CN115073724A - Olefin and epoxide block copolymerization method - Google Patents

Olefin and epoxide block copolymerization method Download PDF

Info

Publication number
CN115073724A
CN115073724A CN202110261669.6A CN202110261669A CN115073724A CN 115073724 A CN115073724 A CN 115073724A CN 202110261669 A CN202110261669 A CN 202110261669A CN 115073724 A CN115073724 A CN 115073724A
Authority
CN
China
Prior art keywords
olefin
epoxide
ethylene oxide
dimethylamino
tert
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202110261669.6A
Other languages
Chinese (zh)
Other versions
CN115073724B (en
Inventor
赵俊鹏
李恒
何冠辰
张广照
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
South China University of Technology SCUT
Original Assignee
South China University of Technology SCUT
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by South China University of Technology SCUT filed Critical South China University of Technology SCUT
Priority to CN202110261669.6A priority Critical patent/CN115073724B/en
Publication of CN115073724A publication Critical patent/CN115073724A/en
Application granted granted Critical
Publication of CN115073724B publication Critical patent/CN115073724B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • 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
    • C08G65/2603—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 the other compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • 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
    • C08G65/2642—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 characterised by the catalyst used
    • C08G65/2645—Metals or compounds thereof, e.g. salts
    • C08G65/2654—Aluminium or boron; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • 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
    • C08G65/2642—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 characterised by the catalyst used
    • C08G65/2669—Non-metals or compounds thereof
    • C08G65/2675—Phosphorus or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • 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
    • C08G65/2642—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 characterised by the catalyst used
    • C08G65/269—Mixed catalyst systems, i.e. containing more than one reactive component or catalysts formed in-situ
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Landscapes

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

Abstract

本发明公开了一种烯烃和环氧化物嵌段共聚的方法。包括以下步骤：在惰性气氛中，以有机锂引发烯烃的阴离子双键加成聚合，并使用环氧乙烷进行封端。随后以环氧乙烷封端的活性聚烯烃为大分子引发剂，加以有机碱和烷基硼组成的双组分有机/无金属催化剂，实施环氧化物的阴离子开环聚合，得聚烯烃‑聚醚嵌段共聚物。本发明提供了一种原位活性转换策略，能在温和的条件下实现烯烃和环氧化物的连续嵌段共聚，一锅法制备分子量、嵌段比例、侧基组合均可灵活调控的聚烯烃‑聚醚嵌段共聚物。The invention discloses a method for block copolymerization of olefin and epoxide. It includes the following steps: in an inert atmosphere, an anionic double bond addition polymerization of olefins is initiated with organolithium, and ethylene oxide is used for end-capping. Subsequently, the ethylene oxide-terminated active polyolefin is used as a macroinitiator, and a two-component organic/metal-free catalyst composed of an organic base and an alkyl boron is added to carry out anionic ring-opening polymerization of epoxides to obtain polyolefin-polyethylene Ether block copolymers. The invention provides an in-situ active conversion strategy, which can realize continuous block copolymerization of olefin and epoxide under mild conditions, and prepare polyolefins whose molecular weight, block ratio and side group combination can be flexibly adjusted by one-pot method. ‑Polyether block copolymers.

