CN112480292A - Method for preparing high molecular polymer by anionic polymerization of alkyl acrylate polar monomer - Google Patents

Method for preparing high molecular polymer by anionic polymerization of alkyl acrylate polar monomer Download PDF

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CN112480292A
CN112480292A CN202011375378.1A CN202011375378A CN112480292A CN 112480292 A CN112480292 A CN 112480292A CN 202011375378 A CN202011375378 A CN 202011375378A CN 112480292 A CN112480292 A CN 112480292A
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added
monomer
tetrahydrofuran
alkyl acrylate
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于胜楠
朱思琪
卢俊典
刘晓杰
李嵬
刘歌
陈二中
燕晓宇
鄂彦鹏
张娇
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Shenyang Research Institute of Chemical Industry Co Ltd
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Shenyang Research Institute of Chemical Industry Co Ltd
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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
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/10—Esters
    • C08F120/12—Esters of monohydric alcohols or phenols
    • C08F120/14—Methyl esters, e.g. methyl (meth)acrylate
    • 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
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • 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
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/04—Reduction, e.g. hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers

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Abstract

The invention belongs to the field of high molecular polymers, and particularly relates to a method for preparing a high molecular polymer by anionic polymerization of alkyl acrylate polar monomers and application of the high molecular polymer. In a system which does not use tetrahydrofuran as a solvent or a main component of the solvent, the polymerization reaction temperature is close to or higher than 0 ℃, under the assistance of a cap monomer, a certain amount of tetrahydrofuran is introduced to play a role in inhibiting the side reaction of the carbonyl of the alkyl acrylate polar monomer, and the molecular weight of the obtained product presents unimodal distribution. The side reaction inhibitor used in the invention is easier to obtain, has lower cost, simpler operation and lower danger. The product prepared by the method of the invention is used as a plastic and/or rubber blending modification compatibilizer, and the obtained blend (polymer alloy) has improved mechanical properties.

Description

Method for preparing high molecular polymer by anionic polymerization of alkyl acrylate polar monomer
Technical Field
The invention belongs to the field of high molecular polymers, and particularly relates to a method for preparing a high molecular polymer by anionic polymerization of alkyl acrylate polar monomers and application of the high molecular polymer.
Background
Anionic polymerization is a polymer preparation technology with a promising development prospect, has a simple reaction mechanism, has the characteristics of no termination and no chain transfer, and has remarkable advantages in the aspects of preparing polymers with narrow molecular weight distribution, block polymers, telechelic polymers and the like. In the anionic polymerization system, the commonly used monomers include olefin and alkyl acrylate, wherein the olefin monomer is relatively easy to polymerize and is industrially produced; the polymerization of alkyl acrylate monomers is a difficult point because the polar group of the polar monomers is easy to generate carbonyl side reaction in an anionic polymerization system, so that the molecular weight distribution of the product is widened, or the active species is terminated early, and the expected product is difficult to obtain. Capping with a capping agent having a large steric hindrance (e.g., 1-stilbene, DPE) before the polar monomer is added can suppress side reactions of the polar monomer. However, this method is generally effective only for the first or few polar monomers behind the capping monomer, and the range of action is very limited. To further suppress side reactions, it is common to lower the reaction temperature to cryogenic conditions (-78 ℃), and to introduce ligands/additives. The use of cryogenic conditions, while helpful in achieving the desired polymer product, is generally not suitable for commercial scale production due to its high cost constraints. Therefore, it is necessary to search a method for anionic polymerization of alkyl acrylate polar monomers under conditions suitable for industrial production. The literature: high molecular chemistry: 5 th edition, Beijing: chemical industry press, 2011: 168-179.
At present, the related preparation technology has more literature reports. Lee, Wudi, etc. utilize lithium chloride (LiCl) to complex active species to inhibit side reactions at-78 ℃. The literature: european Polymer Journal, 2011, 47 (4): 800-804; elastomer, 2020, 30 (2): 46-50.
