CN103193932B - The synthetic method of low molecular weight phenylethylene-maleic anhydride alternate copolymer - Google Patents
The synthetic method of low molecular weight phenylethylene-maleic anhydride alternate copolymer Download PDFInfo
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Abstract
The invention discloses a kind of synthetic method of low molecular weight phenylethylene-maleic anhydride alternate copolymer, vinylbenzene, maleic anhydride and initiator are dissolved in the mixed solvent of aromatic hydrocarbon and ketone, be mixed with mixed solution, wherein: the mol ratio of vinylbenzene and maleic anhydride is 1: 1-5: 1; In mixed solution, the mass percent of aromatic hydrocarbon solvent is 10%-80%; In mixed solution, the mass ratio of ketones solvent and maleic anhydride is 0.5: 1-3: 1; Initiator quality accounts for the 0.5-5% of mixed solution; Dripped in that enter constant temperature, appropriate aromatic hydrocarbon solvent by mixed solution and react, temperature of reaction is 80-100 DEG C, and time for adding is 2-6 hour, drips after terminating and reacts 0.5-2 hour again, obtain low-molecular-weight alternate styrene-maleic anhydride copolymer.The present invention is different from conventional synthesis mode, adopting is dissolved in suitable solvent by all reactants and initiator, drip the mode of carrying out reacting again, can obtain molecular weight at 4000-13000, molecular weight distribution is at the low molecular weight phenylethylene-maleic anhydride alternate copolymer of 1.5-2.2.
Description
Technical field
The present invention relates to the synthetic method of a kind of novel low molecular weight weight phenylethylene-maleic anhydride alternate copolymer.
Background technology
Styrene-maleic anhydride copolymer (SMA) includes random copolymers and alternating copolymer two kinds.Wherein atactic styrene-maleic anhydride copolymer adopts the production technology of similar polystyrene (PS) produced.It, in important automobile inner structure parts application aspect, is used as the product most with economy; Meanwhile, in work, business, have also been obtained and use widely.Because phenylethylene-maleic anhydride random vinyl chloride has wear resistance, high glossiness, easily shaping and well ornamental, so its goods are not only durable, and attractive in appearance, cost is low.
Traditional phenylethylene-maleic anhydride polymkeric substance adopts mass polymerization to synthesize mostly, and temperature of reaction is high, and reaction controlling is difficult, and heat release is large, and the random copolymers molecular weight obtained is large, and molecular weight distribution is wide, and acid number is little.
Maleic anhydride is used directly to mix wiring solution-forming with vinylbenzene as the people such as Shi Zhengjin mention in " styrene-maleic anhydride polymerizing technology " (Chinese patent CN1247876A), when temperature is 100-130 DEG C, do not use initiator, with 2,6-ditertbutylparacresol is terminator, obtain molecular weight 200,000-40 ten thousand random copolymers.
If wrinkle, multitude Paine are at " the bulk-suspension synthesis and characterization research of SMA resin " (" modern plastics processed and applied ", the 1999,4th phase, pp.5-9) in a literary composition, first carry out mass polymerization by the method dripping monomer continuously, when transformation efficiency reaches the method that a half carries out suspension polymerization, prepare random maleic anhydride, styrol copolymer.
And in further studying, the performance of alternating styrene-maleic anhydride starts to highlight.Wherein, the performance of low-molecular-weight alternate styrene-maleic anhydride copolymer is given prominence to, and structure is homogeneous, and in papermaking, weaving, printing and dyeing, coating, the industries such as chemical industry can be used separately as the surface size press of paper, pigment dyestuff dispersion agent, the protective colloid etc. of letex polymerization.But it is produced and the general all more complicated of last handling process, is applied to industrial production cost huge.
The people such as hero as heavy in blue or green wood mention and use arene as solvent in " a kind of preparation method of low molecular weight phenylethylene-maleic anhydride polymer " (the clear 62-197406 of Japanese Patent), dicumyl peroxide is as initiator, adopt dropping initiator mode to react, the styrene-maleic anhydride copolymer of molecular weight at 1000-10000 can be obtained.But because temperature is higher, the reaction times is longer, and molecular weight distribution can not be guaranteed; And vinylbenzene: maleic anhydride is greatly about about 4: 1, and therefore acid number is lower, cannot meet the demand of high acid anhydrides amount.
