weight information Table

Peak	Mp(g/mol)	Mn(g/mol)	Mw(g/mol)	Mz(g/mol)	Mz+1(g/mol)	Mv(g/mol)	PD
								Peak1	76922	51036	94991	165328	265122	153004	1.861

Example 2: the controllable preparation method of the conjugated diene and polar olefin monomer copolymer of the embodiment is carried out according to the following steps:

under argon atmosphere, azodiisobutyronitrile (AIBN,3.7mg,23 mu mol,1equiv.) and 4.4mL of toluene solution are sequentially added into a 50mL reaction bottle, methyl acrylate (2.1mL,23mmol,1000equiv.) and isoprene (2.3mL,23mmol,1000equiv.) are added to form a homogeneous solution, the homogeneous solution is polymerized for 24 hours at 70 ℃, quenched by cold methanol, a polymer is separated out, washed twice by methanol and dried in vacuum to constant weight, and a colloidal polymer, namely a conjugated diene and polar olefin monomer copolymer, is obtained.

As a result: the yield was 62%. Characterized therein by NMR: the 1, 4-selectivity content of the polyisoprene chain segment was 96%, and the 3, 4-selectivity content was 4%. The polar monomer methyl acrylate content is 38%; and (3) GPC characterization: m_n36910g/mol and a molecular weight distribution PDI of 1.6.

Example 3: the controllable preparation method of the conjugated diene and polar olefin monomer copolymer of the embodiment is carried out according to the following steps:

under argon atmosphere, azodiisobutyronitrile (AIBN,3.7mg,23 mu mol,1equiv.) and 22mL of toluene solution are sequentially added into a 50mL reaction bottle, methyl acrylate (2.1mL,23mmol,1000equiv.) and isoprene (2.3mL,23mmol,1000equiv.) are added to form a homogeneous solution, the homogeneous solution is polymerized for 24 hours at 70 ℃, quenched by cold methanol, the polymer is separated out, washed twice by methanol and dried in vacuum to constant weight, and the colloidal polymer, namely the conjugated diene and polar olefin monomer copolymer, is obtained.

As a result: the yield was 53%. Characterized therein by NMR: the 1, 4-selectivity content of the polyisoprene chain segment was 95%, and the 3, 4-selectivity content was 5%. The polar monomer methyl acrylate content is 38%; and (3) GPC characterization: m_nIt was 19820g/mol, and the molecular weight distribution PDI was 1.6.

Example 4: the controllable preparation method of the conjugated diene and polar olefin monomer copolymer of the embodiment is carried out according to the following steps:

under argon atmosphere, azodiisobutyronitrile (AIBN,1.5mg,9.2 mu mol,1equiv.) and 2.2mL of toluene solution are sequentially added into a 50mL reaction bottle, methyl acrylate (4.2mL,46mmol,5000equiv.) and isoprene (4.6mL,46mmol,5000equiv.) are added to form a homogeneous solution, the homogeneous solution is polymerized for 24 hours at 70 ℃, quenched by cold methanol, the polymer is separated out, washed twice by methanol and dried in vacuum to constant weight, and the colloidal polymer, namely the conjugated diene and polar olefin monomer copolymer, is obtained.

As a result: the yield was 50%. Characterized therein by NMR: the 1, 4-selectivity content of the polyisoprene chain segment was 96%, and the 3, 4-selectivity content was 4%. The polar monomer methyl acrylate content is 38%; and (3) GPC characterization: m_n47900g/mol, molecular weight distribution PDI 1.9.

Example 5: the controllable preparation method of the conjugated diene and polar olefin monomer copolymer of the embodiment is carried out according to the following steps:

under argon atmosphere, azodiisobutyronitrile (AIBN,14.8mg,92 mu mol,1equiv.) and 2.2mL of toluene solution are sequentially added into a 50mL reaction bottle, methyl acrylate (2.1mL,23mmol,250equiv.) and isoprene (2.3mL,23mmol,250equiv.) are added to form a homogeneous solution, the homogeneous solution is polymerized for 24 hours at 70 ℃, quenched by cold methanol, a polymer is separated out, washed twice by methanol and dried in vacuum to constant weight, and a colloidal polymer, namely a conjugated diene and polar olefin monomer copolymer, is obtained.

