CN101338007A - Process for preparing cross-linking maleic anhydride-vinyl acetate copolymer - Google Patents
Process for preparing cross-linking maleic anhydride-vinyl acetate copolymer Download PDFInfo
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Abstract
A cross linking maleic anhydride-vinyl acetate copolymer preparation method belongs to the field of copolymers. The invention is characterized in that a polymerization reaction system comprises a reactive monomer, cross linking agents, initiators and medium; the reactive monomer is maleic anhydride and acetate vinyl, and the mol ratio is from 1:9 to 9:1; the mass concentration of the monomer in the polymerization system is from 0.45 percent to 45 percent; the cross linking agents being used are polyfunctionality organic molecules; the initiators being used are organic peroxides or azo compounds; the mass of the initiator is 0.02 percent to 1 percent of the total monomers; the rest is the medium; the copolymerization lasts 4 to 24 hours. The invention does not use stabilizers, does not introduce impurities such as surface active agents, etc. into the surfaces of particles to affect the surface properties of the particles; the preparation process is simple and is easy to control, and the invention can save the cost and is environment-friendly.
Description
Technical field
The present invention relates to the polymerization process of a kind of preparation cross-linked maleic anhydride (MAn)-vinyl acetate (VAc) polymer particle, form the polymerization process of self-stabilized crosslinked dispersion of polymer particle system after particularly relating to a kind of polyreaction and finishing.Utilize this method not only can prepare the cross-linking polymer particle of different-shape, can also keep the activity acid anhydride base of polymer beads sub-surface.
Background technology
The lower linear product polymaleic anhydride-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.About the copolymerization of MAn and VAc, traditional processing method mainly contains solution polymerization process, emulsion polymerization and precipitation polymerization method, and these methods are mainly used in the preparation of linear polymer.
What the solution polymerization process of MAn and VAc was common mainly is its aqueous solution polymerization, and this method is mainly used in synthetic scale inhibitor.For example Ma Tao, Fan Yanfang etc. are in " the synthetic and evaluation of maleic anhydride vinyl acetate copolymer " (" refining of petroleum and chemical industry " the 9th phase in 2004, pp.58-60) in the literary composition, by in the maleic anhydride aqueous solution, dripping the aqueous solution copolymerization that the vinyl acetate solution that contains initiator has realized maleic anhydride-vinyl acetate, prepared polymkeric substance with certain scale inhibition ability.And for example Ma Tao, Zhang Guicai etc. are in " water of maleic anhydride vinyl acetate copolymer is synthetic " (" refining of petroleum and chemical industry " the 2nd phase in 2004, pp.121-126) be solvent with water in the literary composition, oxidation-reduction system is that initiator has synthesized maleic anhydride vinyl acetate copolymer.Do not relate to the formation of polymer particle in the solution polymerization research.
The precipitation polymerization of MAn and VAc mainly carries out in aromatic solvents, obtains the precipitation of polymkeric substance after reaction finishes, but not finely disseminated dispersion system.For example the Deng Xiao tinkling of pieces of jade, Zou Xinxi are in " research of vinyl acetate maleic acid acid anhydride free-atom aqueous solution alternating copolymerization " (" University Of Xiangtan's natural science journal " the 1st phase in 1998, pp.89-97) in the literary composition, be the multipolymer precipitation that obtains maleic anhydride-vinyl acetate after solvent polymeric is finished with toluene.And for example Zhang Ping, Gu Xiaoman etc. are at " research of maleic anhydride and the reaction of vinyl-acetic ester alternative copolymerization " (" Guangzhou chemistry ", 1995, the 1st phase, pp.22-26.) with benzene as reaction medium, and make initiator with dibenzoyl peroxide (BPO) and form the precipitation polymerization system, 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.
(" 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.