Technique prepared by solution method is carried out as the people such as Reinard J.M Steemand introduce the good solvent butanone that have employed maleic anhydride in " a kind of synthesis mode of plasticized polymeric resin " (US Patent No. 4772671A), reaction monomers and initiator are all dissolved in solution and react, and maleic anhydride content is changed to 5-50%.Although this technique can prepare the SMA resin of high maleic anhydride content, but the solvent butanone that this method is introduced not only reduces speed and the efficiency of phenylethylene-maleic anhydride reaction, but also participation chain transfer reaction causes SMA molecular weight and molecular weight, deterioration resin mechanical property, adds complicacy and the energy consumption of multipolymer aftertreatment simultaneously.
In novel electron trade, by lower molecular weight, the photoresist material product that the SMA polymkeric substance of high anhydride content is made, with its superior resolving power and selectivity cleansing power, more and more receives everybody concern.But in the process of alternating copolymerization research, the alternate styrene-maleic anhydride copolymerization mode of common lower molecular weight height anhydride content is not mature enough, is difficult to be applied to industrial production.
As the people such as Chuan Lai rolling department mention the solution polymerization using methyl iso-butyl ketone (MIBK) or pimelinketone as solvent in " a kind of preparation of low molecular weight phenylethylene-maleic anhydride polymer " (the clear 60-206808 of Japanese Patent), Diisopropyl azodicarboxylate is as initiator, temperature of reaction is 110-130 DEG C, drip vinylbenzene and initiator 2 hours, reaction times is 3 hours, obtained molecular weight is at the alternating copolymer of 2000-8000, but need add cyclohexane give is precipitation agent, and aftertreatment comparatively bothers.
Use 1-methyl-4-isopropyl benzene as solvent as the people such as exhausted Nei Bosi mention in " a kind of preparation method of low molecular weight phenylethylene-maleic anhydride polymer " (the clear 56-90816 of Japanese Patent), adopt and drip cinnamic mode, the phenylethylene-maleic anhydride polymkeric substance that molecular weight is 1000 can be obtained, but this method temperature of reaction is high, long reaction time, yield only has about 80%; Simultaneously there are the side reaction products such as the maleic anhydride styrene polymkeric substance of a large amount of dimethyl styrene and high molecular in product, are separated trouble and consuming time, run into very large difficulty when industrial production.
Summary of the invention
Low for above-mentioned lower molecular weight height anhydride content phenylethylene-maleic anhydride industrial production efficiency, the problem of product stability difference, to be solved by this invention is the loaded down with trivial details and technical problem that molecular weight control is more difficult of low molecular weight phenylethylene-maleic anhydride suitability for industrialized production difficulty, for suitability for industrialized production provides a kind of convenient control, the synthetic method of novel low molecular weight weight phenylethylene-maleic anhydride alternate copolymer that production efficiency is high, and the product of high maleic anhydride content can be obtained, its acid anhydrides and cinnamic mol ratio reach as high as 1: 1.
In order to solve the problems of the technologies described above, the synthetic method of low molecular weight phenylethylene-maleic anhydride alternate copolymer provided by the present invention, comprises the following steps:
Maleic anhydride (MAH), vinylbenzene (St) and initiator are dissolved in aromatic hydrocarbon solvent and ketones solvent and are mixed with mixed solution, mixed solution is slowly instilled temperature to react between 80-100 DEG C, in appropriate aromatic hydrocarbon solvent, time for adding 2-6 hour, dropping terminates rear continuation reaction 0.5-2 hour, and aftertreatment obtains low molecular weight phenylethylene-maleic anhydride alternate copolymer;
All reaction monomers are dissolved in solvent by the present invention together with initiator, then react in the mode dripped, and the preparation of SMA are a kind of novel synthesis modes.Adopt in this way, maleic anhydride, vinylbenzene and initiator are reacted with identical ratio all the time, both ensure that product structure is homogeneous, also make heat release in reaction process stablize, reaction controlling is convenient, can obtain the SMA resin of the narrow molecular weight distribution of estimated molecular weight easily.
