WO2017201964A1 - 一种由高碳数烃类混合物直接制备的功能性共聚物及制备方法 - Google Patents

一种由高碳数烃类混合物直接制备的功能性共聚物及制备方法 Download PDF

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WO2017201964A1
WO2017201964A1 PCT/CN2016/103475 CN2016103475W WO2017201964A1 WO 2017201964 A1 WO2017201964 A1 WO 2017201964A1 CN 2016103475 W CN2016103475 W CN 2016103475W WO 2017201964 A1 WO2017201964 A1 WO 2017201964A1
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fraction
copolymer
fractions
mah
coal tar
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杨万泰
陈延昭
陈冬
王力
马育红
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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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
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/04—Anhydrides, e.g. cyclic anhydrides
    • C08F222/06—Maleic anhydride
    • C08F222/08—Maleic anhydride with vinyl aromatic monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/04—Polymerisation in solution
    • C08F2/06—Organic solvent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/04—Anhydrides, e.g. cyclic anhydrides
    • 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
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/04—Anhydrides, e.g. cyclic anhydrides
    • C08F222/06—Maleic anhydride

Definitions

  • the invention belongs to the field of resource application of C8, C9 fraction and coal tar light fraction in petroleum cracking and reforming, and particularly relates to the direct use of these mixture fractions with maleic anhydride (MAH), maleimide and its derivatives, clothing One or several reactions of the anhydride are used to prepare a functional copolymer.
  • MAH maleic anhydride
  • maleimide maleimide
  • clothing One or several reactions of the anhydride are used to prepare a functional copolymer.
  • the C8 and C9 fractions are mainly derived from the steam cracking ethylene process and the naphtha platinum reforming process, and some are derived from toluene disproportionation or transalkylation products and coal tar, etc., and their compositions are shown in Tables 1-4.
  • the C8 fraction mainly contains unsaturated hydrocarbons including styrene, allylbenzene, vinyl toluene, hydrazine, formazan, etc., and further rectification can be carried out to obtain a main component of xylene/ethylbenzene (60%-65). %), a mixture of styrene (about 30%).
  • the C9 fraction is a mixture of C9 aromatics and olefins. There are two main sources: one is reforming C9, mainly from the refinery of the refinery, and the other is from the ethylene production. product. As can be seen from Table 3, the composition of the C9 fractions of different manufacturers is substantially the same.
  • the cracked C 9 fraction contains a large amount of unsaturated hydrocarbons, and its composition is very complicated, and the boiling points are close to each other, which makes it difficult to perform fine separation.
  • the output of ethylene which represents the level of industrial development, has also increased significantly, so the production of C8 and C9 fractions as ethylene by-products has also increased. Therefore, how to effectively utilize high carbon number mixed by-products has become an important issue in the petroleum industry.
  • the light oil component in coal tar mainly contains styrene, ⁇ -methylstyrene, alkylbenzene, vinyltoluene, dicyclopentadiene, benzofuran, anthracene, formazan and methylbenzofuran, etc. Mainly used as a dark-light color coumarone resin raw material.
  • China's C8 fraction is mainly used in the production of para-xylene, blended gasoline and solvents.
  • Paraxylene is the basic raw material for the production of polyester, and unsaturated mixtures such as styrene and derivatives have not been utilized. .
  • the advantage of extracting styrene from pyrolysis gasoline is more obvious, while the C8 fraction contains more styrene, so the C8 extraction styrene technology has received more and more attention.
  • the first step in C8 extraction of styrene is to selectively convert the phenylacetylene in the C8 fraction to styrene through a selective hydrogenation reactor, and then separate the styrene from the other C8 components by extractive rectification. .
  • C8 extraction of styrene has a long process route, which is very difficult in practical operation.
  • First, the relative volatility of styrene and o-xylene in C8 is very small, and second, there is a trace amount of phenylacetylene in styrene.
  • the product styrene is colored for purity reasons.
  • C9 petroleum resin is a thermoplastic resin with a molecular weight of about 300-3000.
  • the production process of C9 petroleum resin mainly includes three methods of catalytic polymerization, free radical initiated polymerization and thermal polymerization, and catalytic polymerization is the most commonly used polymerization method.
  • the polymerization temperature is usually set at about 50 ° C
  • the reaction time is about 1-5 h
  • the reaction temperature and reaction time are not too high.
  • the most widely used catalytic polymerization method in the industry is an acid-catalyzed polymerization process using Lewis acid as a catalyst.
  • the catalytic polymerization process has the advantages of high polymerization speed and mild regulation, but it is easy to generate a large amount of industrial wastewater when the catalyst is removed. It is described in US Pat. No. 6,479,598 that the catalyst is coated on the catalyst support during the catalytic polymerization of the C9 fraction, thereby eliminating catalyst recovery and post-treatment.
  • the production of C9 petroleum resin is complicated, the production line is long, and a large amount of industrial wastewater is easily generated. Therefore, the production rate of C9 petroleum resin has been low, which greatly limits the reuse of C9 fraction resources.
  • Synthesis method of copolymer a method for synthesizing a low molecular weight styrene/maleic anhydride alternating copolymer disclosed in Chinese Patent No. ZL 200910079490.8, the disclosure of which is incorporated herein by reference.
  • a method of alternating copolymers of itaconic anhydride with a styrenic monomer discloses a process for preparing a series of monodisperse polymer microspheres of different sizes and compositions by self-stabilizing precipitation polymerization.
  • a cross-linking structure of monodisperse functional copolymer microspheres can be prepared by adding a crosslinking agent to a self-stabilizing precipitation polymerization system, and a crosslinked structure is disclosed in a series of patents.
