CN101979417A - Novel method for preparing itaconic anhydride-styrene monomer alternating copolymer - Google Patents
Novel method for preparing itaconic anhydride-styrene monomer alternating copolymer Download PDFInfo
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Abstract
The invention discloses a novel method for preparing an itaconic anhydride-styrene monomer alternating copolymer, which belongs to the field of polymer. The method comprises the following steps of: once adding itaconic anhydride, styrene monomers, an initiator and a reaction medium into a reaction vessel for complete dissolution and shaking up, performing reaction at 60 to 70 DEG C for 6 to 8 hours under the protection of nitrogen, separating a product out of emulsion in a centrifugation way, and oven-drying the product in a vacuum drying oven of 50 DEG C to obtain the white powder of the itaconic anhydride-styrene monomer alternating copolymer, wherein the reaction medium may be an organic acid alkyl ester, or the mixed solution of the organic acid alkyl ester and acetone or cyclohexane; and the initiator is a conventional thermally-decomposed initiator. In the method of the invention, stirring and the addition of any stabilizing agent are avoided, and the reaction medium has low toxicity; microspheres with cleaning surfaces and the particle sizes of 350 to 1,000nm can be directly obtained; the copolymer has high thermal properties; and the microspheres with the particle sizes of more than 800nm can be synthesized by adding a crosslinker, and the gel content can reach 75 percent.
Description
Technical field
The present invention relates to the method that a kind of self stabilization precipitation polymerization prepares itaconic anhydride and styrene monomer alternating copolymer, belong to polymeric material field.
Background technology
Itaconic anhydride is the important monomer of synthesized polymer material, is widely used in the production of synthetic resins, synthon, ion exchange resin, tensio-active agent, boiler detergent, slip additive, tackiness agent and non-toxic packaging materials etc.Itaconic anhydride is produced at subsurface fermentation by carbohydrate, or makes methylene-succinic acid by aqueous citric acid solution heating, pressurization decomposition, generates itaconic anhydride with the thionyl chloride effect again.
After oil crisis, the modern is to energy problem's growing interest, and green non-poisonous reproducible raw material has caused people's extensive interest.Current, with the maleic anhydride of its structural similitude be a kind of widely used industrial chemicals, but its preparation generally is to be made by petroleum products such as benzene or butylene, and easily distillation has toxic its application in special aspects that limited, and itaconic anhydride is a kind of a kind of novel nontoxic renewable industrial chemicals that can be produced by saccharide compound fermentation, it is expected to replace maleic anhydride and is applied to every field in aspect superior performances such as synthetic resins, plastics.
Similar with maleic anhydride, itaconic anhydride is because space steric effect and polarity effect are difficult to homopolymerization.Its molecule has intensive electrophilic characteristic, is a kind of electron acceptor(EA), and it can form charge transfer complex (CTC) with multiple power supply molecule.When these power supply bodies were monomer, then itaconic anhydride tended to take place with it the alternating copolymerization reaction.At present, the polymerization process of itaconic anhydride is mainly based on solution polymerization, and a small amount of letex polymerization is arranged.
(US 3355438 at " Ethylene-itaconic anhydride copolymers " for Lyons etc., 1967-11-28) in the literary composition, select for use basic solution as reaction medium, successfully synthesize ethene-itaconic anhydride multipolymer, and, find that polymkeric substance has excellent mechanical property by the test sign.
Miles etc. are at " Preparation and characterization of (monomethyl itaconate)-(methylmethacrylate) and of (itaconic anhydride)-(methyl methacrylate) copolymers " (European Polymer Journal, Volume 27, Issue 2,1991, be solvent with benzene in the literary composition 165-170), the multipolymer that has prepared itaconic anhydride and methacrylic ester, and speed of reaction, thermal property etc. carried out phenetic analysis.
Shurui Shang etc. are at " Synthesis and characterization of itaconic anhydride andstearyl methacrylate copolymers " (Polymer, Volume 50, Issue 14,2009, be solvent with the ethyl acetate in the literary composition 3119-3127), by solution polymerization itaconic anhydride and methacrylic acid octadecane ester, and chemical structure, the thermomechanical property of polymkeric substance characterized.
Werner Mormann etc. are at " Copolymers from tert-butyl methacrylate and itaconicanhydride-reactivity ratios and polymer analogous reactions " (European PolymerJournal, Volume 39, Issue 3,2003,489-496) in the literary composition by letex polymerization, synthesize butyl methacrylate and itaconic anhydride multipolymer, and studied the relation of reactivity ratio of monomer emphatically.