Xing Changmin, Yang Wantai are at " A Novel; Facile Method for the Preparation of Uniform; Reactive MaleicAnhydride/Vinyl Acetate Copolymer Micro-and Nanospheres " (Macromol.Rapid Commun.2004,25,1568-1574
) and " Stabilizer-Free Dispersion Copolymerization of Maleic Anhydride and Vinyl Acetate.I.Effects of Principal Factors on Microspheres " (J.Polym.Sci., Part A:Polym.Chem.2005 (43), 3760-3770), introduced a kind of not adding under any stablizer condition, the polymerization process of preparation maleic anhydride vinyl acetate copolymer microballoon dispersion system.This method of introducing can be used for preparing surface cleaning, uniform particle diameter and the controlled linear microballoon of multipolymer.
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.In the various application of microballoon, the physicochemical property of microballoon there is different requirements.Not only Xian Xing polymer microballoon has a wide range of applications, and crosslinked copolymer beads also has important use.
Our invention in understanding and grasp to maleic anhydride-vinyl acetate linear polymer preparation, proposes new preparation route and method, thereby has prepared crosslinked maleic anhydride vinyl acetate copolymer particle just.This preparation method does not need to add any stablizer or tensio-active agent yet in polymerization system, can realize just that by the reasonably combined of polymerization system the oneself of polymeric system disperses, and we are called the precipitation polymerization of self stabilization.We can prepare that surface cleaning, pattern are controlled, the copolymer particle of controllable size precipitation polymerization by self stabilization.The preparation method of cross-linking maleic anhydride-vinyl acetate cross-linking copolymer particle does not appear in the newspapers up to now.The self stabilization polymerization prepares the cross-linking copolymer particle and has characteristics: (1) does not use stablizer, can not introduce impurity molecules such as tensio-active agent at particle surface and has influence on the surface properties of particle; (2) preparation technology simply is easy to control; Can save the protection that cost also helps environment when (3) avoiding using tensio-active agent or stablizer.
Summary of the invention
The objective of the invention is to propose the novel method of a kind of preparation cross-linked maleic anhydride (MAn)-vinyl acetate (VAc) copolymer particle, need not to add any stablizer.In the dispersion system of polymer particle, the polymer particle surface cleaning, the polymer particle pattern is controlled, the controllable size of polymer particle.
In this invention of preparation of cross-linked maleic anhydride (MAn)-vinyl acetate (VAc) polymer particle, the technical characterictic that the self stabilization precipitation polymerization prepares cross-linking polymer particle is: do not need to add any tensio-active agent or stablizer, after the polymerization system polymerization that contains a certain linking agent is finished, form the dispersion system of polymer particle, keep stable within a certain period of time and the cohesion or the precipitation of polymkeric substance do not take place.In this invention of preparation of cross-linked maleic anhydride (MAn)-vinyl acetate (VAc) polymer particle, its major technology is characterized as: need not to add under the condition of any stablizer and co-stabilizer in polymerization system, copolyreaction 4～24h obtains the dispersion system of cross-linking polymer particle; Reaction monomers maleic anhydride and vinyl acetate, mol ratio is 1: 9～9: 1; Used linking agent is the polyfunctionality organic molecule, the shared mass concentration in polymerization system of linking agent has corresponding proper concentration with the difference of linking agent kind, and the shared mass concentration scope of linking agent was 0.2%～10% when for example linking agent was aliphatic divinyl ester; The mass concentration of monomer in polymerization reaction system is 0.45%～45%; Initiator is organo-peroxide or azo-compound, and the amount of used initiator is 0.02%～1% of a used monomer total amount; The medium of reaction is done corresponding adjustment (comprising consumption and kind) with the different needs of linking agent kind and consumption, and the resulting polymers particle presents different patterns with the variation of the concentration of linking agent kind, dosage of crosslinking agent and polymerization system.
The initiator that can be used for self stabilization precipitation 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, 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 amount of initiator in this polymerization reaction system is 0.02%～1% of used monomer total mass, and reasonable is between 0.05%～0.5%.