  • a method of preparing copolymer microspheres For example, "A Method for Preparing a Crosslinked Maleic Anhydride-Vinyl Acetate Copolymer", which is disclosed in Chinese Patent Application No. 200810118553.1, discloses a crosslinked maleic anhydride-styrene copolymer disclosed in Chinese Patent Application No. 200810118552.7.
  • the object of the present invention is to prepare a copolymer containing a functional group in a one-step reaction using a high carbon number hydrocarbon mixture as a raw material.
  • the C8, C9 fraction and the coal tar light fraction in the petroleum cracking and reforming are directly subjected to copolymerization reaction with one or more of MAH, maleimide and its derivatives, and itaconic anhydride.
  • the functional copolymer is prepared by a stable precipitation polymerization method using a high carbon number hydrocarbon mixture as a raw material.
  • the monomer in the reaction system is composed of an electron donating monomer and an electron accepting monomer, wherein the electron donating monomer is composed of C8 and C9 fractions and Olefins in coal tar light fractions (styrene, allylbenzene, vinyl toluene, hydrazine, formamidine, dihydrodicyclopentadiene, dihydromethyldicyclopentadiene, dihydrodimethyldicyclopentadiene) One or several components of cyclopentadiene, methylcyclopentadiene, methyldicyclopentadiene, ⁇ -methylstyrene, dicyclopentadiene, benzofuran and methylbenzofuran;
  • the electron-accepting monomer is composed of one or more of MAH, maleimide and its derivative, itaconic an
  • the initiator used in the polymerization system is a common oil-soluble free radical initiator well known to those skilled in the art, and may be an azo initiator or a peroxide initiator.
  • the initiator content in the system is 0.05 to 10 wt% of the mass of the monomer. %, preferably 1 to 3 wt%.
  • the azo initiator includes: azobisisobutyronitrile, azobisisoheptanyl, azobisisobutyric acid a methyl ester or the like;
  • the peroxide initiator includes: dibenzoyl peroxide, dicumyl peroxide, bis(2,4-dichlorobenzoyl peroxide), di-tert-butyl peroxide, peroxidation Dodecyl, tert-butyl peroxybenzoate, diisopropyl peroxydicarbonate and dicyclohexyl peroxydicarbonate.
  • the solvent of the polymerization system may be an alkyl acid ester of an organic acid, an aromatic hydrocarbon or a mixed solution of a ketone and an alkane.
  • the structural formula of the organic acid alkyl ester is
  • R 1 is an alkyl group having 1 to 8 carbon atoms, a benzyl group, a phenyl group or a substituted phenyl group
  • R 2 is an alkyl group having 1 to 5 atomic atoms.
  • the organic acid alkyl ester includes ethyl formate, propyl formate, isobutyl formate, amyl formate, ethyl acetate, butyl acetate, isobutyl acetate, amyl acetate, isoamyl acetate, benzyl acetate, acetic acid.
  • Phenyl ester methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, butyl butyrate, isobutyl butyrate, butyl Isoamyl acid ester, ethyl isobutyrate, ethyl isovalerate, isoamyl isovalerate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, isoamyl benzoate, An ester solvent such as methyl phenylacetate, ethyl phenylacetate, propyl phenylacetate, butyl phenylacetate or isoamyl phenylacetate; the aromatic hydrocarbon is selected from the group consisting of toluene, xylene, ethylbenzene and the like; and the ketone is mixed with an al
  • the volume fraction of the ketone in the solution is 5%-65%
  • the ketone is selected from the group consisting of acetone, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, methyl isopropyl ketone
  • the alkane is selected from the group consisting of n-pentane
  • An alkane solvent such as an alkane, n-hexane, cyclohexane, n-heptane, n-octane or isooctane.
  • the electron-accepting monomer MAH, maleimide and its derivative, one or several of itaconic anhydride and the initiator are added to the organic solvent medium to be fully dissolved, and then transferred to the reaction system.
  • the mass ratio of electron accepting monomer to C8, C9 fraction and coal tar light fraction in the reaction system is 0.08-0.4, and at 60- The reaction is carried out at 120 ° C for 0.05-6 h.
  • reaction After the reaction is completed, it is centrifuged and dried in vacuo to obtain a C8, C9 fraction and a tar fraction of coal tar and a olefin monomer and MAH, maleimide and its derivative, and itaconic anhydride.
  • a functional copolymer formed by one or several copolymerization reactions.
  • the alkane, aromatic hydrocarbon and other components in the C8, C9 fraction and coal tar light fraction can be used as a poor medium for the reaction system, which is favorable for the formation and stability of the obtained copolymer dispersion system.
  • the beneficial effects of the invention are as follows: (1) The method directly divides the C8, C9 fraction and the coal tar light fraction into raw materials, without refining and separating, greatly reducing the cost, and the C8 fraction contains about 30% of the olefin component, and the C9 fraction is about Containing 37% of the olefin component, about 40% of the olefin component in the coal tar light fraction can be copolymerized as an electron donating monomer with MAH, maleimide and its derivatives, itaconic anhydride, and the rest Alkanes, aromatics and other components can be used as a reaction system medium, which is favorable for the formation and stability of the copolymer dispersion system, and the prepared copolymer anhydride functional group content is very high, so that the C8, C9 fraction and coal tar light fraction Resources are used effectively.
  • the invention also overcomes the problems that the C8, C9 fraction and the coal tar light fraction are complicated in composition, the boiling point is close, and the separation is difficult, so that the application thereof is limited.
  • the method adopts self-stabilized precipitation polymerization, does not require any stabilizer and stabilizer, and has high preparation efficiency, the obtained polymer is easy to be separated, the solvent is easy to be recycled and reused, and the solvent used is an alkyl acid ester, a ketone and an alkane. , low toxicity.