As a result: the yield was 61%. Characterized therein by NMR: the 1, 4-selectivity content of the polyisoprene chain segment was 95%, and the 3, 4-selectivity content was 5%. The polar monomer methyl acrylate content is 38%; and (3) GPC characterization: m_nIt was 29440g/mol, and the molecular weight distribution PDI was 1.6.

Example 6: the controllable preparation method of the conjugated diene and polar olefin monomer copolymer of the embodiment is carried out according to the following steps:

under argon atmosphere, azodiisobutyronitrile (AIBN,37.0mg,230 mu mol,1equiv.) and 2.2mL of toluene solution are sequentially added into a 50mL reaction bottle, methyl acrylate (2.1mL,23mmol,100equiv.) and isoprene (2.3mL,23mmol,100equiv.) are added to form a homogeneous solution, the homogeneous solution is polymerized for 24 hours at 70 ℃, quenched by cold methanol, a polymer is separated out, washed twice by methanol and dried in vacuum to constant weight, and a colloidal polymer, namely a conjugated diene and polar olefin monomer copolymer, is obtained.

As a result: the yield was 72%. Characterized therein by NMR: the 1, 4-selectivity content of the polyisoprene chain segment was 96%, and the 3, 4-selectivity content was 4%. The content of polar monomer methyl acrylate is 37 percent; and (3) GPC characterization: m_n17930g/mol, molecular weight distribution PDI 1.8.

Example 7: the controllable preparation method of the conjugated diene and polar olefin monomer copolymer of the embodiment is carried out according to the following steps:

under argon atmosphere, azodiisobutyronitrile (AIBN,37.0mg,230 mu mol,1equiv.) and 2.3mL of toluene solution are sequentially added into a 50mL reaction bottle, methyl acrylate (0.8mL,9mmol,39equiv.) and isoprene (3.7mL,37mmol,161equiv.) are added to form a homogeneous solution, the homogeneous solution is polymerized for 24 hours at 70 ℃, quenched by cold methanol, a polymer is separated out, washed twice by methanol and dried in vacuum to constant weight, and a colloidal polymer, namely a conjugated diene and polar olefin monomer copolymer, is obtained.

As a result: the yield was 51%. Characterized therein by NMR: the 1, 4-selectivity content of the polyisoprene chain segment was 96%, and the 3, 4-selectivity content was 4%. The content of polar monomer methyl acrylate is 39 percent; and (3) GPC characterization: m_n36210g/mol, the molecular weight distribution PDI is 1.7.

Example 8: the controllable preparation method of the conjugated diene and polar olefin monomer copolymer of the embodiment is carried out according to the following steps:

under argon atmosphere, azodiisobutyronitrile (AIBN,37.0mg,230 mu mol,1equiv.) and 2.3mL of toluene solution are sequentially added into a 50mL reaction bottle, methyl acrylate (3.4mL,37mmol,161equiv.) and isoprene (0.9mL,9mmol,39equiv.) are added to form a homogeneous solution, the homogeneous solution is polymerized for 24 hours at 70 ℃, quenched by cold methanol, a polymer is separated out, washed twice by methanol and dried in vacuum to constant weight, and a colloidal polymer, namely a conjugated diene and polar olefin monomer copolymer, is obtained.

As a result: yield of>99 percent. Characterized therein by NMR: the 1, 4-selectivity content of the polyisoprene block was 94%, and the 3, 4-selectivity content was 6%. The content of polar monomer methyl acrylate is 79 percent; and (3) GPC characterization: m_nIt was 183620g/mol, and the molecular weight distribution PDI was 2.3.

Example 9: the controllable preparation method of the conjugated diene and polar olefin monomer copolymer of the embodiment is carried out according to the following steps:

under argon atmosphere, in a 50mL reaction bottle, adding dibenzoyl peroxide (BPO,56mg, 230. mu. mol,1equiv.) and 2.2mL of toluene solution in sequence, adding methyl acrylate (2.1mL,23mmol,100equiv.) and isoprene (2.3mL,23mmol,100equiv.) to form a homogeneous solution, carrying out polymerization reaction at 70 ℃ for 24h, quenching with cold methanol, separating out a polymer, washing with methanol twice, and drying in vacuum to constant weight to obtain a colloidal polymer, namely a conjugated diene and polar olefin monomer copolymer.

As a result: the yield was 51%. Characterized therein by NMR: the 1, 4-selectivity content of the polyisoprene chain segment was 95%, and the 3, 4-selectivity content was 5%. The content of polar monomer methyl acrylate is 40 percent; and (3) GPC characterization: m_n30130g/mol, the molecular weight distribution PDI is 1.6.