Zundel, Zune, etc. utilize hexamethylcyclotrisiloxane (D)3) Complexing with initiator sec-butyl lithium (s-BuLi) to obtain active seed Bu (Me)2) SiOLi inhibits side reactions, and Methyl Methacrylate (MMA) homopolymers and copolymers with other alkyl acrylate polar monomers are prepared in toluene solvent at 0 ℃. The molecular structure of the used sec-butyl lithium has great influence on inhibiting side reaction, and the selection range of the initiator is limited; due to D3Can self-polymerize under the action of a polar regulator (such as tetrahydrofuran and the like) commonly used in anionic polymerization, and limits the selection range of a copolymer system. The literature: macromolecules, 1998, 31 (8): 2433-2439; journal of Polymer Science Part A Polymer Chemistry, 1999, 37 (14): 2525-2535.
Yigarbin et al utilize the steric hindrance of t-butyl methacrylate (TBMA) itself to inhibit side reactions by employing toluene/tetrahydrofuran mixture as the solvent at 10 ℃. The selection range of the monomer is limited by special requirements on the monomer type. The literature: journal of Polymer Materials, 1998, 15 (1): 67-72; chemical science and technology, 1999, 7 (1): 31-34; petrochemical, 2000, 29 (6): 428-431.
Series researches are carried out around the principle and the action of inhibiting side reactions of potassium tert-butoxide (t-BuOK), potassium phenoxide (K-O-Ar) and lithium phenoxide (Li-O-Ar) by using captain, Zheng Sonar, Zou, plum shining, Zhang and the like, but the types of the used inhibitors are not easy to obtain, or specific preparation steps are required to be added. The literature: polymer journal, 2015, (7): 835-844; RSC Advances, 2017, 7 (85): 53996-; chinese Journal of Chemistry, 2018, 36 (10): 934-; RSC Advances, 2019, 9 (28): 16049-16056; journal of Polymer Science Part A Polymer Chemistry, 2019, 57 (10): 1130-1139; macromolecular Chemistry and Physics, 2019, 220 (24): 1900390, respectively; CN 101429256B; CN 104672359B.
Plum blossom and the like, in the presence of cyclohexane at a temperature of 0 ℃. Trace amount of tetrahydrofuran (used in an amount of 1/50-1/5eq, most preferably 1/10eq, wherein 1eq represents the molar amount of macromolecules in a polymerization reaction system) is used for adjusting the content of the 1, 4-addition structure of the polyisoprene block to more than 93 percent and plays a role in accelerating the reaction. Carbonyl side reactions are suppressed by virtue of the non-polarity of the solvent cyclohexane used. Since the polar polymethyl methacrylate (PMMA) segment of the polymerization product is hardly soluble in nonpolar cyclohexane, the product is precipitated from the reaction system in a precipitated state. The product can be used as a polyvinyl chloride (PVC), styrene-butadiene copolymer elastomer (SBS) compatibilizer, and PMMA toughener. The literature: RSC Advances, 2017, 7 (16): 9933-9940.
Tetrahydrofuran is a common solvent or polar additive for anionic polymerization systems. In a system of a nonpolar solvent, the active species tend to associate, and the reaction efficiency is lowered. Tetrahydrofuran is introduced into the system, so that active species can be dissociated, and the reaction efficiency is improved. The literature: theory and application of anionic polymerization, beijing: chinese friendship publishing company, 1990: 75-87.
The above methods and documents disclose that anionic polymerization processes containing polar monomers of the alkyl acrylates type, limited by the susceptibility to carbonyl side reactions, are generally carried out at cryogenic temperatures of-78 ℃ and with the addition of specific side reaction inhibitors; even if the reaction temperature is raised to 0 ℃ or above, a corresponding specific inhibitor is added. The prior related art has complex and tedious operation and insufficient industrial application value, and the side reaction inhibitor is relatively difficult to obtain or needs to add corresponding preparation steps, has high cost and/or has specific dangers.
The above factors significantly restrict the application of alkyl acrylate polar monomer anionic polymerization systems in industrial production, and therefore it is necessary to search for polar monomer anionic polymerization systems more suitable for industrial production applications.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method for preparing a high molecular polymer by anionic polymerization of alkyl acrylate polar monomers. In order to achieve the purpose, the invention adopts the technical scheme that:
a method for preparing high molecular polymer by anionic polymerization of alkyl acrylate polar monomer features that in the anionic solution polymerization system, the polymerization reaction temp is-10-30 deg.C, and the tetrahydrofuran as carbonyl by-reaction inhibitor is introduced to make the alkyl acrylate polar monomer undergo the polymerization reaction to obtain the desired high molecular polymer.