Description

Olefin and epoxide block copolymerization method
Technical Field
The invention belongs to the technical field of block copolymer synthesis, and particularly relates to a method for preparing a polyolefin-polyether block copolymer by utilizing an in-situ catalytic activity conversion strategy in one pot.
Background
The amphiphilic block copolymer refers to a polymer (a solvent generally refers to water) with a solvent-philic chain segment and a solvent-phobic chain segment which are connected by a covalent bond in a high molecular structure, can be used as an emulsifier, a dispersant, a stabilizer, a molding inhibitor, a surface modifier of plastics, a polymer blending compatibilizer and the like, and is widely concerned and researched for decades. The amphiphilic block copolymer is constructed by taking polyethylene oxide (PEO) with water solubility and biocompatibility as a hydrophilic chain segment and polyolefin such as Polybutadiene (PB), Polyisoprene (PI) or Polystyrene (PS) as a hydrophobic chain segment, and comprises PB-b-PEO, PI-b-PEO, PS-b-PEO and the like, and has remarkable basic and application research values because epoxy monomers and olefin monomers have the advantages of high yield, low price, wide sources and the like. In addition to PEO, block copolymers of aliphatic polyethers derived from other epoxides (e.g. propylene oxide, PO) with the above-mentioned polyolefins also have similar amphiphilic properties.
The molecular weight, relative content and microstructure of the solvophilic and solvophobic segments are the basic means for regulating and controlling the performance of the amphiphilic block copolymer. Organolithium-initiated living anionic polymerization is the preferred method for controlled synthesis of terminally active and monodisperse PB, PI, and PS segments. However, when these reactive polyolefin chains are used as macroinitiators for the synthesis of PB-b-PEO, PI-b-PEO, PS-b-PEO, copolymers having the desired block structure cannot be obtained. This is due to the PB-CH formed after the reaction of Ethylene Oxide (EO) with the carbanion 2 CH 2 OLi、PI-CH 2 CH 2 OLi、PS-CH 2 CH 2 OLi (lithium alkoxide) has a strong anion-cation interaction and ion pair association, resulting in a very low oxyanion reactivity that cannot be polymerized by further reaction with EO. In relatively early studies, a common approach to this problem was to replace the lithium ion with a sodium or potassium ion that interacts weakly with oxygen anions. In this case, however, the EO polymerization takes a longer time at a higher temperature to achieve a higher conversion and to form a block copolymer. It was subsequently found that if an organic phosphazene superbase is added to the polymerization system t BuP 4 As a catalyst, EO can be smoothly ring-opened from the polyolefin chain end at room temperature to 50 ℃. Wherein, t BuP 4 plays a role of being complexed with lithium ions to form t BuP 4 Li] + Thereby increasing the size of the counter ions, reducing the interaction of anions and cations and inhibiting the association of ion pairs, and further improving the activity of oxygen anions. However, EO still takes 2 to 3 days to be completely consumed. In 2010, researchers found that excess triisobutylaluminum was substituted for triisobutylaluminum t BuP 4 Is added to the polymerization systemIn (2), EO can be converted to a high degree within a few hours at room temperature. They believe that an equal amount of triisobutylaluminum can react with the lithium alkoxide at the end of the macroinitiator chain to form a lithium-aluminate complex, thereby inhibiting the aggregation of lithium salts and enhancing the nucleophilic attack activity of the chain end on EO. And the rest triisobutyl aluminum plays a role in activating EO and improving the activity of ring-opening polymerization. The structure of the obtained PI-b-PEO, PS-b-PEO block copolymer is controllable within the designed molecular weight of PEO chain segment of 10 kg/mol. However, due to the chain transfer reaction of the system, the initiation efficiency of the active polyolefin macromolecules is about 80%, and additional separation and purification are needed to obtain the block copolymer with a definite structure. In addition, when lithium alkoxide is used as the initiator, the initiator is not a nucleophilic organic strong base t BuP 4 Also, triisobutylaluminum is usually only suitable for the ring-opening polymerization of EO, but has a poor catalytic effect on the ring-opening polymerization of a monosubstituted epoxy monomer (such as PO), and the chain transfer to the monosubstituted epoxy monomer makes it difficult to break through the limit of 5.0kg/mol of the molecular weight of the polyether chain segment under the premise of narrow dispersion.
In summary, how to perform efficient and controllable ring-opening polymerization of epoxy monomers such as EO and PO under relatively mild conditions by using lithium macroalkoxide as an initiator is the biggest problem in preparing polyolefin-polyether amphiphilic block copolymers by a living anionic polymerization one-pot method.
Disclosure of Invention
In order to solve the defects and shortcomings of the prior art, the invention aims to provide a method for block copolymerization of olefin and epoxide, in particular to a method for preparing a polyolefin-polyether block copolymer by using an in-situ catalytic activity conversion strategy in one pot.
The method is based on the initiation of an alkoxy lithium macroinitiator and the catalysis and control of an organic/metal-free Lewis acid-base pair, so that the anionic double bond addition polymerization of an olefin monomer initiated by organic lithium and the anionic ring-opening polymerization of an epoxide initiated by polyolefin macromolecular alkoxy lithium are continuously and controllably carried out in the same reactor, and the polyolefin-polyether block copolymer is synthesized by a one-pot method. The method has the advantages of wide raw material source, mild reaction condition, simple and convenient operation, flexible and accurate regulation and control of the molecular weight and the block proportion of the product (mainly amphiphilic block copolymer), and the like.
The purpose of the invention is realized by the following technical scheme:
a process for the block copolymerization of olefins and epoxides comprising the steps of:
in an inert or nitrogen atmosphere, olefin is taken as a monomer, organic lithium is taken as an initiator, the anionic polymerization reaction of the olefin is carried out in a solution, and then ethylene oxide is added to carry out end capping on the polyolefin, so as to prepare the active polyolefin with the chain end being alkoxy lithium; active polyolefin with chain end being alkoxy lithium is taken as a macroinitiator, epoxide monomer and organic/metal-free Lewis acid-base pair catalyst consisting of organic base and alkyl boron are added to carry out ring-opening polymerization reaction, and the polyolefin-polyether block copolymer with controllable structure is prepared by a one-pot method.
Further, the olefin monomer is at least one of (1) butadiene, (2) isoprene, (3) styrene, (4) 2-methylstyrene, (5) 3-methylstyrene, (6) 4-methylstyrene, (7) 4-methoxystyrene, (8)2, 4-dimethylstyrene and (9)2, 5-dimethylstyrene.
Figure BDA0002970297070000031
Still further, the olefin monomer is at least one of isoprene, butadiene, and styrene.
Further, the organic lithium initiator is R-Li, wherein R is one of alkyl, cycloalkyl or aryl with 1-14 carbon atoms, and Li is a lithium atom. Preferably n-butyllithium and/or sec-butyllithium.
Further, the solvent is at least one of tetrahydrofuran, benzene, n-hexane and cyclohexane.
