CN105693963A - Preparation method of styrene-vinyl pyridine two-block copolymer - Google Patents

Preparation method of styrene-vinyl pyridine two-block copolymer Download PDF

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Publication number
CN105693963A
CN105693963A CN201610125363.7A CN201610125363A CN105693963A CN 105693963 A CN105693963 A CN 105693963A CN 201610125363 A CN201610125363 A CN 201610125363A CN 105693963 A CN105693963 A CN 105693963A
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China
Prior art keywords
styrene
block copolymer
polymerization
preparation
pyridines
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CN201610125363.7A
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Chinese (zh)
Inventor
胡玉兵
陈锐
李凯
杨桂宝
邢建生
唐先龙
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Anhui Guoxing Biochemistry Co Ltd
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Anhui Guoxing Biochemistry Co Ltd
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Priority to CN201610125363.7A priority Critical patent/CN105693963A/en
Publication of CN105693963A publication Critical patent/CN105693963A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/04—Polymerisation in solution
    • C08F2/06—Organic solvent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

The invention relates to a preparation method of a styrene-vinyl pyridine two-block copolymer and belongs to the technical field of polymer synthesis. The method mainly includes the two steps that firstly, lithium alkylide serves as an initiator to initiate styrene to carry out anionic polymerization to form a styrene polymer containing an active center, vinyl pyridine monomers are added for block polymerization, and finally the two-block copolymer containing styrene and vinyl pyridine chain segments is formed. Synthesis of styrene-vinyl pyridine is achieved in a polar or weakly-polar solvent, preparation of the block copolymer containing polyvinyl pyridine is achieved, the synthesis method is an anion dispersion polymerization method, and polymer micro-spheres are directly obtained in the polymerization process.