The preparation of [A] cross-linked maleic anhydride (MAn)-vinyl acetate (VAc) copolymer microsphere
The technical characterictic that the self stabilization precipitation polymerization prepares cross-linked maleic anhydride (MAn)-vinyl acetate (VAc) polymer microballoon is: need not to add under the condition of any stablizer and co-stabilizer in polymerization system, copolyreaction 4～24h obtains the dispersion system of cross-linked polymer microsphere; Reaction monomers maleic anhydride and vinyl acetate, two monomeric mol ratios are 1: 1; The mass concentration of monomer in polymerization reaction system is 0.45%～30%; Initiator is organo-peroxide or azo-compound, and the amount of used initiator is 0.02%～1% of a used monomer total mass; Used linking agent is aliphatic divinyl ester, as Diethylene Glycol base dimethacrylate (EGDMA), and Diethylene Glycol base diethyl acrylate etc.; The medium of reaction changes with the difference of dosage of crosslinking agent: when linking agent be the consumption of aliphatic divinyl ester be used monomer total mass 1.1%～26.9% the time, medium is the organic acid alkyl ester, 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.; When linking agent be the consumption of aliphatic divinyl ester be used monomer total mass 26.9%～53.8% the time, medium be organic ketone for example: acetone, butanone, pimelinketone, hexone etc., organic ketone in polymerization system shared massfraction with the increasing and increase of dosage of crosslinking agent, used reaction medium in whole reaction system shared mass concentration scope 93.6%～98.8%.
The gained cross-linking polymer particle is monodispersed polymer microballoon under the present technique condition, and microsphere average grain diameter is at 460nm～2000nm, and particle diameter statistics dispersion coefficient is 1.005～1.145.
Present technique realizes the self stabilization precipitation cross-linking polymerization of MAn and VAc by selecting suitable aliphatic ester linking agent and reaction medium, its characteristics are: need not to add any stablizer and co-stabilizer in (1) this polymerization system, have the dispersion effect of self stabilization; (2) disperse phase is a monodisperse cross-linked polymer microspheres in the polymerization system, the microsphere surface cleaning, and particle diameter is controlled, and narrow particle size distribution.
Polymerization reaction system of the present invention is fairly simple, except several components of monomer, initiator, linking agent and medium,
Do not need traditional dispersion polymerization system must add a large amount of stablizer and co-stabilizer like that.
The technological operation of polyreaction of the present invention is as follows: monomer, initiator, linking agent and medium are dosed in the reactor that nitrogen protection, agitator, prolong and thermometer are housed by preset proportion is disposable.Monomer, linking agent 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 cross-linking copolymer dispersion system of white emulsion shape, obtain the solid product of PMV cross-linking copolymer 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 60～90 ℃ as dibenzoyl peroxide, and Diisopropyl azodicarboxylate is suitable for 45～80 ℃, and so on.According to the difference that reaction system is formed, the speed of polyreaction is different, approximately reacts 4～24h.
From polymerization system, take a sample, observe the form of polymer microballoon with scanning electronic microscope (SEM).The size of microballoon represents that with median size (Dn) size-grade distribution represents that with dispersion coefficient (U) formula is as follows:
U＝D
w/D
n (3)
Wherein, D
iBe the diameter (nm) of i particle, n is a size of a sample, D
wMathematic(al) mean particle diameter for definition.
By the prepared crosslinked 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 460～2000nm; And very even with the granularity of the polymer microballoon of this method preparation, its dispersion coefficient is between 1.005～1.145, for monodispersity or near monodispersity.In addition, self stabilization precipitation polymerization process system of the present invention is 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.
Self stabilization precipitation polymerization of the present invention, the stable of system is due to the solvation special between resulting polymers and reaction medium.This special solvation between particle surface polymer molecular chain and reaction medium does not just keep the dispersive state thereby cohesion just can not take place the polymer particle that precipitating is come out in the reaction.
[B] cross-linked maleic anhydride (MAn)-vinyl acetate (VAc) multipolymer tandem type and tendril shape ball of string type particle preparation
The technical characterictic that the self stabilization precipitation polymerization prepares cross-linked maleic anhydride (MAn)-vinyl acetate (VAc) tandem type and ball of string type copolymer particle is: need not to add under the condition of any stablizer and co-stabilizer in polymerization system, copolyreaction 4～8h obtains the dispersion system of polymer particle; Reaction monomers maleic anhydride and vinyl acetate, two monomeric mol ratios are 1: 9～9: 1; The mass concentration of monomer in polymerization reaction system is 0.5%～45%; Initiator is organo-peroxide or azo-compound, and the consumption of initiator is 0.02%～1% of a used monomer total mass; Used linking agent is aromatic diolefine, Vinylstyrene (DVB) for example, and divinyl toluene etc., linking agent shared mass concentration in polymerization system is: 0.1%～2%; 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.
A comparatively uniform microballoon tandem of gained cross-linking polymer particle radial dimension or a tendril shape ball of string under the present technique condition, the radial dimension of this type of particle is at 60nm～500nm.
Present technique realizes the self stabilization precipitation cross-linking polymerization of MAn and VAc by selecting suitable aromatic hydrocarbon based linking agent and reaction medium, its characteristics are: need not to add any stablizer and co-stabilizer in (1) this polymerization system, have the dispersion effect of self stabilization; (2) disperse phase is comparatively the copolymer microsphere tandem or the tendril shape multipolymer ball of string of homogeneous of radial dimension in the polymerization system, and the size and the pattern of multipolymer are controlled.
Polymerization reaction system of the present invention is fairly simple, except several components of monomer, initiator, linking agent and medium,
Do not need traditional dispersion polymerization system must add a large amount of stablizer and co-stabilizer like that.
The technological operation of polyreaction of the present invention is as follows.Monomer, initiator, linking agent and medium are dosed in the reactor that nitrogen protection, agitator, prolong and thermometer are housed by preset proportion is disposable.Monomer, linking agent 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 cross-linking copolymer dispersion system of white emulsion shape, obtain the solid product of PMV cross-linking copolymer 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 60～90 ℃ as dibenzoyl peroxide, and Diisopropyl azodicarboxylate is suitable for 45～80 ℃, and so on.According to the difference that reaction system is formed, the speed of polyreaction is different, approximately reacts 4～8h.
From polymerization system, take a sample, observe the form of polymer particle with scanning electronic microscope (SEM).The size of polymer particle radial dimension represents that with average radial size (Ln) formula is as follows:
L wherein
nBe average radial size, L
iBe i the radial dimension of being got.
Present technique can prepare cross-linked maleic anhydride (MAn) and the tandem type of vinyl acetate (VAc) or the ball of string type particle of tendril shape with different radial dimensions and physical size, the preparation system is simple, preparation technology is easy to control, material is purified and is separated simply the little and recyclable utilization of solvent toxicity.
Description of drawings
Fig. 1 is the surface sweeping electron micrograph (magnification 10000) of the crosslinked PMV polymer microballoon of embodiment 1.
Fig. 2 is the surface sweeping electron micrograph (magnification 10000) of the crosslinked PMV polymer microballoon of embodiment 5.
Fig. 3 is the surface sweeping electron micrograph (magnification 10000) of the crosslinked PMV polymer microballoon of embodiment 7.
Fig. 4 is the surface sweeping electron micrograph (magnification 10000) of the crosslinked PMV polymer microballoon of embodiment 8.
Fig. 5 is the surface sweeping electron micrograph (magnification 10000) of the crosslinked poly-PMV compound microballoon of embodiment 9.
Fig. 6 is the surface sweeping electron micrograph (magnification 10000) of the crosslinked PMV polymer microballoon of embodiment 10.
Fig. 7 is the surface sweeping electron micrograph (magnification 10000) of the crosslinked PMV polymer microballoon of embodiment 11.
Fig. 8 is the surface sweeping electron micrograph (magnification 10000) of the crosslinked PMV polymer microballoon of embodiment 12.
Fig. 9 is the surface sweeping electron micrograph (magnification 25000) of the crosslinked PMV polymkeric substance tandem of embodiment 13.