Further, the molar ratio of the organolithium initiator to the olefin monomer is 1: (10 to 2000), preferably 1: (10-800).
Furthermore, the molar ratio of the ethylene oxide to the organic lithium initiator is (1-1.5): 1.
The epoxide monomer is at least one of (1) ethylene oxide, (2) linear alkyl-substituted ethylene oxide with alkyl carbon number of 1-20, (3) linear alkyl glycidyl ether with alkyl carbon number of 1-16, (4) isopropyl glycidyl ether, (5) tert-butyl glycidyl ether, (6) 2-ethylhexyl glycidyl ether, (7) phenyl glycidyl ether, (8) benzyl glycidyl ether, (9) allyl glycidyl ether, (10) propargyl glycidyl ether, (11) glycidyl methacrylate and (12) glycidyl butyrate. The specific structural formula is as follows:
Figure BDA0002970297070000041
still further, the epoxide monomer is at least one of ethylene oxide, propylene oxide and butylene oxide.
Further, the organic base is a tertiary amine, amidine, guanidine, triaminophosphine or phosphazene base; the tertiary amine is triethylene Diamine (DABCO), pentamethyl diethylenetriamine (PMDETA) or tri- (2-dimethylaminoethyl) amine (ME) 6 TREN) and sparteine (sparteine); the amidine is 1, 5-diazabicyclo [4.3.0]At least one of non-5-ene (DBN) and 1, 8-diazabicycloundec-7-ene (DBU); the guanidine is 7-methyl-1, 5, 7-triazabicyclo [4.4.0]At least one of dec-5-ene (MTBD), 1,3, 3-Tetramethylguanidine (TMG), and 1,1,2,3, 3-Pentamethylguanidine (PMG); the triaminophosphine is tris (dimethylamino) phosphine (HMTP), tris (diethylamino) phosphine (HETP), 2,8, 9-trimethyl-2, 5,8, 9-tetraaza-1-phosphobicyclo (3,3,3) undecane (TMAP) and 2,8, 9-triisopropyl-2, 5,8, 9-tetraaza-1-phosphobicyclo [3.3.3]At least one of undecane (TIPAP); the phosphazene base is 2-tert-butylimino-2-diethylamino-1, 3-dimethyl perhydro-1, 3, 2-diazaphosphorus (BEMP), tert-butylimino-tris (dimethylamino) phosphorane (B-N-methyl-N-butyl-N-methyl-2-ethyl-N-butyl-N-methyl-2-amino-1, 3, 2-diazaphosphorus (BEMP) t BuP 1 ) T-butylimino-tris (pyrrolidino) phosphine: (a), (b), and (c) t BuP 1 (pyrr)), 1-tert-butyl-2, 2,4,4, 4-pentakis (dimethylamino) -2 lambda 5 ,4λ 5 Chain di (phosphazenes) (b) t BuP 2 ) 1-ethyl-2, 2,4,4, 4-pentakis (dimethylamino) -2 lambda 5 ,4λ 5 -chain bis (phosphazenes) (EtP 2 ) And 1-tert-butyl-4, 4, 4-tris (dimethylamino) -2, 2-bis [ tris (dimethylamino) -phosphinideneamino]-2λ 5 ,4λ 5 Chain di (phosphazenes) (b) t BuP 4 ) At least one of (a). The specific structural formula is as follows:
Figure BDA0002970297070000051
further, the organic base is 1, 8-diazabicycloundecen-7-ene (DBU), 7-methyl-1, 5, 7-triazabicyclo [ 4.4.0%]Dec-5-ene (MTBD), 2-tert-butylimino-2-diethylamino-1, 3-dimethylperhydro-1, 3, 2-diazaphosphorus (BEMP), tert-butylimino-tris (dimethylamino) phosphorane ((M)) t BuP 1 ) 1-tert-butyl-2, 2,4,4, 4-pentakis (dimethylamino) -2 lambda 5 ,4λ 5 -a chain of bis (phosphazenes) t BuP 2 ) And 1-tert-butyl-4, 4, 4-tris (dimethylamino) -2, 2-bis [ tris (dimethylamino) -phosphinideneamino]-2λ 5 ,4λ 5 Chain di (phosphazenes) (b) t BuP 4 ) At least one of (a).
Further, the alkyl boron is B-isopinocampheyl-9-borabicyclo [3.3.1]Nonane (S-Alphine-Borane), tri-sec-butylborane (T) s BuB), triisopropylborane (T) i At least one of PrB), trimethyl borane (TMB) and tri-linear alkyl borane, wherein the number of carbon atoms of linear alkyl in the tri-linear alkyl borane is 2-8. The specific structural formula is as follows:
Figure BDA0002970297070000052
still further, the alkyl boron is at least one of triethylboron and triisopropylboron.
Further, the amount of the organic/metal-free Lewis acid-base pair can be adjusted according to the designed molecular weight and the required reaction time.
Further, the polyolefin macroinitiator, the epoxide, the organic base and the alkyl boron are present in a molar ratio of 1: (10-3000): (0.05-10): (0.05-10), preferably 1: (10-1000): (0.1-3): (0.1 to 3).
Further, before the anionic polymerization reaction, the concentration of the olefin monomer is 1-8 mol/L; before the ring-opening polymerization reaction, the concentration of the epoxy monomer is 1-10 mol/L.
Furthermore, the polymerization reaction temperature is-80-60 ℃, the polymerization reaction time is 1-48 h, and the ethylene oxide end capping reaction time is 1-60 min.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the invention uses an organic/metal-free catalytic system consisting of organic alkali and alkyl boron for ring-opening polymerization of an epoxy monomer initiated by alkoxy lithium, so that the anionic double bond addition polymerization of an olefin monomer initiated by organic lithium and the ring-opening polymerization of an epoxide anion initiated by polyolefin macromolecular alkoxy lithium can be continuously and controllably carried out in the same reaction kettle, and the polyolefin-polyether block copolymer is synthesized by a one-pot method.
(2) The polymerization method provided by the invention can completely convert the monomers into the polymer within a few hours at room temperature, has mild polymerization conditions and shortens the polymerization reaction time. Meanwhile, the problems of insufficient polymerization activity and controllability, limited monomer application range, inflexible catalytic activity adjustment and the like in the existing catalytic initiation system are solved. The reaction time is prolonged after the monomers are completely consumed, and the polymer structure is not changed.
(3) The organic lithium initiating system has universality for olefin monomers, and is suitable for polymerization of various olefin monomers, so that the polyolefin macromolecular initiator with a chain end with rich structure and alkoxy lithium can be prepared. Meanwhile, the macromolecular initiator can completely initiate the controllable ring-opening polymerization of the ethylene oxide and the derivatives thereof in situ to obtain a complete block copolymer, and the initiation efficiency of the block copolymer is not influenced by monomer combination.
(4) The organic/metal-free catalytic system composed of the organic base and the alkyl boron has universality on ring-opening polymerization of epoxide initiated by the alkoxy lithium, has high chemical selectivity on functional groups participating in the reaction, and completely avoids destructive chain transfer reaction, so that the side group functional group introduced by the epoxy monomer is completely maintained, and the polyolefin-polyether block copolymer with a plurality of definite structures can be prepared.
(5) The invention can control the component proportion of monomer units and the molecular weight (within the range of 1.0-100.0 kg/mol) of the copolymer accurately by regulating and controlling the use amounts and the proportion of organic lithium, olefin monomer, epoxy monomer, organic alkali and alkyl boron, and the molecular weight dispersion degree of the copolymer is controlled
Figure BDA0002970297070000061
Generally below 1.2. In addition, the mass ratio of the polyolefin to the polyether can be controlled to be (10-90%): (90-10%), the difference of glass transition temperature and mechanical property between different copolymers is large, thereby enriching the structure and performance of the polyolefin-polyether block copolymer.
(6) The amphiphilic block copolymer provided by the invention has the advantages of easily available raw materials and simple synthesis method, and is suitable for industrial generation.
Drawings
FIG. 1 is a SEC curve of a polyisoprene macroinitiator (PI) and polyisoprene-b-polyethylene oxide (PI-b-PEO) prepared in example 6 of the present invention.
FIG. 2 shows the preparation of polyisoprene-b-polyethylene oxide (PI-b-PEO) prepared in example 6 of the present invention 1 H NMR spectrum.