Example 10: the controllable preparation method of the conjugated diene and polar olefin monomer copolymer of the embodiment is carried out according to the following steps:

under argon atmosphere, azodiisobutyronitrile (AIBN,37.0mg,230 mu mol,1equiv.) and 2.8mL of toluene solution are sequentially added into a 50mL reaction bottle, tert-butyl acrylate (3.3mL,23mmol,100equiv.) and isoprene (2.3mL,23mmol,100equiv.) are added to form a homogeneous solution, the homogeneous solution is polymerized for 24 hours at 70 ℃, quenched by cold methanol, a polymer is separated out, washed twice by methanol and dried in vacuum to constant weight, and a colloidal polymer, namely a conjugated diene and polar olefin monomer copolymer, is obtained.

As a result: the yield was 69%. Characterized therein by NMR: the 1, 4-selectivity content of the polyisoprene chain segment was 95%, and the 3, 4-selectivity content was 5%. The content of polar monomer tert-butyl acrylate is 37 percent; and (3) GPC characterization: m_n16710g/mol, molecular weight distribution PDI 1.9.

Example 11: the controllable preparation method of the conjugated diene and polar olefin monomer copolymer of the embodiment is carried out according to the following steps:

under argon atmosphere, azodiisobutyronitrile (AIBN,37.0mg,230 mu mol,1equiv.) and 1.9mL of toluene solution are sequentially added into a 50mL reaction bottle, then acrylonitrile (1.5mL,23mmol,100equiv.) and isoprene (2.3mL,23mmol,100equiv.) are added to form a homogeneous solution, the homogeneous solution is polymerized for 24 hours at 70 ℃, quenched by cold methanol, the polymer is separated out, washed twice by methanol and dried in vacuum to constant weight, and the colloidal polymer, namely the conjugated diene and polar olefin monomer copolymer, is obtained.

As a result: the yield was 64%. Characterized therein by NMR: the 1, 4-selectivity content of the polyisoprene chain segment was 95%, and the 3, 4-selectivity content was 5%. Polar monomer acrylonitrile content of43 percent; and (3) GPC characterization: m_nIt was 36730g/mol, and the molecular weight distribution PDI was 1.9.

Example 12: the controllable preparation method of the conjugated diene and polar olefin monomer copolymer of the embodiment is carried out according to the following steps:

under argon atmosphere, azodiisobutyronitrile (AIBN,37.0mg,230 mu mol,1equiv.) and 2.9mL of toluene solution are sequentially added into a 50mL reaction bottle, ethyl sorbate (3.5mL,23mmol,100equiv.) and isoprene (2.3mL,23mmol,100equiv.) are added to form a homogeneous solution, the homogeneous solution is polymerized for 24 hours at 70 ℃, quenched by cold methanol, a polymer is separated out, washed twice by methanol and dried in vacuum to constant weight, and a colloidal polymer, namely a conjugated diene and polar olefin monomer copolymer, is obtained.

As a result: the yield was 54%. Characterized therein by NMR: the 1, 4-selectivity content of the polyisoprene block was 93%, and the 3, 4-selectivity content was 7%. The content of polar monomer ethyl sorbate is 36%; and (3) GPC characterization: m_n23390g/mol, the molecular weight distribution PDI was 2.0.

Example 13: the controllable preparation method of the conjugated diene and polar olefin monomer copolymer of the embodiment is carried out according to the following steps:

under argon atmosphere, azodiisobutyronitrile (AIBN,37.0mg,230 mu mol,1equiv.) and 2.2mL of toluene solution are sequentially added into a 50mL reaction bottle, methyl methacrylate (2.4mL,23mmol,100equiv.) and isoprene (2.3mL,23mmol,100equiv.) are added to form a homogeneous solution, the homogeneous solution is polymerized for 24 hours at 70 ℃, quenched by cold methanol, a polymer is separated out, washed twice by methanol and dried in vacuum to constant weight, and a colloidal polymer, namely a conjugated diene and polar olefin monomer copolymer, is obtained.

As a result: the yield was 71%. Characterized therein by NMR: the 1, 4-selectivity content of the polyisoprene block was 94%, and the 3, 4-selectivity content was 6%. The content of polar monomer methyl methacrylate is 37 percent; and (3) GPC characterization: m_nIt was 33260g/mol, and had a molecular weight distribution PDI of 2.0.