Figure 10 is the surface sweeping electron micrograph (magnification 25000) of the crosslinked PMV polymkeric substance tandem of embodiment 14.
Figure 11 is the surface sweeping electron micrograph (magnification 10000) of the crosslinked PMV polymkeric substance tendril shape ball of string of embodiment 15.
Figure 12 is the surface sweeping electron micrograph (magnification 10000) of the crosslinked PMV polymkeric substance tendril shape ball of string of embodiment 16.
Figure 13 is the surface sweeping electron micrograph (magnification 10000) of the crosslinked PMV polymkeric substance tendril shape ball of string of embodiment 17.
Figure 14 is the surface sweeping electron micrograph (magnification 10000) of the crosslinked PMV polymkeric substance tendril shape ball of string of embodiment 18.
Embodiment
Embodiment 1
MAn 4.903g, VAc4.3045g; Initiator is dibenzoyl peroxide (BPO), 0.0969g; Linking agent Diethylene Glycol base dimethacrylate (EGDMA), 0.0991g; Medium is a butylacetate, 43mL.Adopt heating in water bath, reaction is 4 hours under 80 ℃ temperature, obtains median size (Dn), dispersion coefficient (U) and the polymerization yield (C of crosslinked PMV copolymer microsphere
p), the results are shown in Table 1, the electron scanning micrograph of cross-linked polymer is as shown in Figure 1.
Embodiment 2
MAn 4.903g, VAc4.3045g; Initiator is a di-tert-butyl peroxide, 0.0018g; Linking agent Diethylene Glycol base diethyl acrylate, 0.2973g; Medium is a pentyl acetate, 22mL.Adopt heating in water bath, reaction is 8 hours under 80 ℃ temperature, obtains median size (Dn), dispersion coefficient (U) and the polymerization yield (C of crosslinked PMV copolymer microsphere
p), the results are shown in Table 1
Embodiment 3
MAn 4.903g, VAc4.3045g; Initiator is a dicumyl peroxide, 0.00469g; Linking agent Diethylene Glycol base diethyl acrylate, 0.4955g; Medium is an ethyl butyrate, 43mL.Adopt heating in water bath, reaction is 6 hours under 80 ℃ temperature, obtains median size (Dn), dispersion coefficient (U) and the polymerization yield (C of crosslinked PMV copolymer microsphere
p), the results are shown in Table 1
Embodiment 4
MAn 4.903g, VAc4.3045g; Initiator is the peroxy dicarbonate diisopropyl ester, 0.0465g; Linking agent EGDMA, 0.6937g; Medium is an Isoamyl Acetate FCC, 43mL.Adopt heating in water bath, reaction is 12 hours under 80 ℃ temperature, obtains median size (Dn), dispersion coefficient (U) and the polymerization yield (C of crosslinked PMV copolymer microsphere
p), the results are shown in Table 1
Embodiment 5
MAn 4.903g, VAc4.3045g; Initiator is a di-cyclohexylperoxy dicarbonate, 0.0969g; Linking agent Diethylene Glycol base diethyl acrylate, 0.8919g; Medium is a butylacetate, 43mL.Adopt heating in water bath, reaction is 24 hours under 80 ℃ temperature, obtains median size (Dn), dispersion coefficient (U) and the polymerization yield (C of crosslinked PMV copolymer microsphere
p), the results are shown in Table 1, the electron scanning micrograph of cross-linked polymer is as shown in Figure 2.
Embodiment 6
MAn 4.903g, VAc4.3045g; Initiator is a 2,2'-Azobis(2,4-dimethylvaleronitrile), 00969g; Linking agent EGDMA, 1.4865g; Medium is an Isoamyl Acetate FCC, 43mL.Adopt heating in water bath, reaction is 6 hours under 80 ℃ temperature, obtains median size (Dn), dispersion coefficient (U) and the polymerization yield (C of crosslinked PMV copolymer microsphere
p), the results are shown in Table 1
Embodiment 7
MAn 4.903g, VAc4.3045g; Initiator is the special butyl ester of peroxidation phenylformic acid, 0.0969g; Linking agent Diethylene Glycol base diethyl acrylate, 1.982g; Medium is an ethyl benzoate, 43mL.Adopt heating in water bath, reaction is 6 hours under 80 ℃ temperature, obtains median size (Dn), dispersion coefficient (U) and the polymerization yield (C of crosslinked PMV copolymer microsphere
p), the results are shown in Table 1, the electron scanning micrograph of cross-linked polymer is as shown in Figure 3.