The gas, solvent and monomer used in polymerization reaction must be fully removed of water oxygen impurity, especially water before adding into reaction system, and the water content of refined monomer must be generally not higher than 10 ppm. The method for purifying the solvent and the monomer may be any method known in the art, and is not particularly limited in the present invention.
Dispersing the active species into a solvent; wherein, the active species is small molecule or macromolecule active species.
The small molecule active species is obtained by reacting an initiator with a cap monomer, wherein the cap monomer comprises but is not limited to: 1, 1-stilbene (DPE), triphenyldivinyl, amino functionalized DPE, and the like. DPE is preferred. Such initiators include, but are not limited to: n-butyllithium, sec-butyllithium, tert-butyllithium, and naphthyllithium, etc., preferably n-butyllithium or sec-butyllithium, more preferably n-butyllithium.
The macromolecular active species is obtained by anionic solution polymerization of mono-olefin and/or multi-olefin and then reaction of mono-olefin and/or multi-olefin with a capping monomer, wherein the mono-olefin is preferably aryl olefin, such as styrene, methyl styrene and the like; the polyene is preferably a conjugated diene such as 1, 3-butadiene, isoprene, and the like. If tetrahydrofuran is used as the structure-regulating agent in the preparation of the macromolecular active species, the amount of this tetrahydrofuran is recommended to be not more than 1 to 300eq (1eq represents the molar amount of the macromolecule in the polymerization reaction system).
The solvent is C5-C15The alkane, benzene, toluene, xylene, ethylbenzene, propylbenzene, naphtha, preferably hexane (n-hexane, cyclohexane), heptane, octane, nonane, decane, undecane-tetradecane (i.e. C)11-C14) Methyl cyclohexane-butyl cyclohexane (i.e., methyl/ethyl/propyl/butyl cyclohexane), benzene, toluene, xylene, ethylbenzene, propylbenzene, naphtha, and the like. More preferably cyclohexane, toluene or a mixture of both. The use of pure nonpolar solvents (single-component or multicomponent mixtures) is not advisable, since the resulting polymers of polar monomers are poorly soluble in the system, can precipitate out of the system in the precipitated state during the reaction, and can be disadvantageous for the subsequent polymerization, coupling reaction and/or fluid transport steps.
After the above active species are dispersed in the solvent, the solid content of the reaction system is 0 (none) -40%, preferably 5-20%, more preferably 10-15%.
The inhibitor tetrahydrofuran is added before the polar monomer is added, and the dosage is 1-300eq, preferably 5-75eq, more preferably 40-60 eq. If tetrahydrofuran is used as a structure regulator in the process of preparing the macromolecular active species, the adding amount of the tetrahydrofuran used as an inhibitor is adjusted, so that the total amount of the tetrahydrofuran in the reaction system meets the requirement of the dosage of the inhibitor.
Reducing the temperature of the reaction system to-10-30 ℃, preferably-5-20 ℃, more preferably-2-18 ℃, and adding alkyl acrylate polar monomers for polymerization reaction.
The acrylic alkyl ester polar monomer is methacrylic acid C1-C15Alkyl esters or acrylic acids C1-C15Examples of the alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, and lauryl (meth) acrylate.
After the polar monomer is polymerized, a coupling agent can be added according to the requirement to prepare a star-shaped high-molecular polymer of a 'first arm and second core' type; among them, the coupling agent may be Divinylbenzene (DVB) or alkyl acrylate containing multiple alkenyl groups, more preferably ethylene dimethacrylate (EGDMA) and/or 1, 4-butylene dimethacrylate (BDDMA). The amount of the coupling agent to be used depends on the number of arms of the desired star-shaped product and is not particularly limited in the present invention. The arm number of the star product obtained is generally from 2 to 50, preferably from 2 to 40, more preferably from 2 to 30.
