CN105315396B - A kind of solvent and its application method for vinyl acetate polymerisation in solution - Google Patents
A kind of solvent and its application method for vinyl acetate polymerisation in solution Download PDFInfo
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- CN105315396B CN105315396B CN201410405919.9A CN201410405919A CN105315396B CN 105315396 B CN105315396 B CN 105315396B CN 201410405919 A CN201410405919 A CN 201410405919A CN 105315396 B CN105315396 B CN 105315396B
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- methanol
- solvent
- polymerization
- dimethyl carbonate
- vinyl acetate
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- 239000002904 solvent Substances 0.000 title claims abstract description 61
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title abstract description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 201
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 38
- 239000011118 polyvinyl acetate Substances 0.000 claims description 38
- 239000000178 monomer Substances 0.000 claims description 27
- 239000003999 initiator Substances 0.000 claims description 20
- 238000010792 warming Methods 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 46
- 229920000642 polymer Polymers 0.000 abstract description 11
- 231100000252 nontoxic Toxicity 0.000 abstract description 4
- 230000003000 nontoxic effect Effects 0.000 abstract description 4
- 231100000614 poison Toxicity 0.000 abstract description 3
- 230000007096 poisonous effect Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- 239000003292 glue Substances 0.000 description 18
- 238000010992 reflux Methods 0.000 description 18
- 238000003756 stirring Methods 0.000 description 18
- 229920002451 polyvinyl alcohol Polymers 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 14
- 239000004372 Polyvinyl alcohol Substances 0.000 description 14
- 239000007787 solid Substances 0.000 description 11
- -1 polyethylene Polymers 0.000 description 10
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 239000012065 filter cake Substances 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 230000004044 response Effects 0.000 description 9
- GRONZTPUWOOUFQ-UHFFFAOYSA-M sodium;methanol;hydroxide Chemical compound [OH-].[Na+].OC GRONZTPUWOOUFQ-UHFFFAOYSA-M 0.000 description 9
- 238000009834 vaporization Methods 0.000 description 9
- 230000008016 vaporization Effects 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 7
- 229960001826 dimethylphthalate Drugs 0.000 description 7
- 238000012546 transfer Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 239000002609 medium Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 2
- 238000006136 alcoholysis reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000035622 drinking Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 238000006276 transfer reaction Methods 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 229940022682 acetone Drugs 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229940076134 benzene Drugs 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000003694 hair properties Effects 0.000 description 1
- 208000021760 high fever Diseases 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 229960002415 trichloroethylene Drugs 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
A kind of solvent for vinyl acetate polymerisation in solution, include following components：Dimethyl carbonate, methanol.Its application method is that the composition dimethyl carbonate and methanol in the solvent during polymerizeing for vinyl acetate are used separately respectively, are separately added into the different time in reaction.The present invention uses dimethyl carbonate and methanol as polymer solvent, polymerization for vinyl acetate, because solvent is mainly based on dimethyl carbonate, reduce the usage amount of methanol, reduce the composition of poisonous and harmful substance in course of reaction, most important dimethyl carbonate is nontoxic, polymerization process safety, more easy to operate；And power consumption is few, safety and environmental protection.
Description
Technical field
The invention belongs to the preparing technical field of polyvinyl acetate, is related to a kind of solvent for vinyl acetate polymerisation in solution
And its application method.
Background technology
The polymerization of polyvinyl acetate (PVAc) mainly has four kinds：(1) solution polymerization process, i.e. VAC and initiator are dissolved in
The polymerization carried out in solvent, this method belong to radical polymerization, and its polymerization reaction mechanism is divided into Four processes：Chain triggers, chain
Growth, chain tra nsfer and chain termination.The advantages of polymerisation in solution is：The viscosity step-down of reaction system, is advantageous to material after addition solvent
Mixing and conveying, while the temperature of reaction can also be controlled by the use of solvent as heat transfer medium, not easily cause hot-spot；
But due to the chain tra nsfer effect of solvent molecule, the resulting PVA degree of polymerization is relatively low, generally no greater than 3000；Solvent is dilute simultaneously
The concentration of monomer has been released, has made rate of polymerization slack-off, monomer conversion reduces；Need to carry out purifying recovery to product during using solvent
Solvent, which increases production cost.(2) mass polymerization, i.e. monomer are being added without any solvent, decentralized medium and initiator
Under conditions of (or only adding a small amount of initiator), the liquid-phase polymerization itself carried out is triggered by heat, light or radiation etc..This
Body polymerization is simplest one kind in polymerization, has product purity high, and monomer utilization ratio is big, and production is quick, technological process
Short, the advantages that device is simple.But because not having heat eliminating medium, and monomer and polymer specific heat capacity and thermal conductivity factor are all smaller,
With the progress of reaction so that polymerization reaction heat is not easy to take out of and cause reaction temperature to be difficult to control, and easily causes hot-spot, very
To generation implode phenomenon；In addition with the progress of reaction, then reaction system viscosity constantly increases, and causes molecule diffusion difficult, easily
The molecular weight distribution of product is set to broaden.(3) suspension polymerization, i.e. monomer as dispersed phase suspending agent and initiator effect
Under, it is dispersed into small liquid pearl and is suspended in system and is polymerize.Because suspension polymerisation is generally using water as continuous phase, water has higher
Thermal capacity and thermal conductivity factor, can as the excellent transmitting medium of polymerization reaction heat, radiate and the polymerisation in solution of temperature control ratio hold
Easily, therefore to obtain polyvinyl acetate molecular weight higher than solution polymerization process, but due to system form it is complicated, in product residue compared with
It is more, cause product purity to reduce, post processing is complicated, improves production cost.(4) emulsion polymerization, i.e. monomer are in water, water solubility
The polymerization of emulsion form progress is dispersed into the presence of initiator, emulsifying agent.Emulsion polymerization is due to water compositing dispersion medium, cost
It is low, also reaction system viscosity can be made to diminish, be easy to radiating and the control of temperature；And rate of polymerization is big, macromolecule can be obtained
The polymer of amount.But polymerize after emulsion need by cohesion, washing, dehydration and dry etc. postprocessing working procedures, can just isolate poly-
Compound, production cost is higher, and the polymer purity of gained is not high.In the industrial production of Polymer Solution polymerization, the choosing of solvent
Select and dosage has important influence to the molecular structure and polymerization rate of polymer.It is anti-that solvent does not participate in polymerization directly
Should, but must be able to dissolve each other with monomer, initiator and polymerizate, to ensure that whole reaction system is in homogeneous state.Macromolecular
The respond of living chain and monomer will be far longer than the chain reaction ability to function of molecular activity chain and solvent, otherwise just easily occur
Solvent chain transfer reaction, it not only have impact on the degree of polymerization but also reduced aggregate rate, thus when selecting solvent, it is normal to be typically chosen chain tra nsfer
The small solvent of number.The solvent species of vinyl acetate polymerization is more, there is methanol, chlorobenzene, toluene, acetone, trichloro ethylene, benzene, acetic acid
Ethyl ester, absolute ethyl alcohol etc..Above-mentioned solvent all has larger toxic in addition to ethanol, wherein industrially widely using methanol conduct
Polymer solvent.Reaction can be taken away because first, methanol boiling point is close with polymeric reaction temperature, during reaction by the evaporation of methanol
Heat；Second, the chain transfer constant of methanol is small, does not easily cause solvent chain transfer reaction；Finally, poly-vinegar acid second is generated after polymerization
Alkene methanol, without the separation for carrying out methanol, it is possible to carry out next step alcoholysis reaction.
Patent CN101081880A describes a kind of preparation of water-soluble poval, and its characteristic is in the reactor with altogether
With the mode for adding or being individually added dropwise telomerization monomer, add VAM, methanol, vinyl telomerization monomer, initiator and enter
Row polymerization, obtains highly water-soluble polyvinyl alcohol.
Patent CN101054426A describes a kind of preparation method of polyvinyl alcohol with low degree of polymerization, is by VAM
Mixed with methanol, addition accounts for initiator and transfer agent, and the polyvinyl acetate of low polymerization degree is made；And be dissolved in methanol, add hydrogen
The methanol of sodium oxide molybdena carries out alcoholysis as alkali lye, and this method can obtain the polyethylene for the low polymerization degree that the degree of polymerization is 50-500
Alcohol.