Embodiment 8
MAn 4.903g, VAc4.3045g; Initiator is a Diisopropyl azodicarboxylate, 0.0969g; Linking agent EGDMA, 2.4775g; Medium is an isoamyl isovalerate, 43mL.Adopt heating in water bath, reaction is 6 hours under 80 ℃ temperature, obtains median size (Dn), dispersion coefficient (U) and the polymerization yield (C of crosslinked PMV copolymer microsphere
p), the results are shown in Table 1, the electron scanning micrograph of cross-linked polymer is as shown in Figure 4.
Embodiment 9
MAn 4.903g, VAc4.3045g; Initiator is BPO, 0.0969g; Linking agent Diethylene Glycol base diethyl acrylate, 2.4775g; Medium is a hexone ketone, 172mL.Adopt heating in water bath, reaction is 24 hours under 80 ℃ temperature, obtains median size (Dn), dispersion coefficient (U) and the polymerization yield (C of crosslinked PMV copolymer microsphere
p), the results are shown in Table 1, the electron scanning micrograph of cross-linked polymer is as shown in Figure 5.
Embodiment 10
MAn 1.226g, VAc1.0762g; Initiator is a dicumyl peroxide, 0.0969g; Linking agent EGDMA, 1.239g; Medium is a pimelinketone, 172mL.Adopt heating in water bath, reaction is 24 hours under 80 ℃ temperature, obtains median size (Dn), dispersion coefficient (U) and the polymerization yield (C of crosslinked PMV copolymer microsphere
p), the results are shown in Table 1, the electron scanning micrograph of cross-linked polymer is as shown in Figure 6.
Embodiment 11
MAn 1.226g, VAc1.0762g; Initiator is a Diisopropyl azodicarboxylate, 0.0969g; Linking agent Diethylene Glycol base diethyl acrylate, 1.239g; Medium is an acetone, 258mL.Adopt heating in water bath, reaction is 24 hours under 54 ℃ temperature, obtains median size (Dn), dispersion coefficient (U) and the polymerization yield (Cp) of crosslinked PMV copolymer microsphere, the results are shown in Table 1, and the electron scanning micrograph of cross-linked polymer as shown in Figure 7.
Embodiment 12
MAn 1.226g, VAc1.0762g; Initiator is BPO, 0.0969g; Linking agent Diethylene Glycol base diethyl acrylate, 1.239g; Medium is a butanone, 301mL.Adopt heating in water bath, reaction is 24 hours under 80 ℃ temperature, obtains median size (Dn), dispersion coefficient (U) and the polymerization yield (C of crosslinked PMV copolymer microsphere
p), the results are shown in Table 1, the electron scanning micrograph of cross-linked polymer is as shown in Figure 8.
Embodiment 13
MAn 4.903g, VAc4.3045g; Initiator is the peroxy dicarbonate diisopropyl ester, 0.0018g; Linking agent Vinylstyrene (DVB), 0.009g; Medium is a butylacetate, 43mL.Adopt heating in water bath, reaction is 4 hours under 80 ℃ temperature, obtains the average radial size Ln and the polymerization yield (C of crosslinked PMV copolymer particle
p), the results are shown in Table 2, the electron scanning micrograph of cross-linked polymer is as shown in Figure 9.
Embodiment 14
MAn 4.903g, VAc4.3045g; Initiator is BPO, 0.0920g; The linking agent divinyl toluene, 0.185g; Medium is a butylacetate, 43mL.Adopt heating in water bath, reaction is 6 hours under 80 ℃ temperature, obtains the average radial size Ln and the polymerization yield (C of crosslinked PMV copolymer particle
p), the results are shown in Table 2, the electron scanning micrograph of cross-linked polymer is as shown in figure 10.