After the polymerization reaction is completed, a terminator is added to terminate the reaction. The kind and amount of the terminator to be used are not particularly limited in the present invention, and examples thereof include water (steam), hydrogen, methanol, ethanol, isopropanol, butanol, pentanol, hexanol, etc., preferably isopropanol.
The high molecular polymer obtained by the method is solid, mainly white, powdery, blocky or gelatinous; the molecular structure of the copolymer is a homopolymer and a copolymer of acrylic alkyl ester polar monomers or a (block, block-like) copolymer containing the acrylic alkyl ester polar monomers, and the copolymer is linear or star-shaped; the alkyl acrylate fraction of the linear product has an average molecular weight of usually 0.01 to 10 ten thousand, preferably 0.3 to 3 ten thousand, more preferably 0.5 to 2 ten thousand, and a molecular weight distribution breadth (polydispersity) of usually 1.0 to 1.6, preferably 1.0 to 1.5, more preferably 1.0 to 1.3; the star-shaped product is formed by coupling the linear products, and the molecular weight and the distribution width of the star-shaped product are different according to factors such as the coupling technical route adopted, the difference of the dosage of the coupling agent and the like.
The application of the high molecular polymer prepared by the method and the application of the high molecular polymer obtained by the copolymerization of the conjugated diene monomer in the selective hydrogenation reaction.
The product obtained by the copolymerization of the conjugated diene monomer can be selectively hydrogenated according to requirements, so that carbon-carbon double bonds left after the polymerization of the conjugated diene monomer are saturated, and the heat resistance is improved. The hydrogenation and post-hydrogenation catalyst removal methods used can be any method known in the art and are not specifically limited in the present invention, and the hydrogenation using a Ziegler-Natta catalyst and the catalyst removal using citric acid are preferred. The degree of hydrogenation of the carbon-carbon double bond of the obtained product is usually not less than 90%, preferably not less than 95%, more preferably not less than 98%; the residual catalyst (in the case of Ziegler-Natta catalysts) generally has a nickel content of not more than 30mg/kg, preferably not more than 20mg/kg, more preferably not more than 10 mg/kg.
The product with the nonpolar/weak polar chain segment and the polar chain segment prepared by the method is used as a plastic and/or rubber blending modification compatibilizer; the resulting blends (polymer alloys) have improved properties, such as mechanical properties. Non-polar/weakly polar components that may be used for blending are exemplified by: polyethylene (PE), polypropylene (PP), Butadiene Rubber (BR), Isoprene Rubber (IR), butyl rubber (IIR), styrene-butadiene rubber (SBR), Polystyrene (PS), styrene-conjugated diene copolymer elastomer (SBS/SIS/SEBS/SEPS), ethylene-propylene rubber (PPE/EPR/EPM/EPDM), polyolefin elastomer (POE), polyphenylene oxide (PPO), and the like; polar components are for example: polyamide (PA), Polycarbonate (PC), Polyurethane (PU), Polyoxymethylene (POM), polyethylene terephthalate (PET) and its copolyester (PETG), polybutylene terephthalate (PBT), polymethyl methacrylate (PMMA), polyvinyl chloride (PVC), chlorinated polyvinyl chloride (CPVC), polyvinyl alcohol (PVA), ethylene-vinyl acetate copolymer (EVA), ethylene-vinyl alcohol copolymer (EVOH), and the like. The literature is, for example: physico-chemical newspaper, 1998, 14 (2): 188-192.
The invention has the advantages and positive effects that:
under the condition of easy realization in industrial production at 0 ℃ or higher than 0 ℃, the invention leads the polar monomer of alkyl acrylate to participate in anionic polymerization reaction, and inhibits carbonyl side reaction under the action of a certain amount of tetrahydrofuran, thus obtaining polymer products with narrow molecular weight distribution and meeting expectations; different from the prior technical scheme, the reaction system used in the invention is relatively simple, the side reaction inhibitor is easier to obtain, the cost is lower, the operation is simpler and more convenient, and the potential risk is lower; the reaction conditions are favorable for overcoming the potential difficulties in the aspects of reaction mass transfer and fluid conveying in the prior technical scheme, and are more favorable for industrial production operation.
Detailed Description
The present invention will be further described with reference to the following examples.