  • Figure 1 is a nuclear magnetic resonance ( 1 H-NMR) spectrum of a C8-MAH copolymer.
  • Figure 2 is a nuclear magnetic resonance ( 1 H-NMR) spectrum of a C9-MAH copolymer.
  • Figure 3 is an infrared spectrum of the C8-MAH and C9-MAH copolymers.
  • reaction product was centrifuged at 4000 rpm for 10 minutes, washed with petroleum ether, centrifuged three times, and dried under vacuum to constant weight to obtain 1.27 g of a C8-MAH copolymer in a yield of 94.23%. .
  • the copolymer was analyzed by three elements of C, H and O. The results are shown in Table 5. It was found that the content of the C element in the obtained C8-MAH copolymer was about 72.06%, the content of the H element was about 5.42%, and the content of the O element was about 22.52%. Since only the maleic anhydride monomer unit contains oxygen in the C8-MAH copolymer, the mass fraction of maleic anhydride in the C8-MAH copolymer is about 45.97%. By calculation, about 30% of the olefin component in the C8 fraction can be used as a comonomer for alternate copolymerization with MAH.
  • the nuclear magnetic resonance ( 1 H-NMR) spectrum of C8-MAH polymer is shown in Figure 1;
  • Figure 3 is the infrared spectrum of C8-MAH copolymer, where 1223 cm -1 is the stretching of the five-membered ring in maleic anhydride.
  • reaction product was centrifuged at 4000 rpm for 10 minutes, and washed with petroleum ether and centrifuged three times. Drying under vacuum to constant weight gave 1.91 g of a C8-MAH copolymer in a yield of 90.55%.
  • reaction product was centrifuged at 4000 rpm for 10 minutes, and washed with petroleum ether and centrifuged three times. The mixture was vacuum dried to constant weight to obtain 0.63 g of a C8-iconic anhydride copolymer, and the yield was 88.47%.
  • reaction product was centrifuged at 4000 rpm for 10 minutes, and washed with petroleum ether and centrifuged three times. Drying under vacuum to constant weight gave 4.24 g of a C8-maleimide copolymer in a yield of 89.19%.
  • xylene as a solvent for the reaction system, 5.0 g of maleic anhydride and 0.487 g of azobisisobutyronitrile were dissolved in 12.5 g of a C9 fraction (composition shown in Table 2, olefin content 38.78%) and 12.5 mL of xylene, so that ultrasonication was carried out. It is fully dissolved and mixed After homogenization, the mass ratio of MAH to C9 fraction in the reaction system was 0.40; the system was purged with nitrogen for 20 minutes, the reaction temperature was 60 ° C, and the reaction time was 6 hours.
  • reaction product was centrifuged at 4000 rpm for 10 minutes, and washed with petroleum ether and centrifuged three times. Drying under vacuum to constant weight gave 9.17 g of a C9-MAH copolymer in a yield of 93.10%.
  • the copolymer was analyzed by three elements of C, H and O. The results are shown in Table 6. It is understood that the content of the C element in the obtained C9-MAH copolymer is about 71.87%, the content of the H element is about 5.83%, and the content of the O element is about 22.30%. Since only the maleic anhydride monomer contains oxygen in the C9-MAH copolymer, the mass fraction of maleic anhydride in the C9-MAH copolymer is about 45.52%. By calculation, about 37% of the monomers in the C9 fraction can participate in the copolymerization reaction.
  • the nuclear magnetic resonance ( 1 H-NMR) spectrum of C9-MAH polymer is shown in Figure 2;
  • Figure 3 is the infrared spectrum of C9-MAH copolymer, where 1223 cm -1 is the stretching of the five-membered ring in maleic anhydride.
  • reaction product was centrifuged at 4000 rpm for 10 minutes, and washed with petroleum ether and centrifuged three times. Drying under vacuum to constant weight gave 9.33 g of a C9-MAH copolymer in a yield of 94.74%.
  • ethyl butyrate as a solvent for the reaction system, 3.0 g of maleimide and 0.097 g of dibenzoyl peroxide were dissolved in 12.5 g of C9 fraction (composition shown in Table 2, olefin content 38.78%) and 12.5 mL.
  • the mass ratio of the maleimide to the C9 fraction in the reaction system was 0.24 after the ultrasonic solution was sufficiently dissolved and uniformly mixed; the system was purged with nitrogen for 20 minutes, the reaction temperature was 95 ° C, and the reaction time was 6 hours.
  • reaction product was centrifuged at 4000 rpm for 10 minutes, and washed with petroleum ether and centrifuged three times. Drying under vacuum to constant weight gave 6.68 g of a C9-maleimide copolymer in a yield of 85.11%.
  • reaction product was centrifuged at 4000 rpm for 10 minutes, and washed with petroleum ether and centrifuged three times. Drying under vacuum to constant weight gave 1.32 g of a C9-iconic anhydride copolymer in a yield of 93.81%.
  • reaction product was centrifuged at 4000 rpm for 10 minutes, and washed with petroleum ether and centrifuged three times. Drying under vacuum to constant weight gave 8.78 g of coal tar-maleimide copolymer in a yield of 90.01%.