FIG. 3 is a SEC curve of polystyrene-b-polyisoprene macroinitiator (PS-b-PI), polystyrene-b-polyisoprene-b-polyethylene oxide (PS-b-PI-b-PEO) and polystyrene-b-polyisoprene-b-polyethylene oxide-b-polypropylene oxide (PS-b-PI-b-PEO-b-PPO) prepared in example 14 of the present invention.
FIG. 4 shows the preparation of polystyrene-b-polyisoprene-b-polyethylene oxide-b-polypropylene oxide (PS-b-PI-b-PEO-b-PPO) prepared in example 14 of the present invention 1 H NMR spectrum.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
Those who do not specify specific conditions in the examples of the present invention follow conventional conditions or conditions recommended by the manufacturer. The raw materials, reagents and the like which are not indicated for manufacturers are all conventional products which can be obtained by commercial purchase.
The conversion of the monomers and the structural characteristics of the copolymer were measured by Bruker AV400 liquid NMR spectrometer, the solvent being deuterated chloroform.
The molecular weight and molecular weight dispersity of the polymer are measured by volume exclusion chromatography (SEC), the instrument adopts a volume exclusion chromatograph of America Agilent 1260Infinity model, the mobile phase is tetrahydrofuran, the column temperature is 35 ℃, and the flow rate is 1 mL/min; calibration curves were prepared with a series of polystyrene standards.
The parts described in the formulations in the examples below are all molar parts.
Example 1
Anionic polymerization of isoprene was performed in tetrahydrofuran with n-butyllithium as an initiator, and capping was performed with ethylene oxide. And then, taking the active polyisoprene terminated by ethylene oxide as a macroinitiator and an organic/metal-free Lewis acid-base pair as a catalyst, carrying out ring-opening polymerization on the ethylene oxide, and preparing the polyisoprene-polyethylene oxide amphiphilic block copolymer by a one-pot method. The specific operation is as follows:
isoprene, ethylene oxide and tetrahydrofuran are all used after water removal treatment. 1 part of n-butyllithium, 150 parts of isoprene and tetrahydrofuran (isoprene initial concentration of 1.5mol/L) were added to a reactor previously cooled to-78 ℃ under an inert atmosphere and stirred for 12 hours. 300 parts of ethylene oxide are subsequently added to the reactor and stirring is continued for 30min at-78 ℃. Thereafter, 1 part of phosphazene base is added t BuP 1 And 3 parts of a tetrahydrofuran solution of triethylboron, the ethylene oxide concentration before ring-opening polymerization was 2.6mol/L, and the mixture was stirred at room temperature for 12 hours. Terminating the reaction with acetic acid, collecting a crude product, precipitating with diethyl ether, and drying in vacuum to obtain the final product. The crude product had a molecular weight of 25.2kg/mol and a dispersity of 1.08 as determined by SEC. 1 H NMR measurement of isoprene and ethylene oxideThe conversion rates were all 100%. Theoretical number average molecular weight M calculated by feeding ratio and conversion rate of n-butyllithium, isoprene and ethylene oxide n,th (PI-b-PEO) was 23.5 kg/mol. In the catalytic initiation system described in this example, the molar ratio of n-butyllithium, organic base, and boron alkyl was 1: 1: 3.
example 2
Anionic polymerization of isoprene was performed in tetrahydrofuran with n-butyllithium as an initiator, and capping was performed with ethylene oxide. And then, taking the active polyisoprene terminated by ethylene oxide as a macroinitiator and an organic/metal-free Lewis acid-base pair as a catalyst, carrying out ring-opening polymerization on the ethylene oxide, and preparing the polyisoprene-polyethylene oxide amphiphilic block copolymer by a one-pot method. The specific operation is as follows:
isoprene, ethylene oxide and tetrahydrofuran are all used after being dried. 1 part of n-butyllithium, 1000 parts of isoprene and an appropriate amount of tetrahydrofuran (isoprene initial concentration of 3.0mol/L) were added to a reactor previously cooled to-78 ℃ and stirred for 24 hours under an inert atmosphere. 2000 parts of ethylene oxide were subsequently added to the reactor and stirring was continued for 10min at-78 ℃. Thereafter, 1 part of phosphazene base is added t BuP 2 And 3 parts of a tetrahydrofuran solution of triethylboron, the ethylene oxide concentration before ring-opening polymerization was 4.6mol/L, and the mixture was stirred at room temperature for 24 hours. Stopping the reaction with acetic acid, collecting the crude product, precipitating with diethyl ether, and vacuum drying to obtain the final product. The crude product had a molecular weight of 126.6kg/mol, dispersity of 1.15 by SEC. 1 H NMR determined 100% conversion of both isoprene and ethylene oxide. Theoretical number average molecular weight M calculated by feeding ratio and conversion rate of n-butyllithium, isoprene and ethylene oxide n,th (PI-b-PEO) was 156.2 kg/mol. In the catalytic initiation system described in this example, the molar ratio of n-butyllithium, organic base, and boron alkyl was 1: 1: 3.
example 3
Anionic polymerization of isoprene was performed in tetrahydrofuran with n-butyllithium as an initiator, and capping was performed with ethylene oxide. And then, taking ethylene oxide-terminated active polyisoprene as a macroinitiator and an organic/metal-free Lewis acid-base pair as a catalyst, carrying out ring-opening polymerization on propylene oxide, and preparing the polyisoprene-polypropylene oxide block copolymer by a one-pot method. The specific operation is as follows:
isoprene, ethylene oxide, propylene oxide and tetrahydrofuran are all used after dehydration treatment. 1 part of n-butyllithium, 150 parts of isoprene and an appropriate amount of tetrahydrofuran (initial concentration of isoprene: 5.0mol/L) were added to a reactor previously cooled to-78 ℃ under an inert atmosphere and stirred for 12 hours. 1 part of ethylene oxide was then added to the reactor and stirring was continued for 20min at-78 ℃. Then 300 parts of propylene oxide and 1 part of phosphazene base are added t BuP 4 And 3 parts of a tetrahydrofuran solution of triethylboron, the concentration of propylene oxide before ring-opening polymerization was 5.9mol/L, and the mixture was stirred at room temperature for 24 hours. Terminating the reaction with acetic acid, collecting the crude product, and vacuum drying to obtain the final product. The crude product has a molecular weight of 30.1kg/mol and a dispersity of 1.13 as determined by SEC. 1 H NMR showed 100% conversion of both isoprene and propylene oxide. Theoretical number average molecular weight M calculated by feeding ratio of n-butyllithium, isoprene and propylene oxide and conversion rate n,th (PI-b-PPO) was 27.7 kg/mol. In the catalytic initiation system described in this example, the molar ratio of n-butyllithium, organic base, and boron alkyl was 1: 1: 3.
example 4
Anionic polymerization of isoprene was performed in tetrahydrofuran with n-butyllithium as an initiator, and capping was performed with ethylene oxide. And then, taking the polyisoprene terminated by ethylene oxide as a macroinitiator, taking an organic/metal-free Lewis acid-base pair as a catalyst, carrying out ring-opening polymerization on the butylene oxide, and preparing the polyisoprene-polybutylene oxide block copolymer by a one-pot method. The specific operation is as follows:
isoprene, ethylene oxide, butylene oxide and tetrahydrofuran are all used after dehydration treatment. 1 part of n-butyllithium, 100 parts of isoprene and an appropriate amount of tetrahydrofuran (initial concentration of isoprene: 5.0mol/L) were added to a reactor previously cooled to-78 ℃ under a nitrogen atmosphere and stirred for 12 hours. 1 part of ethylene oxide was then added to the reactor and stirring was continued for 10min at-78 ℃. Then 300 parts of butylene oxide and 1 part of phosphazene base are added t BuP 2 And 2 parts of a tetrahydrofuran solution of triethylboron, the concentration of butylene oxide before ring-opening polymerization was 6.5mol/L, and the mixture was stirred at room temperature for 24 hours. Terminating the reaction with acetic acid, collecting the crude product, and vacuum drying to obtain the final product. The crude product had a molecular weight of 26.4kg/mol and a dispersity of 1.12 as determined by SEC. 1 H NMR determined 100% conversion of both isoprene and butylene oxide. Theoretical number average molecular weight M calculated by feeding ratio of n-butyllithium, isoprene and butylene oxide and conversion rate n,th (PI-b-PBO) was 28.5 kg/mol. In the catalytic initiation system described in this example, the molar ratio of n-butyllithium, organic base, and boron alkyl was 1: 1: 2.
example 5
Anionic copolymerization of isoprene and butadiene was performed in tetrahydrofuran using n-butyllithium as an initiator, and capping was performed using ethylene oxide. And then, taking ethylene oxide-terminated polyolefin as a macroinitiator and an organic/metal-free Lewis acid-base pair as a catalyst to carry out ring-opening polymerization on the ethylene oxide, and preparing the poly (isoprene-co-butadiene) -polyethylene oxide amphiphilic block copolymer by a one-pot method. The specific operation is as follows:
isoprene, butadiene, ethylene oxide and tetrahydrofuran are all used after dehydration treatment. 1 part of n-butyllithium, 200 parts of isoprene, 200 parts of butadiene and an appropriate amount of tetrahydrofuran (the initial concentrations of isoprene and butadiene are each 2.0mol/L) were added to a reactor previously cooled to-78 ℃ under an inert atmosphere and stirred for 12 hours. 400 parts of ethylene oxide are subsequently added to the reactor and stirring is continued for 40min at-78 ℃. Thereafter, 1 part of phosphazene base is added t BuP 4 And 5 parts of a tetrahydrofuran solution of triisopropylboron, the ethylene oxide concentration before ring-opening polymerization was 3.3mol/L, and the mixture was stirred at 50 ℃ for 6 hours. Stopping the reaction with acetic acid, collecting the crude product, precipitating with methanol, and vacuum drying. The crude product had a molecular weight of 38.6kg/mol and a dispersity of 1.18 as determined by SEC. 1 H NMR determined 100% conversion of isoprene, butadiene and ethylene oxide. Theoretical number average molecular weight M calculated by feeding ratio and conversion rate of n-butyllithium, isoprene, butadiene and ethylene oxide n,th (P (I-co-B) -B-PEO) was 42.1 kg/mol. This implementationExample the molar ratio of n-butyllithium, organic base and boron alkyl in the catalytically initiated system was 1: 1: 5.
example 6
The anionic polymerization of isoprene was carried out in benzene with sec-butyllithium as an initiator and end-capping was carried out with ethylene oxide. And then, taking the polyisoprene terminated by ethylene oxide as a macroinitiator, taking an organic/metal-free Lewis acid-base pair as a catalyst, carrying out ring-opening polymerization on the ethylene oxide, and preparing the polyisoprene-polyethylene oxide amphiphilic block copolymer by a one-pot method. The specific operation is as follows:
isoprene, ethylene oxide and benzene are all used after dehydration treatment. 1 part of sec-butyllithium, 150 parts of isoprene and an appropriate amount of benzene (isoprene initial concentration of 2.0mol/L) were added to a dry reactor under an inert atmosphere, and stirred at room temperature for 12 hours. 300 parts of ethylene oxide are subsequently added to the reactor and stirring is continued at room temperature for 30 min. Then, 1 part of cycloamidine DBU and 10 parts of a tetrahydrofuran solution of triethylboron were added, and the concentration of ethylene oxide before ring-opening polymerization was 3.3mol/L, followed by stirring at room temperature for 12 hours. Stopping the reaction with acetic acid, collecting the crude product, precipitating with diethyl ether, and vacuum drying to obtain the final product. The crude product had a molecular weight of 24.6kg/mol, dispersity of 1.06 by SEC. 1 H NMR determined 100% conversion of both isoprene and ethylene oxide. Theoretical number average molecular weight M calculated by feeding ratio of sec-butyl lithium, isoprene and ethylene oxide and conversion rate n,th (PI-b-PEO) was 23.5 kg/mol. In this example, the molar ratio of sec-butyllithium, organic base, and boron alkyl in the catalytic initiation system was 1: 1: 10.
example 7
The solvent was changed to a mixture of tetrahydrofuran and benzene in a volume ratio of 1:4, and the initial concentrations of isoprene and ethylene oxide were unchanged, except that the same procedure as in example 6 was conducted, to obtain a polyisoprene-polyethylene oxide block copolymer. The crude product had a molecular weight of 21.1kg/mol and a dispersity of 1.15 as determined by SEC. 1 H NMR determined 100% conversion of both isoprene and ethylene oxide. Theoretical number average molecular weight M calculated by feeding ratio of sec-butyl lithium, isoprene and ethylene oxide and conversion rate n,th (PI-b-PEO) was 23.5 kg/mol.
Example 8
Styrene was anionically polymerized in benzene with sec-butyl lithium as initiator and capped with ethylene oxide. And then, using ethylene oxide-terminated polystyrene as a macroinitiator and an organic/metal-free Lewis acid-base pair as a catalyst to carry out ring-opening polymerization on the ethylene oxide, and preparing the polystyrene-polyethylene oxide amphiphilic block copolymer by a one-pot method. The specific operation is as follows:
styrene, ethylene oxide and benzene are all used after dehydration treatment. 1 part of sec-butyllithium, 200 parts of styrene and an appropriate amount of benzene (initial styrene concentration of 5.0mol/L) were charged into a dry reactor under an inert atmosphere, and stirred at room temperature for 12 hours. Subsequently, 500 parts of ethylene oxide were added to the reactor, and stirring was continued at room temperature for 10 min. Thereafter, 0.75 part of phosphazene base is added t BuP 4 And 3 parts of a tetrahydrofuran solution of triethylboron, the ethylene oxide concentration before ring-opening polymerization was 7.7mol/L, and the mixture was stirred at room temperature for 24 hours. Stopping the reaction with acetic acid, collecting the crude product, precipitating with diethyl ether, and vacuum drying to obtain the final product. The crude product has a molecular weight of 46.6kg/mol and a dispersity of 1.10 as determined by SEC. 1 The conversions of both styrene and ethylene oxide were 100% by H NMR. Theoretical number average molecular weight M calculated by feeding ratio of sec-butyl lithium, styrene and ethylene oxide and conversion rate n,th (PS-b-PEO) was 42.9 kg/mol. In the catalytic initiation system described in this example, the molar ratio of sec-butyl lithium, organic base, and alkyl boron is 1: 0.75: 3.
example 9
Polystyrene-polyethylene oxide amphiphilic block copolymers were obtained in the same manner as in example 8 except that the amounts of styrene and ethylene oxide used were changed to 1000 and 2000 parts, respectively (the initial concentrations of styrene and ethylene oxide were 5.0mol/L and 6.7mol/L, respectively). The crude product had a molecular weight of 153.4kg/mol by SEC and a dispersity of 1.19. 1 The conversions of both styrene and ethylene oxide were 100% by H NMR. Theoretical number average molecular weight M calculated by feeding ratio of sec-butyl lithium, styrene and ethylene oxide and conversion rate n,th (PS-b-PEO) 192.1 kg/mol.
Example 10