Description

A kind of preparation method of styrene-ethylene yl pyridines di-block copolymer
Technical field
The invention belongs to macromolecular compound synthesis technical field, the preparation method particularly relating to a kind of styrene-ethylene yl pyridines di-block copolymer。
Background technology
Amphiphilic block copolymers is the compatilizer between a kind of polarity non-polar material, it is widely used in polymer modification field and field of fine chemical etc., amphiphilic structure due to its polar-nonpolar, polarity can be made inconsistent biphase dispersed, as can be used as the surface conditioning agent of tyre cord, the surfactant etc. that polymer powder is modifies。Anionic polymerisation is a kind of method preparing block copolymer, and it is highly developed that the anionic polymerisation of non-polar monomer such as styrene, butadiene, isoprene etc. controls technology, and has multiple block copolymer product to come out。At present, polar-nonpolar amphiphilic block polymers has wider application field, but adopts anionic polymerisation process preparation relatively big containing polar block copolymer difficulty, this is because the anionic polymerisation speed of polar monomer is fast, it is difficult to control to, and there is side reaction；Additionally, the polymer of vinylpyridine is insoluble in non-polar solvens such as hexamethylene, so adopting the anionic polymerisation preparation block copolymer containing vinylpyridine segment, its reaction mainly carries out in polar solvent。J.Robert etc. prepare the block copolymer (Macromolecules containing 4-vinylpridine in the pyridine/THF of 9:1,1997,30-1,5596), this reaction carries out in polar solvent, due to the solvation effect that polar solvent is stronger so that polymerization site is dissociated into free ion, therefore polymerization rate is quickly。Generally the unsaturated monomer with substituent group is to carry out chain growth in the way of inserting active center ion pair, when ion pair is more loose or completely dissociates into into free ion, this it be inserted on direction in space and be not limited completely, cause that the block polymer stereoregularity obtained is poor, molecular weight distribution is wider, simultaneously because response speed is higher, there is more side reaction。This method selects low pole or nonpolar as reaction dissolvent, by controlling the polymerization temperature of second comonomer, it is achieved the preparation of styrene-ethylene yl pyridines di-block copolymer in nonpolar or Weak solvent。
Summary of the invention
In order to overcome the defect of prior art, the preparation method that it is an object of the invention to provide a kind of styrene-ethylene yl pyridines di-block copolymer, the reaction temperature of conservative control polymerization, it is to avoid the generation of side reaction, save production cost。
The preparation method of a kind of styrene-ethylene yl pyridines di-block copolymer, comprises the following steps:
(1) under dry, nitrogen state, nonpolar or weak polar solvent, alkyl lithium initiator initiation styrene monomer polymerization is added in polymerization flask, polymerization temperature is 30 DEG C～60 DEG C, polymerization time is 1～3 hour, wherein said nonpolar or weak polar solvent is hexamethylene, toluene or dioxane, and alkyl lithium initiator is n-BuLi, isobutyl group lithium or pi-allyl lithium；
(2) vinylpyridine monomers is added after-10 DEG C～20 DEG C conditions carry out block polymerization 0.5～1.5 hour, add methanol to terminate, adding ethanol to resolve, be filtered after standing, vacuum drying obtains styrene-ethylene yl pyridines di-block copolymer。
Optimizing further, described vinylpyridine monomers is one or both mixture in 2-vinylpyridine and 4-vinylpridine。
Optimizing further, described alkyl lithium initiator is n-BuLi, and the mol ratio of its consumption and vinylpyridine monomers is 1:100～1000。
Optimizing further, the mass ratio of the consumption of described vinylpyridine monomers and styrene monomer consumption is 3:7～7:3。
Compared with prior art, provide the benefit that: the present invention adopts the synthesis realizing styrene-ethylene yl pyridines in polarity or weak polar solvent, achieve the preparation of block copolymer containing polyvinylpyridine, this synthetic method is a kind of anion disperse polymerization, and polymerization process directly obtains polymer microballoon。
Detailed description of the invention
Example below is for the method further illustrating the present invention, but should not be limited thereto。
Embodiment 1
The polymerization flask taking a 250ml dries more than 4 hours under 120 DEG C of conditions in baking oven, reaction pre-polymerization flask evacuation-baking-inflated with nitrogen protection, three times repeatedly；120ml hexamethylene is added in polymerization flask, 20g styrene monomer, 0.2mmol n-BuLi, after being polymerized 2 hours under 45 DEG C of conditions, add 8g2-vinylpyridine monomers polyreaction 1 hour under 20 DEG C of conditions, carry out end-blocking with methanol to terminate, add ethanol to resolve, obtain polymer precipitation, filtration final vacuum dries and obtains styrene-ethylene yl pyridines di-block copolymer, its state of aggregation is nucleocapsid structure, outer layer is styrene polymer, internal layer is poly-2 vinylpyridines, it is 8.9 ten thousand that GPC tests resulting polymers molecular weight Mn, molecular weight distribution is 2.1, monomer conversion is 82.7%。
Embodiment 2
The polymerization flask taking a 100ml dries more than 4 hours under 120 DEG C of conditions in baking oven, reaction pre-polymerization flask evacuation-baking-inflated with nitrogen protection, three times repeatedly, 100g1 is added to polymerization flask, 4-dioxane, 12.5g styrene monomer, 0.01mmol n-BuLi, after being polymerized 2 hours under 60 DEG C of conditions, add 6g2-vinylpyridine monomers polyreaction 1 hour under 20 DEG C of conditions, terminate with methanol, add a large amount of ethanol to resolve, obtain polymer precipitation, filtration final vacuum dries and obtains styrene-ethylene yl pyridines di-block copolymer, its state of aggregation is nucleocapsid structure, outer layer is styrene polymer, internal layer is poly-2 vinylpyridines, it is 7.2 ten thousand that GPC tests resulting polymers molecular weight Mn, molecular weight distribution is 2.45 monomer conversions is 81.2%。
Embodiment 3
Polymerization flask processes as described in embodiment 1 or 2, 100g hexamethylene is added to polymerization flask, 12.5g styrene monomer, 0.01mmol n-BuLi, after being polymerized 2 hours under 60 DEG C of conditions, add 6g2-vinylpyridine monomers polyreaction 1 hour under-10 DEG C of conditions, terminate with methanol, add a large amount of ethanol to resolve, obtain polymer precipitation, filtration final vacuum dries and obtains styrene-ethylene yl pyridines di-block copolymer, its state of aggregation is nucleocapsid structure, outer layer is styrene polymer, internal layer is poly-2 vinylpyridines, it is 13.6 ten thousand that GPC tests resulting polymers molecular weight Mn, molecular weight distribution is 1.78, monomer conversion is 89.6%。
Embodiment 4
Polymerization flask processes as described in embodiment 1 or 2, 100g hexamethylene is added to polymerization flask, 12.5g styrene monomer, 0.01mmol n-BuLi, after being polymerized 2 hours under 60 DEG C of conditions, add 6g2-vinylpyridine monomers polyreaction 1 hour under-20 DEG C of conditions, terminate with methanol, add a large amount of ethanol to resolve, obtain polymer precipitation, filtration final vacuum dries and obtains styrene-ethylene yl pyridines di-block copolymer, its state of aggregation is nucleocapsid structure, outer layer is styrene polymer, internal layer is poly-2 vinylpyridines, it is 22.3 ten thousand that GPC tests resulting polymers molecular weight Mn, molecular weight distribution is 1.35, monomer conversion is 96.6%。
Embodiment 5
Polymerization flask processes as described in embodiment 1 or 2, 100g1 is added to polymerization flask, 4-dioxane, 12.5g styrene monomer, 0.01mmol n-BuLi, after being polymerized 2 hours under 60 DEG C of conditions, add 6g2-vinylpyridine monomers polyreaction 1 hour under-20 DEG C of conditions, terminate with methanol, add a large amount of ethanol to resolve, obtain polymer precipitation, filtration final vacuum dries and obtains styrene-ethylene yl pyridines di-block copolymer, its state of aggregation is nucleocapsid structure, outer layer is styrene polymer, internal layer is poly-2 vinylpyridines, it is 16.8 ten thousand that GPC tests resulting polymers molecular weight Mn, molecular weight distribution is 1.67 monomer conversions is 91.2%。