Wallach etc. are at " Copolymers derived from itaconic anhydride and vinyl stearate " (Polymeric Materials Science and Engineering, 80,1999,596) synthesized itaconic anhydride-vinyl stearate ester copolymer in the literary composition, and product has been done phenetic analysis such as structure, performance.
Hong Wang etc. are at " Study on copolymerization of itaconic anhydride and MMA " (Gongneng Gaofenzi xuebao, 9 (4), 1996,495-500) literary composition is solvent with the tetrahydrofuran (THF), benzoyl peroxide is an initiator, has synthesized itaconic anhydride-methylmethacrylate copolymer by the method for solution polymerization.
Tsuda etc. are at " Thermoplastic resin compositions " (JP 61258812A, be solvent with the butanone 1986-11-17), synthesize itaconic anhydride-styrenic thermoplastic compound resin by solution polymerization process, highlighted the thermomechanical property of polymkeric substance.
Xij un Liu etc. are at " Synthesis of PBA/P (MMA-ITA) latex particles with core-shellstructure " (Hecheng Shuzhi Ji Suliao, 26 (6), 2009,27-30) synthesized the latex particle of butyl acrylate, methyl methacrylate and methylene-succinic acid nucleocapsid structure in the literary composition with seed emulsion polymerization, size of particles is about 330nm.
Monomer concentration is lower in the solution polymerization, and speed of response is slower, easily causes chain transfer reaction, makes the molecular weight of resulting polymers corresponding lower; Polymer product must come out from separated from solvent, and the Ex-all solvent ratio is difficulty, and reclaims trouble, and plant factor is low.Letex polymerization needs emulsion is handled through operations such as cohesion, washing, dehydration, dryings in order to obtain solid polymer, and aftertreatment trouble and cost height are left over the emulsifying agent that is difficult to eliminate in the product, influence the performance of product, as decreasing electrical property etc.
Precipitation polymerization is a kind of good method for preparing polymkeric substance, and this system does not need to add any stablizer or emulsifying agent fully, prepared polymer particle surface cleaning, inclusion-free.Zhang Guoyun is at " preparation and the application of SMA type Surface Size " (" papermaking chemical product ", 2005,17 (3), be initiator with benzoyl peroxide (BPO) in the literary composition pp.30-32), toluene is solvent, has synthesized vinylbenzene and maleic anhydride random copolymer by the method for precipitation polymerization.But toluene toxicity is bigger, is reaction medium with toluene, contaminate environment.Yang Wantai, Xing Changmin etc. are at " A novel facile method for the preparation of uniform reactive maleicanhydride/vinyl acetate copolymer micro-nanospheres " (Macromolecular RapidCommunications, 2004,25:1568-1574) select a new precipitation polymerization system in the literary composition for use, both maleic anhydride and vinyl acetate two monomers were that reaction medium carries out polymerization with the organic acid alkyl ester, had prepared stable colloidal particle.
And be reaction medium with the organic acid alkyl ester, select conventional thermolysis type initiator for use, prepare the polymerization process of itaconic anhydride and styrene monomer alternating copolymer by the self stabilization precipitation polymerization, rarely have report so far.
Summary of the invention
The object of the present invention is to provide a kind of simple and fast, eco-friendly method prepares itaconic anhydride and styrene monomer alternating copolymer.
Purpose of the present invention reaches by following measure: according to charge transfer complex (CTC) mechanism, adopt reinforced method of a step to prepare multipolymer.Joining in the reaction vessel monomer itaconic anhydride, styrene monomer, initiator, reaction medium fully simultaneously, dissolving shakes up; under protection of nitrogen gas, react 6-8h in 60-70 ℃; product is separated from emulsion by whizzer is centrifugal; in 50 ℃ of vacuum drying ovens, dry, obtain the white powder of itaconic anhydride and vinylbenzene alternating copolymer.
Wherein used initiator is conventional thermolysis type initiator, and as organic superoxide dibenzoyl peroxide and azo-compound Diisopropyl azodicarboxylate, the add-on of initiator is 0.5～1% of a monomer total mass; Reaction medium is the mixing solutions of Isoamyl Acetate FCC, n-amyl acetate, butylacetate, ethyl butyrate, Isoamyl Acetate FCC and acetone or hexanaphthene, and wherein acetone or the hexanaphthene volume fraction in mixing solutions is 10～25%; The mol ratio of monomer itaconic anhydride and styrene monomer is 1: 4～4: 1, and two monomeric total mass concentrations are 5%～25%, and preferred molar ratio is 1: 2～2: 1 in reaction system, and mass concentration is 10～15%.