Anionic copolymerization of isoprene and butadiene in benzene with sec-butyl lithium as initiator and capping with ethylene oxide. And then, using ethylene oxide-terminated poly (isoprene-co-butadiene) as a macroinitiator and an organic/metal-free Lewis acid-base pair as a catalyst to carry out ring-opening polymerization on the ethylene oxide, and preparing the poly (isoprene-co-butadiene) -polyethylene oxide amphiphilic block copolymer by a one-pot method. The specific operation is as follows:
isoprene, butadiene, ethylene oxide and benzene are all used after dehydration treatment. 1 part of sec-butyllithium, 200 parts of isoprene, 300 parts of butadiene and an appropriate amount of benzene (initial concentrations of isoprene and butadiene were 2.0mol/L and 3.0mol/L, respectively) were added to a dry reactor under an inert atmosphere, and stirred at room temperature for 12 hours. 1000 parts of ethylene oxide are then added to the reactor and stirring is continued for 20min at room temperature. Then, 1 part of phosphazene base BEMP and 10 parts of triethylboron in tetrahydrofuran were added, and the ethylene oxide concentration before ring-opening polymerization was 6.7mol/L, and the mixture was stirred at room temperature for 24 hours. Stopping the reaction with acetic acid, collecting the crude product, precipitating with diethyl ether, and vacuum drying to obtain the final product. The crude product had a molecular weight of 68.5kg/mol and a dispersity of 1.15 as determined by SEC. 1 H NMR determined 100% conversion of isoprene, butadiene and ethylene oxide. Theoretical number average molecular weight M calculated by feeding ratio of sec-butyl lithium, isoprene, butadiene and ethylene oxide and conversion rate n,th (P (I-co-B) -B-PEO) was 73.9 kg/mol. In this example, the molar ratio of sec-butyllithium, organic base, and boron alkyl in the catalytic initiation system was 1: 1: 10.
example 11
Poly (isoprene-co-styrene) -polyethylene oxide amphiphilic block copolymer was obtained in the same manner as in example 10 except that the copolymerized olefin monomer was changed to isoprene and styrene in the amounts of 200 parts and 100 parts, respectively (initial concentrations of isoprene, butadiene and ethylene oxide were 2.0mol/L, 1.0mol/L and 6.7mol/L, respectively). The crude product had a molecular weight of 66.3kg/mol, dispersity of 1.10 by SEC. 1 The conversions of isoprene, styrene and ethylene oxide were all 100% by H NMR.Theoretical number average molecular weight M calculated by feeding ratio and conversion rate of sec-butyl lithium, isoprene, styrene and ethylene oxide n,th (P (I-co-S) -b-PEO) was 68.1 kg/mol.
Example 12
Poly (butadiene-co-styrene) -polyethylene oxide amphiphilic block copolymers were obtained by changing the copolymerized olefin monomers to butadiene and styrene in amounts of 400 parts, 50 parts and 500 parts, respectively, of butadiene, styrene and ethylene oxide (initial concentrations of butadiene, styrene and ethylene oxide were 2.0mol/L, 0.25mol/L and 4.0mol/L, respectively), otherwise as in example 10. The crude product had a molecular weight of 58.8kg/mol and a dispersity of 1.21 as determined by SEC. 1 The conversions of butadiene, styrene and ethylene oxide were all 100% by H NMR. Theoretical number average molecular weight M calculated by feeding ratio of sec-butyl lithium, butadiene, styrene and ethylene oxide and conversion rate n,th (P (B-co-S) -B-PEO) was 48.9 kg/mol.
Example 13
Anionic block copolymerization of butadiene and isoprene was carried out in benzene with sec-butyllithium as initiator and end-capping was carried out with ethylene oxide. Then, taking polybutadiene-b-polyisoprene terminated by ethylene oxide as a macroinitiator and taking organic/metal-free Lewis acid-base pair as a catalyst to carry out ring-opening polymerization on the epoxy butane, and preparing the polybutadiene-polyisoprene-polybutylene oxide triblock copolymer by a one-pot method. The specific operation is as follows:
butadiene, isoprene, ethylene oxide, butylene oxide and benzene are all used after water removal treatment. 1 part of sec-butyllithium, 100 parts of butadiene and the appropriate amount of benzene (initial butadiene concentration of 2.0mol/L) were added to a dry reactor under an inert atmosphere, and stirred at room temperature for 12 hours. Then 200 parts of isoprene was added to the reactor and stirred at room temperature for 12 hours. 1 part of ethylene oxide was then added to the reactor and stirring was continued at room temperature for 30 min. Then, 300 parts of butylene oxide, 5 parts of guanidine MTBD and 10 parts of triisopropylborane in tetrahydrofuran were added in this order, the concentration of butylene oxide before ring-opening polymerization was 3.1mol/L, and the mixture was stirred at room temperature for 6 hours. Stopping the reaction with acetic acid, collecting the crude product, precipitating with methanol, and vacuum drying to obtain. The crude product had a molecular weight of 39.8kg/mol and a dispersity of 1.18 as determined by SEC. 1 The conversions of butadiene, isoprene and butylene oxide were all 100% by H NMR. Theoretical number average molecular weight M calculated by feeding ratio of sec-butyl lithium, butadiene, isoprene and butylene oxide and conversion rate n,th (PI-b-PB-b-PBO) was 40.7 kg/mol. In the catalytic initiation system described in this example, the molar ratio of sec-butyl lithium, organic base, and alkyl boron is 1: 5: 10.
example 14
Using sec-butyl lithium as an initiator, carrying out anionic block copolymerization of styrene and isoprene in benzene, and carrying out end capping by using ethylene oxide; and then, sequentially carrying out ring-opening polymerization on the ethylene oxide and the propylene oxide by taking the ethylene oxide-terminated polystyrene-b-polyisoprene as a macroinitiator and an organic/metal-free Lewis acid-base pair as a catalyst, and preparing the polystyrene-polyisoprene-polyethylene oxide-polypropylene oxide tetrablock copolymer by a one-pot method. The specific operation is as follows:
styrene, isoprene, ethylene oxide, propylene oxide and benzene are all used after dehydration treatment. 1 part of sec-butyllithium, 100 parts of styrene and an appropriate amount of benzene (initial concentration of styrene: 4.0mol/L) were charged into a dry reactor under an inert atmosphere, and stirred at room temperature for 12 hours. 200 parts of isoprene are then added to the reactor and stirred at room temperature for 12 h. Then 100 parts of ethylene oxide is added, and after stirring for 20min at room temperature, 2 parts of phosphazene base is added t BuP 2 And 5 parts of a tetrahydrofuran solution of triethylboron, the ethylene oxide concentration before ring-opening polymerization was 2.0mol/L, and the mixture was stirred at room temperature for 3 hours. Then, 100 parts of propylene oxide was added thereto, and the mixture was stirred at room temperature for 6 hours. Stopping the reaction with acetic acid, collecting the crude product, precipitating with methanol, and vacuum drying. The crude product has a molecular weight of 43.6kg/mol and a dispersity of 1.20 as determined by SEC. 1 The conversions of styrene, isoprene, ethylene oxide and propylene oxide were all 100% by H NMR. Theoretical number average molecular weight M calculated by feeding ratio and conversion rate of sec-butyl lithium, styrene, isoprene, ethylene oxide and propylene oxide n,th (PS-b-PI-b-PEO-b-PPO) was 34.3 kg/mol. The catalyst initiation system described in this example contains sec-butyllithiumThe molar ratio of the organic base to the alkyl boron is 1: 2: 5.