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Abstract

一种由高碳数烃类混合物直接制备的功能性共聚物及制备方法，属于石油资源应用领域，在氮气保护的条件下，将MAH、马来酰亚胺及其衍生物、衣康酸酐的一种或者几种和油溶性自由基引发剂加入到所选溶剂中充分溶解后，再将上述C8、C9馏分及煤焦油轻馏分的一种或几种加入上述体系中混合均匀，并于60-120℃反应，反应结束后，经分离干燥，得到由上述混合物中烯烃组分与马来酸酐共聚形成的功能性共聚物。本发明直接以C8、C9馏分及煤焦油轻馏分为原料，一步反应制备含有功能性基团的共聚物，工艺简单，反应条件温和，且制备效率高，所制备共聚物与非聚合组分分离容易，共聚物的功能性基团含量非常高，可使C8、C9馏分及煤焦油轻馏分资源得到合理有效的利用。

Description

一种由高碳数烃类混合物直接制备的功能性共聚物及制备方法 技术领域
本发明属于石油裂解和重整中的C8、C9馏分和煤焦油轻馏分的资源应用领域，具体涉及用这些混合物馏分直接与马来酸酐(MAH)、马来酰亚胺及其衍生物、衣康酸酐的一种或者几种反应制备功能性共聚物。
背景技术
C8和C9馏分主要来源于蒸汽裂解制乙烯工艺和石脑油铂重整工艺，还有一部分来源于甲苯歧化或烷基转移产物及煤焦油等,它们的组成见表1～4。
表1.C8馏分组成
Figure PCTCN2016103475-appb-000001
表2.C9馏分组成
Figure PCTCN2016103475-appb-000002
Figure PCTCN2016103475-appb-000003
表3.不同厂家的C9馏分组成
Figure PCTCN2016103475-appb-000004
表4.煤焦油轻馏分组成
Figure PCTCN2016103475-appb-000005
Figure PCTCN2016103475-appb-000006
由表1可见C8馏分主要含有不饱和烃包括苯乙烯、烯丙苯、乙烯基甲苯、茚、甲茚等，将其进一步精馏可得到主要成分为二甲苯/乙苯(占60％-65％)、苯乙烯(30％左右)的混合物。C9馏分是一种C9芳烃和烯烃混合物，其来源主要有两种：一种是重整C9，主要是来自炼油厂的重整装置二苯塔底油；还有一种是来自于乙烯生产的副产物。从表3中可知，不同厂家的C9馏分各组成成分大致相同。裂解C9馏分中含有大量的不饱和烃，其成分十分复杂，并且沸点相接近，导致精细分离的难度较大。随着我国的石油化工行业的快速发展，代表工业发展水平的乙烯的产量也大大增高，所以作为乙烯副产物的C8和C9馏分的产量也随之增高。因此，如何有效地利用好高碳数的混合副产物，也成了石油行业中的一个重要的课题。
煤焦油中的轻油组分主要含苯乙烯、α-甲基苯乙烯、烷基苯、乙烯基甲苯、双环戊二烯、苯并呋喃、茚、甲茚和甲基苯并呋喃等，目前主要作为深色-浅色的古马隆树脂原料。
目前，我国的C8馏分主要用于生产对二甲苯、调和汽油及溶剂，其中对二甲苯是生产聚酯的基础原料，而对其中的不饱和混合物，如苯乙烯及衍生物，还未得以利用。随着近年来乙烯的生产能力逐渐提高，使得从裂解汽油中抽提苯乙烯的优势更加明显，而C8馏分中含有较多的苯乙烯，所以C8抽提苯乙烯技术越来越受到关注。C8抽提苯乙烯第一步是要通过选择性加氢反应器，从而选择性地把C8馏分中的苯乙炔转化为苯乙烯，然后通过萃取精馏把苯乙烯和其他的C8组分分离开。C8抽提苯乙烯工艺路线较长，在实际操作中有很大的难度，一是C8中苯乙烯和邻二甲苯相对挥发度极小，二是苯乙烯中会存在微量的苯乙炔，三是产品苯乙烯由于纯度原因会带有颜色。这些技术上的难点都限制着C8 抽提苯乙烯工艺的发展。
目前，C9馏分较为常用的应用是用来合成芳烃石油树脂和作为溶剂使用，C9石油树脂是一种热塑性树脂，分子量约在300-3000之间。C9石油树脂的生产工艺主要包括催化聚合、自由基引发聚合和热聚合三种方式，其中催化聚合是最常用的聚合方法。聚合反应温度通常设定在50℃左右，反应时间在1-5h左右，反应温度与反应时间都不宜过高。目前工业上应用最广泛的催化聚合方法是，采用Lewis酸作为催化剂的酸催化聚合工艺，该催化聚合工艺的优点是聚合速度快且调节温和，但是在脱除催化剂时容易产生大量的工业废水。US.NO.6479598中介绍了在C9馏分的催化聚合过程中，在催化剂载体上包裹催化剂，从而省掉了催化剂的回收以及后处理过程。但是在日常工业生产中，由于生产C9石油树脂工艺复杂，生产线较长，且容易产生大量的工业废水，所以C9石油树脂的生产普及率一直很低，这大大限制了C9馏分资源的再利用。