Example 14: the controllable preparation method of the conjugated diene and polar olefin monomer copolymer of the embodiment is carried out according to the following steps:

under argon atmosphere, azodiisobutyronitrile (AIBN,37.0mg,230 mu mol,1equiv.) and 2.2mL of toluene solution are sequentially added into a 50mL reaction bottle, methyl methacrylate (2.4mL,23mmol,100equiv.) and butadiene (2.0mL,23mmol,100equiv.) are added to form a homogeneous solution, the homogeneous solution is polymerized for 24 hours at 70 ℃, quenched by cold methanol, a polymer is separated out, washed twice by methanol and dried in vacuum to constant weight, and a colloidal polymer, namely a conjugated diene and polar olefin monomer copolymer, is obtained.

As a result: the yield was 56%. Characterized therein by NMR: the 1, 4-selectivity content of the polybutadiene block was 87%, and the 1, 2-selectivity content was 13%. The polar monomer methyl methacrylate content was 39%, characterized by GPC: m_nIt was 29860g/mol, and the molecular weight distribution PDI was 2.0.

Example 15: the controllable preparation method of the conjugated diene and polar olefin monomer copolymer of the embodiment is carried out according to the following steps:

under argon atmosphere, azodiisobutyronitrile (AIBN,37.0mg,230 mu mol,1equiv.) and 2.05mL of toluene solution are sequentially added into a 50mL reaction bottle, methyl acrylate (2.1mL,23mmol,100equiv.) and butadiene (2.0mL,23mmol,100equiv.) are added to form a homogeneous solution, the homogeneous solution is polymerized for 24 hours at 70 ℃, quenched by cold methanol, the polymer is separated out, washed twice by methanol and dried in vacuum to constant weight, and the colloidal polymer, namely the conjugated diene and polar olefin monomer copolymer, is obtained.

As a result: the yield was 66%. Characterized therein by NMR: the 1, 4-selectivity content of the polybutadiene block was 86%, and the 1, 2-selectivity content was 14%. The content of polar monomer methyl acrylate is 36 percent; and (3) GPC characterization: m_nIt was 32790g/mol, and the molecular weight distribution PDI was 1.9.

Example 16: the controllable preparation method of the conjugated diene and polar olefin monomer copolymer of the embodiment is carried out according to the following steps:

under argon atmosphere, azodiisobutyronitrile (AIBN,37.0mg,230 mu mol,1equiv.) and 2.65mL of toluene solution are sequentially added into a 50mL reaction bottle, tert-butyl acrylate (3.3mL,23mmol,100equiv.) and butadiene (2.0mL,23mmol,100equiv.) are added to form a homogeneous solution, the homogeneous solution is polymerized for 24 hours at 70 ℃, quenched by cold methanol, a polymer is separated out, washed twice by methanol and dried in vacuum to constant weight, and a colloidal polymer, namely a conjugated diene and polar olefin monomer copolymer, is obtained.

As a result: the yield was 50%. Characterized therein by NMR: the 1, 4-selectivity content of the polybutadiene block was 84%, and the 1, 2-selectivity content was 16%. The content of polar monomer tert-butyl acrylate is 41 percent; and (3) GPC characterization: m_nIt was 45752g/mol, and the molecular weight distribution PDI was 1.6.

Example 17: the controllable preparation method of the conjugated diene and polar olefin monomer copolymer of the embodiment is carried out according to the following steps:

under argon atmosphere, azodiisobutyronitrile (AIBN,37.0mg,230 mu mol,1equiv.) and 1.75mL of toluene solution are sequentially added into a 50mL reaction bottle, then acrylonitrile (1.5mL,23mmol,100equiv.) and butadiene (2.0mL,23mmol,100equiv.) are added to form a homogeneous solution, the homogeneous solution is polymerized for 24 hours at 70 ℃, quenched by cold methanol, the polymer is separated out, washed twice by methanol and dried in vacuum to constant weight, and the colloidal polymer, namely the conjugated diene and polar olefin monomer copolymer, is obtained.

As a result: the yield was 78%. Characterized therein by NMR: the 1, 4-selectivity content of the polybutadiene block was 91%, and the 1, 2-selectivity content was 9%. The polar monomer acrylonitrile content is 42%; and (3) GPC characterization: m_nIt was 37020g/mol, and the molecular weight distribution PDI was 1.9.