In this type of reaction system, the chemical constitution of reaction medium realizes smoothly that to polymeric it has crucial effects, and the solvent of selecting for use must all have good solubility to monomer itaconic anhydride and vinylbenzene and initiator, and can not dissolve the multipolymer that generates.The physical parameter of solvent especially solubility parameters, polarity parameter, viscosity even density all may have material impact to the formation and the stable dispersion of polymkeric substance.For this polymerization system, have only a few alkyl esters medium to meet the requirements, as isobutyl acetate, n-amyl acetate, Isoamyl Acetate FCC, ethyl butyrate, this type of medium toxic low, advantage such as have no irritating odor; Consider that acetone is the good solvent of multipolymer, hexanaphthene is the non-solvent of multipolymer, they are mixed by different ratios with the alkyl esters medium respectively, but the physical parameter of regulator solution solubility parameters especially, and then change the form of polymkeric substance.Learn that by experiment the solubility parameters that the reaction medium of this system suits is between 16.2～17.5, the polarity parameter is 4.8～5.1.
Styrene monomer selects vinylbenzene, alpha-methyl styrene for use, to methoxy styrene, 3,4-dimethyl styrene, 4-ethyl styrene.
On the basis of above-mentioned reaction: can also select for use ethylene glycol dimethacrylate EGDMA to prepare itaconic anhydride-vinylbenzene cross-linking copolymer as linking agent, the consumption of linking agent is 1～15% of a monomer total mass, preferred 5～10%.
Itaconic anhydride by the preparation of this system and styrene monomer polymkeric substance all can be stable be dispersed in the reaction medium, resulting polymers is the microspheroidal pattern, has strict alternating copolymerization structure, and surface cleaning, evenly, particle diameter is controlled, particle size range is between 350～800nm, and the size distribution coefficient is between 1～8%.The number-average molecular weight of reaction synthetic multipolymer is all about 10000g/mol, and distribution coefficient is less.The second-order transition temperature of multipolymer (Tg) is between 35～50 ℃, and the thermal weight loss temperature is compared with maleic anhydride-styrene copolymers about 380 ℃, has better thermotolerance.
The inventive method yield can reach more than 75%, and the gel content of cross-linking copolymer can reach 75%, and the crosslinked copolymer beads particle diameter is more than 800nm.
Compared with the prior art the present invention has following characteristics:
(1) preparation method's technology provided by the invention is simple, system is gentle, and speed of response is very fast, transformation efficiency is high, adopts once reinforced method synthetic polymer of step but separate.
(2) this polymerization system need not to stir, need not to add any stablizer; Reaction medium toxicity is low, recyclable utilization has no irritating odor.
(3) the monomer itaconic anhydride is a kind of novel nontoxic reproducible industrial chemicals, and it has good thermal property in aspect superior performances such as synthetic resins, plastics by DSC, TGA test shows polymkeric substance.
(4) proved that by nuclear-magnetism sign, acid base neutralization titration polymkeric substance has strict alternating copolymerization structure.
(5) resulting polymers all has the microspheroidal pattern, and the microspherulite diameter narrow distribution, surface cleaning, evenly, particle diameter is controlled, all be widely used in various fields such as biological chemistry, medical medicine, plastics additives.
(6) prepared crosslink copolymer gel content height, the crosslinked microsphere particle diameter has tangible increase than the line style microballoon.
Description of drawings
Fig. 1 is the electron scanning micrograph of polystyrene-itaconic anhydride multipolymer of embodiment 1.
Fig. 2 is the electron scanning micrograph of polystyrene-itaconic anhydride multipolymer of embodiment 2.
Fig. 3 is the electron scanning micrograph of polystyrene-itaconic anhydride multipolymer of embodiment 3.
Fig. 4 is the electron scanning micrograph of polystyrene-itaconic anhydride multipolymer of embodiment 4.
Fig. 5 is the electron scanning micrograph of polystyrene-itaconic anhydride multipolymer of embodiment 5.
Fig. 6 is the electron scanning micrograph of polystyrene-itaconic anhydride multipolymer of embodiment 6.
Fig. 7 is the electron scanning micrograph of polystyrene-itaconic anhydride multipolymer of embodiment 7.
Fig. 8 is the electron scanning micrograph of polystyrene-itaconic anhydride multipolymer of embodiment 9.