在以往的研究过程中，本申请人在一系列专利里，公开了自稳定沉淀聚合法制备单分散共聚物微球方法。例如专利号为ZL 200310115329.4的中国专利公开的“马来酸酐与醋酸乙烯酯共聚反应的方法”，专利号为ZL200810101948.0的中国专利公开的“一种苯乙烯/马来酸酐共聚反应的方法”，申请号为200910087181.5的中国专利公开的“一种α-甲基苯乙烯与马来酸酐共聚反应的方法”，申请号为200910087177.9的中国专利公开的“一种高分子量苯乙烯与马来酸酐交替共聚物的合成方法”，专利号为ZL 200910079490.8的中国专利公开的“一种低分子量苯乙烯/马来酸酐交替共聚物的合成方法”，专利号为ZL 201010522333.2的中国专利公开的“一种制备衣康酸酐与苯乙烯类单体交替共聚物的方法”，上述专利公开了通过自稳定沉淀聚合制备一系列尺寸和组成不同的单分散聚合物微球的方法。以上述专利为基础，本申请人进一步提出在自稳定沉淀聚合体系中加入交联剂，可以制备出交联结构的单分散功能性共聚物微球，并在一系列专利里公开了交联结构共聚物微球的制备方法。例如申请号为200810118553.1的中国专利公开的“一种交联马来酸酐-醋酸乙烯酯共聚物的制备方法”，申请号为200810118552.7的中国专利公开的“一种交联马来酸酐-苯乙烯共聚物的制备方法”，申请号为201210138133.6的中国专利公开的“一种C5混合物-马来酸酐制备的含有功能性基团的共聚物及制备方法”，专利号为ZL  201110115705.4的中国专利公开的“一种双环戊二烯与马来酸酐共聚反应的方法”，专利号为ZL 201010130571.9的中国专利公开的“一种马来酸酐/共轭二烯烃共聚反应的方法”。自稳定沉淀聚合法克服常规聚合方法的缺点，工艺简单，反应条件温和，制备效率高，共聚物与非聚合组分分离容易；所制备的聚合物带有酸酐功能性基团，且功能性基团含量非常高。
发明内容
本发明的目的在于以高碳数烃类混合物为原料一步反应制备含有功能性基团的共聚物。本发明中直接以石油裂解和重整中的C8、C9馏分及煤焦油轻馏分为原料与MAH、马来酰亚胺及其衍生物、衣康酸酐的一种或者几种进行共聚合反应，通过自稳定沉淀聚合法制备含有功能性基团的共聚物，其中C8、C9馏分以及煤焦油轻馏分中单烯烃和二烯烃，可作为单体与MAH、马来酰亚胺及其衍生物、衣康酸酐发生交替或无规共聚合反应，而混合物中烷烃、芳烃及其它组分可作为反应体系的介质，有利于所制备共聚物分散体系的形成和稳定；本发明工艺简单，反应条件温和，制备效率高，且共聚物与非聚合组分分离容易；同时共聚物的功能性基团含量非常高，使得C8、C9馏分及煤焦油轻馏分资源得到合理有效的利用。
以高碳数烃类混合物为原料，自稳定沉淀聚合法制备功能性共聚物，反应体系中单体由给电子单体和受电子单体共同组成，其中给电子单体由C8、C9馏分和煤焦油轻馏分中的烯烃类(苯乙烯、烯丙苯、乙烯基甲苯、茚、甲茚、二氢双环戊二烯、二氢甲基双环戊二烯、二氢二甲基双环戊二烯、环戊二烯、甲基环戊二烯、甲基双环戊二烯、α-甲基苯乙烯、双环戊二烯、苯并呋喃和甲基苯并呋喃)的一种或者几种组成；受电子单体由MAH、马来酰亚胺及其衍生物、衣康酸酐的一种或者几种组成；反应体系的单体质量百分比浓度为5％-60％。
聚合体系所用引发剂为本专业的技术人员所熟知的普通油溶性自由基引发剂，可以是偶氮类引发剂或者是过氧化物引发剂，体系中引发剂含量为单体质量的0.05～10wt％，优选1～3wt％。所述的偶氮类引发剂包括：偶氮二异丁氰、偶氮二异庚氰、偶氮二异丁酸二 甲酯等；所述过氧化物引发剂包括：过氧化二苯甲酰、过氧化二异丙苯、过氧化二(2,4二氯苯甲酰)、过氧化二特丁基、过氧化十二酰、过氧化苯甲酸特丁酯、过氧化二碳酸二异丙基酯和过氧化二碳酸二环己酯等。
聚合体系的溶剂可以是有机酸烷基酯、芳烃或者酮与烷烃的混合溶液。其中所述有机酸烷基酯的结构通式为
Figure PCTCN2016103475-appb-000007
其中R1为H、C原子数为1-8的烷基，苄基，苯基或者取代苯基，R2为C原子数为1-5的烷基。有机酸烷基酯包括甲酸乙酯、甲酸丙酯、甲酸异丁酯、甲酸戊酯、乙酸乙酯、乙酸丁酯、乙酸异丁酯、乙酸戊酯、乙酸异戊酯、乙酸苄酯、乙酸苯酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、丙酸丁酯、丁酸甲酯、丁酸乙酯、丁酸丙酯、丁酸丁酯、丁酸异丁酯、丁酸异戊酯、异丁酸乙酯、异戊酸乙酯、异戊酸异戊酯、苯甲酸甲酯、苯甲酸乙酯、苯甲酸丙酯、苯甲酸丁酯、苯甲酸异戊酯、苯乙酸甲酯、苯乙酸乙酯、苯乙酸丙酯、苯乙酸丁酯、苯乙酸异戊酯等酯类溶剂；所述的芳烃选自甲苯、二甲苯、乙苯等溶剂；酮与烷烃混合溶液中酮的体积分数为5％-65％，所述的酮选自丙酮、丁酮、环己酮、甲基异丁基酮、甲基异丙基酮，所述的烷烃选自正戊烷、正己烷、环己烷、正庚烷、正辛烷和异辛烷等烷烃溶剂。
为实现本发明的目的，本发明技术方案如下：
在氮气保护的条件下，将受电子单体MAH、马来酰亚胺及其衍生物、衣康酸酐的一种或者几种和引发剂加入到有机溶剂介质中充分溶解后，再向反应体系中加入C8、C9馏分和煤焦油轻馏分的一种或几种并混合均匀，反应体系中受电子单体与C8、C9馏分和煤焦油轻馏分的质量比为0.08-0.4，并于60-120℃反应0.05-6h，反应结束后，经离心分离，真空干燥，得到C8、C9馏分和煤焦油轻馏分中烯烃单体与MAH、马来酰亚胺及其衍生物、衣康酸酐的一种或几种共聚合反应所形成的功能性共聚物。