Xie Long etc. is that heptonitrile is initiator for solvent and azo two using vinyl acetate as monomer, dimethyl sulfoxide (DMSO), using just
Hand over the polymerisation in solution of the technique study of experiment to prepare the optimised process of high relative molecular mass polyvinyl acetate, be finally synthesizing polymerization
Spend the polyvinyl alcohol for 4000.
Methanol has certain toxicity, and the formaldehyde more stronger than methanol toxicity and formic acid (ant can be oxidized in human metabolism
Acid), drinking 5~10mL methanol by mistake can cause to lose the sight of both eyes, and drinking a certain amount of can cause death；Methanol is inflammable and explosive, meets naked light, high fever
Combustion explosion can be caused, its steam can form explosive mixture with air；The physical property fusing point of methanol is -98.0 DEG C, boiling
Point is 64.5 DEG C, and flash-point is 12 DEG C, heat of vaporization 1100.0kJ/kg.
As can be seen here, traditional vinyl acetate polymerization process, used polymer solvent methanol are poisonous and harmful substance, are waved
Hair property is big, there is larger injury to human body and environment.The flash-point (22 DEG C) of dimethyl carbonate has than the height of methanol (12 DEG C)
Beneficial to the fire-proof and explosion-proof security for improving production process.The heat of vaporization of DMC and methanol is respectively 329.2kJ/kg and 1100.0kJ/
Kg, therefore it is more more energy efficient than methanol to be distilled to recover solvent DMC.In summary, because methanol has certain toxicity, in production process
In have certain toxic action, and DMC is green, environmentally friendly, safety and energy-conservation, more favourable for polymerisation in solution.
Dimethyl carbonate (dimethyl carbonate, DMC) is a kind of green solvent, European in 1992
It is classified as nonpoisonous chemicla.DMC Main physical property fusing point is 3.0 DEG C, and boiling point is 90.2 DEG C, and flash-point is 22 DEG C, and heat of vaporization is
329.2kJ/kg, DMC are a kind of water white transparency at normal temperatures, there is the liquid of aromatic odor, have nontoxic, non-corrosiveness, viscosity
Low, the features such as surface tension is big and intermiscibility is good, and heat of vaporization is low, relative evaporation speed is fast；Due to containing methyl, carbonyl in its molecule
Base, methoxyl group and carbomethoxy, it can be mixed with the almost all of organic matter such as alcohols and ethers.
Therefore, vinyl acetate polymerization process energy-saving and emission-reduction and green how are caused, simple to operate, safety, is ability
The problem of domain scientific research and engineers and technicians' urgent need to resolve.
The content of the invention
In view of the shortcomings of the prior art, invention is a kind of to be used for green solvent and its user that vinyl acetate polymerize to the present invention
Method so that energy consumption is low, green in the course of the polymerization process, simple to operate, safety.
To solve the deficiency of above-mentioned technical problem, technical scheme is as follows：
A kind of solvent for vinyl acetate polymerisation in solution, include following components：Dimethyl carbonate, methanol.
Wherein, the solvent for vinyl acetate polymerisation in solution, by volume percentage, dimethyl carbonate accounts for 60~
95%, methanol accounts for 5%~40%.
A kind of application method of solvent for vinyl acetate polymerisation in solution：It is molten during polymerizeing for vinyl acetate
The composition dimethyl carbonate and methanol of agent are used separately respectively, are separately added into the different time in reaction.
Wherein, it is that vinyl acetate is put into reactor and is warming up to 65~70 DEG C by polymerized monomer, by initiator carbonic acid two
Methyl esters dissolves, and then adds in reactor and progress polymerisation is mixed with polymerized monomer, the reaction time is 1h~4h, in overall reaction
Time 1/6~5/6 when add methanol, after being distilled to recover solvent, that is, obtain polyvinyl acetate.
Wherein, the polymerized monomer of addition and the volume ratio of solvent are 2:1~10:1.
Beneficial effects of the present invention：
The present invention uses dimethyl carbonate and methanol as polymer solvent, for the polymerization of vinyl acetate, because solvent is main
Based on dimethyl carbonate, reduce the usage amount of methanol, reduce the composition of poisonous and harmful substance in course of reaction, it is main
Dimethyl carbonate it is nontoxic, polymerization process safety, it is more easy to operate；The flash-point of further solvent for use dimethyl carbonate compared with
Height, in operationlocation, fire-proof and explosion-proof performance is more preferable；And in solvent for use dimethyl carbonate heat of vaporization (329.2kJ/kg) it is small
In the heat of vaporization (1100.00kJ/kg) of traditional vinyl acetate polymerization solvent for use methanol, easily realized when being distilled to recover solvent,
Power consumption is few, safety and environmental protection.