Fig. 9 is the electron scanning micrograph of polystyrene-itaconic anhydride multipolymer of embodiment 10.
Figure 10 is the electron scanning micrograph of polystyrene-itaconic anhydride cross-linking copolymer of embodiment 11.
Figure 11 is the electron scanning micrograph of poly alpha methylstyrene-itaconic anhydride multipolymer of embodiment 12.
Figure 12 is the nuclear magnetic spectrogram of embodiment 14.
Figure 13 is the TGA graphic representation of embodiment 15.
Embodiment
The technology of the present invention describe below with example in order to illustrate better.
The second-order transition temperature of polymkeric substance, the thermal weight loss temperature STAR of Switzerland METTLER-TOLEDO company
eSystem type DSC/TGA simultaneous thermal analysis instrument is measured.
The chemical constitution of polymkeric substance, structure adopt the Brooker AV600 of company nuclear magnetic resonance spectrometer, the U.S.'s Nexus670 of Buddhist nun's high-tensile strength company infrared spectrometer to measure.
The molecular weight of polymkeric substance and the Waters 1515 gel chromatograph GPC of employing U.S. Waters company that distribute measure.
The crosslinking degree of polymkeric substance characterizes by gel content, adopts the method for bibliographical information, and the polymer particle after will washing earlier is dried to constant weight W
0, then it being immersed among the THF, and using ultra-sonic dispersion, 24h then vibrates under the room temperature condition in shaking table.The centrifugal remaining solid that obtains is gone out colloidal sol for three times with THF washing.Be weighed as W after the residual sample drying
1, gel content calculates according to following formula: gel content (%)=(W
1/ W
0) * 100
The pattern of polymer microballoon adopts Hitachi S-4700 field emission scanning electron microscope to observe, and the formula below utilizing calculates median size (Dn) and size distribution coefficient (CV).
Wherein N is total population of being calculated, d
iIt is the particle diameter of i particle.
The determination of acid value of polymkeric substance: product purification, the SITA crude product is made into 10% butanone solution, filter, desolventize with rotatory evaporator, under 40～60 ℃, vacuum-drying SITA is to constant weight.Determination of acid value accurately takes by weighing 0.10g purified sample, uses acetone solution in Erlenmeyer flask, adds the agent of several phenolphthalein indexs, and the KOH standard solution titration of usefulness 0.1M adds the KOH solution of 2 milliliters of 0.1M to terminal, clogs bottleneck, places after 10 minutes, with the H of 0.1M
2SO
4Standardized solution instead drips to colourless, and does a blank assay.
In the formula, M
1, M
2Be respectively KOH and H
2SO
4The volumetric molar concentration of standardized solution, V
1, V
2Be respectively KOH and H
2SO
4The milliliter number of standardized solution, W are sample heavy (milligram).
Monomer mole ratio 1: 1; total concn is 1mol/L; with vinylbenzene (St) 2.4ml; itaconic anhydride (ITA) 2.24g, initiator Diisopropyl azodicarboxylate (AIBN) 0.0432g, Isoamyl Acetate FCC 40ml; join fully dissolving in the 100ml there-necked flask; under the protection of nitrogen and condensing works, keeping temperature of reaction is 70 ℃, reaction 6h.After reaction finishes, by centrifugal (3500rpm 30min) separates polymkeric substance from emulsion, put into 50 ℃ of vacuum drying ovens and dry, again with Isoamyl Acetate FCC washing three times to remove the oligopolymer that is adsorbed on microsphere surface, obtain purified alternating copolymer.
The resulting polymers microspherulite diameter is 570nm, and the size distribution coefficient is 4.53%, and productive rate is 79.35%, and the number-average molecular weight that records polymkeric substance with GPC is 10200g/mol, and its electron scanning micrograph as shown in Figure 1.
Embodiment 2
Monomer mole ratio 1: 1; total concn is 1mol/L; with St 2.4ml; ITA 2.24g, initiator dibenzoyl peroxide (BPO) 0.0638g, Isoamyl Acetate FCC 40ml; join fully dissolving in the 100ml there-necked flask; under the protection of nitrogen and condensing works, keeping temperature of reaction is 70 ℃, reaction 8h.After reaction finishes, by centrifugal (3500rpm 30min) separates polymkeric substance from emulsion, put into 50 ℃ of vacuum drying ovens and dry, again with Isoamyl Acetate FCC washing three times to remove the oligopolymer that is adsorbed on microsphere surface, obtain purified alternating copolymer.