Embodiment 15
MAn 2.576g, VAc2.452g; Initiator is a dilauroyl peroxide, 0.08g; Linking agent DVB, 0.1g; Medium is a butylacetate, 43mL.Adopt heating in water bath, reaction is 8 hours under 80 ℃ temperature, obtains the average radial size Ln and the polymerization yield (C of crosslinked PMV copolymer particle
p), the results are shown in Table 2, the electron scanning micrograph of cross-linked polymer is as shown in figure 11.
Embodiment 16
MAn 2.476g, VAc2.152g; Initiator is BPO, 0.07g; The linking agent divinyl toluene, 0.05g; Medium is an ethyl benzoate, 43mL.Adopt heating in water bath, reaction is 6 hours under 80 ℃ temperature, obtains the average radial size Ln and the polymerization yield (C of crosslinked PMV copolymer particle
p), the results are shown in Table 2, the electron scanning micrograph of cross-linked polymer is as shown in figure 12.
Embodiment 17
MAn 0.9806g, VAc2.152g; Initiator is a dilauroyl peroxide, 0.0969g; The linking agent divinyl toluene, 0.1g; Medium is an isoamyl isovalerate, 43mL.Adopt heating in water bath, reaction is 5 hours under 80 ℃ temperature, obtains the average radial size Ln and the polymerization yield (C of crosslinked PMV copolymer particle
p), the results are shown in Table 2, the electron scanning micrograph of cross-linked polymer is as shown in figure 13.
Embodiment 18
MAn 1.4709g, VAc2.152g; Initiator is the special butyl ester of peroxidation phenylformic acid, 0.0969g; Linking agent DVB, 0.1g; Medium is an Isoamyl Acetate FCC, 43mL.Adopt heating in water bath, reaction is 8 hours under 80 ℃ temperature, obtains the average radial size Ln and the polymerization yield (C of crosslinked PMV copolymer particle
p), the results are shown in Table 2, the electron scanning micrograph of cross-linked polymer is as shown in figure 14.
Embodiment 19
MAn 0.9806g, VAc7.7481g; Initiator is BPO, 0.0969g; Linking agent divinyl propyl benzene, 0.1g; Medium is an ethyl butyrate, 43mL.Adopt heating in water bath, reaction is 8 hours under 80 ℃ temperature, obtains the average radial size Ln and the polymerization yield (C of crosslinked PMV copolymer particle
p), the results are shown in Table 2.
Embodiment 20
MAn 8.8254g, VAc0.8609g; Initiator is a dicumyl peroxide, 0.0969g; Linking agent divinyl ethylbenzene, 0.1g; Medium is a pentyl acetate, 43mL.Adopt heating in water bath, reaction is 8 hours under 80 ℃ temperature, obtains the average radial size Ln and the polymerization yield (C of crosslinked PMV copolymer particle
p), the results are shown in Table 2.
Detect as can be known by infrared spectra in all embodiments, kept activity in the resulting polymers and got the acid anhydride base.And the oyster white dispersion system of resulting polymers kept stable and sedimentation does not take place in 2～200 days.