Embodiment
The present invention is further described referring to embodiment, to make those skilled in the art with reference to specification text
Word can be implemented according to this, and the scope of the present invention is not limited to embodiments of the present invention.Raw material used is in embodiment
VAM made from biological ethane method, reactor are three-necked flask.
Embodiment 1
Measure 100mL vinyl acetates to add in the three-necked flask equipped with mechanical agitator, thermometer and reflux condensing tube, put
In thermostat water bath, 70 DEG C are warming up to.The accurate azodiisobutyronitrile initiator for weighing 0.0093g, it is dissolved in 7.5mL carbonic acid
In dimethyl ester, and add in three-necked flask, open stirring, timing；Question response is to the methanol for after 120min, adding 2.5mL.After
After continuous reaction 60min, product is poured out, after cooling down and removing unreacted monomer and solvent, that is, obtains polyvinyl acetate solid.
The methanol for measuring 150mL is added in the three-necked flask equipped with mechanical agitator and reflux condensing tube, is placed in 70 DEG C
Constant temperature water bath in, add 9g solid polyvinyl acetate, open stirring.After polyvinyl acetate all dissolving, by water-bath
Temperature is down to 40 DEG C, is slowly added dropwise into 20g/L sodium hydroxide methanol, when frozen glue occurs, speed of agitator is adjusted into maximum rapidly,
Frozen glue is broken up, continues to react 30min, filtering, filter cake is washed to neutrality with methanol, then is placed in 40 DEG C of drying boxes and is dried to perseverance
Weight, obtains polyvinyl alcohol.Its degree of polymerization is measured as 3318 finally by formula viscosimeter difficult to understand.
Embodiment 2
Measure 100mL vinyl acetates to add in the three-necked flask equipped with mechanical agitator, thermometer and reflux condensing tube, put
In thermostat water bath, 70 DEG C are warming up to.The accurate azodiisobutyronitrile initiator for weighing 0.0093g, it is dissolved in 11.7mL carbon
In dimethyl phthalate, and add in three-necked flask, open stirring, timing；Question response is to the methanol for after 140min, adding 3.3mL.
Continue after reacting 70min, product is poured out, after cooling down and removing unreacted monomer and solvent, that is, polyvinyl acetate is obtained and consolidates
Body.
The methanol for measuring 150mL is added in the three-necked flask equipped with mechanical agitator and reflux condensing tube, is placed in 70 DEG C
Constant temperature water bath in, add 9g solid polyvinyl acetate, open stirring.After polyvinyl acetate all dissolving, by water-bath
Temperature is down to 40 DEG C, is slowly added dropwise into 20g/L sodium hydroxide methanol, when frozen glue occurs, speed of agitator is adjusted into maximum rapidly,
Frozen glue is broken up, continues to react 30min, filtering, filter cake is washed to neutrality with methanol, then is placed in 40 DEG C of drying boxes and is dried to perseverance
Weight, obtains polyvinyl alcohol.Its degree of polymerization is measured as 3281 finally by formula viscosimeter difficult to understand.
Embodiment 3
Measure 100mL vinyl acetates to add in the three-necked flask equipped with mechanical agitator, thermometer and reflux condensing tube, put
In thermostat water bath, 70 DEG C are warming up to.The accurate azodiisobutyronitrile initiator for weighing 0.0093g, it is dissolved in 16.0mL carbon
In dimethyl phthalate, and add in three-necked flask, open stirring, timing；Question response is to the methanol for after 100min, adding 4.0mL.
Continue after reacting 50min, product is poured out, after cooling down and removing unreacted monomer and solvent, that is, polyvinyl acetate is obtained and consolidates
Body.