The resulting polymers microspherulite diameter is 590nm, and the size distribution coefficient is 5.99%, and productive rate is 81.15%, and the number-average molecular weight that records polymkeric substance with GPC is 9500g/mol, and its electron scanning micrograph as shown in Figure 2.
Monomer mole ratio 1: 1, total concn is 1mol/L, A:St 2.4ml, ITA 2.24g, AIBN 0.0432g, n-amyl acetate 40ml, B:St 2.4ml, ITA 2.24g, AIBN 0.0432g, butylacetate 40ml, C:St 2.4ml, ITA 2.24g, AIBN 0.0432g, ethyl butyrate 40ml.Reactant is joined fully dissolving in 3 100ml there-necked flasks respectively by prescription A, B, C, and under the protection of nitrogen and condensing works, keeping temperature of reaction is 70 ℃, reaction 6h.After reaction finishes, (3500rpm 30min) separates polymkeric substance from emulsion, puts into 50 ℃ of vacuum drying ovens and dries by centrifugal, wash three times to remove the oligopolymer that is adsorbed on microsphere surface with corresponding reaction medium again, obtain purified alternating copolymer.
By prescription A resulting polymers microspherulite diameter is 595nm, the size distribution coefficient is 6.46%, productive rate is 76.33%, by prescription B resulting polymers microspherulite diameter is 610nm, and the size distribution coefficient is 5.33%, and productive rate is 73.32%, by prescription C resulting polymers microspherulite diameter is 513nm, the size distribution coefficient is 3.45%, and productive rate is 81.25%, and its electron scanning micrograph as shown in Figure 3.
Embodiment 4
Monomer mole ratio 1: 1, total concn are 1mol/L, with St 2.4ml, and ITA 2.24g; AIBN 0.0432g, Isoamyl Acetate FCC 35ml, hexanaphthene 5ml join fully dissolving in the 100ml there-necked flask; under the protection of nitrogen and condensing works, keeping temperature of reaction is 70 ℃, reaction 6h.After reaction finishes, by centrifugal (3500rpm 30min) separates polymkeric substance from emulsion, put into 50 ℃ of vacuum drying ovens and dry, again with Isoamyl Acetate FCC washing three times to remove the oligopolymer that is adsorbed on microsphere surface, obtain purified alternating copolymer.
The resulting polymers microspherulite diameter is 520nm, and the size distribution coefficient is 4.45%, and productive rate is 75.35%, and its electron scanning micrograph as shown in Figure 4.
Embodiment 5
Monomer mole ratio 1: 1, total concn are 1mol/L, with St 2.4ml, and ITA 2.24g; AIBN 0.0432g, Isoamyl Acetate FCC 35ml, acetone 5ml join fully dissolving in the 100ml there-necked flask; under the protection of nitrogen and condensing works, keeping temperature of reaction is 70 ℃, reaction 6h.After reaction finishes, by centrifugal (3500rpm 30min) separates polymkeric substance from emulsion, put into 50 ℃ of vacuum drying ovens and dry, again with Isoamyl Acetate FCC washing three times to remove the oligopolymer that is adsorbed on microsphere surface, obtain purified alternating copolymer.
The resulting polymers microspherulite diameter is 610nm, and the size distribution coefficient is 6.45%, and productive rate is 72.33%, and its electron scanning micrograph as shown in Figure 5.
Embodiment 6
Monomer mole ratio St: ITA=3: 1, total concn is 2mol/L, with St 7.2ml; ITA 2.24g, AIBN0.0848g, Isoamyl Acetate FCC 40ml join fully dissolving in the 100ml there-necked flask; under the protection of nitrogen and condensing works, keeping temperature of reaction is 70 ℃, reaction 6h.After reaction finishes, by centrifugal (3500rpm 30min) separates polymkeric substance from emulsion, put into 50 ℃ of vacuum drying ovens and dry, again with Isoamyl Acetate FCC washing three times to remove the oligopolymer that is adsorbed on microsphere surface, obtain purified alternating copolymer.
The resulting polymers microspherulite diameter is 790nm, and the size distribution coefficient is 7.74%, and productive rate is 70.15%, and the number-average molecular weight that records polymkeric substance with GPC is 11500g/mol, and its electron scanning micrograph as shown in Figure 6.