In the present invention, maleic anhydride and cinnamic magnitude relation, with mixed solvent be configured to dropping liquid at 1: 1-1: 5 in molar ratio, wherein aromatic hydrocarbon solvent ratio is the 10%-80% of this mixed solution mass ratio, and ketones solvent amount is with maleic anhydride mass ratio 0.5: 1-3: 1.
In the present invention, the hydro carbons containing phenyl ring of described aromatic hydrocarbon solvent to be carbonatoms be 7-10, as toluene, o-Xylol, m-xylene, p-Xylol, ethylbenzene, 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene, propyl benzene, isopropyl benzene, diethylbenzene, butylbenzene, isobutyl-benzene, p-Methylisopropylbenzene etc.Wherein preferred toluene, isopropyl benzene, sym-trimethylbenzene, but do not limit above solvent.
The structure of this kind solvent is similar to vinylbenzene, and polarity is little, is conducive to the generation of alternating structure; This kind solvent does not have solvability substantially for product in addition, and the styrene-maleic anhydride copolymer meeting that reaction generates Precipitation in this solvent system at once, had both reached the effect controlling molecular weight, and in turn simplify the step of aftertreatment.
In the present invention, the ketone of described ketone to be carbonatoms be 3-8, as acetone, butanone, methylacetone, 2 pentanone, propione, 3-methyl-2-butanone, methyl-n-butyl ketone, 3-hexanone, 2-methyl-3 pentanone, 3,3-dimethyl-2-butanone, 4-methyl-2 pentanone, 2-heptanone, 3-heptanone, dipropyl ketone, 2,4-dimethyl-3 pentanone, methyln-hexyl ketone, valerone, cyclopentanone, pimelinketone, suberone etc.Preferred butanone, pimelinketone, but do not limit above solvent.
Because aromatic hydrocarbon solvent polarity is little, so extremely low to the solvability of maleic anhydride, the ketones solvent of interpolation mainly plays the effect of hydrotropy, ketone polarity on the one hand different in addition also slightly difference, different to the dissolution degree of product, some differences of molecular weight of product can be caused.When ketones solvent addition is too low, then maleic anhydride is difficult to be dissolved in the middle of solution, cannot obtain mixed solution and drip; On the other hand, when the words that ketones solvent is too high can make molecular weight of product rise, product even may be caused not to be precipitated out in system, to add the difficulty of aftertreatment.
In the present invention, described initiator is azo type free radical initiator or peroxidation type free base initiator, as organic peroxide, benzoyl peroxide, dicumyl peroxide, hydrogen phosphide cumene, di-tert-butyl peroxide, dilauroyl peroxide, perbenzoic acid special butyl ester, diisopropyl peroxydicarbonate etc., or as azo compound, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) etc.
Described low molecular weight phenylethylene-copolymer-maleic anhydride molecular weight controlled, by conditions such as adjustment temperature of reaction, initiator addition, maleic anhydride styrene ratios, can obtain molecular weight 4000-13000, range of molecular weight distributions is the product of 1.5-2.2.Certainly the SMA molecular weight of product synthesized by the present invention is not limited to 4000-13000.
Relative to prior art, it is low that the present invention is devoted to solve low molecular weight phenylethylene-maleic anhydride industrial production efficiency, the problem of product stability difference.By large quantifier elimination, carried out a large amount of screenings to reactive mode, solvent composition, reaction conditions etc., the final novel synthesis mode proposing a kind of efficient stable, be very applicable to suitability for industrialized production, synthetic method of the present invention has following advantage:
(1) suitable polarity and deliquescent reaction system, contributes to the formation of alternating structure and the stable of product.