Example 18: the controllable preparation method of the conjugated diene and polar olefin monomer copolymer of the embodiment is carried out according to the following steps:

under argon atmosphere, azodiisobutyronitrile (AIBN,1.5mg,9.2 mu mol,1equiv.) and 1.75mL of toluene solution are sequentially added into a 50mL reaction bottle, then acrylonitrile (1.5mL,23mmol,2500equiv.) and butadiene (2.0mL,23mmol,2500equiv.) are added to form a homogeneous solution, the homogeneous solution is polymerized for 24 hours at 70 ℃, quenched by cold methanol, a polymer is separated out, washed twice by methanol and dried in vacuum to constant weight, and a colloidal polymer, namely a conjugated diene and polar olefin monomer copolymer, is obtained.

As a result: the yield was 49%. Characterized therein by NMR: polybutylene terephthalateThe 1, 4-selectivity content of the olefin segment was 95%, and the 1, 2-selectivity content was 5%. The polar monomer acrylonitrile content is 42%; and (3) GPC characterization: m_nIt was 142610g/mol, and the molecular weight distribution PDI was 2.1.

Example 19: the controllable preparation method of the conjugated diene and polar olefin monomer copolymer of the embodiment is carried out according to the following steps:

under argon atmosphere, azodiisobutyronitrile (AIBN,37.0mg,230 mu mol,1equiv.) and 2.75mL of toluene solution are sequentially added into a 50mL reaction bottle, and then ethyl sorbate (3.5mL,23mmol,100equiv.) and butadiene (2.0mL,23mmol,100equiv.) are added to form a homogeneous solution, the homogeneous solution is polymerized for 24 hours at 70 ℃, quenched by cold methanol, the polymer is separated out, washed twice by methanol and dried in vacuum to constant weight, and the colloidal polymer, namely the conjugated diene and polar olefin monomer copolymer, is obtained.

As a result: the yield was 63%. Characterized therein by NMR: the 1, 4-selectivity content of the polybutadiene block was 91%, and the 1, 2-selectivity content was 9%. The content of polar monomer ethyl sorbate is 38%; and (3) GPC characterization: m_nIt was 85643g/mol, and the molecular weight distribution PDI was 1.8.

Example 20: the controllable preparation method of the conjugated diene and polar olefin monomer copolymer of the embodiment is carried out according to the following steps:

under argon atmosphere, azodiisobutyronitrile (AIBN,37.0mg,230 mu mol,1equiv.) and 3.1mL of toluene solution are sequentially added into a 50mL reaction bottle, methyl acrylate (2.1mL,23mmol,100equiv.) and beta-myrcene (4.0mL,23mmol,100equiv.) are added to form a homogeneous solution, the homogeneous solution is polymerized for 24 hours at 70 ℃, quenched by cold methanol, the polymer is separated out, washed twice by methanol and dried in vacuum to constant weight, and the colloidal polymer, namely the conjugated diene and polar olefin monomer copolymer, is obtained.

As a result: the yield was 66%. Characterized therein by NMR: the 1, 4-selectivity content of the poly beta-myrcene chain segment is 88 percent, and the 3, 4-selectivity content is 12 percent. . The polar monomer methyl acrylate content is 38%; and (3) GPC characterization: m_nIt was 78536g/mol, and the molecular weight distribution PDI was 1.8.

Example 21: the controllable preparation method of the conjugated diene and polar olefin monomer copolymer of the embodiment is carried out according to the following steps:

under argon atmosphere, azodiisobutyronitrile (AIBN,37.0mg,230 mu mol,1equiv.) and 2.2mL of toluene solution are sequentially added into a 50mL reaction bottle, then methyl methacrylate (2.4mL,23mmol,100equiv.) and beta-myrcene (4.0mL,23mmol,100equiv.) are added to form a homogeneous solution, the homogeneous solution is polymerized for 24 hours at 70 ℃, quenched with cold methanol to separate out a polymer, washed twice with methanol and dried in vacuum to constant weight, and a colloidal polymer, namely a conjugated diene and polar olefin monomer copolymer, is obtained.

As a result: the yield was 55%. Characterized therein by NMR: the 1, 4-selectivity content of the poly beta-myrcene chain segment is 85 percent, and the 3, 4-selectivity content is 15 percent. The content of polar monomer methyl methacrylate is 36 percent; and (3) GPC characterization: m_n69046g/mol, molecular weight distribution PDI 1.8.