可确定C8馏分中约含有30％的烯烃组分可作为给电子单体与MAH、马来酰亚胺及其衍生物、衣康酸酐进行共聚合反应；C9馏分中约含有37％的烯烃组分可作为给电子单体 与MAH、马来酰亚胺及其衍生物、衣康酸酐进行共聚合反应；煤焦油轻馏分中约含有40％的烯烃组分可作为给电子单体与MAH、马来酰亚胺及其衍生物、衣康酸酐进行共聚合反应。C8、C9馏分和煤焦油轻馏分与MAH、马来酰亚胺及其衍生物、衣康酸酐共聚合所制备的共聚物由C8、C9馏分及煤焦油轻馏分中的烯烃类物质(苯乙烯、烯丙苯、乙烯基甲苯、茚、甲茚、二氢双环戊二烯、二氢甲基双环戊二烯、二氢二甲基双环戊二烯、环戊二烯、甲基环戊二烯、甲基双环戊二烯、α-甲基苯乙烯、双环戊二烯、苯并呋喃和甲基苯并呋喃)与MAH、马来酰亚胺及其衍生物、衣康酸酐的一种或几种交替或无规共聚合所形成的功能性共聚物组成。
C8、C9馏分和煤焦油轻馏分中中烷烃、芳烃及其它组分可作为反应体系的不良介质，有利于所得共聚物分散体系的形成和稳定。
本发明的有益效果在于：(1)该方法直接以C8、C9馏分和煤焦油轻馏分为原料，无需精制分离，大大降低成本，C8馏分中约含有30％的烯烃组分，C9馏分中约含有37％的烯烃组分，煤焦油轻馏分中约含有40％的烯烃组分可作为给电子单体与MAH、马来酰亚胺及其衍生物、衣康酸酐进行共聚合反应，剩余的烷烃、芳烃及其它组分可作为反应体系介质，有利于生成共聚物分散体系的形成和稳定，且所制备的共聚物酸酐功能性基团含量非常高，使C8、C9馏分和煤焦油轻馏分资源得到有效利用。同时，本发明还克服了C8、C9馏分和煤焦油轻馏分因组成非常复杂，沸点接近，分离难度大，从而使其应用受到限制的问题。(2)该方法采用自稳定沉淀聚合，无需任何稳定剂和住稳定剂，制备效率较高，所得聚合物容易分离，溶剂易于回收重复使用，且所用溶剂为有机酸烷基酯、酮和烷烃，毒性较低。
附图说明
图1是C8-MAH共聚物的核磁共振(1H-NMR)谱图。
图2是C9-MAH共聚物的核磁共振(1H-NMR)谱图。
图3是C8-MAH和C9-MAH共聚物的红外光谱图。
具体实施方式
实施例1
以二甲苯作为反应体系的溶剂，将0.8g马来酸酐及0.084g偶氮二异丁腈溶于2.0g的C8馏分(组成见表1，烯烃含量27.64％)及6mL的二甲苯中，超声使其充分溶解并混合均匀后，反应体系中MAH与C8馏分的质量比为0.40；体系通氮气20分钟，反应温度为70℃，反应时间6小时。反应完成后，将反应产物在4000转每分钟的转速下离心分离10分钟，并加入石油醚洗涤、离心三次，真空干燥至恒重，即得到C8-MAH共聚物1.27g，收率为94.23％。
将共聚物做C、H、O三种元素分析，结果如表5所示。可知所得的C8-MAH共聚物中C元素的含量约72.06％，H元素的含量约5.42％，O元素的含量约22.52％。因为C8-MAH共聚物中只有马来酸酐单体单元含有氧元素，因此C8-MAH共聚物中马来酸酐的质量分数约为45.97％。通过计算可得，C8馏分中约有30％的烯烃成分，可作为共聚单体与MAH进行交替共聚合反应。C8-MAH聚合物核磁共振(1H-NMR)谱图如图1所示；图3是C8-MAH共聚物的红外光谱图，其中，1223cm-1处为马来酸酐中五元环的伸缩振动吸收峰，1785cm-1处为马来酸酐中酸酐基团C＝O的对称伸缩振动吸收峰，1859cm-1处为马来酸酐中酸酐基团C＝O的非对称伸缩振动吸收峰。从以上的特征峰可以表明制备的共聚物为C8-MAH共聚物。
实施例2
以乙酸异戊酯和正庚烷混合溶剂作为反应体系的溶剂，将1.0g马来酸酐及0.090g偶氮二异丁腈溶于4.0g的C8馏分(组成见表1，烯烃含量27.64％)及4mL乙酸异戊酯和2mL正庚烷中，超声使其充分溶解并混合均匀后，反应体系中MAH与C8馏分的质量比为0.40；体系通氮气20分钟，反应温度为75℃，反应时间6小时。反应完成后，将反应产物在4000转每分钟的转速下离心分离10分钟，并加入石油醚洗涤、离心三次。真空干燥至恒重，即得到C8-MAH共聚物1.91g，收率为90.55％。
实施例3
以乙酸异戊酯作为反应体系的溶剂，将0.4g马来酰亚胺及0.072g过氧化二异丙苯溶于2.0g的C8馏分(组成见表1，烯烃含量27.64％)及2mL的乙酸异戊酯中，超声使其充分溶解并混合均匀后，反应体系中马来酰亚胺与C8馏分的质量比为0.20；体系通氮气 20分钟，反应温度为120℃，反应时间6小时。反应完成后，将反应产物在4000转每分钟的转速下离心分离10分钟，并加入石油醚洗涤、离心三次。真空干燥至恒重，即得到C8-马来酰亚胺共聚物0.86g，收率为90.05％。
实施例4
