CN1618826A - Method of copolymerization of maleic anhydride and vinyl acetate - Google Patents
Method of copolymerization of maleic anhydride and vinyl acetate Download PDFInfo
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Abstract
A process for the copolymerizing reaction between maleic acid anhydride and vinyl acetate to obtain the dispersed microspherical copolymer without stabilizer features that its trigger (concentration 0.05-1%) is the organic peroxide or aza compound and its medium is the alkyl ester of organic acid. Said microspheres have smooth surface and controllable and uniform granularity.
Description
Technical field
The present invention relates to a kind of maleic anhydride (MAn) and the method that vinyl acetate (VAc) carries out copolyreaction, particularly relate to the dispersion polymerization processes of a kind of MAn and VAc.Utilize this method can prepare the monodisperse polymer micro-sphere that contains reactive group.
Background technology
Product polymaleic anhydride-the vinyl acetate (PMV) of MAn and VAc copolyreaction is a kind of important polymer fine chemicals, is used as dispersion agent, water quality stabilizer, drilling mud diluent, leather composite tanning agent etc. widely.In addition, preparation and application that a focus of present functional high polymer material field is a polymer microballoon, nano level to micron-sized polymer microballoon because of specific physique such as have that specific surface area is big, adsorptivity is strong, cohesion is big and the surface reaction ability is strong, be widely used for many high-technology fields such as analytical chemistry, biomedicine, standard metering, solid phase carrier, high performance liquid chromatography.
About the copolymerization of MAn and VAc, traditional processing method mainly contains solution polymerization process, emulsion polymerization and precipitation polymerization method.
Seung-Wook Lee etc. are at " Miscibility of nylon 6 with poly (maleicanhydride-co-vinyl acetate) and hydroxylated poly (maleic anhydride-co-vinylacetate) blends " (Polymer, 1996, Vol.37 No.15 pp.3347-3352.) has reported the copolyreaction of carrying out MAn and VAc with solution polymerization process in the literary composition.Solvent for use is a methylethylketone, and makees initiator with Diisopropyl azodicarboxylate (AIBN), reacts 72h under 60 ℃ temperature, then reaction product is precipitated in normal hexane, has obtained the PMV multipolymer.But the speed of reaction of this solution polymerization system is very slow, and solvent is difficult to recycle contaminate environment; The polymerisate that obtains by precipitate and separate is a blocks of solid in addition, can not get polymer microballoon.
(" Beijing Forestry University's journal ", 1994, the 4 phases pp.85-91.) have been reported the copolyreaction of carrying out MAn and VAc with emulsion polymerization in the literary composition to Wei Zheng, king Lu screen in " research of vinyl acetate homopolymerization emulsion copolymerization modification ".Form the compound emulsification system with polyvinyl alcohol (PVA), polyoxyethylene nonylphenol ether (OP-10) and anion surfactant, and make initiator, in the different media environment of pH=3.65-5.10, implemented the copolyreaction of MAn and VAc with ammonium persulphate.Its experimental result shows, the product that obtains by emulsion polymerization is the polymer microballoon of particle diameter 2～7 μ m, but because MAn can generate toxilic acid with the reaction of the water in the emulsion, its reactive activity is reduced greatly, so the emulsion polymerization of MAn and VAc is difficult to normally carry out, it is very slow to show as rate of polymerization, final transformation efficiency very low (＜40%), and practical application is restricted.
(" Guangzhou chemistry ", 1995, the 1 phases pp.22-26.) have been reported the copolyreaction of carrying out MAn and VAc with precipitation polymerization method in the literary composition in " research of maleic anhydride and the reaction of vinyl-acetic ester alternative copolymerization " for Zhang Ping, Gu Xiaoman etc., and make initiator with dibenzoyl peroxide (BPO) and form the precipitation polymerization system as reaction medium with benzene, under agitation react with 65 ℃ of heating in water bath.In the precipitation polymerization reaction process, product is precipitated out with Powdered or particulate state gradually, and it is of a size of macroscopic millimeter level, and shape irregularity very, thus precipitation polymerization method obtain neither polymer microballoon.Used medium benzene has the intensive carcinogenesis in this system in addition, is the very strong chemical of a kind of toxicity, does not meet the development trend of Green Chemistry.
Proposed a kind of new polymerization process---dispersion copolymerization method by Britain ICI company the seventies in 20th century.Diffuse-aggregate system is formed and is comprised monomer, initiator and stablizer, and each component all is dissolved in and is homogeneous system in the medium before the reaction beginning; And the polymkeric substance that is generated can not be dissolved in this medium, after polymer chain reaches certain critical length just from medium precipitating come out.In order to guarantee that the polymerisate that precipitating is come out can stably be suspended in the medium with the form of microballoon, rather than precipitate down with Powdered or particulate state in precipitation polymerization, stablizer plays a part very important in the dispersion polymerization system.Stablizer commonly used has polyvinylpyrrolidone (PVP), hydroxypropylcellulose (HPC), polyacrylic acid (PAA), polyoxyethylene glycol (PEG) and dextrin etc.Diffuse-aggregate advantage is more, and is simple such as technology, and heat radiation is easy, the product separate easily, and especially outstanding a bit is the monodisperse polymer micro-sphere that can prepare different-grain diameter rank (0.1～10 μ m) step.Present dispersion polymerization system is primarily aimed at vinylbenzene (St) and methyl methacrylate (MMA) waits a few monomer, the product of preparation is mainly the microballoon (Cao Tongyu etc. of polystyrene (PS) and polymethylmethacrylate (PMMA) composition, " polymer circular ", 1994, the 3rd phase, pp.174-180.).But, by the copolyreaction of dispersion copolymerization method enforcement MAn and VAc, prepare the PMV copolymer microsphere that contains reactive acid anhydride base, have not yet to see document and patent report.
In the dispersion polymerization system of routine, the consumption of stablizer is generally all bigger, especially when some the time when adding co-stabilizer again, the total content of stablizer will account for 3～10% of whole reaction system, sometimes even higher (Zhang Kai, " chemistry world ", 2002, the 7 phases, pp.378-381.).A large amount of uses of stablizer can bring a series of problem, mainly contain: (1) all has detrimentally affect to many performances such as electrical property, optical property, surface property, water tolerance and the film-forming properties etc. of product; (2) existence of stablizer has increased the complicacy of system and the difficulty of technology controlling and process; (3) stablizer has certain pollution to environment; (4) stablizer is more expensive usually, can increase the cost of product.The relevant correlation technique of not using any stablizer and co-stabilizer in dispersion polymerization is not seen bibliographical information at present as yet yet.
Summary of the invention
The objective of the invention is to propose to carry out the novel method that the dispersion polymerization preparation contains the PMV copolymer microsphere of reactive acid anhydride base with MAn and VAc, in the dispersion system of polymer microballoon, the polymer microballoon surface cleaning, particle diameter is controlled, and narrow particle size distribution; And solve the drawback that to use stablizer to bring in traditional dispersion polymerization system.
Usually, the composition of dispersion polymerization system comprises monomer and initiator, and each components dissolved of system in medium, is carried out copolyreaction being equal to or higher than under the decomposition temperature condition of initiator, obtain the dispersion system of multipolymer, again through separating the solid product that obtains multipolymer; The technical characterictic of the dispersion polymerization processes of maleic anhydride of the present invention and vinyl acetate copolymerized reaction is: need not to add under the condition of any stablizer and co-stabilizer in the dispersion polymerization system, polymeric reaction temperature is at 20～100 ℃, copolyreaction 5～10h obtains the dispersion system of polymer microballoon; Reaction monomers maleic anhydride and vinyl acetate, two monomeric mol ratios are 1: 2～2: 1; The mass concentration of monomer in the dispersion polymerization system is 5%～60%; Initiator is organo-peroxide or azo-compound, and the mass concentration of initiator in the dispersion polymerization system is 0.05%～1%; Medium is the organic acid alkyl ester, and chemical structural formula is:
Wherein, R
1Be hydrogen atom, C
1～C
5Alkyl, phenyl or benzyl, R
2Be C
1～C
5Alkyl.
R preferably in the chemical structural formula of organic acid alkyl ester
1Be C
1～C
5Alkyl, R
2Be C
1～C
5Alkyl.
The organic acid alkyl ester that the present invention adopts, for example: ethyl formate, propyl formate, tetryl formate, pentyl formate, ethyl acetate, butylacetate, isobutyl acetate, sec-butyl acetate, pentyl acetate, Isoamyl Acetate FCC, jasmal, methyl propionate, ethyl propionate, butyl propionate, methyl-butyrate, ethyl butyrate, butyl butyrate, isoamyl butyrate, Ethylisovalerate, isoamyl isovalerate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, isoamyl benzoate, methyl phenylacetate or Phenylacetic acid ethylester etc.
The mol ratio of two reaction monomers maleic anhydrides of the present invention and vinyl acetate is preferably 1: 1.
The initiator that can be used for dispersion polymerization system of the present invention is conventional thermolysis type initiator, comprise for known this compounds of professional and technical personnel: (1) organo-peroxide, for example: dibenzoyl peroxide, dicumyl peroxide, peroxidation two (2,4 dichloro benzene formyl), di-tert-butyl peroxide, dilauroyl peroxide, the special butyl ester of peroxidation phenylformic acid, peroxy dicarbonate diisopropyl ester, di-cyclohexylperoxy dicarbonate etc.; (2) azo-compound, for example: Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) etc.The mass concentration of initiator in this dispersion polymerization system can be 0.05%～1%, and reasonable is between 0.1%～0.5%.
The present invention is in the dispersion system of polymer microballoon, and the median size of polymer microballoon is at 90～520nm; Dispersion coefficient is 2.1%～3.2%.
The present invention is by selecting suitable media implementation MAn and the dispersion polymerization of VAc, and its characteristics are: need not to add any stablizer and co-stabilizer in (1) this dispersion polymerization system, have " disperseing certainly " effect; (2) in the dispersion polymerization system monodisperse polymer micro-sphere, the microsphere surface cleaning, particle diameter is controlled, and narrow particle size distribution.
The monomer that can be used for dispersion polymerization system of the present invention is the bicomponent system of MAn and VAc.Known as the professional and technical personnel, these two kinds monomeric polarity difference are bigger, and the polarity parameter e=2.25 of MAn is typical electrophilic monomer; And the polarity parameter e=-0.22 of VAc is a kind of power supply monomer, and the two very easily forms 1: 1 charge transfer complex (CTC) and then the alternating copolymerization reaction takes place.So the optimum ratio (mol ratio) when MAn and VAc polyreaction is 1: 1.(mol ratio 1: 2～2: 1) also can carry out the polyreaction of MAn and VAc under other conditions of mixture ratios in principle, but the yield of product, purity and performance all can descend.Such as, if MAn is excessive, then because himself can not polymerization under usual conditions and finally remain in the product; If VAc is excessive, then can not generate strict alternating copolymer, perhaps generate the homopolymer of VAc and make product impure.Two kinds of monomeric total concns (mass concentration) can be between 5%～60% in this dispersion polymerization system, and reasonable is between 20%～40%.
The selection of reaction medium is for realizing that MAn is crucial unusually with the dispersion polymerization of VAc among the present invention, and its fundamental principle is: (1) medium all has good solvency action for MAn with two kinds of monomers of VAc and initiator, is homogeneous system before reacting with assurance; (2) medium can not dissolve for the PMV multipolymer that is generated, after macromolecular chain reaches certain critical length just from medium precipitating come out; (3) polymkeric substance that comes out of precipitating precipitates down with Powdered or block can not be in precipitation polymerization, but stably is suspended in the medium with the form of microballoon, forms the stable dispersion that is similar to polymer emulsion.The organic acid alkyl esters is the chemical substance that meets above condition, can be used as the medium of dispersion polymerization system of the present invention, has following chemical structure:
Wherein, R
1Be hydrogen atom, C
1～C
5Alkyl, phenyl or benzyl, R
2Be C
1～C
5Alkyl.Consider that medium need have polarity, solubility parameter and the viscosity of appropriateness, R
1Be preferably C
1～C
5Alkyl, R
2Be preferably C
1～C
5Alkyl.This type of medium is that its toxicity is lower in the advantage aspect industrial operation and the environmental protection, and mostly has no irritating odor.
Dispersion polymerization system of the present invention is fairly simple, except several components of monomer, initiator and medium, does not need must add a large amount of stablizer and co-stabilizer as traditional dispersion polymerization system.
The technological operation of dispersion polymerization of the present invention is as follows.Monomer, initiator and medium are dosed in the reactor that nitrogen protection, agitator, prolong and thermometer are housed by preset proportion is disposable.Start stirring, monomer and initiator are dissolved in the medium fully, form the homogeneous phase solution of clear.Logical nitrogen uses water-bath (or oil bath) heating to react with the oxygen in the system of removing then.The whole process of reaction has nitrogen protection.Obtain the PMV copolymer dispersion system of white emulsion shape, obtain the solid product of PMV multipolymer again by centrifugation, calculate polymerization yield (C
p).
According to technique known, polymeric reaction temperature is determined by the decomposition temperature of initiator, be suitable for 50～100 ℃ as dibenzoyl peroxide, peroxidation two (2,4 dichloro benzene formyl) is suitable for 30～80 ℃, Diisopropyl azodicarboxylate is suitable for 45～90 ℃, 2,2'-Azobis(2,4-dimethylvaleronitrile) is suitable for 20～90 ℃, or the like (see " polymer experimental technique ", Fudan University polymer science system and polymer science institute write, 1996 the 2nd edition, pp363-365).According to the difference that reaction system is formed, the speed of polyreaction is different, approximately reacts 5～10 hours.
From the dispersion polymerization system, take a sample, observe the form of polymer microballoon with transmission electron microscope (TEM).The size of microballoon represents that with median size (d) size-grade distribution is weighed with standard variance (δ) and dispersion coefficient (ε), and formula is as follows:
ε＝δ/d????????????????????????????????(3)
Wherein, d
iBe the diameter (nm) of single particle, n is a size of a sample.
The functional group on the PMV multipolymer macromolecular chain that the stable mechanism of dispersion polymerization system of the present invention is to generate and the ester group of used medium (COO) have good affinity interaction, thereby the PMV multipolymer that generates itself have played function of stabilizer.This polymerization system has " disperseing certainly " effect thus.By the prepared PMV polymer microballoon of technology of the present invention, its particle diameter can be controlled by processing parameters such as reaction times, monomer concentration, reaction mediums, and scope is between 90～520nm; And very even with the granularity of the polymer microballoon of this method preparation, its dispersion coefficient is between 2.1%～3.2%, near monodispersity.In addition, " disperseing certainly " of the present invention, the polymerization technique system was simple, and speed of reaction is fast, final transformation efficiency height, and the product separate easily, used reaction medium belongs to low toxicity chemical and recyclable utilization.
MAn proposed by the invention and VAc carry out copolyreaction and " disperse " polymerization technique certainly, possess following advantage: (1) owing to need not to add any stablizer and co-stabilizer, reaction system is very simple, and technology controlling and process is easy; (2) polymer microballoon surface cleaning, and particle diameter is controlled, narrow particle size distribution; (3) " disperse " polymerization system highly stable certainly, the product separate easily, reaction medium toxicity is little and recyclable; (4) in addition, do not need stablizer can also save cost, reduce environmental pollution.
Description of drawings
Fig. 1 is the transmission electron microscope photo (magnification 20000) of the polymer microballoon of embodiment 2.
Fig. 2 is the transmission electron microscope photo (magnification 20000) of the polymer microballoon of embodiment 3.
Fig. 3 is the transmission electron microscope photo (magnification 20000) of the polymer microballoon of embodiment 4.
Embodiment
Embodiment 1
MAn and VAc mole proportioning 1: 1, MAn 1.24g wherein, VAc 1.09g; Initiator is BPO, 0.5g; Medium is a butylacetate, 50mL.Adopt heating in water bath, reaction is 10 hours under 80 ℃ temperature, obtains median size (d), dispersion coefficient (ε) and the polymerization yield (C of PMV copolymer microsphere
p), the results are shown in Table 1, the transmission electron microscope photo of polymer microballoon is seen Fig. 1.
Embodiment 2
MAn and VAc mole proportioning 1: 1, MAn 2.48g wherein, VAc 2.18g; Initiator is dibenzoyl peroxide (BPO), 0.2g; Medium is a butylacetate, 45mL.Adopt heating in water bath, reaction is 5 hours under 80 ℃ temperature, obtains median size (d), dispersion coefficient (ε) and the polymerization yield (C of PMV copolymer microsphere
p), the results are shown in Table 1, the transmission electron microscope photo of polymer microballoon is seen Fig. 2.
MAn and VAc mole proportioning 1: 1, MAn 4.96g wherein, VAc 4.36g; Initiator is BPO, 0.2g; Medium is a butylacetate, 40mL.Adopt heating in water bath, reaction is 5 hours under 80 ℃ temperature, obtains median size (d), dispersion coefficient (ε) and the polymerization yield (C of PMV copolymer microsphere
p), the results are shown in Table 1, the transmission electron microscope photo of polymer microballoon is seen Fig. 3.
Embodiment 4
MAn and VAc mole proportioning 1: 1, MAn 7.44g wherein, VAc 6.54g; Initiator is BPO, 0.1g; Medium is a butylacetate, 35mL.Adopt heating in water bath, reaction is 5 hours under 80 ℃ temperature, obtains median size (d), dispersion coefficient (ε) and the polymerization yield (C of PMV copolymer microsphere
p), the results are shown in Table 1.
Embodiment 5
MAn and VAc mole proportioning 1: 1, MAn 14.88g wherein, VAc 13.08g; Initiator is BPO, 0.025g; Medium is a butylacetate, 25mL.Adopt heating in water bath, reaction is 8 hours under 70 ℃ temperature, obtains median size (d), dispersion coefficient (ε) and the polymerization yield (C of PMV copolymer microsphere
p), the results are shown in Table 1.
Embodiment 6
MAn and VAc mole proportioning 1: 1, MAn 4.96g wherein, VAc 4.36g; Initiator is AIBN, 0.1g; Medium is a butylacetate, 40mL.Adopt heating in water bath, reaction is 5 hours under 60 ℃ temperature, obtains median size (d), dispersion coefficient (ε) and the polymerization yield (C of PMV copolymer microsphere
p), the results are shown in Table 1.
Embodiment 7
MAn and VAc mole proportioning 1: 2, MAn 3.27g wherein, VAc 5.73g; Initiator is BPO, 0.1g; Medium is a butylacetate, 40mL.Adopt heating in water bath, reaction is 5 hours under 80 ℃ temperature, obtains median size (d), dispersion coefficient (ε) and the polymerization yield (C of PMV copolymer microsphere
p), the results are shown in Table 1.
Embodiment 8
MAn and VAc mole proportioning 2: 1, MAn 6.53g wherein, VAc 2.87g; Initiator is BPO, 0.1g; Medium is a butylacetate, 40mL.Adopt heating in water bath, reaction is 5 hours under 80 ℃ temperature, obtains median size (d), dispersion coefficient (ε) and the polymerization yield (C of PMV copolymer microsphere
p), the results are shown in Table 1.
Embodiment 9
MAn and VAc mole proportioning 1: 1, MAn 4.96g wherein, VAc 4.36g; Initiator is BPO, 0.1g; Medium is an isobutyl acetate, 40mL.Adopt heating in water bath, reaction is 5 hours under 80 ℃ temperature, obtains median size (d), dispersion coefficient (ε) and the polymerization yield (C of PMV copolymer microsphere
p), the results are shown in Table 1.
Embodiment 10
MAn and VAc mole proportioning 1: 1, MAn 4.96g, VAc 4.36g; Initiator is BPO, 0.1g; Medium is an ethyl propionate, 40mL.Adopt heating in water bath, reaction is 5 hours under 80 ℃ temperature, obtains median size (d), dispersion coefficient (ε) and the polymerization yield (C of PMV copolymer microsphere
p), the results are shown in Table 1.
Comparative Examples 1
MAn and VAc mole proportioning 1: 1, MAn 4.96g wherein, VAc 4.36g; Initiator is BPO, 0.1g; Medium is a toluene, 40mL.Adopt heating in water bath, reaction is 5 hours under 80 ℃ temperature, obtains median size (d), dispersion coefficient (ε) and the polymerization yield (C of PMV copolymer microsphere
p), the results are shown in Table 1.
Comparative Examples 2
MAn and VAc mole proportioning 1: 1, MAn 4.96g wherein, VAc 4.36g; Initiator is BPO, 0.1g; Medium is a dimethylbenzene, 40mL.Adopt heating in water bath, reaction is 5 hours under 80 ℃ temperature, obtains median size (d), dispersion coefficient (ε) and the polymerization yield (C of PMV copolymer microsphere
p), the results are shown in Table 1.
Table 1
| The reaction system outward appearance | Polymerization technique | Median size (d) | Dispersion coefficient (ε) | Polymerization yield (C p) | |
| Embodiment 1 | Milky white stable dispersion | " disperse " polymerization certainly | ????90nm | ??3.2％ | ??88％ |
| Embodiment 2 | Milky white stable dispersion | " disperse " polymerization certainly | ????160nm | ??2.5％ | ??92％ |
| Embodiment 3 | Milky white stable dispersion | " disperse " polymerization certainly | ????220nm | ??2.1％ | ??94％ |
| Embodiment 4 | Milky white stable dispersion | " disperse " polymerization certainly | ????440nm | ??2.3％ | ??90％ |
| Embodiment 5 | Milky white stable dispersion | " disperse " polymerization certainly | ????520nm | ??2.4％ | ??89％ |
| Embodiment 6 | Milky white stable dispersion | " disperse " polymerization certainly | ????214nm | ??2.6％ | ??84％ |
| Embodiment 7 | Milky white stable dispersion | " disperse " polymerization certainly | ????206nm | ??2.8％ | ??76％ |
| Embodiment 8 | Milky white stable dispersion | " disperse " polymerization certainly | ????218nm | ??3.0％ | ??61％ |
| Embodiment 9 | Milky white stable dispersion | " disperse " polymerization certainly | ????205nm | ??2.5％ | ??86％ |
| Embodiment 10 | Milky white stable dispersion | " disperse " polymerization certainly | ????212nm | ??2.2％ | ??90％ |
| Comparative Examples 1 | Sallow pasty state precipitation | Precipitation polymerization | ????- | ??- | ??82％ |
| Comparative Examples 2 | Sallow pasty state precipitation | Precipitation polymerization | ????- | ??- | ??79％ |
Claims (7)
1, the dispersion polymerization processes of maleic anhydride and vinyl acetate copolymerized reaction, the composition of dispersion polymerization system comprises monomer and initiator, with each components dissolved of system in medium, carry out copolyreaction being equal to or higher than under the decomposition temperature condition of initiator, obtain the dispersion system of multipolymer, again through separating the solid product that obtains multipolymer, it is characterized in that: in the dispersion polymerization system, need not to add under the condition of any stablizer and co-stabilizer, polymeric reaction temperature is at 20～100 ℃, copolyreaction 5～10h obtains the dispersion system of polymer microballoon; Reaction monomers maleic anhydride and vinyl acetate, two monomeric mol ratios are 1: 2～2: 1; The mass concentration of monomer in the dispersion polymerization system is 5%～60%; Initiator is organo-peroxide or azo-compound, and the mass concentration of initiator in the dispersion polymerization system is 0.05%～1%; Medium is the organic acid alkyl ester, and chemical structural formula is:
Wherein, R
1Be hydrogen atom, C
1～C
5Alkyl, phenyl or benzyl, R
2Be C
1～C
5Alkyl.
2, method according to claim 1 is characterized in that: R in the chemical structural formula of organic acid alkyl ester
1Be C
1～C
5Alkyl, R
2Be C
1～C
5Alkyl.
3, method according to claim 1 is characterized in that: the organic acid alkyl ester is an ethyl formate, propyl formate, tetryl formate, pentyl formate, ethyl acetate, butylacetate, isobutyl acetate, sec-butyl acetate, pentyl acetate, Isoamyl Acetate FCC, jasmal, methyl propionate, ethyl propionate, butyl propionate, methyl-butyrate, ethyl butyrate, butyl butyrate, isoamyl butyrate, Ethylisovalerate, isoamyl isovalerate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, isoamyl benzoate, methyl phenylacetate or Phenylacetic acid ethylester.
4, method according to claim 1 is characterized in that: the mol ratio of two reaction monomers maleic anhydrides and vinyl acetate is 1: 1.
5, method according to claim 1, it is characterized in that: organic peroxide evocating agent is dibenzoyl peroxide, dicumyl peroxide, peroxidation two (2,4 dichloro benzene formyl), di-tert-butyl peroxide, dilauroyl peroxide, the special butyl ester of peroxidation phenylformic acid, peroxy dicarbonate diisopropyl ester or di-cyclohexylperoxy dicarbonate.
6, method according to claim 1 is characterized in that: the azo-compound initiator is Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile).
7, method according to claim 1 is characterized in that: in the dispersion system of polymer microballoon, the median size of microballoon is at 90～520nm; Dispersion coefficient is 2.1%～3.2%.
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| CN102643378A (en) * | 2012-05-10 | 2012-08-22 | 西北师范大学 | Emulsifier-free vinyl acetate-maleic anhydride copolymer emulsion and preparation and application thereof |
| CN111100447A (en) * | 2018-10-26 | 2020-05-05 | 中国石油化工股份有限公司 | Polyamide-polyester alloy composition and polyamide-6-polybutylene terephthalate alloy |
| CN111100447B (en) * | 2018-10-26 | 2022-07-12 | 中国石油化工股份有限公司 | Polyamide-polyester alloy composition and polyamide-6-polybutylene terephthalate alloy |
| CN112708029A (en) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | Polymer composite microsphere containing vinyl acetate-maleic anhydride and preparation method and application thereof |
| CN112708029B (en) * | 2019-10-25 | 2022-11-18 | 中国石油化工股份有限公司 | Polymer composite microsphere containing vinyl acetate-maleic anhydride and preparation method and application thereof |
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