The methanol for measuring 150mL is added in the three-necked flask equipped with mechanical agitator and reflux condensing tube, is placed in 70 DEG C
Constant temperature water bath in, add 9g solid polyvinyl acetate, open stirring.After polyvinyl acetate all dissolving, by water-bath
Temperature is down to 40 DEG C, is slowly added dropwise into 20g/L sodium hydroxide methanol, when frozen glue occurs, speed of agitator is adjusted into maximum rapidly,
Frozen glue is broken up, continues to react 30min, filtering, filter cake is washed to neutrality with methanol, then is placed in 40 DEG C of drying boxes and is dried to perseverance
Weight, obtains polyvinyl alcohol.Its degree of polymerization is measured as 3477 finally by formula viscosimeter difficult to understand.
Embodiment 4
Measure 100mL vinyl acetates to add in the three-necked flask equipped with mechanical agitator, thermometer and reflux condensing tube, put
In thermostat water bath, 70 DEG C are warming up to.The accurate azodiisobutyronitrile initiator for weighing 0.0140g, it is dissolved in 7.8mL carbonic acid
In dimethyl ester, and add in three-necked flask, open stirring, timing；Question response is to the methanol for after 100min, adding 2.2mL.After
After continuous reaction 50min, product is poured out, after cooling down and removing unreacted monomer and solvent, that is, obtains polyvinyl acetate solid.
The methanol for measuring 150mL is added in the three-necked flask equipped with mechanical agitator and reflux condensing tube, is placed in 70 DEG C
Constant temperature water bath in, add 9g solid polyvinyl acetate, open stirring.After polyvinyl acetate all dissolving, by water-bath
Temperature is down to 40 DEG C, is slowly added dropwise into 20g/L sodium hydroxide methanol, when frozen glue occurs, speed of agitator is adjusted into maximum rapidly,
Frozen glue is broken up, continues to react 30min, filtering, filter cake is washed to neutrality with methanol, then is placed in 40 DEG C of drying boxes and is dried to perseverance
Weight, obtains polyvinyl alcohol.Its degree of polymerization is measured as 3410 finally by formula viscosimeter difficult to understand.
Embodiment 5
Measure 100mL vinyl acetates to add in the three-necked flask equipped with mechanical agitator, thermometer and reflux condensing tube, put
In thermostat water bath, 70 DEG C are warming up to.The accurate azodiisobutyronitrile initiator for weighing 0.0140g, it is dissolved in 16.4mL carbon
In dimethyl phthalate, and add in three-necked flask, open stirring, timing；Question response is to the methanol for after 120min, adding 3.6mL.
Continue after reacting 60min, product is poured out, after cooling down and removing unreacted monomer and solvent, that is, polyvinyl acetate is obtained and consolidates
Body.
The methanol for measuring 150mL is added in the three-necked flask equipped with mechanical agitator and reflux condensing tube, is placed in 70 DEG C
Constant temperature water bath in, add 9g solid polyvinyl acetate, open stirring.After polyvinyl acetate all dissolving, by water-bath
Temperature is down to 40 DEG C, is slowly added dropwise into 20g/L sodium hydroxide methanol, when frozen glue occurs, speed of agitator is adjusted into maximum rapidly,
Frozen glue is broken up, continues to react 30min, filtering, filter cake is washed to neutrality with methanol, then is placed in 40 DEG C of drying boxes and is dried to perseverance
Weight, obtains polyvinyl alcohol.Its degree of polymerization is measured as 3177 finally by formula viscosimeter difficult to understand.
Embodiment 6
Measure 100mL vinyl acetates to add in the three-necked flask equipped with mechanical agitator, thermometer and reflux condensing tube, put
In thermostat water bath, 70 DEG C are warming up to.The accurate azodiisobutyronitrile initiator for weighing 0.0140g, it is dissolved in 20.0mL carbon
In dimethyl phthalate, and add in three-necked flask, open stirring, timing；Question response is to the methanol for after 140min, adding 5.0mL.
Continue after reacting 70min, product is poured out, after cooling down and removing unreacted monomer and solvent, that is, polyvinyl acetate is obtained and consolidates
Body.