Claims (4)

1. the preparation method of a styrene-ethylene yl pyridines di-block copolymer, it is characterised in that comprise the following steps:
(1) under dry, nitrogen state, nonpolar or weak polar solvent, alkyl lithium initiator initiation styrene monomer polymerization is added in polymerization flask, polymerization temperature is 30 DEG C～60 DEG C, polymerization time is 1～3 hour, wherein said nonpolar or weak polar solvent is hexamethylene, toluene or dioxane, and alkyl lithium initiator is n-BuLi, isobutyl group lithium or pi-allyl lithium；
(2) vinylpyridine monomers is added after-10 DEG C～20 DEG C conditions carry out block polymerization 0.5～1.5 hour, add methanol to terminate, adding ethanol to resolve, be filtered after standing, vacuum drying obtains styrene-ethylene yl pyridines di-block copolymer。
2. the preparation method of styrene-ethylene yl pyridines di-block copolymer according to claim 1, it is characterised in that described vinylpyridine monomers is one or both mixture in 2-vinylpyridine and 4-vinylpridine。
3. the preparation method of styrene-ethylene yl pyridines di-block copolymer according to claim 1, it is characterised in that the consumption of described n-BuLi and the mol ratio of styrene monomer are 1:100～1000。
4. the preparation method of styrene-ethylene yl pyridines di-block copolymer according to claim 1, it is characterised in that the mass ratio of the consumption of described vinylpyridine monomers and styrene monomer consumption is 3:7～7:3。
CN201610125363.7A 2016-03-04 2016-03-04 Preparation method of styrene-vinyl pyridine two-block copolymer Pending CN105693963A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1676539A (en) * 2004-04-02 2005-10-05 中国石化集团巴陵石油化工有限责任公司 Polarized SDS and preparation method thereof
CN1688620A (en) * 2002-08-01 2005-10-26 阿尔伯麦尔公司 Anionic polymerization process
CN101045766A (en) * 2007-04-20 2007-10-03 北京化工大学 Anionic polymerization method for synthesing isotactic polystyrene
CN101104654A (en) * 2007-07-05 2008-01-16 复旦大学 Polymer containing multiple functional groups at end of the same and preparation method thereof
CN102286200A (en) * 2010-06-18 2011-12-21 中国石油化工股份有限公司 PA/PP (polyamide/polypropylene) composite material and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1688620A (en) * 2002-08-01 2005-10-26 阿尔伯麦尔公司 Anionic polymerization process
CN1676539A (en) * 2004-04-02 2005-10-05 中国石化集团巴陵石油化工有限责任公司 Polarized SDS and preparation method thereof
CN101045766A (en) * 2007-04-20 2007-10-03 北京化工大学 Anionic polymerization method for synthesing isotactic polystyrene
CN101104654A (en) * 2007-07-05 2008-01-16 复旦大学 Polymer containing multiple functional groups at end of the same and preparation method thereof
CN102286200A (en) * 2010-06-18 2011-12-21 中国石油化工股份有限公司 PA/PP (polyamide/polypropylene) composite material and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
李春刚等: "苯乙烯-2-乙烯基吡啶两嵌段共聚物的合成与表征", 《高分子学报》 *
陕西科学技术出版社: "《高分子科学实验方法》", 31 March 1998, 陕西科学技术出版社 *

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Application publication date: 20160622