In a system which does not use tetrahydrofuran as a solvent or a main component of the solvent, the polymerization reaction temperature is close to or higher than 0 ℃, so that the alkyl acrylate polar monomer participates in the anionic polymerization reaction, and a certain amount of tetrahydrofuran is utilized to play a role in inhibiting the side reaction of the polar monomer carbonyl with the help of a cap monomer. The molecular weight of the obtained product presents unimodal distribution, and the width (polydispersity) d of the molecular weight distribution is less than or equal to 1.5, even can reach about 1.3.
The product prepared by the method of the invention is used as a plastic and/or rubber blending modification compatibilizer, and the obtained blend (polymer alloy) has improved mechanical properties.
The gas, solvent and monomer used in the technical scheme are added into the reaction system to fully remove water oxygen impurities, particularly water, and the water content of the refined material is generally not higher than 10 ppm. The reaction vessel is a 5L stainless steel pressure reaction kettle, and is provided with fittings such as a pressure vacuum meter, a jacket, shaft cooling, mechanical stirring, a feeding pipeline (a feeding port), a gas pipeline, a vacuum pipeline and the like, wherein a reaction solvent is used for washing and cleaning before feeding, nitrogen gas (or other inert gases such as argon gas) is filled, and the cyclic pretreatment is carried out for at least 3 times by vacuumizing. The mechanical stirring is kept on during the reaction process, and the rotating speed is 1-1000 rpm. The medium in the jacket of the reaction kettle is a mixture of ethylene glycol (or propylene glycol, glycerol and the like) and water, and the temperature is controlled by using water bath equipment with circulating and refrigerating functions. The initiator was a 2.5mol/L n-butyllithium hexane solution.
Example 1: a methyl methacrylate homopolymer.
1241g of toluene and 2.0g of 1, 1-diphenylethylene are added into the reaction kettle under the temperature condition of 25 ℃. 1.85mL of n-butyllithium in hexane was added to initiate the reaction for 1 h. The temperature was reduced to 12 ℃ and 7.8g of tetrahydrofuran (46eq) was added and the reaction was carried out for 1 h. 13.9g of methyl methacrylate was added and reacted for 1 hour. After the reaction was completed, isopropanol was added to terminate the reaction. The product was precipitated with ethanol and washed and dried in vacuo at 40 ℃ for 12 h. The product was analyzed by Gel Permeation Chromatography (GPC) and had a number average molecular weight Mn＝5.8×103And the molecular weight distribution width (polydispersity) d is 1.44.
Example 2: methyl methacrylate-n-butyl acrylate copolymer.
1089g of toluene and 1.8g of 1, 1-diphenylethylene are added into the reaction kettle under the temperature condition of 21 ℃. 1.76mL of n-butyllithium in hexane was added to initiate the reaction for 1 hour. The temperature was reduced to 8 ℃ and 7.2g of tetrahydrofuran (43eq) was added and the reaction was carried out for 1 h. 9.0g of methyl methacrylate and 5.4g of n-butyl acrylate were added and reacted for 1 hour. After the reaction was completed, isopropanol was added to terminate the reaction. The product was precipitated with ethanol and washed and dried in vacuo at 40 ℃ for 12 h. Analysis of the product by GPC, its Mn＝6.2×103、d＝1.41。
Example 3: styrene-methyl methacrylate copolymer.
1003g of toluene and 66.3g of styrene were added to the autoclave at a temperature of 24 ℃. 1.70mL of n-butyllithium in hexane was added to initiate the reaction for 1 hour. 1.7g of 1, 1-diphenylethylene was added and reacted for 0.5 h. The temperature was reduced to 6 ℃ and 6.8g of tetrahydrofuran (40eq) was added and the reaction was carried out for 1 h. 19.7g of methyl methacrylate were added and reacted for 1 hour. After the reaction was completed, isopropanol was added to terminate the reaction. The product was precipitated with ethanol and washed and dried in vacuo at 40 ℃ for 12 h. Analysis of the product by GPC, its Mn＝3.7×104、d＝1.27。
Comparative example 1: styrene-methyl methacrylate copolymer.