以丁酮和正己烷混合溶剂作为反应体系的溶剂，将0.16g衣康酸酐及0.081g过氧化二苯甲酰溶于2.0g的C8馏分(组成见表1，烯烃含量27.64％)及1.5mL丁酮和0.5mL正己烷中，超声使其充分溶解并混合均匀后，反应体系中衣康酸酐与C8馏分的质量比为0.08；体系通氮气20分钟，反应温度为75℃，反应时间6小时。反应完成后，将反应产物在4000转每分钟的转速下离心分离10分钟，并加入石油醚洗涤、离心三次。真空干燥至恒重，即得到C8-衣康酸酐共聚物0.63g，收率为88.47％。
实施例5
以二甲苯作为反应体系的溶剂，将5.0g马来酸酐及0.2437g偶氮二异丁腈溶于12.5g的C8精馏馏分(烯烃含量30％)及12.5mL的二甲苯中，超声使其充分溶解并混合均匀后，反应体系中马来酸酐与C8精馏馏分的质量比为0.40；体系通氮气20分钟，反应温度为65℃，反应时间6小时。反应完成后，将反应产物在4000转每分钟的转速下离心分离10分钟，并加入石油醚洗涤、离心三次。真空干燥至恒重，即得到C8-马来酸酐共聚物8.37g，收率为95.63％。
实施例6
以乙酸异戊酯和正庚烷混合溶剂作为反应体系的溶剂，将1.0g马来酰亚胺及0.142g过氧化二苯甲酰溶于12.5g的C8精馏馏分(烯烃含量30％)及10mL乙酸异戊酯和2.5mL正庚烷中，超声使其充分溶解并混合均匀后，反应体系中马来酰亚胺与C8精馏馏分的质量比为0.08；体系通氮气20分钟，反应温度为85℃，反应时间6小时。反应完成后，将反应产物在4000转每分钟的转速下离心分离10分钟，并加入石油醚洗涤、离心三次。真空干燥至恒重，即得到C8-马来酰亚胺共聚物4.24g，收率为89.19％。
实施例7
以二甲苯作为反应体系的溶剂，将5.0g马来酸酐及0.487g偶氮二异丁腈溶于12.5g的C9馏分(组成见表2，烯烃含量38.78％)及12.5mL的二甲苯中，超声使其充分溶解并混 合均匀后，，反应体系中MAH与C9馏分的质量比为0.40；体系通氮气20分钟，反应温度为60℃，反应时间6小时。反应完成后，将反应产物在4000转每分钟的转速下离心分离10分钟，并加入石油醚洗涤、离心三次。真空干燥至恒重，即得到C9-MAH共聚物9.17g，收率为93.10％。
将共聚物做C、H、O三种元素分析，结果如表6所示。可知所得的C9-MAH共聚物中的C元素的含量约71.87％，H元素的含量约5.83％，O元素的含量约22.30％。因为在C9-MAH共聚物中只有马来酸酐单体含有氧元素，因此C9-MAH共聚物中马来酸酐的质量分数约为45.52％左右。通过计算可得，C9馏分中约有37％左右的单体可参加共聚反应。C9-MAH聚合物核磁共振(1H-NMR)谱图如图2所示；图3是C9-MAH共聚物的红外光谱图，其中，1223cm-1处为马来酸酐中五元环的伸缩振动吸收峰，1785cm-1处为马来酸酐中酸酐基团C＝O的对称伸缩振动吸收峰，1859cm-1处为马来酸酐中酸酐基团C＝O的非对称伸缩振动吸收峰。从以上的特征峰可以表明制备的共聚物为C9-MAH共聚物。
实施例8
以乙酸异戊酯和正庚烷混合溶剂作为反应体系的溶剂，将5.0g马来酸酐及0.487g偶氮二异丁腈溶于12.5g的C9馏分(组成见表2，烯烃含量38.78％)及10mL乙酸异戊酯和2.5mL正庚烷中，超声使其充分溶解并混合均匀后，反应体系中MAH与C9馏分的质量比为0.40；体系通氮气20分钟，反应温度为60℃，反应时间6小时。反应完成后，将反应产物在4000转每分钟的转速下离心分离10分钟，并加入石油醚洗涤、离心三次。真空干燥至恒重，即得到C9-MAH共聚物9.33g，收率为94.74％。
实施例9
以丁酸乙酯作为反应体系的溶剂，将3.0g马来酰亚胺及0.097g过氧化二苯甲酰溶于12.5g的C9馏分(组成见表2，烯烃含量38.78％)及12.5mL的丁酸乙酯中，超声使其充分溶解并混合均匀后，反应体系中马来酰亚胺与C9馏分的质量比为0.24；体系通氮气20分钟，反应温度为95℃，反应时间6小时。反应完成后，将反应产物在4000转每分钟的转速下离心分离10分钟，并加入石油醚洗涤、离心三次。真空干燥至恒重，即得到C9-马来酰亚胺共聚物6.68g，收率为85.11％。
实施例10
以丁酮和正己烷混合溶剂作为反应体系的溶剂，将0.24g衣康酸酐及0.058g过氧化二苯甲酰溶于3g的C9馏分(组成见表2，烯烃含量38.78％)及15mL丁酮和5mL正己烷中，超声使其充分溶解并混合均匀后，反应体系中衣康酸酐与C9馏分的质量比为0.08；体系通氮气20分钟，反应温度为80℃，反应时间6小时。反应完成后，将反应产物在4000转每分钟的转速下离心分离10分钟，并加入石油醚洗涤、离心三次。真空干燥至恒重，即得到C9-衣康酸酐共聚物1.32g，收率为93.81％。
实施例11
以二甲苯作为反应体系的溶剂，将5.0g马来酸酐及0.2437g偶氮二异丁腈溶于12.5g的煤焦油(组成见表4，烯烃含量70％)及12.5mL的二甲苯中，超声使其充分溶解并混合均匀后，反应体系中马来酸酐与煤焦油的质量比为0.40；体系通氮气20分钟，反应温度为65℃，反应时间6小时。反应完成后，将反应产物在4000转每分钟的转速下离心分离10分钟，并加入石油醚洗涤、离心三次。真空干燥至恒重，即得到煤焦油-马来酸酐共聚物12.78g，收率为92.95％。