Embodiment 7
Monomer mole ratio St: ITA=1: 3, total concn is 2mol/L, with St 2.4ml; ITA 6.72g, AIBN0.0800g, Isoamyl Acetate FCC 40ml join fully dissolving in the 100ml there-necked flask; under the protection of nitrogen and condensing works, keeping temperature of reaction is 70 ℃, reaction 6h.After reaction finishes, by centrifugal (3500rpm 30min) separates polymkeric substance from emulsion, put into 50 ℃ of vacuum drying ovens and dry, again with Isoamyl Acetate FCC washing three times to remove the oligopolymer that is adsorbed on microsphere surface, obtain purified alternating copolymer.
The resulting polymers microspherulite diameter is 410nm, and the size distribution coefficient is 3.45%, and productive rate is 68.15%, and the number-average molecular weight that records polymkeric substance with GPC is 9800g/mol, and its electron scanning micrograph as shown in Figure 7.
Monomer mole ratio St: ITA=1: 4 (4: 1), total concn are 2mol/L.Reaction system A:St 2.4ml, ITA8.96g, AIBN 0.1024g, Isoamyl Acetate FCC 50ml; Reaction system B:St 9.6ml, ITA 2.24g, AIBN0.1052g, Isoamyl Acetate FCC 50ml.Reactant is joined fully dissolving in the 100ml there-necked flask respectively by reaction system A, B prescription, and under the protection of nitrogen and condensing works, keeping temperature of reaction is 70 ℃, reaction 6h.After reaction finishes, by centrifugal (3500rpm 30min) separates polymkeric substance from emulsion, put into 50 ℃ of vacuum drying ovens and dry, again with Isoamyl Acetate FCC washing three times to remove the oligopolymer that is adsorbed on microsphere surface, obtain purified alternating copolymer.
By prescription A resulting polymers microspherulite diameter is 380nm, and the size distribution coefficient is 5.01%, and productive rate is 65.21%.By prescription B resulting polymers microspherulite diameter is 815nm, and the size distribution coefficient is 7.13%, and productive rate is 53.22%.
Embodiment 9
Monomer mole ratio 1: 1, total concn are 1.5mol/L, with St 2.4ml; ITA 2.24g, AIBN 0.0432g, Isoamyl Acetate FCC 27ml join fully dissolving in the 100ml there-necked flask; under the protection of nitrogen and condensing works, keeping temperature of reaction is 70 ℃, reaction 6h.After reaction finishes, by centrifugal (3500rpm 30min) separates polymkeric substance from emulsion, put into 50 ℃ of vacuum drying ovens and dry, again with Isoamyl Acetate FCC washing three times to remove the oligopolymer that is adsorbed on microsphere surface, obtain purified alternating copolymer.
The resulting polymers microspherulite diameter is 780nm, and the size distribution coefficient is 7.45%, and productive rate is 65.38%, and the number-average molecular weight that records polymkeric substance with GPC is 13400g/mol, and its electron scanning micrograph as shown in Figure 8.
Embodiment 10
Monomer mole ratio 1: 1, total concn are 0.5mol/L, with St 2.4ml; ITA 2.24g, AIBN 0.0432g, Isoamyl Acetate FCC 80ml join fully dissolving in the 250ml there-necked flask; under the protection of nitrogen and condensing works, keeping temperature of reaction is 70 ℃, reaction 6h.After reaction finishes, by centrifugal (3500rpm 30min) separates polymkeric substance from emulsion, put into 50 ℃ of vacuum drying ovens and dry, again with Isoamyl Acetate FCC washing three times to remove the oligopolymer that is adsorbed on microsphere surface, obtain purified alternating copolymer.
The resulting polymers microspherulite diameter is 370nm, and the size distribution coefficient is 2.77%, and productive rate is 72.15%, and the number-average molecular weight that records polymkeric substance with GPC is 8400g/mol, and its electron scanning micrograph as shown in Figure 9.
Embodiment 11
Monomer mole ratio 1: 1, total concn are 1mol/L, with St 2.4ml, and ITA 2.24g; AIBN 0.0432g, linking agent EGDMA 0.2ml, Isoamyl Acetate FCC 40m1 join fully dissolving in the 100ml there-necked flask; under the protection of nitrogen and condensing works, keeping temperature of reaction is 70 ℃, reaction 6h.After reaction finishes, by centrifugal (3500rpm 30min) separates polymkeric substance from emulsion, put into 50 ℃ of vacuum drying ovens and dry, again with Isoamyl Acetate FCC washing three times to remove the oligopolymer that is adsorbed on microsphere surface, obtain purified alternating copolymer.
The resulting polymers microspherulite diameter is 690nh, and the size distribution coefficient is 6.58%, and productive rate is 75.64%, gel content 77%, and its electron scanning micrograph is as shown in figure 10.