1017g of toluene and 63.8g of styrene are added into the reaction kettle under the temperature condition of 27 ℃. 1.79mL of n-butyllithium in hexane was added to initiate the reaction for 1 h. 1.7g of 1, 1-diphenylethylene was added and reacted for 0.5 h. The temperature was reduced to 4 ℃ and 0.02g of tetrahydrofuran (0.1eq) was added and the reaction was carried out for 1 h. 16.9g of methyl methacrylate were added and reacted for 1 hour. After the reaction was completed, isopropanol was added to terminate the reaction. The product was precipitated with ethanol and washed and dried in vacuo at 40 ℃ for 12 h. The product was analyzed by GPC and appeared bimodal, indicating the occurrence of a carbonyl side reaction of methyl methacrylate.
Comparative example 2: styrene-methyl methacrylate copolymer.
Under the temperature condition of 28 ℃, 998g of toluene and 71.0g of styrene are added into a reaction kettle. 1.93mL of n-butyllithium in hexane was added to initiate the reaction for 1 hour. 1.6g of 1, 1-diphenylethylene was added and reacted for 0.5 h. The temperature was reduced to 3 ℃ and 18.9g of tetrahydrofuran (100eq) was added and the reaction was carried out for 1 h. 17.5g of methyl methacrylate was added and reacted for 1 hour. After the reaction was completed, isopropanol was added to terminate the reaction. The product was precipitated with ethanol and washed and dried in vacuo at 40 ℃ for 12 h. Analysis of the product by GPC, its Mn＝3.4×104、d＝1.43。
Comparative example 3: styrene-methyl methacrylate copolymer.
977g of toluene and 62.0g of styrene were charged into the reactor at a temperature of 22 ℃. 1.95mL of n-butyllithium in hexane was added to initiate the reaction for 1 hour. 1.6g of 1, 1-diphenylethylene was added and reacted for 0.5 h. The temperature was reduced to 2 ℃ and 14.8g of tetrahydrofuran (88eq) and 0.9g of lithium chloride (10eq) were added and reacted for 1 hour. 15.7g of methyl methacrylate were added and reacted for 1 hour. After the reaction was completed, isopropanol was added to terminate the reaction. The product was precipitated with ethanol and washed and dried in vacuo at 40 ℃ for 12 h. Analysis of the product by GPC, its Mn＝2.9×104、d＝1.48。
Comparative example 4: styrene-methyl methacrylate copolymer.
Under the temperature condition of 29 ℃, 1015g of toluene and 60.8g of styrene are added into the reaction kettle. 1.66mL of n-butyllithium in hexane was added to initiate the reaction for 1 hour. 1.7g of 1, 1-diphenylethylene was added and reacted for 0.5 h. The temperature was reduced to 0 ℃ and 0.2g of hexamethylcyclotrisiloxane (0.3eq) was added and the reaction was carried out for 20 h. 12.8g of methyl methacrylate was added and reacted for 1 hour. After the reaction was completed, isopropanol was added to terminate the reaction. The product was precipitated with ethanol and washed and dried in vacuo at 40 ℃ for 12 h. The product was analyzed by GPC and appeared bimodal, indicating the occurrence of a carbonyl side reaction of methyl methacrylate.
Comparative example 5: styrene-methyl methacrylate copolymer.
587g of toluene, 522g of cyclohexane and 49.6g of styrene were charged into the reactor at 30 ℃. 2.01mL of n-butyllithium in hexane was added to initiate the reaction for 1 hour. 2.2g of 1, 1-diphenylethylene was added and reacted for 0.5 h. The temperature was reduced to-1 ℃ and 40.5g of tetrahydrofuran (227eq) was added and the reaction was carried out for 1 h. 10.7g of methyl methacrylate were added and reacted for 1 hour. After the reaction was completed, isopropanol was added to terminate the reaction. The product was precipitated with ethanol and washed and dried in vacuo at 40 ℃ for 12 h. Analysis of the product by GPC, its Mn＝2.1×104、d＝1.54。
Comparative example 6: styrene-methyl methacrylate copolymer.