实施例12
以乙酸异戊酯和正庚烷混合溶剂作为反应体系的溶剂，将1.0g马来酰亚胺及0.142g过氧化二苯甲酰溶于12.5g的煤焦油(组成见表4，烯烃含量70％)及10mL乙酸异戊酯和2.5mL正庚烷中，超声使其充分溶解并混合均匀后，反应体系中马来酰亚胺与煤焦油的质量比为0.08；体系通氮气20分钟，反应温度为85℃，反应时间6小时。反应完成后，将反应产物在4000转每分钟的转速下离心分离10分钟，并加入石油醚洗涤、离心三次。真空干燥至恒重，即得到煤焦油-马来酰亚胺共聚物8.78g，收率为90.01％。
表5.C8-MAH共聚物的元素分析结果
Figure PCTCN2016103475-appb-000008
表6.C9-MAH共聚物的元素分析结果
Figure PCTCN2016103475-appb-000009

Claims (6)

  1. 一种由高碳数烃类混合物直接制备的功能性共聚物，高碳数烃类混合物为石油裂解和重整中的C8、C9馏分及煤焦油轻馏分，其特征在于：
    对于石油裂解和重整中的C8和C9馏分，所制备的功能性共聚物包括C8和C9馏分中苯乙烯、烯丙苯、乙烯基甲苯、茚、甲茚、二氢双环戊二烯、二氢甲基双环戊二烯、二氢二甲基双环戊二烯、环戊二烯、甲基环戊二烯、甲基双环戊二烯的一种或几种与马来酸酐MAH、马来酰亚胺及其衍生物、衣康酸酐的一种或者几种交替或无规共聚合所形成的共聚物；
    对于煤焦油轻馏分，所制备的功能性共聚物包括煤焦油轻馏分中苯乙烯、α-甲基苯乙烯、乙烯基甲苯、双环戊二烯、苯并呋喃、茚、甲茚和甲基苯并呋喃的一种或几种与MAH、马来酰亚胺及其衍生物、衣康酸酐的一种或者几种交替或无规共聚合所形成的共聚物。
  2. 制备如权利要求1所述的功能性共聚物的方法，其特征在于，所述功能性共聚物直接通过自稳定沉淀聚合方法制备，具体包括以下步骤：
    首先，将单体MAH、马来酰亚胺及其衍生物、衣康酸酐的一种或者几种和油溶性引发剂加入到溶剂中充分溶解，之后向反应体系中加入C8、C9馏分和煤焦油轻馏分的一种或几种并混合均匀；
    其次，反应体系在氮气保护条件下，于60-120℃反应4-8小时，得到C8、C9馏分和煤焦油轻馏分与MAH、马来酰亚胺及其衍生物、衣康酸酐的一种或几种共聚合反应所形成的功能性共聚物的稳定固液分散体系；
    最终，固液分散体系离心分离，真空干燥。
  3. 根据权利要求2所述的方法，其特征在于，反应体系中单体由给电子单体和受电子单体共同组成，其中给电子单体由各种组成的C8，C9馏分，其中含苯乙烯、烯丙苯、乙烯基甲苯、茚、甲茚、二氢双环戊二烯、二氢甲基双环戊二烯、二氢二甲基双环戊二烯、环戊二烯、甲基环戊二烯、甲基双环戊二烯，以及各种组成的煤焦油轻馏分，其中含苯乙烯、α-甲基苯乙烯、乙烯基甲苯、双环戊二烯、苯并呋喃、茚、甲茚和甲基苯并呋喃 的一种或者几种组成；受电子单体由MAH、马来酰亚胺及其衍生物、衣康酸酐的一种或者几种组成。
  4. 根据权利要求2所述的方法，其特征在于，反应体系中MAH、马来酰亚胺及其衍生物、衣康酸酐与C8、C9馏分和煤焦油轻馏分的质量比为0.08-0.4；反应体系中总的单体质量百分比浓度为5-60％。
  5. 根据权利要求2所述的方法，其特征在于，反应体系中溶剂为有机酸烷基酯、芳烃或者酮与烷烃的混合溶液；其中所述有机酸烷基酯的结构通式为
    Figure PCTCN2016103475-appb-100001
    其中R1为H，C原子数为1-8的烷基，苄基，苯基或者取代苯基，R2为C原子数为1-5的烷基；所述的芳烃选自甲苯、乙苯或二甲苯；酮与烷烃混合溶液中酮的体积分数为5％-65％，所述的酮选自丙酮、丁酮、环己酮、甲基异丁基酮或甲基异丙基酮，所述的烷烃选自正戊烷、正己烷、环己烷、正庚烷、正辛烷或异辛烷。
  6. 根据权利要求2所述的方法，其特征在于，引发剂为偶氮类或过氧化物自由基引发剂的一种或者几种组成，体系中引发剂用量为单体质量的0.05～10wt％。
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CN116640249A (zh) * 2023-05-29 2023-08-25 江苏扬农化工集团有限公司 一种合成烯烃功能聚合物并联产烷烃的方法
CN116751323A (zh) * 2023-06-19 2023-09-15 江苏扬农化工集团有限公司 一种烯烃功能聚合物作为粘接剂制备电极浆料的方法
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CN119285852A (zh) * 2024-11-06 2025-01-10 清华大学 一种费托合成产品的自稳定沉淀聚合方法

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