Embodiment 12
Monomer mole ratio 1: 1, total concn are 1mol/L, with alpha-methyl styrene (AMS) 2.6ml; ITA 2.24g, AIBN 0.0452g, Isoamyl Acetate FCC 40ml join fully dissolving in the 100ml there-necked flask; under the protection of nitrogen and condensing works, keeping temperature of reaction is 70 ℃, reaction 16h.After reaction finishes, by centrifugal (3500rpm 30min) separates polymkeric substance from emulsion, put into 50 ℃ of vacuum drying ovens and dry, again with Isoamyl Acetate FCC washing three times to remove the oligopolymer that is adsorbed on microsphere surface, obtain purified alternating copolymer.
The resulting polymers microspherulite diameter is 1100nm, and the size distribution coefficient is 3.58%, and productive rate is 25.36%, and the number-average molecular weight that records polymkeric substance with GPC is 9600g/mol, and its electron scanning micrograph as shown in figure 11.
Embodiment 13
Monomer mole ratio 1: 1, total concn are 1mol/L, reaction system A: to methoxy styrene 2.68g, ITA2.24g, AIBN 0.0512g, Isoamyl Acetate FCC 40ml; Reaction system B:3,4-dimethyl styrene 2.64g, ITA 2.24g, AIBN 0.0508g, Isoamyl Acetate FCC 40ml; Reaction system C:4-ethyl styrene 2.64g, ITA 2.24g, AIBN 0.0508g, Isoamyl Acetate FCC 40ml.Reactant is joined fully dissolving in 3 100ml there-necked flasks respectively by reaction system A, B, C prescription, and under the protection of nitrogen and condensing works, keeping temperature of reaction is 70 ℃, reaction 16h.After reaction finishes, by centrifugal (3500rpm 30min) separates polymkeric substance from emulsion, put into 50 ℃ of vacuum drying ovens and dry, again with Isoamyl Acetate FCC washing three times to remove the oligopolymer that is adsorbed on microsphere surface, obtain purified alternating copolymer.
By prescription A resulting polymers microspherulite diameter is 915nm, and productive rate is 22.13%.By prescription B resulting polymers microspherulite diameter is 1050nm, and productive rate is 25.45%.By prescription C resulting polymers microspherulite diameter is 1120nm, and productive rate is 19.28%.
Embodiment 14
The SITA crude product of example 1 is made into 10% butanone solution, filters, desolventize with rotatory evaporator, under 40～60 ℃, vacuum-drying SITA is to constant weight.Accurately take by weighing 0.10g purified sample, use acetone solution in Erlenmeyer flask, add the agent of several phenolphthalein indexs, the KOH standard solution titration of usefulness 0.1M adds the KOH solution of 2 milliliters of 0.1M to terminal, clogs bottleneck, places after 10 minutes, with the H of 0.1M
2SO
4Standardized solution instead drips to colourless, and has done a blank assay.Consume KOH6.5ml altogether, H
2SO
42ml.In addition, the refining sample that takes a morsel is dissolved in the deuterated acetone solution and has done
13The test of C NMR nuclear-magnetism.
Getting the polymkeric substance acid number as calculated is 504.2, thereby the molar content of calculating ITA among the SITA is 48.3%, can determine substantially that product is vinylbenzene and maleic anhydride alternate copolymer.Find from nuclear magnetic spectrogram, tertiary carbon atom (177ppm) on carbon atom of anhydride group in the ITA unit (174ppm, 169ppm) and the St unit phenyl ring skeleton is very sensitive to the microcosmic sequential structure of copolymer chain, the absorption peak of above-mentioned three chemical shifts place is all unimodal, this shows that they are in the identical chemical environment, thereby the proof polymerisate is the alternating copolymerization structure, and its nuclear magnetic spectrogram as shown in figure 12.
Embodiment 15
The SITA crude product that makes under the different monomers proportioning (1: 3～3: 1) is made into 10% butanone solution, filters, desolventize with rotatory evaporator, under 40～60 ℃, vacuum-drying SITA is to constant weight.The refining sample that takes a morsel has been DSC respectively, the TGA test, and wherein heat-up rate is 10 ℃/min.
The second-order transition temperature that records sample is between 35～50 ℃, and the thermal weight loss temperature is about 380 ℃.Its TGA curve as shown in figure 13.