The methanol for measuring 150mL is added in the three-necked flask equipped with mechanical agitator and reflux condensing tube, is placed in 70 DEG C
Constant temperature water bath in, add 9g solid polyvinyl acetate, open stirring.After polyvinyl acetate all dissolving, by water-bath
Temperature is down to 40 DEG C, is slowly added dropwise into 20g/L sodium hydroxide methanol, when frozen glue occurs, speed of agitator is adjusted into maximum rapidly,
Frozen glue is broken up, continues to react 30min, filtering, filter cake is washed to neutrality with methanol, then is placed in 40 DEG C of drying boxes and is dried to perseverance
Weight, obtains polyvinyl alcohol.Its degree of polymerization is measured as 3122 finally by formula viscosimeter difficult to understand.
Embodiment 7
Measure 100mL vinyl acetates to add in the three-necked flask equipped with mechanical agitator, thermometer and reflux condensing tube, put
In thermostat water bath, 70 DEG C are warming up to.The accurate azodiisobutyronitrile initiator for weighing 0.0186g, it is dissolved in 12.3mL carbon
In dimethyl phthalate, and add in three-necked flask, open stirring, timing；Question response is to the methanol for after 100min, adding 2.7mL.
Continue after reacting 50min, product is poured out, after cooling down and removing unreacted monomer and solvent, that is, polyvinyl acetate is obtained and consolidates
Body.
The methanol for measuring 150mL is added in the three-necked flask equipped with mechanical agitator and reflux condensing tube, is placed in 70 DEG C
Constant temperature water bath in, add 9g solid polyvinyl acetate, open stirring.After polyvinyl acetate all dissolving, by water-bath
Temperature is down to 40 DEG C, is slowly added dropwise into 20g/L sodium hydroxide methanol, when frozen glue occurs, speed of agitator is adjusted into maximum rapidly,
Frozen glue is broken up, continues to react 30min, filtering, filter cake is washed to neutrality with methanol, then is placed in 40 DEG C of drying boxes and is dried to perseverance
Weight, obtains polyvinyl alcohol.Its degree of polymerization is measured as 3087 finally by formula viscosimeter difficult to understand.
Embodiment 8
Measure 100mL vinyl acetates to add in the three-necked flask equipped with mechanical agitator, thermometer and reflux condensing tube, put
In thermostat water bath, 70 DEG C are warming up to.The accurate azodiisobutyronitrile initiator for weighing 0.0186g, it is dissolved in 15.0mL carbon
In dimethyl phthalate, and add in three-necked flask, open stirring, timing；Question response is to the methanol for after 140min, adding 5.0mL.
Continue after reacting 70min, product is poured out, after cooling down and removing unreacted monomer and solvent, that is, polyvinyl acetate is obtained and consolidates
Body.
The methanol for measuring 150mL is added in the three-necked flask equipped with mechanical agitator and reflux condensing tube, is placed in 70 DEG C
Constant temperature water bath in, add 9g solid polyvinyl acetate, open stirring.After polyvinyl acetate all dissolving, by water-bath
Temperature is down to 40 DEG C, is slowly added dropwise into 20g/L sodium hydroxide methanol, when frozen glue occurs, speed of agitator is adjusted into maximum rapidly,
Frozen glue is broken up, continues to react 30min, filtering, filter cake is washed to neutrality with methanol, then is placed in 40 DEG C of drying boxes and is dried to perseverance
Weight, obtains polyvinyl alcohol.Its degree of polymerization is measured as 3047 finally by formula viscosimeter difficult to understand.
Embodiment 9
Measure 100mL vinyl acetates to add in the three-necked flask equipped with mechanical agitator, thermometer and reflux condensing tube, put
In thermostat water bath, 70 DEG C are warming up to.The accurate azodiisobutyronitrile initiator for weighing 0.0233g, it is dissolved in 16.7mL carbon
In dimethyl phthalate, and add in three-necked flask, open stirring, timing；Question response is to the methanol for after 100min, adding 8.3mL.
Continue after reacting 50min, product is poured out, after cooling down and removing unreacted monomer and solvent, that is, polyvinyl acetate is obtained and consolidates
Body.
The methanol for measuring 150mL is added in the three-necked flask equipped with mechanical agitator and reflux condensing tube, is placed in 70 DEG C
Constant temperature water bath in, add 9g solid polyvinyl acetate, open stirring.After polyvinyl acetate all dissolving, by water-bath
Temperature is down to 40 DEG C, is slowly added dropwise into 20g/L sodium hydroxide methanol, when frozen glue occurs, speed of agitator is adjusted into maximum rapidly,
Frozen glue is broken up, continues to react 30min, filtering, filter cake is washed to neutrality with methanol, then is placed in 40 DEG C of drying boxes and is dried to perseverance
Weight, obtains polyvinyl alcohol.Its degree of polymerization is measured as 3237 finally by formula viscosimeter difficult to understand.