the above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1.一种烯烃和环氧化物嵌段共聚的方法，其特征在于，包括如下步骤：1. a method for olefin and epoxide block copolymerization, is characterized in that, comprises the steps: 在惰性或氮气气氛中，以烯烃为单体，有机锂为引发剂，在溶液中进行烯烃的阴离子聚合反应，随后加入环氧乙烷对聚烯烃进行封端，制得链末端为烷氧基锂的活性聚烯烃；以链末端为烷氧基锂的活性聚烯烃为大分子引发剂，加入环氧化物单体以及有机碱和烷基硼组成的有机/无金属路易斯酸碱对催化剂，进行开环聚合反应，一锅法制得结构可控的聚烯烃-聚醚嵌段共聚物。In an inert or nitrogen atmosphere, using olefins as monomers and organolithium as initiators, anionic polymerization of olefins is carried out in solution, and then ethylene oxide is added to cap the polyolefins to obtain chain ends with alkoxyl groups. Lithium active polyolefin; using active polyolefin whose chain end is lithium alkoxide as macromolecular initiator, adding epoxide monomer and organic/metal-free Lewis acid-base catalyst composed of organic base and alkyl boron, A polyolefin-polyether block copolymer with controllable structure is prepared by a one-pot method through ring-opening polymerization. 2.根据权利要求1所述一种烯烃和环氧化物嵌段共聚的方法，其特征在于，所述有机锂引发剂与烯烃单体的摩尔比为1：(10～2000)；所述聚烯烃大分子引发剂、环氧化物、有机碱和烷基硼的摩尔比为1：(10～3000)：(0.05～10)：(0.05～10)；所述环氧乙烷与有机锂引发剂的摩尔比为(1～1.5)：1。2 . The method for block copolymerization of olefin and epoxide according to claim 1 , wherein the molar ratio of the organic lithium initiator to the olefin monomer is 1: (10～2000); the polymer The molar ratio of olefin macromolecular initiator, epoxide, organic base and alkyl boron is 1:(10-3000):(0.05-10):(0.05-10); the ethylene oxide and organolithium initiate The molar ratio of the agent is (1-1.5):1. 3.根据权利要求2所述一种烯烃和环氧化物嵌段共聚的方法，其特征在于，所述有机锂引发剂与烯烃单体的摩尔比为1：(10～800)；所述聚烯烃大分子引发剂、环氧化物、有机碱和烷基硼的摩尔比为1：(10～1000)：(0.1～3)：(0.1～3)。3 . The method for block copolymerization of olefin and epoxide according to claim 2 , wherein the molar ratio of the organic lithium initiator to the olefin monomer is 1: (10-800); the polymer The molar ratio of olefin macroinitiator, epoxide, organic base and alkyl boron is 1:(10-1000):(0.1-3):(0.1-3). 4.根据权利要求1所述一种烯烃和环氧化物嵌段共聚的方法，其特征在于，所述聚合温度均为-80～60℃，时间均为1～48h；环氧乙烷封端反应的时间为1～60min。4 . The method for block copolymerization of olefin and epoxide according to claim 1 , wherein the polymerization temperature is -80 to 60° C., and the time is 1 to 48 h; ethylene oxide is terminated. The reaction time is 1 to 60 min. 5.根据权利要求1所述一种烯烃和环氧化物嵌段共聚的方法，其特征在于，所述有机锂引发剂为R-Li，R为碳原子数为1～14的烷基、环烷基或芳基中的一种，Li为锂原子；5. the method for a kind of olefin and epoxide block copolymerization according to claim 1, is characterized in that, described organolithium initiator is R-Li, and R is the alkyl that carbon number is 1～14, ring One of the alkyl group or the aryl group, Li is a lithium atom; 所述有机碱为三级胺、脒、胍、三氨基膦或磷腈碱；所述三级胺为三乙烯二胺、五甲基二乙烯三胺、三-(2-二甲氨基乙基)胺和金雀花碱中的至少一种；所述脒为1,5-二氮杂二环[4.3.0]壬-5-烯和1,8-二氮杂二环十一碳-7-烯中的至少一种；所述胍为7-甲基-1,5,7-三氮杂二环[4.4.0]癸-5-烯、1,1,3,3-四甲基胍和1,1,2,3,3-五甲基胍中的至少一种；所述三氨基膦为三(二甲胺基)膦、三(二乙氨基)膦、2,8,9-三甲基-2,5,8,9-四氮杂-1-磷双环(3,3,3)十一烷和2,8,9-三异丙基-2,5,8,9-四氮杂-1-磷杂双环[3.3.3]十一烷中的至少一种；所述磷腈碱为2-叔丁基亚氨基-2-二乙基氨基-1,3-二甲基全氢-1,3,2-二氮杂磷、叔丁基亚氨基-三(二甲氨基)正膦、叔丁基亚氨基-三(吡咯烷)膦、1-叔丁基-2,2,4,4,4-五(二甲氨基)-2λ5,4λ5-链二(磷腈)、1-乙基-2,2,4,4,4-五(二甲氨基)-2λ5,4λ5-链二(磷腈)和1-叔丁基-4,4,4-三(二甲基氨基)-2,2-双[三(二甲基氨基)-膦亚基氨基]-2λ5,4λ5-链二(磷腈)中的至少一种；The organic base is tertiary amine, amidine, guanidine, triaminophosphine or phosphazene base; the tertiary amine is triethylenediamine, pentamethyldiethylenetriamine, tri-(2-dimethylaminoethyl) ) at least one of amines and genistein; the amidines are 1,5-diazabicyclo[4.3.0]non-5-ene and 1,8-diazabicycloundec- At least one of 7-ene; the guanidine is 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1,1,3,3-tetramethyl at least one of guanidine and 1,1,2,3,3-pentamethylguanidine; the triaminophosphine is tris(dimethylamino)phosphine, tris(diethylamino)phosphine, 2,8, 9-trimethyl-2,5,8,9-tetraaza-1-phosphobicyclo(3,3,3)undecane and 2,8,9-triisopropyl-2,5,8, At least one of 9-tetraaza-1-phosphabicyclo[3.3.3]undecane; the phosphazene base is 2-tert-butylimino-2-diethylamino-1,3- Dimethylperhydro-1,3,2-diazaphosphorus, tert-butylimino-tris(dimethylamino)phosphorane, tert-butylimino-tris(pyrrolidine)phosphine, 1-tert-butyl -2,2,4,4,4-Penta(dimethylamino)-2λ 5 ,4λ 5 -chain bis(phosphazene), 1-ethyl-2,2,4,4,4-penta(dimethylamino) amino)-2λ 5 ,4λ 5 -chain bis(phosphazene) and 1-tert-butyl-4,4,4-tris(dimethylamino)-2,2-bis[tris(dimethylamino)- At least one of phosphinoideneamino]-2λ 5 , 4λ 5 -chain di(phosphazene); 所述烷基硼为B-异松蒎基-9-硼二环[3.3.1]壬烷、三仲丁基硼烷、三异丙基硼烷、三甲基硼烷和三直链烷基硼烷中的至少一种，其中三直链烷基硼烷中直链烷基的碳原子数为2～8。The alkylborane is B-isopininyl-9-borabicyclo[3.3.1]nonane, tri-sec-butylborane, triisopropylborane, trimethylborane and trilinear alkane At least one of the alkyl boranes, wherein the straight-chain alkyl group in the tri-straight-chain alkyl borane has 2-8 carbon atoms. 6.根据权利要求5所述一种烯烃和环氧化物嵌段共聚的方法，其特征在于，所述有机锂引发剂为正丁基锂和/或仲丁基锂；所述有机碱为1,8-二氮杂二环十一碳-7-烯、7-甲基-1,5,7-三氮杂二环[4.4.0]癸-5-烯、2-叔丁基亚氨基-2-二乙基氨基-1,3-二甲基全氢-1,3,2-二氮杂磷、叔丁基亚氨基-三(二甲氨基)正膦、1-叔丁基-2,2,4,4,4-五(二甲氨基)-2λ5,4λ5-链二(磷腈)和1-叔丁基-4,4,4-三(二甲基氨基)-2,2-双[三(二甲基氨基)-膦亚基氨基]-2λ5,4λ5-链二(磷腈)中的至少一种；所述烷基硼为三乙基硼和三异丙基硼中的至少一种。6. the method for a kind of olefin and epoxide block copolymerization according to claim 5, is characterized in that, described organic lithium initiator is n-butyl lithium and/or sec-butyl lithium; Described organic base is 1 ,8-diazabicycloundec-7-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 2-tert-butylimino -2-Diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorus, tert-butylimino-tris(dimethylamino)phosphorane, 1-tert-butyl- 2,2,4,4,4-Penta(dimethylamino)-2λ 5 ,4λ 5 -chain bis(phosphazene) and 1-tert-butyl-4,4,4-tris(dimethylamino)- At least one of 2,2-bis[tris(dimethylamino)-phosphineylideneamino]-2λ 5 ,4λ 5 -chain two (phosphazene); the alkylboron is triethylboron and triethylboron At least one of isopropylboron. 7.根据权利要求1所述一种烯烃和环氧化物嵌段共聚的方法，其特征在于，所述烯烃单体为丁二烯、异戊二烯、苯乙烯、2-甲基苯乙烯、3-甲基苯乙烯、4-甲基苯乙烯、4-甲氧基苯乙烯、2,4-二甲基苯乙烯和2,5-二甲基苯乙烯中至少一种；7. the method for a kind of olefin and epoxide block copolymerization according to claim 1, is characterized in that, described olefin monomer is butadiene, isoprene, styrene, 2-methylstyrene, At least one of 3-methylstyrene, 4-methylstyrene, 4-methoxystyrene, 2,4-dimethylstyrene and 2,5-dimethylstyrene; 所述环氧化物单体为环氧乙烷、烷基碳原子数为1～20的直链烷基取代的环氧乙烷、烷基碳原子数为1～16的直链烷基缩水甘油醚、异丙基缩水甘油醚、叔丁基缩水甘油醚、2-乙基己基缩水甘油醚、苯基缩水甘油醚、苄基缩水甘油醚、烯丙基缩水甘油醚、炔丙基缩水甘油醚、甲基丙烯酸缩水甘油酯和丁酸缩水甘油酯中的至少一种。The epoxide monomer is ethylene oxide, ethylene oxide substituted with a straight-chain alkyl group having 1-20 alkyl carbon atoms, and straight-chain alkyl glycidol having 1-16 alkyl carbon atoms ether, isopropyl glycidyl ether, tert-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, benzyl glycidyl ether, allyl glycidyl ether, propargyl glycidyl ether , at least one of glycidyl methacrylate and glycidyl butyrate. 8.根据权利要求7所述一种烯烃和环氧化物嵌段共聚的方法，其特征在于，所述烯烃单体为异戊二烯、丁二烯和苯乙烯中的至少一种；所述环氧化物单体为环氧乙烷、环氧丙烷和环氧丁烷中的至少一种。8. the method for a kind of olefin and epoxide block copolymerization according to claim 7, is characterized in that, described olefin monomer is at least one in isoprene, butadiene and styrene; The epoxide monomer is at least one of ethylene oxide, propylene oxide and butylene oxide. 9.根据权利要求1所述一种烯烃和环氧化物嵌段共聚的方法，其特征在于，阴离子聚合前，烯烃单体的浓度为1～8mol/L；开环聚合反应前，环氧化物单体的浓度为1～10mol/L。9 . The method for block copolymerization of olefin and epoxide according to claim 1 , wherein, before the anionic polymerization, the concentration of the olefin monomer is 1 to 8 mol/L; before the ring-opening polymerization, the epoxide The concentration of the monomer is 1 to 10 mol/L. 10.根据权利要求1所述一种烯烃和环氧化物嵌段共聚的方法，其特征在于，所述溶剂为四氢呋喃、苯、正己烷和环己烷中至少一种。10 . The method for block copolymerization of olefin and epoxide according to claim 1 , wherein the solvent is at least one of tetrahydrofuran, benzene, n-hexane and cyclohexane. 11 .
CN202110261669.6A 2021-03-10 2021-03-10 A kind of method of olefin and epoxide block copolymerization Active CN115073724B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110261669.6A CN115073724B (en) 2021-03-10 2021-03-10 A kind of method of olefin and epoxide block copolymerization

