CN102690393B - 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 directly with maleic anhydride (MAn), react with the C5 mixture the highly cross-linked multipolymer that preparation contains functional groups.
Background technology
China has abundant C5 resource, but, due to some technology, the chemical utilization rate of C5 is all the time all lower.How rationally effectively the C5 utilization of resources being got up, to resource, deficienter China's meaning is very great comparatively speaking.At present, the emphasis of the C5 utilization of resources mainly utilizes aspect the fine chemical product two that the single-component production added value is high after producing large Chemicals of having a large capacity and a wide range and C 5 fraction cracking.Wherein, the report reacted with maleic anhydride about C 5 fraction mainly contains following several respects.
The C5 petroleum resin are C5 fractions that petroleum cracking produces, through a kind of thermoplastic resin of the explained hereafter such as pre-treatment, polymerization, distillation.The C5 petroleum resin because it is cheap, compatibility is good, fusing point is low, the advantage such as water-fast, anti-ethanol and chemical, can be widely used in multiple industry and the fields such as rubber, tackiness agent, coating, papermaking, printing ink.According to different concrete purposes, need just can use afterwards C5 is petroleum resin modified, and maleic anhydride is the most general to the modification of C5 petroleum resin.
In US.NO.3929736, introduced with maleic anhydride modified C5 petroleum resin, again the resin after sour modification is reacted with monohydroxy-alcohol, thereby obtain softening temperature more than 100 ℃ and can be dissolved in the resin of non-aromatic hydrocarbon solvent, this resin is mainly for the preparation of various types of printing-inks.With traditional resol, compare, the C5 petroleum resin lighter color after sour modification, printing performance is good, and viscosity performance is stable.
Introduced in US.NO.3825624 with maleic anhydride modified C5 petroleum resin, then the resin after sour modification is stirred and makes its saponification under 100 ℃ in basic solution, obtained water-soluble sizing agent.This resin is water-soluble obviously is better than natural resin with the applying glue effect, and the color transparency is good.
In US.NO.4235981, C 5 fraction is added at a certain temperature to thermal distillation and obtain the dicyclopentadiene (DCPC) that purity is 85%, dicyclopentadiene and maleic anhydride are mixed in xylene solvent, and under 270 ℃ reaction can to obtain softening temperature be the maleic anhydride modified resin that 92.5 ℃ of acid numbers are 226.This resin is mainly used to prepare the coating composition of solvent-free or water-solubility printing ink, but this coating composition fast setting under uviolizing and heating condition.
In US.NO.3976590 with the maleic anhydride of C5 mixture and melting under 100 ~ 130 ℃ with certain speed countercurrent reaction, 30 ~ 50% interior methyl tetrahydro phthalic anhydride, 4-methyl-tetrahydrophthalic anhydride of 30 ~ 45% and 3-methyl-tetrahydrophthalic anhydride of 10 ~ 25%, these three kinds of homology tetrahydrophthalic anhydride mixture fusing points are at 40 ~ 60 ℃, and productive rate is 99% left and right.What in this reaction, in the C5 mixture, mainly react is approximately 50% isoprene, m-pentadiene and cyclopentadiene of content, and these three kinds of diolefine primitive reactions are complete.But be easy to form gelatinous by product while by this method, preparing tetrahydrophthalic anhydride, so introduced in US.NO.5237074 with the method for methyl tetrahydro phthalic anhydride in Diels-Alder reaction preparation occurs 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 application.The polymerization of the 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) has been discussed in a literary composition and dicyclopentadiene (DCPD) be take dioxane as solvent, lauroyl peroxide is that initiator is 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 " Dicyclopentadiene-Maleic Anhydride Freeradical Copolymerization " (" petrochemical complex ", 2005,34(5): 474:477) take benzoyl peroxide in a literary composition as initiator, butanone is solvent, and dicyclopentadiene and maleic anhydride are carried out to copolymerization generation MA-DCPC polymkeric substance under 70 ℃.
Introduced the standby molecular weight of radical polymerization in US.No.4748196 at alpha-olefin-maleic anhydride polymer of 200 to 3000; under nitrogen protection and agitation condition, polymerization occurs comprising isopentene and maleic anhydride, under 80 ℃, reaction obtains isopentene-maleic anhydride polymer in 3 hours.
But because the C5 compositions of mixtures is very complicated, boiling point approaches, and can form to each other more than 30 kind of azeotrope, and the easy polymerization of diolefine, and the separating difficulty of C 5 fraction is very large, after therefore C 5 fraction being separated, applying is a kind of uneconomic method again.Also mention in above-mentioned report with the C5 mixture and directly with maleic anhydride, react the required polymkeric substance of preparation, but its polymerization process complexity, polymerization technique requires high, what in the C5 mixture, react only has diolefine, C5 mixture effective rate of utilization is not high, and resulting polymers is homology tetrahydrophthalic anhydride mixture, and product types is single.
Summary of the invention
The object of the invention is to take the highly cross-linked multipolymer that the C5 mixture contains functional groups as the preparation of raw material single step reaction.The highly cross-linked multipolymer that the C5 mixture of directly take in the present invention contains functional groups as the preparation of raw material single step reaction, in 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, make the C5 resource be reasonably and effectively used, similarly method has no report up to now.
For realizing purpose of the present invention, technical solution of the present invention is as follows:
Under the condition of nitrogen protection; after monomer maleic anhydride and initiator azo-bis-isobutyl cyanide (AIBN) are joined in ester class medium and fully dissolve; add again the C5 mixture to dissolve in system; the mol ratio of maleic anhydride and C5 mixture is 1:1; and, in 50 ~ 90 ℃ of reaction 0.05 ~ 7h, obtain the milky stable solid-liquid dispersing system of C5 and copolymer-maleic anhydride, through centrifugation; vacuum-drying, obtain the white solid powder of C5 and copolymer-maleic anhydride.
Can determine in the C5 mixture that approximately 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, are conducive to the formation of gained copolymer dispersion system and stable.
Beneficial effect of the present invention is: (1) the method directly be take the C5 mixture as raw material, without refining separation of C 5 mixtures, greatly reduce reaction cost, the monoolefine and the diolefine that account for 60% component in the C5 mixture all react with maleic anhydride simultaneously, and in the C5 mixture, the component of residue 40% can be used as the impedance dielectric of reaction system, be conducive to generate the formation of copolymer dispersion system and stablize, can effectively utilize the C5 resource.It is very complicated because forming that the present invention has also overcome the C5 mixture, and boiling point approaches, and the separating difficulty of C 5 fraction is very large, thereby limits its application, and the present invention adopts single stage method, has separated monoolefine and diolefine, also makes C5 effectively utilize simultaneously.(2) the method be take the highly cross-linked copolymer microsphere that the C5 mixture contains functional groups as raw material single step reaction preparation, and technique is simple, operates controlled.
For example in the embodiment of the present invention 4, A, B, C, D are the identical four groups of parallel laboratory tests of reaction conditions, by acetone extracting one day for the C5-maleic anhydride polymer of last gained, wash clean, do C, H, tri-kinds of ultimate analyses of O, can calculate the ratio of maleic anhydride and C5 mixture in polymkeric substance according to 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 approaches 100% very much, illustrates in polymkeric substance and only has C, H, tri-kinds of elements of O.(2) convert that to obtain maleic anhydride and C5 mol ratio in polymkeric substance be 1.3 ~ 1.4:1, illustrate that this polymkeric substance is highly cross-linked polymkeric substance.C5-maleic anhydride polymer microsphere solid nucleus magnetic resonance (13C-NMR) spectrogram is as Fig. 1.
The accompanying drawing explanation
Fig. 1 C5-copolymer-maleic anhydride solid-state nuclear magnetic resonance (13C-NMR) spectrogram.
Embodiment
Embodiment 1
Under nitrogen protection, heating in water bath is 70 ℃; 2.9434g maleic anhydride and 0.2174g Diisopropyl azodicarboxylate are dissolved in 60mL Isoamyl Acetate FCC medium; ultrasonic dissolution obtains colourless transparent solution; add again 2.3426g C5 mixture; isothermal reaction 7h under nitrogen protection; obtain C5 and maleic anhydride (MAn) multipolymer 3.1025g, yield is 58.49%.
Embodiment 2
Under nitrogen protection, heating in water bath is 80 ℃; 1.9626g maleic anhydride and 0.1121g Diisopropyl azodicarboxylate are dissolved in 30mL Isoamyl Acetate FCC medium; ultrasonic dissolution obtains colourless transparent solution; add again 1.5612g C5 mixture; isothermal reaction 7h under nitrogen protection; obtain C5 and maleic anhydride (MAn) multipolymer 2.1571g, yield is 61.21%.
Embodiment 3
Under nitrogen protection, heating in water bath is 90 ℃; 0.9812g maleic anhydride and 0.0608g Diisopropyl azodicarboxylate are dissolved in 15mL Isoamyl Acetate FCC medium; ultrasonic dissolution obtains colourless transparent solution; add again 0.7814g C5 mixture; isothermal reaction 7h under nitrogen protection; obtain C5 and maleic anhydride (MAn) multipolymer 0.9379g, yield is 53.21%.
Embodiment 4
Under nitrogen protection, heating in water bath is 70 ℃; 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 obtains colourless transparent solution; add again the C5 mixture on a certain amount of; isothermal reaction 7h under nitrogen protection, obtain C5 and maleic anhydride (MAn) multipolymer.
In reaction system, the formula of each material is as shown in table 3, 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 are joined in the Isoamyl Acetate FCC medium and fully dissolve, comprise isoprene according to the diolefine in the C5 mixture and monoolefine again, cyclopentadiene, dicyclopentadiene, 1, the 4-pentadiene, m-pentadiene, the 1-amylene, the 2-amylene, cyclopentenes, the ratio of 2-methyl-1-butene alkene and 2-methyl-2-butene adds in system and dissolves respectively, and in 50 ~ 90 ℃ of reaction 0.05 ~ 7h, obtain the dispersion system of corresponding monoolefine or diolefine and copolymer-maleic anhydride, through centrifugation, vacuum-drying, obtain the white solid powder of corresponding monoolefine or diolefine and copolymer-maleic anhydride.
By acetone extracting one day for above-described embodiment gained C5-maleic anhydride polymer, wash clean, do C, H, tri-kinds of ultimate analyses of O, can calculate the ratio of maleic anhydride and C5 mixture in polymkeric substance according to result.In table 2, A, B, C, D are the identical four groups of parallel laboratory tests of reaction conditions (embodiment 4).Can draw following experiment conclusion by table 2: (1) C, H, O element total content approaches 100% very much, illustrates in polymkeric substance and only has C, H, tri-kinds of elements of O.(2) in polymkeric substance, maleic anhydride and C5 mol ratio are 1.3 ~ 1.4:1, illustrate that this polymkeric substance is highly cross-linked polymkeric substance.C5-maleic anhydride polymer microsphere solid nucleus magnetic resonance (13C-NMR) spectrogram is as Fig. 1.
Above-described embodiment relatively obtains identical material with corresponding reference example, therefore can determine in the C5 mixture that approximately 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, are conducive to the formation of gained copolymer dispersion system and stablize.
Claims (2)
1. a multipolymer that contains functional groups prepared by C5 mixture-maleic anhydride, is characterized in that, the preparation method of this polymkeric substance comprises the following steps:
Under the condition of nitrogen protection; after monomer maleic anhydride and initiator Diisopropyl azodicarboxylate (AIBN) are joined in ester class medium and fully dissolve; add again the C5 mixture to dissolve in system; the mol ratio of maleic anhydride and C5 mixture is 1:1; and, in 50～90 ℃ of reaction 0.05～7h, obtain the milky stable solid-liquid dispersing system of C5 and copolymer-maleic anhydride, through centrifugation; vacuum-drying, obtain the white solid powder of C5 and copolymer-maleic anhydride.
2. a C5 mixture reacts the preparation method of the multipolymer that contains functional groups of preparation with maleic anhydride, it is characterized in that, comprises the following steps:
Under the condition of nitrogen protection; after monomer maleic anhydride and initiator azo-bis-isobutyl cyanide (AIBN) are joined in ester class medium and fully dissolve; add again the C5 mixture to dissolve in system; the mol ratio of maleic anhydride and C5 mixture is 1:1; and, in 50～90 ℃ of reaction 0.05～7h, obtain the milky stable solid-liquid dispersing system of C5 and copolymer-maleic anhydride, through centrifugation; vacuum-drying, obtain the white solid powder of C5 and copolymer-maleic anhydride.
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| CN105949388B (en) * | 2016-05-23 | 2019-03-29 | 北京化工大学 | A kind of functional copolymer directly prepared by higher carbon number hydrocarbon class mixture and preparation method |
| 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 |
| 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 |
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 |
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| 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 |
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