CN102690393A - Copolymer containing functional group and prepared by C5 mixture and maleic anhydride, and preparation of copolymer - Google Patents
Copolymer containing functional group and prepared by C5 mixture and maleic anhydride, and preparation of copolymer Download PDFInfo
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Abstract
The invention provides a copolymer containing a functional group and prepared by a C5 mixture and maleic anhydride and a preparation of the copolymer, belonging to the field of applications of C5 resource. The preparation method comprises the following steps of: adding monomer maleic anhydride and initiator azobisisobutyronitrile (AIBN) into ester medium under the protection of nitrogen, dissolving completely, adding C5 mixture into the system, and dissolving, wherein the mol ratio of the maleic anhydride and the C5 is 1:1, reacting for 0.05-7 hours at 50-90 DEG C so as to obtain a milky and stable solid-liquid disperse system of the copolymer of C5 and maleic anhydride, centrifugally separating and drying at vacuum condition so as to obtain the white solid powder of copolymer of C5 and maleic anhydride. According to the invention, the C5 mixture is directly used as the raw material to prepare the highly crosslinked copolymer containing the functional group in one-step reaction, in this way, the C5 resource is used reasonably and effectively.
Description
Technical field
The invention belongs to C5 resource Application Areas, be specifically related to the C5 mixture directly and maleic anhydride (MAn) prepared in reaction contain the highly cross-linked multipolymer of functional groups.
Background technology
China has abundant C5 resource, but because some technology, the chemical utilization rate of C5 is all lower all the time.How rational and effective is got up the C5 utilization of resources, and China meaning relatively deficienter comparatively speaking to resource is very great.At present, the emphasis of the C5 utilization of resources mainly utilizes aspect the high fine chemical product of single-component production added value two after producing the large Chemicals that have a large capacity and a wide range and C 5 fraction cracking.Wherein, the report about C 5 fraction and maleic anhydride reaction mainly contains following several respects.
The C5 petroleum resin are C5 fractions that petroleum cracking produces, through a kind of thermoplastic resin of explained hereafter such as pre-treatment, polymerization, distillation.Advantages such as the C5 petroleum resin are cheap because of it, compatibility good, fusing point is low, water-fast, anti-ethanol and chemical can be widely used in multiple industry and fields such as rubber, tackiness agent, coating, papermaking, printing ink.According to different concrete purposes, need C5 just can use after petroleum resin modified, and maleic anhydride is the most general to the modification of C5 petroleum resin.
Introduced among the US.NO.3929736 with maleic anhydride modified C5 petroleum resin; Again with resin after the sour modification and monohydroxy-alcohol reaction; Thereby obtain softening temperature more than 100 ℃ and can be dissolved in the resin of non-aromatic hydrocarbon solvent, this resin is mainly used in the various types of printing-inks of preparation.Compare with traditional resol, the C5 petroleum resin lighter color after the sour modification, printing performance is good, and viscosity performance is stable.
Introduced among the US.NO.3825624 with maleic anhydride modified C5 petroleum resin, the resin after the sour modification has been stirred in basic soln under 100 ℃ make its saponification again, obtained water-soluble sizing agent.This resin is water-soluble obviously to be superior to natural resin with the applying glue effect, and the color transparency is good.
Among the US.NO.4235981 C 5 fraction being added thermal distillation at a certain temperature, to obtain purity be 85% NSC 7352 (DCPC); NSC 7352 and maleic anhydride are mixed in xylene solvent, and can to get softening temperature in 270 ℃ of following reactions be that 92.5 ℃ of acid numbers are 226 maleic anhydride modified resin.This resin mainly is used for preparing the coating composition of solvent-free or water-solubility printing ink, but this coating composition fast setting under uviolizing and heating condition.
Among the US.NO.3976590 with C5 mixture and fused maleic anhydride under 100 ~ 130 ℃ with certain speed countercurrent reaction; 30 ~ 50% interior methyl tetrahydro phthalic anhydride, 4-methyl-THPA of 30 ~ 45% and 3-methyl-THPA of 10 ~ 25%; These three kinds of homology THPA mixture fusing points are at 40 ~ 60 ℃, and productive rate is about 99%.What mainly react in the C5 mixture in this reaction is isoprene, m-pentadiene and the cyclopentadiene of content about 50%, and these three kinds of diolefine primitive reactions are complete.But be easy to form gelatinous by product when preparing THPA with this method; So introduced among the US.NO.5237074 with the method that methyl tetrahydro phthalic anhydride in the Diels-Alder prepared in reaction takes place under C 5 fraction and the maleic anhydride condition that radical polymerization inhibitor exists in the oxygen atmosphere, this method is economical and practical and can effectively suppress the generation of gum polymers.
It is exactly the application of each single-component after its cracking that C 5 fraction also has an important use.The polymerization of monoolefine after the C 5 fraction cracking and diolefin and maleic anhydride also has some reports.
Edina Rusen; Bogdan Marculescu etc. are at " Copolymerization of the pair maleic anhydride-dicyclopentadiene: I .Copolymerization and postcopolymerization at high conversion " (Polymer International; 2005; 54:215-220) maleic anhydride (MA) and NSC 7352 (DCPD) being discussed in the literary composition is solvent with the DIOXANE; Lauroyl peroxide be initiator under argon shield, regulate monomer ratio and generate the linearity of different structure and crosslinked MA-DCPC polymkeric substance.Zhang Xu; Wang Xiaomei etc. are in " NSC 7352-maleic anhydride is free-radical polymerized " (" petrochemical complex "; 2005; 34 (5): be initiator with the Lucidol in the literary composition 474:477), butanone is a solvent, NSC 7352 and maleic anhydride is carried out copolymerization generate the MA-DCPC polymkeric substance under 70 ℃.
Introduced radical polymerization among the US.No.4748196 and be equipped with molecular weight at terminal olefin-maleic anhydride polymkeric substance of 200 to 3000; Comprising isopentene and maleic anhydride polymerization takes place under nitrogen protection and agitation condition, reaction got isopentene-maleic anhydride polymkeric substance in 3 hours under 80 ℃.
But because the C5 mixture is formed very complicacy, boiling point is approaching, can form more than 30 kind of azeotrope to each other, and the easy polymerization of diolefine, and the separating difficulty of C 5 fraction is very big, and using after therefore C 5 fraction being separated is a kind of uneconomic method again.Also mention the direct and required polymkeric substance of maleic anhydride prepared in reaction in the above-mentioned report with the C5 mixture; But its polymerization method is complicated; Polymerization technique requires high, and what react in the C5 mixture has only diolefine, and C5 mixture effective rate of utilization is not high; And resulting polymers is homology THPA mixture, and product types is single.
Summary of the invention
The objective of the invention is to the C5 mixture is the highly cross-linked multipolymer that the preparation of raw material single step reaction contains functional groups.Be the highly cross-linked multipolymer that the preparation of raw material single step reaction contains functional groups directly among the present invention with the C5 mixture; Alkene and diolefine all react with maleic anhydride in the C5 mixture; Alkane, alkynes and other component can be used as the medium of reaction system in the C5 mixture; Make the C5 resource be reasonably and effectively used, similarly method is not appeared in the newspapers up to now.
For realizing the object of the invention, technical scheme of the present invention is following:
Under the condition of nitrogen protection, monomer maleic anhydride and initiator azo-bis-isobutyl cyanide (AIBN) joined in the ester class medium fully dissolving after, add the C5 mixture again and in system, dissolve; The mol ratio of maleic anhydride and C5 mixture is 1:1; And, obtain the milky stable solid-liquid dispersion system of C5 and copolymer-maleic anhydride, through spinning in 50 ~ 90 ℃ of reaction 0.05 ~ 7h; Vacuum-drying obtains the white solid powder of C5 and copolymer-maleic anhydride.
Can confirm in the C5 mixture about 60% monoolefine and diolefine component as monomer all with the maleic anhydride reaction, alkane, alkynes and other component can be used as the impedance dielectric of reaction system, help the formation of gained copolymer dispersion system and stable.
Beneficial effect of the present invention is: (1) this method is a raw material with the C5 mixture directly; Need not refining separation of C 5 mixtures; Reduce reaction cost greatly, the monoolefine and the diolefine that account for simultaneously 60% component in the C5 mixture all react with maleic anhydride, and remain the impedance dielectric that 40% component can be used as reaction system in the C5 mixture; Help generating the formation of copolymer dispersion system and stablizing, can effectively utilize the C5 resource.It is very complicated because of forming that the present invention has also overcome the C5 mixture, and boiling point is approaching, and the separating difficulty of C 5 fraction is very big, thereby limits its application, and the present invention adopts single stage method, has promptly separated monoolefine and diolefine, simultaneously C5 is effectively utilized.(2) this method is the highly cross-linked copolymer microsphere that the preparation of raw material single step reaction contains functional groups with the C5 mixture, and technology is simple, operates controlled.
For example A, B, C, D are the identical four groups of parallel laboratory tests of reaction conditions in the embodiment of the invention 4; With the C5-maleic anhydride polymkeric substance of last gained with acetone extracting one day; Wash clean; Do C, H, three kinds of ultimate analyses of O, can calculate the ratio of maleic anhydride and C5 mixture in the polymkeric substance according to the result, its results of elemental analyses is as shown in table 2.Can draw following experiment conclusion by table 2: (1) C, H, O element total content explain and have only C in the polymkeric substance very near 100%, H, three kinds of elements of O.(2) convert and to obtain that maleic anhydride and C5 mol ratio are 1.3 ~ 1.4:1 in the polymkeric substance, explain that this polymkeric substance is highly cross-linked polymkeric substance.C5-maleic anhydride polymer microballoon solid-state nuclear magnetic resonance (13C-NMR) spectrogram such as Fig. 1.
Description of drawings
Fig. 1 C5-copolymer-maleic anhydride solid-state nuclear magnetic resonance (13C-NMR) spectrogram.
Embodiment
Embodiment 1
Heating in water bath is 70 ℃ under nitrogen protection; 2.9434g maleic anhydride and 0.2174g Diisopropyl azodicarboxylate are dissolved in the 60mL Isoamyl Acetate FCC medium; Ultrasonic dissolution gets colourless transparent solution, adds 2.3426g C5 mixture again, isothermal reaction 7h under nitrogen protection; Get C5 and maleic anhydride (MAn) multipolymer 3.1025g, yield is 58.49%.
Embodiment 2
Heating in water bath is 80 ℃ under nitrogen protection; 1.9626g maleic anhydride and 0.1121g Diisopropyl azodicarboxylate are dissolved in the 30mL Isoamyl Acetate FCC medium; Ultrasonic dissolution gets colourless transparent solution, adds 1.5612g C5 mixture again, isothermal reaction 7h under nitrogen protection; Get C5 and maleic anhydride (MAn) multipolymer 2.1571g, yield is 61.21%.
Embodiment 3
Heating in water bath is 90 ℃ under nitrogen protection; 0.9812g maleic anhydride and 0.0608g Diisopropyl azodicarboxylate are dissolved in the 15mL Isoamyl Acetate FCC medium; Ultrasonic dissolution gets colourless transparent solution, adds 0.7814g C5 mixture again, isothermal reaction 7h under nitrogen protection; Get C5 and maleic anhydride (MAn) multipolymer 0.9379g, yield is 53.21%.
Embodiment 4
Heating in water bath is 70 ℃ under nitrogen protection; A certain amount of maleic anhydride and Diisopropyl azodicarboxylate are dissolved in a certain amount of Isoamyl Acetate FCC/normal hexane blending agent; Ultrasonic dissolution gets colourless transparent solution; Add the C5 mixture on a certain amount of again, isothermal reaction 7h under nitrogen protection, C5 and maleic anhydride (MAn) multipolymer.
The prescription of each material is as shown in table 3 in the reaction system, and A, B, C, D are four groups of parallel laboratory tests.
The composition of table 1C5 mixture
The ultimate analysis of table 2C5-maleic anhydride (MAn) polymer microballoon
The preparation of table 3C5 and maleic anhydride (MAn) multipolymer
Reference example 1
Under the condition of nitrogen protection; After monomer maleic anhydride and initiator azo-bis-isobutyl cyanide joined in the Isoamyl Acetate FCC medium fully dissolving; Comprise isoprene, cyclopentadiene, NSC 7352,1 according to diolefine in the C5 mixture and monoolefine again; Dissolve in the ratio adding system respectively of 4-pentadiene, m-pentadiene, 1-amylene, 2-amylene, cyclopentenes, 2-methyl-1-butene alkene and 2-methyl-2-butene; And, obtain the dispersion system of corresponding monoolefine or diolefine and copolymer-maleic anhydride, through spinning in 50 ~ 90 ℃ of reaction 0.05 ~ 7h; Vacuum-drying obtains the white solid powder of corresponding monoolefine or diolefine and copolymer-maleic anhydride.
With acetone extracting one day, wash clean was done C, H, three kinds of ultimate analyses of O with the foregoing description gained C5-maleic anhydride polymkeric substance, can calculate the ratio of maleic anhydride and C5 mixture in the polymkeric substance according to the result.A, B, C, D are the identical four groups of parallel laboratory tests of reaction conditions (embodiment 4) in the table 2.Can draw following experiment conclusion by table 2: (1) C, H, O element total content explain and have only C in the polymkeric substance very near 100%, H, three kinds of elements of O.(2) maleic anhydride and C5 mol ratio are 1.3 ~ 1.4:1 in the polymkeric substance, explain that this polymkeric substance is highly cross-linked polymkeric substance.C5-maleic anhydride polymer microballoon solid-state nuclear magnetic resonance (13C-NMR) spectrogram such as Fig. 1.
The foregoing description relatively obtains identical material with corresponding reference example; Therefore can confirm in the C5 mixture that about 60% monoolefine and diolefine component all react with maleic anhydride as monomer; Alkane, alkynes and other component can be used as the impedance dielectric of reaction system, help the formation of gained copolymer dispersion system and stable.
Claims (2)
1. the multipolymer that contains functional groups of a C5 mixture-maleic anhydride preparation is characterized in that the preparation method of this polymkeric substance may further comprise the steps:
Under the condition of nitrogen protection, monomer maleic anhydride and initiator azo-bis-isobutyl cyanide (AIBN) joined in the ester class medium fully dissolving after, add the C5 mixture again and in system, dissolve; The mol ratio of maleic anhydride and C5 mixture is 1:1; And, obtain the milky stable solid-liquid dispersion system of C5 and copolymer-maleic anhydride, through spinning in 50 ~ 90 ℃ of reaction 0.05 ~ 7h; Vacuum-drying obtains the white solid powder of C5 and copolymer-maleic anhydride.
2. the method for the multipolymer that contains functional groups of C5 mixture and maleic anhydride prepared in reaction is characterized in that, may further comprise the steps:
Under the condition of nitrogen protection, monomer maleic anhydride and initiator azo-bis-isobutyl cyanide (AIBN) joined in the ester class medium fully dissolving after, add the C5 mixture again and in system, dissolve; The mol ratio of maleic anhydride and C5 mixture is 1:1; And, obtain the milky stable solid-liquid dispersion system of C5 and copolymer-maleic anhydride, through spinning in 50 ~ 90 ℃ of reaction 0.05 ~ 7h; Vacuum-drying obtains the white solid powder of C5 and copolymer-maleic anhydride.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017201964A1 (en) * | 2016-05-23 | 2017-11-30 | 北京化工大学 | Functional copolymer directly prepared from higher hydrocarbons mixture and preparation method therefor |
| CN107879876A (en) * | 2016-09-30 | 2018-04-06 | 中国石油化工股份有限公司 | A kind of method and apparatus of light hydrocarbon feedstocks production ethene and propylene |
| CN107879887A (en) * | 2016-09-30 | 2018-04-06 | 中国石油化工股份有限公司 | A kind of method and apparatus of ethane production ethene and propylene |
| CN107879875A (en) * | 2016-09-30 | 2018-04-06 | 中国石油化工股份有限公司 | A kind of method and apparatus of propane production ethene and propylene |
| CN107879873A (en) * | 2016-09-30 | 2018-04-06 | 中国石油化工股份有限公司 | A kind of method and apparatus of normal butane production ethene and propylene |
| CN113563152A (en) * | 2020-04-29 | 2021-10-29 | 清华大学 | Method for treating C five fraction and use of olefinic bond-containing compound |
| CN115181201A (en) * | 2022-07-06 | 2022-10-14 | 中国石油天然气股份有限公司 | Copolymerization method of C4-C8 alpha-monoolefin and maleic anhydride |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1114324A (en) * | 1994-06-10 | 1996-01-03 | 兰州大学 | Process for producing solid petroleum resin with light colour |
| CN101659736A (en) * | 2009-09-04 | 2010-03-03 | 广东新华粤石化股份有限公司 | Modification method of petroleum resin |
| CN101921367A (en) * | 2010-08-27 | 2010-12-22 | 朗盈科技（北京）有限公司 | A kind of production method of petroleum resin |
-
2012
- 2012-05-04 CN CN2012101381336A patent/CN102690393B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1114324A (en) * | 1994-06-10 | 1996-01-03 | 兰州大学 | Process for producing solid petroleum resin with light colour |
| CN101659736A (en) * | 2009-09-04 | 2010-03-03 | 广东新华粤石化股份有限公司 | Modification method of petroleum resin |
| CN101921367A (en) * | 2010-08-27 | 2010-12-22 | 朗盈科技（北京）有限公司 | A kind of production method of petroleum resin |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017201964A1 (en) * | 2016-05-23 | 2017-11-30 | 北京化工大学 | Functional copolymer directly prepared from higher hydrocarbons mixture and preparation method therefor |
| CN107879876A (en) * | 2016-09-30 | 2018-04-06 | 中国石油化工股份有限公司 | A kind of method and apparatus of light hydrocarbon feedstocks production ethene and propylene |
| CN107879887A (en) * | 2016-09-30 | 2018-04-06 | 中国石油化工股份有限公司 | A kind of method and apparatus of ethane production ethene and propylene |
| CN107879875A (en) * | 2016-09-30 | 2018-04-06 | 中国石油化工股份有限公司 | A kind of method and apparatus of propane production ethene and propylene |
| CN107879873A (en) * | 2016-09-30 | 2018-04-06 | 中国石油化工股份有限公司 | A kind of method and apparatus of normal butane production ethene and propylene |
| CN107879873B (en) * | 2016-09-30 | 2020-07-24 | 中国石油化工股份有限公司 | Method and device for producing ethylene and propylene from n-butane |
| CN107879887B (en) * | 2016-09-30 | 2020-07-24 | 中国石油化工股份有限公司 | Method and device for producing ethylene and propylene from ethane |
| CN107879876B (en) * | 2016-09-30 | 2020-07-24 | 中国石油化工股份有限公司 | Method and device for producing ethylene and propylene from light hydrocarbon raw material |
| CN107879875B (en) * | 2016-09-30 | 2020-07-24 | 中国石油化工股份有限公司 | Method and device for producing ethylene and propylene from propane |
| CN113563152A (en) * | 2020-04-29 | 2021-10-29 | 清华大学 | Method for treating C five fraction and use of olefinic bond-containing compound |
| CN115181201A (en) * | 2022-07-06 | 2022-10-14 | 中国石油天然气股份有限公司 | Copolymerization method of C4-C8 alpha-monoolefin and maleic anhydride |
| CN115181201B (en) * | 2022-07-06 | 2023-10-24 | 中国石油天然气股份有限公司 | Copolymerization method of C4-C8 alpha-mono-olefin and maleic anhydride |
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