Example 22: the controllable preparation method of the conjugated diene and polar olefin monomer copolymer of the embodiment is carried out according to the following steps:

under argon atmosphere, azodiisobutyronitrile (AIBN,37.0mg,230 mu mol,1equiv.) and 2.8mL of toluene solution are sequentially added into a 50mL reaction bottle, then acrylonitrile (1.5mL,23mmol,100equiv.) and beta-myrcene (4.0mL,23mmol,100equiv.) are added to form a homogeneous solution, the homogeneous solution is polymerized for 24 hours at 70 ℃, quenched by cold methanol, a polymer is separated out, washed twice by methanol and dried in vacuum to constant weight, and a colloidal polymer, namely a conjugated diene and polar olefin monomer copolymer, is obtained.

As a result: the yield was 50%. Characterized therein by NMR: the 1, 4-selectivity content of the poly beta-myrcene segment is 86 percent, and the 3, 4-selectivity content is 14 percent. The content of polar monomer acrylonitrile is 36 percent; and (3) GPC characterization: m_nIt was 60438g/mol, and the molecular weight distribution PDI was 2.1.

Example 23: the controllable preparation method of the conjugated diene and polar olefin monomer copolymer of the embodiment is carried out according to the following steps:

under argon atmosphere, azodiisobutyronitrile (AIBN,37.0mg,230 mu mol,1equiv.) and 3.2mL of toluene solution are sequentially added into a 50mL reaction bottle, and then ethyl sorbate (3.5mL,23mmol,100equiv.) and beta-myrcene (4.0mL,23mmol,100equiv.) are added to form a homogeneous solution, and the homogeneous solution is polymerized for 24 hours at 70 ℃, quenched with cold methanol, precipitated with polymer, washed twice with methanol and dried in vacuum to constant weight to obtain a colloidal polymer, namely a conjugated diene and polar olefin monomer copolymer.

As a result: the yield was 49%. Characterized therein by NMR: the 1, 4-selectivity content of the poly beta-myrcene segment is 86 percent, and the 3, 4-selectivity content is 14 percent. The content of polar monomer ethyl sorbate is 30%; and (3) GPC characterization: m_nIt was 46690g/mol, and the molecular weight distribution PDI was 2.7.

Example 24: the controllable preparation method of the conjugated diene and polar olefin monomer copolymer of the embodiment is carried out according to the following steps:

under argon atmosphere, azodiisobutyronitrile (AIBN,37.0mg,230 mu mol,1equiv.) and 2.2mL of toluene solution are sequentially added into a 50mL reaction bottle, methyl acrylate (2.1mL,23mmol,100equiv.) and beta-farnesene (5.6mL,23mmol,100equiv.) are added to form a homogeneous solution, the homogeneous solution is polymerized for 24 hours at 70 ℃, quenched by cold methanol to separate out a polymer, washed twice by methanol and dried in vacuum to constant weight, and a colloidal polymer, namely a conjugated diene and polar olefin monomer copolymer, is obtained.

As a result: the yield was 45%. Characterized therein by NMR: the 1, 4-selectivity content of the poly beta-farnesene chain segment is 78 percent, and the 3, 4-selectivity content is 22 percent. The polar monomer methyl acrylate content is 38%; and (3) GPC characterization: m_nIt was 102690g/mol and the molecular weight distribution PDI was 1.8.

Example 25: the controllable preparation method of the conjugated diene and polar olefin monomer copolymer of the embodiment is carried out according to the following steps:

under argon atmosphere, azodiisobutyronitrile (AIBN,37.0mg,230 mu mol,1equiv.) and 2.2mL of toluene solution are sequentially added into a 50mL reaction bottle, then acrylonitrile (1.5mL,23mmol,100equiv.) and beta-farnesene (5.6mL,23mmol,100equiv.) are added to form a homogeneous solution, the homogeneous solution is polymerized for 24 hours at 70 ℃, quenched by cold methanol, the polymer is separated out, washed twice by methanol and dried in vacuum to constant weight, and the colloidal polymer, namely the conjugated diene and polar olefin monomer copolymer, is obtained.

As a result: the yield was 48%. Characterized therein by NMR: the 1, 4-selectivity content of the poly beta-farnesene chain segment is 77 percent, and the 3, 4-selectivity content is 23 percent. The polar monomer acrylonitrile content is 38%; and (3) GPC characterization: m_nIt was 112468g/mol, and the molecular weight distribution PDI was 2.0.