1120g of cyclohexane and 57.7g of styrene were added to the autoclave at a temperature of 50 ℃. 2.09mL of n-butyllithium in hexane was added to initiate the reaction for 1 h. 2.3g of 1, 1-diphenylethylene was added and reacted for 0.5 h. Cooling to 10 deg.C (if cooling to below 6 deg.C, macromolecular active species will precipitate out of the system in a precipitate state, which may be adverse to mass transfer of subsequent reaction), adding 0.9g tetrahydrofuran (5eq), and reacting for 1 h. 14.7g of methyl methacrylate were added and reacted for 1 hour. The product precipitates out of the system in a precipitated state during the reaction. After the reaction was completed, isopropanol was added to terminate the reaction. The product was filtered off and washed and dried in vacuo at 40 ℃ for 12 h. Analysis of the product by GPC, its Mn＝2.8×104、d＝1.44。
Comparative example 7: styrene-methyl methacrylate copolymer.
Under 50 ℃ temperature conditions, 58.3g of cyclohexane and 5.2g of styrene were charged into a 0.5L single neck round bottom glass flask. 0.18mL of n-butyllithium in hexane was added to initiate the reaction for 1 h. 0.2g of 1, 1-diphenylethylene was added and reacted for 0.5 h. 56.6g of tetrahydrofuran and 0.1g of lithium chloride (10eq) were added, the mixture was immersed in a dry ice acetone bath and cooled to-78 ℃, and 1.0g of methyl methacrylate was added and reacted for 1 hour. After the reaction is finished, adding isopropanol to stop the reaction. The product was precipitated with ethanol and washed and dried in vacuo at 40 ℃ for 12 h. Analysis of the product by GPC, its Mn＝2.5×104、d＝1.29。
The foregoing comparative examples 1-7 are comparative examples of example 3.
Example 4: styrene-ethyl methacrylate star copolymers.
At a temperature of 22 ℃, 1105g of toluene and 62.3g of styrene are added into the reaction kettle. 1.75mL of n-butyllithium in hexane was added to initiate the reaction for 1 h. 1.8g of 1, 1-diphenylethylene was added and reacted for 0.5 h. The temperature was reduced to 0 ℃ and 7.1g of tetrahydrofuran (43eq) was added and the reaction was carried out for 1 h. 15.0g of ethyl methacrylate was added thereto, and the mixture was reacted for 1 hour. 3.2g of ethylene dimethacrylate and 1.6g of 1, 4-butylene dimethacrylate were added and reacted for 1 hour. After the reaction was completed, isopropanol was added to terminate the reaction. The product was precipitated with ethanol and washed and dried in vacuo at 40 ℃ for 12 h. Analysis of the product by GPC, its Mn＝2.0×105D is 1.59, and the average arm number is 5.9.
Example 5: styrene-isoprene-hexyl methacrylate copolymers.
1129g of toluene, 43.2g of styrene and 88.5g of isoprene were added to the reactor at 25 ℃. 1.99mL of n-butyllithium in hexane was added to initiate the reaction for 1 hour. 1.8g of 1, 1-diphenylethylene was added and reacted for 0.5 h. The temperature was reduced to 3 ℃ and 8.4g of tetrahydrofuran (49eq) was added and the reaction was carried out for 1 h. 13.3g of hexyl methacrylate were added and reacted for 1 hour. After the reaction was completed, isopropanol was added to terminate the reaction. The product was precipitated with ethanol and washed and dried in vacuo at 40 ℃ for 12 h. Analysis of the product by GPC, its Mn＝6.1×104、d＝1.34。
The foregoing examples and comparative table 1 are as follows.
TABLE 1 polymerization conditions and Linear product Properties
Figure BDA0002807065850000071
As can be seen from the above Table 1, when the amount of tetrahydrofuran is insufficient, it is difficult to suppress the side reaction of hydroxyl group of the alkyl acrylate polar monomer; the amount of tetrahydrofuran is gradually increased, and the effect of inhibiting side reactions is better; when the amount of tetrahydrofuran used exceeds a preferable value, the effect of suppressing side reactions becomes poor.
Example 6: hydrogenation of styrene-isoprene-hexyl methacrylate copolymer.
Example 5 the glue solution obtained after the termination of the reaction was introduced into another reactor via a line for hydrogenation. The conditions are as follows: the dosage of the Ziegler-Natta catalyst (main catalyst nickel naphthenate and cocatalyst triisobutyl aluminum) is 4.5mg/g of nickel naphthenate, the molar ratio of aluminum to nickel is 5.9, the hydrogen pressure is 4.0MPa, the temperature is 63.6 ℃, and the time is 3.2 h. The hydrogenated glue solution is washed by citric acid aqueous solution to remove the catalyst, then washed by potassium carbonate aqueous solution to be neutral, and washed by water to remove the salt generated in the previous step. The water used in the washing process is deionized water. Centrifuging the washed glue solution, taking supernatant, precipitating the product with ethanol, washing, and vacuum drying at 40 deg.C for 12 h. The hydrogenation degree of the carbon-carbon double bond of the obtained product is 98.3 percent, and the content of the residual catalyst nickel is 9.8 mg/kg.
Example 7: compatibilized modified polymer blends.
The product obtained in example 6 was used as a compatibilizer for commercially available blends of hydrogenated styrene-butadiene copolymer elastomer (SEBS) and Polycarbonate (PC). The material loading is 85 parts of SEBS, 15 parts of PC and 3 parts of the product of the embodiment 6, the mixture is pressed and molded by a flat vulcanizing machine after being mixed, a sample is cut out by a mold, and the mechanical property is tested by a tensile testing machine according to the national standard GB/T528-one 2009. The tensile strength of the obtained blend is 8.1 MPa.
Comparative example 8: an uncompatibilized modified polymer blend.
The difference from example 7 is that no compatibilizer is added, and other conditions are the same. The tensile strength of the obtained blend is 7.2 MPa.
Comparative example 8 is a comparative example to example 7.
Although the present invention has been described to a certain extent, it is apparent that appropriate changes in the respective conditions may be made without departing from the spirit and scope of the present invention. It is to be understood that the invention is not limited to the described embodiments, but is to be accorded the scope consistent with the claims, including equivalents of each element described.

Claims (8)

1. A method for preparing high molecular polymer by anionic polymerization of alkyl acrylate polar monomers is characterized by comprising the following steps: in an anionic solution polymerization system, the polymerization reaction temperature is-10-30 ℃, and the alkyl acrylate polar monomer is subjected to polymerization reaction by introducing tetrahydrofuran as a carbonyl side reaction inhibitor with the assistance of a capping monomer active species to obtain a high molecular polymer with a molecular weight showing a monomodal distribution.
2. The method of claim 1, wherein: dispersing the active species into a solvent; the active species is micromolecule or macromolecular active species, the micromolecule active species is obtained by reacting an initiator with a cap monomer, and the macromolecular active species is obtained by carrying out anionic solution polymerization on mono-olefin and/or multi-olefin and then reacting with the cap monomer; the solvent is C5-C15And one or more of alkane, benzene, toluene, xylene, ethylbenzene, propylbenzene and naphtha.
3. A method according to claim 1 or 2, characterized in that: the inhibitor tetrahydrofuran is added before or after the cap monomer is added and before or after the reaction system is cooled, and the dosage of the tetrahydrofuran is 1-300 eq.
4. The method of claim 3, wherein: reducing the temperature of the reaction system to-10-30 ℃, and adding alkyl acrylate polar monomer for polymerization reaction; tetrahydrofuran is added as a side reaction inhibitor during the polymerization reaction, wherein the tetrahydrofuran is added before the polar monomer is added.
5. The method of claim 1, wherein: the alkyl acrylate polar monomer is methacrylic acid C1-C15Alkyl esters or acrylic acids C1-C15An alkyl ester.
6. The method of claim 1, wherein: and adding a coupling agent after the polar monomer is subjected to polymerization reaction to prepare the arm-first-core-last star-shaped high-molecular polymer.
7. The use of the polymer according to claim 1, wherein: use of a high molecular weight polymer obtained by homopolymerization or copolymerization of a conjugated diene monomer according to the process of claim 1 or 2 in a selective hydrogenation reaction.
8. The use of the polymer according to claim 1, wherein: use of the product having nonpolar segments and polar segments obtained by the process according to claim 1 as a compatibilizer for modifying plastics and/or rubbers.
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