The present invention uses dimethyl carbonate and methanol instead as green on the basis of the production technology that traditional vinyl acetate polymerize
Color solvent is polymerize, polymerization green solvent used, wherein the dimethyl carbonate containing large scale, the nontoxic nothing of dimethyl carbonate
Evil, have a safety feature with it is green, be the developing direction of Polymer Industry clean manufacturing；Polymerization green solvent is used to carry out
The method of polymerization can also synthesize the polyvinyl alcohol of certain degree of polymerization；The flash-point of dimethyl carbonate is 22 DEG C, and the flash-point of methanol is
12 DEG C, the flash-point of dimethyl carbonate is higher than methanol, then the fire-proof and explosion-proof security of Dichlorodiphenyl Acetate vinyl polymerization operationlocation is more preferable；
Green solvent dimethyl carbonate heat of vaporization is 329.2kJ/kg, the heat of vaporization of methanol is 1100.0kJ/kg, and the former heat of vaporization is remote
Much smaller than the latter, it is distilled to recover solvent and more saves.Meanwhile green solvent is as the product obtained by the polymer solvent of vinyl acetate
The degree of polymerization it is higher.
Claims (3)
- A kind of 1. preparation method of polyvinyl acetate, it is characterised in that the composition of solvent during polymerizeing for vinyl acetate Comprising dimethyl carbonate and methanol, dimethyl carbonate and methanol are used separately respectively, are separately added into the different time in reaction, It is that vinyl acetate is put into reactor and is warming up to 65~70 DEG C i.e. by polymerized monomer, initiator is dissolved with dimethyl carbonate, so Afterwards add reactor in mix with polymerized monomer progress polymerisation, the reaction time is 1h~4h, total reaction time 1/6~ Methanol is added when 5/6, after being distilled to recover solvent, that is, obtains polyvinyl acetate.
- 2. the preparation method of polyvinyl acetate according to claim 1, it is characterised in that：It is described to gather for vinyl acetate solution The solvent of conjunction, by volume percentage, dimethyl carbonate accounts for 60~95%, and methanol accounts for 5%~40%.
- 3. the preparation method of polyvinyl acetate according to claim 1, it is characterised in that：The polymerized monomer of addition and solvent Volume ratio is 2:1~10:1.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP1241192A1 (en) * | 2001-03-16 | 2002-09-18 | Kuraray Co., Ltd. | Method for manufacturing ethylene-vinyl acetate copolymer and apparatus for manufacturing the same |
| CN101054426A (en) * | 2007-04-27 | 2007-10-17 | 中北大学 | Method of preparing vinyl alcohol with low degree of polymerization |
| CN101081880A (en) * | 2007-07-12 | 2007-12-05 | 四川大学 | Preparation of highly water-soluble polyvinyl alcohol |
| CN101787172A (en) * | 2010-03-12 | 2010-07-28 | 杭州电子科技大学 | Preparation method of EVA sole surface treating agent |
| CN103626910A (en) * | 2013-11-29 | 2014-03-12 | 西南化工研究设计院有限公司 | Solid ethylene-vinyl acetate copolymer and preparation method thereof |
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| EP1241192A1 (en) * | 2001-03-16 | 2002-09-18 | Kuraray Co., Ltd. | Method for manufacturing ethylene-vinyl acetate copolymer and apparatus for manufacturing the same |
| CN101054426A (en) * | 2007-04-27 | 2007-10-17 | 中北大学 | Method of preparing vinyl alcohol with low degree of polymerization |
| CN101081880A (en) * | 2007-07-12 | 2007-12-05 | 四川大学 | Preparation of highly water-soluble polyvinyl alcohol |
| CN101787172A (en) * | 2010-03-12 | 2010-07-28 | 杭州电子科技大学 | Preparation method of EVA sole surface treating agent |
| CN103626910A (en) * | 2013-11-29 | 2014-03-12 | 西南化工研究设计院有限公司 | Solid ethylene-vinyl acetate copolymer and preparation method thereof |
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