(2) premix of reactant and initiator drips, and maleic anhydride, vinylbenzene and initiator is reacted with identical ratio all the time, both ensure that product structure is homogeneous, and also make heat release in reaction process stablize, reaction controlling is convenient.
(3) by the control to temperature of reaction, initiator addition, maleic anhydride and vinylbenzene ratio, solvent etc., conveniently can control the structure of product, anhydride content and molecular size range, obtain the product subscribed.
(4) product Direct precipitation in reaction system, convenient post-treatment.
(5) reaction medium reclaims easy to use, and industrial production cost is low.
(6) reaction repeatability is high, and after optimizing, productive rate reaches more than 95%.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.These embodiments are interpreted as only being not used in for illustration of the present invention limiting the scope of the invention.After the content of having read the present invention's record, those skilled in the art can make various changes or modifications the present invention, and these equivalence changes and modification fall into the scope of the claims in the present invention equally.
Embodiment 1
Adding solution medium in reactor is toluene 300kg, oil bath, temperature 100 DEG C.MAH and St mol ratio 1: 1, wherein MAH38.812kg, St 41.188kg, initiator is Diisopropyl azodicarboxylate (AIBN) 4kg, dissolves to mix to obtain mixed solution with solvent toluene 120kg, butanone 39kg.Mixed solution is dripped by dropping mode and enters reactor, drips 4 hours, continues reaction 1 hour after dripping.Filter, dry, obtain SMA powder, weight-average molecular weight is 8865kg/mol.Molecular weight distribution, acid number and polymerization yield details are in table 1.
Embodiment 2
Adding solution medium in reactor is isopropyl benzene 300kg, oil bath, temperature 80 DEG C.MAH and St mol ratio 1: 1, wherein MAH38.812kg, St 41.188kg, initiator is Diisopropyl azodicarboxylate (AIBN) 4kg, dissolves to mix to obtain mixed solution with solvent isopropyl benzene 120kg, butanone 39kg.Mixed solution is dripped by dropping mode and enters reactor, drips 2 hours, continues reaction 2 hours.Filter, dry, obtaining SMA powder weight-average molecular weight is 11235kg/mol.Molecular weight distribution, acid number and polymerization yield details are in table 1.
Embodiment 3
Adding solution medium in reactor is sym-trimethylbenzene 300kg, oil bath, temperature 90 DEG C.MAH and St mol ratio 1: 1, wherein MAH38.812kg, St 41.188kg, initiator is Diisopropyl azodicarboxylate (AIBN) 4kg, dissolves to mix to obtain mixed solution with solvent sym-trimethylbenzene 120kg, butanone 39kg.Mixed solution is dripped by dropping mode and enters reactor, drips 4 hours, continues reaction 1 hour.Filter, dry, obtaining SMA powder weight-average molecular weight is 6635kg/mol.Molecular weight distribution, acid number and polymerization yield details are in table 1.
Embodiment 4
Adding solution medium in reactor is sym-trimethylbenzene 300kg, oil bath, temperature 95 DEG C.MAH and St mol ratio 1: 1, wherein MAH38.812kg, St 41.188kg, initiator is benzoyl peroxide (BPO) 4kg, dissolves to mix to obtain mixed solution with solvent sym-trimethylbenzene 120kg, butanone 39kg.Mixed solution is dripped by dropping mode and enters reactor, drips 4 hours, continues reaction 1 hour.Filter, dry, obtaining SMA powder weight-average molecular weight is 6860kg/mol.Molecular weight distribution, acid number and polymerization yield details are in table 1.
Embodiment 5
Adding solution medium in reactor is sym-trimethylbenzene 300kg, oil bath, temperature 90 DEG C.MAH and St mol ratio 1: 1, wherein MAH38.812kg, St 41.188kg, initiator is hydrogen phosphide cumene 4kg, dissolves to mix to obtain mixed solution with solvent sym-trimethylbenzene 120kg, butanone 39kg.Mixed solution is dripped by dropping mode and enters reactor, drips 4 hours, continues reaction 1 hour.Filter, dry, obtaining SMA powder weight-average molecular weight is 5868kg/mol.Molecular weight distribution, acid number and polymerization yield details are in table 1.
Embodiment 6
Adding solution medium in reactor is isopropyl benzene 300kg, oil bath, temperature 90 DEG C.MAH and St mol ratio 1: 3, wherein MAH19.122kg, St 60.878kg, initiator is Diisopropyl azodicarboxylate (AIBN) 4kg, dissolves to mix to obtain mixed solution with solvent isopropyl benzene 120kg, butanone 9.561kg.Mixed solution is dripped by dropping mode and enters reactor, drips 4 hours, continues reaction 1 hour.Filter, dry, obtaining SMA powder weight-average molecular weight is 7865kg/mol.Molecular weight distribution, acid number and polymerization yield details are in table 1.
Embodiment 7
Adding solution medium in reactor is isopropyl benzene 300kg, oil bath, temperature 90 DEG C.MAH and St mol ratio 1: 5, wherein MAH12.686kg, St 67.314kg, initiator is Diisopropyl azodicarboxylate (AIBN) 4kg, dissolves to mix to obtain mixed solution with solvent isopropyl benzene 120kg, pimelinketone 38.058kg.Mixed solution is dripped by dropping mode and enters reactor, drips 4 hours, continues reaction 1 hour.Filter, dry, obtaining SMA powder weight-average molecular weight is 10248kg/mol.Molecular weight distribution, acid number and polymerization yield details are in table 1.
Embodiment 8
Adding solution medium in reactor is toluene 100kg, oil bath, temperature 90 DEG C.MAH and St mol ratio 1: 1, wherein MAH25.228kg, St 26.772kg, initiator is Diisopropyl azodicarboxylate (AIBN) 2kg, dissolves to mix to obtain mixed solution with solvent toluene 320kg, cyclopentanone 26kg.Mixed solution is dripped by dropping mode and enters reactor, drips 6 hours, continues reaction 0.5 hour.Filter, dry, obtaining SMA powder weight-average molecular weight is 12920kg/mol.Molecular weight distribution, acid number and polymerization yield details are in table 1.
Embodiment 9
Adding solution medium in reactor is isopropyl benzene 350kg, oil bath, temperature 90 DEG C.MAH and St mol ratio 1: 1, wherein MAH38.812kg, St 41.188kg, initiator is Diisopropyl azodicarboxylate (AIBN) 7kg, dissolves to mix to obtain mixed solution with solvent isopropyl benzene 14kg, butanone 39kg.Mixed solution is dripped by dropping mode and enters reactor, drips 2 hours, continues reaction 2 hours.Filter, dry, obtaining SMA powder weight-average molecular weight is 4010kg/mol.Molecular weight distribution, acid number and polymerization yield details are in table 1.
Table 1
| Embodiment | Weight-average molecular weight (Mw) | Molecular weight distribution | Acid number mgKOH/g | Polymerization yield % |
| 1 | 8865 | 1.87 | 515.12 | 95.2 |
| 2 | 11235 | 1.84 | 512.52 | 94.8 |
| 3 | 6635 | 1.68 | 509.55 | 95.6 |
| 4 | 6860 | 1.65 | 517.78 | 95.4 |
| 5 | 5868 | 1.7 | 526.47 | 93.6 |
| 6 | 7865 | 1.6 | 288.56 | 96.5 |
| 7 | 10248 | 1.69 | 198.31 | 90.1 |
| 8 | 12920 | 1.85 | 508.25 | 94.2 |
| 9 | 4010 | 2.12 | 516.84 | 93.5 |
In table 1, weight-average molecular weight and distribution adopt gel chromatograph to detect, and moving phase is tetrahydrofuran (THF), and detector is parallax detector; Acid number adopts titration method to detect, and titrating solution is the aqueous sodium hydroxide solution of 0.1mol/L, and indicator is phenolphthalein; Polymerization yield is the ratio of actual product amount and charging capacity.