Claims (6)
1. novel method for preparing itaconic anhydride and styrene monomer alternating copolymer, it is characterized in that, adopt reinforced method of a step to prepare multipolymer, may further comprise the steps: joining in the reaction vessel monomer itaconic anhydride, styrene monomer, initiator, reaction medium fully simultaneously, dissolving shakes up, under protection of nitrogen gas, react 6-8h in 60-70 ℃, product is separated from emulsion by whizzer is centrifugal, in 50 ℃ of vacuum drying ovens, dry, obtain the white powder of itaconic anhydride and vinylbenzene alternating copolymer;
Wherein styrene monomer select vinylbenzene, alpha-methyl styrene for use, to methoxy styrene, 3,4-dimethyl styrene, 4-ethyl styrene; Reaction medium is the mixing solutions of Isoamyl Acetate FCC, n-amyl acetate, butylacetate, ethyl butyrate, Isoamyl Acetate FCC and acetone or hexanaphthene, and the solubility parameters of reaction medium is 16.2～17.5, and the polarity parameter is 4.8～5.1.
2. in accordance with the method for claim 1, it is characterized in that the mol ratio of monomer itaconic anhydride and styrene monomer is 1: 4～4: 1, two monomeric total mass concentrations are 5%～25%.
3. in accordance with the method for claim 2, it is characterized in that the mol ratio of monomer itaconic anhydride and styrene monomer is 1: 2～2: 1, two monomeric total mass concentrations are 10%～15%.
4. in accordance with the method for claim 1, it is characterized in that initiator is conventional thermolysis type initiator, add-on is 0.5～1% of a monomer total mass.
5. in accordance with the method for claim 1, it is characterized in that acetone or the hexanaphthene volume fraction in mixing solutions is 10～25%.
6. in accordance with the method for claim 1, it is characterized in that can also add ethylene glycol dimethacrylate EGDMA and prepare crosslinked copolymer beads as linking agent in reaction system, the consumption of linking agent is 1～15% of a monomer total mass.
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| CN102212166A (en) * | 2011-05-05 | 2011-10-12 | 北京化工大学 | Novel method for performing copolymerization reaction of dicyclopentadiene and maleic anhydride |
| WO2013113930A1 (en) | 2012-02-03 | 2013-08-08 | Dsm Ip Assets B.V. | Block copolymer, process and composition |
| CN105949388A (en) * | 2016-05-23 | 2016-09-21 | 北京化工大学 | Functional copolymer directly prepared from higher olefin mixture and preparation method |
| CN111040077A (en) * | 2019-12-31 | 2020-04-21 | 广东巴德富新材料有限公司 | Modified itaconic acid and maleic acid copolymer, preparation method and application thereof |
| CN111087493A (en) * | 2018-10-24 | 2020-05-01 | 中国石油化工股份有限公司 | Reaction device and method for preparing styrene series alternating copolymerization microspheres |
| CN111087492A (en) * | 2018-10-24 | 2020-05-01 | 中国石油化工股份有限公司 | Reaction device and method for preparing light hydrocarbon alternating copolymerization microspheres |
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| CN102212166A (en) * | 2011-05-05 | 2011-10-12 | 北京化工大学 | Novel method for performing copolymerization reaction of dicyclopentadiene and maleic anhydride |
| CN102212166B (en) * | 2011-05-05 | 2013-07-03 | 北京化工大学 | Novel method for performing copolymerization reaction of dicyclopentadiene and maleic anhydride |
| WO2013113930A1 (en) | 2012-02-03 | 2013-08-08 | Dsm Ip Assets B.V. | Block copolymer, process and composition |
| WO2013113933A1 (en) | 2012-02-03 | 2013-08-08 | Dsm Ip Assets B.V. | Polymer, process and composition |
| CN105949388A (en) * | 2016-05-23 | 2016-09-21 | 北京化工大学 | Functional copolymer directly prepared from higher olefin mixture and preparation method |
| CN111087493A (en) * | 2018-10-24 | 2020-05-01 | 中国石油化工股份有限公司 | Reaction device and method for preparing styrene series alternating copolymerization microspheres |
| CN111087492A (en) * | 2018-10-24 | 2020-05-01 | 中国石油化工股份有限公司 | Reaction device and method for preparing light hydrocarbon alternating copolymerization microspheres |
| CN111040077A (en) * | 2019-12-31 | 2020-04-21 | 广东巴德富新材料有限公司 | Modified itaconic acid and maleic acid copolymer, preparation method and application thereof |
| CN114426617A (en) * | 2020-10-14 | 2022-05-03 | 中国石油化工股份有限公司 | Maleic anhydride-styrene copolymer microsphere and preparation method and application thereof |
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