Table 1
| Implementation example | The system outward appearance | Polymerization process | Median size/nm | Dispersion coefficient U | Polymer particle productive rate Cp/% |
| Embodiment 1 | The oyster white dispersion system | The self stabilization dispersion polymerization | 460 | 1.018 | 86 |
| Embodiment 2 | The oyster white dispersion system | The self stabilization dispersion polymerization | 533 | 1.02 | 85 |
| Embodiment 3 | The oyster white dispersion system | The self stabilization dispersion polymerization | 535 | 1.04 | 87 |
| Embodiment 4 | The oyster white dispersion system | The self stabilization dispersion polymerization | 605 | 1.041 | 85 |
| Embodiment 5 | The oyster white dispersion system | The self stabilization dispersion polymerization | 708 | 1.052 | 87 |
| Embodiment 6 | The oyster white dispersion system | The self stabilization dispersion polymerization | 747 | 1.052 | 88 |
| Embodiment 7 | The oyster white dispersion system | The self stabilization dispersion polymerization | 805 | 1.025 | 86 |
| Embodiment 8 | The oyster white dispersion system | The self stabilization dispersion polymerization | 848 | 1.045 | 85 |
| Embodiment 9 | The oyster white dispersion system | The self stabilization dispersion polymerization | 1221 | 1.038 | 78 |
| Embodiment 10 | The oyster white dispersion system | The self stabilization dispersion polymerization | 1582 | 1.052 | 75 |
| Embodiment 11 | The oyster white dispersion system | The self stabilization dispersion polymerization | 2000 | 1.03 | 70 |
| Embodiment 12 | The oyster white dispersion system | The self stabilization dispersion polymerization | 1145 | 1.013 | 76 |
Table 2
| Implementation example | The system outward appearance | Polymerization process | Average radial size/nm | Polymer particle productive rate Cp/% |
| Embodiment 13 | The oyster white dispersion system | The self stabilization dispersion polymerization | 500 | 80 |
| Embodiment 14 | The oyster white dispersion system | The self stabilization dispersion polymerization | 114 | 82 |
| Embodiment 15 | The oyster white dispersion system | The self stabilization dispersion polymerization | 192 | 81 |
| Embodiment 16 | The oyster white dispersion system | The self stabilization dispersion polymerization | 193 | 82 |
| Embodiment 17 | The oyster white dispersion system | The self stabilization dispersion polymerization | 73 | 81 |
| Embodiment 18 | The oyster white dispersion system | The self stabilization dispersion polymerization | 68 | 80 |
| Embodiment 19 | The oyster white dispersion system | The self stabilization dispersion polymerization | 60 | 79 |
| Embodiment 20 | The oyster white dispersion system | The self stabilization dispersion polymerization | 65 | 85 |
Claims (3)
1, a kind of preparation method of cross-linking maleic anhydride-vinyl acetate copolymer is characterized in that: polymerization reaction system comprises reaction monomers, linking agent, initiator and medium; Reaction monomers is maleic anhydride and vinyl acetate, and mol ratio is 1: 9～9: 1, and the mass concentration of monomer in polymerization reaction system is 0.45%～45%; Used linking agent is the polyfunctionality organic molecule; Used initiator is organo-peroxide or azo-compound, and the quality of initiator is 0.02%～1% of a monomer total amount, and all the other are medium, copolyreaction 4～24h.
2, method according to claim 1, it is characterized in that: when preparing the copolymer microsphere dispersion system of cross-linking maleic anhydride-vinyl acetate, the mol ratio of reaction monomers maleic anhydride and vinyl acetate is 1: 1, and the mass concentration of monomer in polymerization reaction system is 0.45%～30%; Used linking agent is aliphatic divinyl ester, when divinyl ester consumption be the monomer total mass 1.1%～26.9% the time, medium is the organic acid alkyl ester, chemical structural formula is:
Wherein, R1 is alkyl, phenyl or the benzyl of hydrogen atom, C1～C5, and R2 is the alkyl of C1～C5; When the consumption of divinyl ester be used monomer total mass 26.9%～53.8% the time, medium is an organic ketone, and organic ketone answers mass concentration scope shared in the reaction system 93.6%～98.8% in polymerization.
3, method according to claim 1 is characterized in that: when preparation tandem type and tendril shape ball of string type particle, the mass concentration of monomer in polymerization reaction system is 0.5%～45%; Used linking agent is aromatic diolefine, and linking agent shared mass concentration in polymerization system is 0.1%～2%; Medium is the organic acid alkyl ester, and chemical structural formula is:
Wherein, R1 is alkyl, phenyl or the benzyl of hydrogen atom, C1～C5, and R2 is the alkyl of C1～C5, copolyreaction 4～8h.
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