As can be seen from Table 1, this synthesis mode is by adjustment solution system, solution proportion, and the means such as initiator, low molecular weight phenylethylene-the copolymer-maleic anhydride of molecular weight within the scope of 4000-13000 can be obtained, can meet now electron trade to the demand of low molecular weight phenylethylene-copolymer-maleic anhydride; The molecular weight distribution of product is stabilized between 1.5-2.2, and this synthesis mode can obtain the styrene-maleic anhydride copolymer of homogeneous, the low distribution of structure as seen; Acid number has showed the content of maleic anhydride in this product, and the advantage of high maleic anhydride is that the group of modification increases, photocurable resin material that obtain different performance by means such as esterifications, that can meet electronic industry production.By adjustment vinylbenzene and the ratio of maleic anhydride, control suitable reaction system, this ratio can at vinylbenzene: maleic anhydride be 1: 1-1: 5 scope in adjust; The ratio being less than 1: 5 in theory also can meet, but and be not suitable for the category of high maleic anhydride content, therefore do not add and discuss and describe; The ultimate yield of this synthesis mode is all more than 90%, and after being optimized more than 95%, be applicable to very much the standard of suitability for industrialized production, and synthetic method is simple, product Direct precipitation is separated out, and convenient post-treatment is that a kind of economy efficiently synthesizes the mode of production efficiently.
Claims (6)
1. a synthetic method for low molecular weight phenylethylene-maleic anhydride alternate copolymer, is characterized in that, comprises the following steps:
Vinylbenzene, maleic anhydride and initiator are dissolved in the mixed solvent of aromatic hydrocarbon and ketone, are mixed with mixed solution, wherein: the mol ratio of vinylbenzene and maleic anhydride is 1:1-5:1; In mixed solution, the mass percent of aromatic hydrocarbon solvent is 10%-80%; In mixed solution, the mass ratio of ketones solvent and maleic anhydride is 0.5:1-3:1; Initiator quality accounts for the 0.5-5% of mixed solution; Described aromatic hydrocarbon solvent is the aromatic hydrocarbon solvent of 7-10 carbonatoms;
Dripped in that enter constant temperature, appropriate aromatic hydrocarbon solvent by mixed solution and react, temperature of reaction is 80-100 DEG C, and time for adding is 2-6 hour, drips after terminating and reacts 0.5-2 hour again, obtain low-molecular-weight alternate styrene-maleic anhydride copolymer.
2. synthetic method according to claim 1, is characterized in that, aromatic hydrocarbon solvent is toluene, o-Xylol, m-xylene, p-Xylol, ethylbenzene, 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene, propyl benzene, isopropyl benzene, diethylbenzene, butylbenzene, isobutyl-benzene or p-Methylisopropylbenzene.
3. synthetic method according to claim 1, is characterized in that, described ketones solvent is the ketones solvent of 3-8 carbonatoms.
4. synthetic method according to claim 3, it is characterized in that, described ketones solvent is acetone, butanone, methylacetone, 2 pentanone, propione, 3-methyl-2-butanone, methyl-n-butyl ketone, 3-hexanone, 2-methyl-3 pentanone, 3,3-dimethyl-2-butanone, 4-methyl-2 pentanone, 2-heptanone, 3-heptanone, dipropyl ketone, 2,4-dimethyl-3 pentanone, methyln-hexyl ketone, valerone, cyclopentanone, pimelinketone or suberone.
5. synthetic method according to claim 1, is characterized in that, described initiator is azo type free radical initiator or peroxidation type free base initiator.
6. synthetic method according to claim 5, it is characterized in that, peroxidation type free base initiator is benzoyl peroxide, dicumyl peroxide, hydrogen phosphide cumene, di-tert-butyl peroxide, dilauroyl peroxide, the special butyl ester of perbenzoic acid or diisopropyl peroxydicarbonate, and azo type free radical initiator is Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile).
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| CN105754433A (en) * | 2014-12-16 | 2016-07-13 | 深圳市莱莉雅环保科技有限公司 | Method for preparing water-based glaze top coat for alloy shell of digital product |
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