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110261669.6A CN115073724B (en) 2021-03-10 2021-03-10 A kind of method of olefin and epoxide block copolymerization

Publications (2)

Publication Number Publication Date
CN115073724A true CN115073724A (en) 2022-09-20
CN115073724B CN115073724B (en) 2023-07-18

Family

ID=83240614

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110261669.6A Active CN115073724B (en) 2021-03-10 2021-03-10 A kind of method of olefin and epoxide block copolymerization

Country Status (1)

Country Link
CN (1) CN115073724B (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117186378A (en) * 2022-12-27 2023-12-08 辽宁奥克药业股份有限公司 Catalyst and preparation method for preparing polyethylene oxide, and preparation method of polyethylene oxide
CN118406224A (en) * 2024-07-03 2024-07-30 新疆天利石化股份有限公司 Amphiphilic polyisoprene-polyethylene glycol block copolymerization liquid rubber and preparation method thereof
CN121343148A (en) * 2025-12-22 2026-01-16 山东一诺威新材料有限公司 Natural latex polyether polyols, their preparation methods and applications

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105237695A (en) * 2015-10-14 2016-01-13 中国石油化工股份有限公司 Preparation method of epoxy group-terminated styrene-butadiene-styrene (SBS) ternary block copolymer
CN105237757A (en) * 2014-07-11 2016-01-13 中国石油化工股份有限公司 Catalyst for ring-opening copolymerization of oxyalkylene and lactide
CN107057005A (en) * 2017-03-30 2017-08-18 刘青 A kind of block copolymer of fragrant alkene, conjugated diene and epoxides and preparation method thereof
CN109517158A (en) * 2018-10-12 2019-03-26 华南理工大学 A method of causing system without metal catalytic based on three components and prepares polyethers

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105237757A (en) * 2014-07-11 2016-01-13 中国石油化工股份有限公司 Catalyst for ring-opening copolymerization of oxyalkylene and lactide
CN105237695A (en) * 2015-10-14 2016-01-13 中国石油化工股份有限公司 Preparation method of epoxy group-terminated styrene-butadiene-styrene (SBS) ternary block copolymer
CN107057005A (en) * 2017-03-30 2017-08-18 刘青 A kind of block copolymer of fragrant alkene, conjugated diene and epoxides and preparation method thereof
CN109517158A (en) * 2018-10-12 2019-03-26 华南理工大学 A method of causing system without metal catalytic based on three components and prepares polyethers

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
YE CHEN等: "High Efficiency Organic Lewis Pair Catalyst for Ring-Opening Polymerization of Epoxides with Chemoselectivity", 《MACROMOLECULES》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117186378A (en) * 2022-12-27 2023-12-08 辽宁奥克药业股份有限公司 Catalyst and preparation method for preparing polyethylene oxide, and preparation method of polyethylene oxide
CN118406224A (en) * 2024-07-03 2024-07-30 新疆天利石化股份有限公司 Amphiphilic polyisoprene-polyethylene glycol block copolymerization liquid rubber and preparation method thereof
CN118406224B (en) * 2024-07-03 2024-10-01 新疆天利石化股份有限公司 Amphiphilic polyisoprene-polyethylene glycol block copolymerization liquid rubber and preparation method thereof
CN121343148A (en) * 2025-12-22 2026-01-16 山东一诺威新材料有限公司 Natural latex polyether polyols, their preparation methods and applications

Also Published As

Publication number Publication date
CN115073724B (en) 2023-07-18

Similar Documents

Publication Publication Date Title
CN115028787B (en) Polar modifier system for high vinyl block copolymerization
CN115073724B (en) A kind of method of olefin and epoxide block copolymerization
EP3103820B1 (en) Novel anionic polymerization initiator and method for preparing conjugated diene-based polymer using same
CN102101902A (en) Method for preparing irregular copolymer of conjugated diene and vinyl arene
CN102344529B (en) A kind of preparation method of star-shaped solution-polymerized styrene-butadiene rubber with wide molecular weight distribution
KR100806402B1 (en) Star block copolymers and preparation method thereof
JP5780406B2 (en) Method for producing vinyl aromatic hydrocarbon-conjugated diene block copolymer using coupling reaction with improved ionic stability
CN102020757A (en) Linear high-impact butadiene/isoprene/styrene terpolymer resin and preparation method thereof
Baskaran et al. Anionic Vinyl Polymerization
CN104119522A (en) Polarized butadiene/styrene copolymer containing polyethylene oxide blocks and preparing method thereof
US20070173576A1 (en) Method for the anionic polymerization of oxirans
CN109134788B (en) Carboxyl-terminated SBS, preparation and application thereof in asphalt modification
JP7390201B2 (en) Method for manufacturing acrylic polymer
CN101429256B (en) Method for controlling anionic polymerization reaction
JP6033845B2 (en) Method for producing vinyl polymer
JP2020533464A (en) Modified polymerization initiator and its production method
CN117567687B (en) Random solution-polymerized styrene-butadiene rubber with high styrene content and low vinyl content and preparation method thereof
CN114106273B (en) Application of 1, 2-dialkoxypropane as polar regulator for synthesizing high-vinyl aryl ethylene-conjugated diene block copolymer
US20070100097A1 (en) Method for the anionic polymerisation of oxiranes
US20200131292A1 (en) Process for preparing a statistical copolymer based on acyclic diene monomers and cyclic diene monomers, copolymers and compositions containing same
WO2010083657A1 (en) Method for controlling anionic polymerization
EP3387022B1 (en) Method for the preparation of hydroxylated polyolefins
CN105712960A (en) Barium dibenzofuranoate compound and its preparation method, anion initiating system and preparation method of conjugated diene polymer
CN105585646A (en) Linear poly(1,3-pentadiene) having low allyl content and narrow molecular weight distribution and preparing method thereof
Ishizu et al. Anionic polymerization of t-butyl methacrylate using a new type of bifunctional initiator

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant