CN117624423A - Production method of polyvinyl acetate - Google Patents
Production method of polyvinyl acetate Download PDFInfo
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- CN117624423A CN117624423A CN202311721948.1A CN202311721948A CN117624423A CN 117624423 A CN117624423 A CN 117624423A CN 202311721948 A CN202311721948 A CN 202311721948A CN 117624423 A CN117624423 A CN 117624423A
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- polyvinyl acetate
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- 229920002689 polyvinyl acetate Polymers 0.000 title claims abstract description 74
- 239000011118 polyvinyl acetate Substances 0.000 title claims abstract description 74
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 40
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 180
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000003999 initiator Substances 0.000 claims abstract description 66
- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical group CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- 239000002002 slurry Substances 0.000 claims abstract description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 17
- 239000011550 stock solution Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 2
- 239000012535 impurity Substances 0.000 abstract description 8
- 230000000977 initiatory effect Effects 0.000 abstract description 8
- 229920000620 organic polymer Polymers 0.000 abstract description 2
- 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 33
- 239000000203 mixture Substances 0.000 description 31
- 239000007789 gas Substances 0.000 description 18
- 238000006136 alcoholysis reaction Methods 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 239000000178 monomer Substances 0.000 description 9
- 230000035484 reaction time Effects 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 description 7
- 238000007664 blowing Methods 0.000 description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 238000005086 pumping Methods 0.000 description 6
- 238000004064 recycling Methods 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- OOYGSFOGFJDDHP-KMCOLRRFSA-N kanamycin A sulfate Chemical group OS(O)(=O)=O.O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CN)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O[C@@H]2[C@@H]([C@@H](N)[C@H](O)[C@@H](CO)O2)O)[C@H](N)C[C@@H]1N OOYGSFOGFJDDHP-KMCOLRRFSA-N 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000005057 refrigeration Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- MRMOZBOQVYRSEM-UHFFFAOYSA-N tetraethyllead Chemical compound CC[Pb](CC)(CC)CC MRMOZBOQVYRSEM-UHFFFAOYSA-N 0.000 description 2
- WOFMVUZGDHWHLJ-UHFFFAOYSA-N 7,7-dimethyloctanoyl chloride Chemical compound CC(C)(C)CCCCCC(Cl)=O WOFMVUZGDHWHLJ-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- ALIFPGGMJDWMJH-UHFFFAOYSA-N n-phenyldiazenylaniline Chemical compound C=1C=CC=CC=1NN=NC1=CC=CC=C1 ALIFPGGMJDWMJH-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a production method of polyvinyl acetate, which belongs to the technical field of organic polymer production, and comprises the following steps: preheating vinyl acetate monomer and methanol to 55-57 ℃, sequentially adding the vinyl acetate monomer and the methanol into a reaction kettle, and then adding an initiator to perform polyaddition reaction for 4.2-5.2h; the slurry after separating vinyl acetate monomer after stopping the reaction is polyvinyl acetate; the initiator is tert-butyl peroxyneodecanoate solution with the concentration of 0.5 percent. The initiator adopted by the invention has high initiation efficiency, greatly reduces the addition rate of the initiator, simultaneously has less use amount of the initiator, effectively reduces the production cost of the polyvinyl acetate, and in addition, no other impurities are introduced in the preparation process, so that the produced polyvinyl acetate has high product quality, and the quality of the polyvinyl acetate is effectively ensured; the preparation method is simple and efficient, reduces the frequency of personnel preparation and reduces the labor intensity.
Description
Technical Field
The invention belongs to the technical field of organic polymer production, and particularly relates to a production method of polyvinyl acetate.
Background
Polyvinyl acetate is a general resin with high yield and excellent comprehensive performance, and the product polyvinyl alcohol has excellent mechanical properties, flame retardance, transparency, chemical resistance and the like, and is widely used in the fields of industry, building, agriculture, public utilities and the like. The production method of polyvinyl acetate is various, such as bulk polymerization, emulsion polymerization, suspension polymerization, etc., and the vinyl acetate solution polymerization is a typical free radical polymerization, and its main reaction is divided into 4 processes of chain initiation, chain growth and chain transfer, and chain termination, and initiation and decomposition of initiator are main factors for controlling polymerization rate, and in order to ensure higher reaction rate and balanced heat release rate, the selection of initiator is a crucial link.
The common vinyl acetate polymerization initiator is more than two hundred of dibenzoyl peroxide, hydrogen peroxide, diazo aminobenzene, tetraethyl lead, azo compounds and the like, wherein the most used is azobisisobutyronitrile. However, azobisisobutyronitrile is heated in various solvents to decompose and release nitrogen to produce dimethylethylcyano radical; in addition, the decomposition speed of the azodiisobutyronitrile is not greatly related to the solvent, and in the decomposition process, an initial coincidence effect exists, namely the interaction of the initially decomposed free radicals is generated, so that an inactive substance is generated; thus, the initiation efficiency of azobisisobutyronitrile is reduced, and the value thereof is generally in the range of 0.6 to 0.8. The activation energy of the decomposition of azobisisobutyronitrile into free radicals is relatively large, about 30 kcal/gram-molecule, so that the polymerization temperature should not be lower than 40-50℃when vinyl acetate is used as an initiator. The reason why azobisisobutyronitrile is used in most industrial processes is: it is decomposed into free radicals at a proper speed at 50-70 ℃; it is not exploded in collision and ignition, has weak combustibility and is safe to use. At the same time it is cheaper. At above 20 ℃, the azodiisobutyronitrile can be decomposed by visible light and air, so the storage temperature must be below 20 ℃ and the air should be isolated, and the storage time is not more than three months. When methanol is used as the solvent for vinyl acetate polymerization, azobisisobutyronitrile is generally formulated as a methanol solution which must also be stored at a temperature below 20 c, otherwise decomposition is accelerated. With the continuous increase of domestic polyvinyl alcohol productivity, the azo-diisobutyronitrile as an initiator has the problems of low initiation efficiency, high use and addition rate, high labor intensity of personnel, influence on the quality of finished products and the like in production, so that the application range of the azo-diisobutyronitrile is limited; the novel initiator tert-butyl peroxyneodecanoate is used as an initiator for high polymer polymerization, has the advantages of high initiation activity, uniform reaction speed, good product quality and the like in vinyl acetate polymerization reaction, and is widely applied to a solution method vinyl acetate polymerization method.
Patent document CN111423350B provides a solvent type tert-butyl peroxyneodecanoate initiator and application thereof, and by introducing a mixed solution of a homogeneous agent and an antifreezing agent, the product is still uniform and stable when being used at-20 ℃, no ice flowers and ice scraps are separated out, the steps of deep refrigeration and ice filtering of a raw liquid in the production of the solvent type product can be omitted, the labor intensity and the production period are effectively reduced, the PVC production cost is reduced, and the resin quality is improved. Patent document CN108440360a provides a method for synthesizing tert-butyl peroxyneodecanoate as an initiator for polyvinyl chloride, which takes tert-butyl peroxyneodecanoate, alkali liquor and neodecanoyl chloride as raw materials, and the tert-butyl peroxyneodecanoate obtained by alkalization reaction and esterification reaction in turn can effectively shorten the polymerization reaction time of polyvinyl chloride. However, the above solvent type t-butyl peroxyneodecanoate initiator requires the addition of other component substances, which complicates the whole production process and increases the uncertainty factor for the internal quality of the product.
Disclosure of Invention
The invention aims to provide a production method of polyvinyl acetate, which aims to solve the problems of large initiator addition and low finished product quality in the production process of polyvinyl acetate.
The aim of the invention can be achieved by the following technical scheme:
a method for producing polyvinyl acetate, comprising the following steps:
preheating vinyl acetate monomer and methanol to 55-57 ℃, sequentially adding the vinyl acetate monomer and the methanol into a reaction kettle, and then adding an initiator to perform polyaddition reaction for 4.2-5.2h; separating unreacted monomers after stopping the reaction and recovering the unreacted monomers; the slurry after separating the monomers is polyvinyl acetate.
Further, the polymerization degree of the polyvinyl acetate is 400-3000.
Further, the proportion of the methanol is 10-45%, the proportion of the methanol is the percentage of the mass of the methanol to the total mass of the methanol and the vinyl acetate monomer, and the calculation formula is as follows
Further, the addition rate of the initiator is 0.0015-0.01%, the addition rate of the initiator is the percentage of the mass of the initiator to the mass of the vinyl acetate monomer, and the calculation formula is as follows
Further, the preparation method of the initiator comprises the following steps:
taking out the tert-butyl peroxyneodecanoate stock solution stored at the temperature of less than or equal to minus 15 ℃, mixing the stock solution with methanol at the temperature of less than or equal to 0 ℃ for 120min, and obtaining the uniformly dispersed tert-butyl peroxyneodecanoate solution with the concentration of 0.5 percent.
Further, the concentration of the tert-butyl peroxyneodecanoate stock solution is more than or equal to 92%.
Further, the concentration of methanol was 99.8%.
Further, the mass ratio of the tert-butyl peroxyneodecanoate stock solution to the methanol is 20kg:4203kg.
The invention has the beneficial effects that:
1. the invention provides a production method of polyvinyl acetate, wherein a tert-butyl peroxyneodecanoate solution is adopted as a novel initiator, methanol is adopted as a chain transfer agent, the initiation efficiency of the initiator in the reaction process is high, the addition rate of the initiator is greatly reduced, and meanwhile, the use amount of the initiator is less, so that the production cost of the polyvinyl acetate is effectively reduced.
2. According to the invention, other impurities are not introduced into the tert-butyl peroxyneodecanoate solution in the preparation process, so that the produced polyvinyl acetate has high quality, and the quality of the polyvinyl acetate is effectively ensured; the preparation method is simple and efficient, reduces the frequency of personnel preparation and reduces the labor intensity.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the following examples, unless otherwise specified, the methods of operation used were conventional, and the equipment used was conventional.
Example 1
The preparation method of the initiator comprises the following steps:
4203kg (4500L) of methanol with the concentration of 99.8% is added into the preparation tank through a feed pump under the temperature of less than or equal to 0 ℃, 20kg of primary solution of tert-butyl peroxyneodecanoate with the concentration of more than or equal to 92% taken out from a low-temperature (less than or equal to-15 ℃) refrigeration house is added, and the primary solution is stirred and mixed for 120min at the rotating speed of 500r/min, so as to prepare the initiator tert-butyl peroxyneodecanoate solution with the concentration of 0.5%.
The initiators described in the examples below were prepared according to the preparation method described above.
Example 2
A method for producing polyvinyl acetate, comprising the following steps:
s1, preheating vinyl acetate monomer and methanol with the proportion of 10% -45% from a preheater to 55-57 ℃, sequentially adding the vinyl acetate monomer and methanol into a polymerization kettle, pumping an initiator tert-butyl peroxyneodecanoate solution with the concentration of 0.5% out from a liquid-discharging pipeline of the preheater, and directly adding the initiator tert-butyl peroxyneodecanoate solution into the polymerization kettle, wherein the addition rate of the initiator tert-butyl peroxyneodecanoate solution is 0.0015% -0.01%; after the raw materials are subjected to primary reaction in a first kettle, the materials in the first kettle are sent into a second kettle, and the reaction is continued; obtaining a mixture containing unreacted vinyl acetate monomer and polyvinyl acetate; the reaction time in the first polymerization kettle and the second polymerization kettle is the same, and the total reaction time is 4.2-5.2 hours;
s2, rectifying a mixture containing unreacted vinyl acetate monomer and polyvinyl acetate to remove the monomer, adding the mixture containing unreacted vinyl acetate monomer and polyvinyl acetate into a tower, blowing methanol gas (adding methanol to gasify through a reboiler and recycling gas and blowing methanol gas phase) from the bottom of the tower, distilling the unreacted vinyl acetate monomer, methanol and a small amount of water and impurities from the top of the tower, condensing the mixture through a tower condenser, feeding a distillate part serving as a second tower, taking a part of the distillate part as a first tower reflux liquid, and feeding the mixture to a tank site cell resin tank after regulating the mixture to a certain temperature through a cooling plate for use in an alcoholysis process.
Example 3
A method for producing conventional 17-99 polyvinyl acetate, which comprises the following steps:
s1, preheating vinyl acetate monomer and 21% methanol from a preheater to 56 ℃, sequentially adding the vinyl acetate monomer and the 21% methanol into a polymerization kettle, pumping an initiator tert-butyl peroxyneodecanoate solution with the concentration of 0.5% out of a liquid outlet pipeline of the preheater through an initiator pump, and directly adding the initiator tert-butyl peroxyneodecanoate solution into the polymerization kettle, wherein the addition rate of the initiator tert-butyl peroxyneodecanoate solution is 0.009%; after the raw materials are subjected to preliminary reaction in a kettle, the residence time of the first kettle is 2.15 hours, the materials in the first kettle are sent into a second kettle for continuous reaction, the residence time of the second kettle is 2.15 hours, after the materials in the first kettle are sent into the second kettle, the vinyl acetate monomer is further consumed along with the extension of the reaction time, the polymerization rate is gradually improved, and a mixture (polymerization rate 60% and polymerization degree 1800) containing unreacted vinyl acetate monomer and 17-99 polyvinyl acetate is obtained for standby;
s2, rectifying a mixture containing unreacted vinyl acetate monomer and 17-99 polyvinyl acetate to remove the monomer, adding the mixture containing the unreacted vinyl acetate monomer and 17-99 polyvinyl acetate into a tower, blowing methanol gas (adding methanol to gasify through a reboiler and recycling gas to blow methanol gas phase) from the bottom of the tower, distilling the unreacted vinyl acetate monomer, the methanol and a small amount of water and impurities from the top of the tower, condensing the mixture through a tower condenser, feeding a distillate part serving as a second tower, partially serving as a first tower reflux liquid, obtaining 17-99 polyvinyl acetate without the vinyl acetate at the bottom of the tower, regulating the temperature through a cooling plate, and then feeding the mixture into a tank lattice resin tank for alcoholysis working procedures; the polyvinyl alcohol model obtained by alcoholysis of the 17-99 polyvinyl acetate is PVA17-99.
Specific parameters for the production of conventional 17-99 polyvinyl acetate using initiator t-butyl peroxyneodecanoate solution are shown in Table 1.
Example 4
A production method of Kano 17-99 polyvinyl acetate in coastal state comprises the following steps:
s1, preheating vinyl acetate monomer and methanol with the proportion of 24.25% from a preheater to 56 ℃, sequentially adding the vinyl acetate monomer and methanol into a polymerization kettle, pumping an initiator tert-butyl peroxyneodecanoate solution with the concentration of 0.5% out of a liquid-discharging pipeline of the preheater, and directly adding the initiator tert-butyl peroxyneodecanoate solution into the polymerization kettle, wherein the addition rate of the initiator tert-butyl peroxyneodecanoate solution is 0.01%; after the raw materials are subjected to preliminary reaction in a kettle, the retention time of the first kettle is 2.15h, the first kettle material is fed into a second kettle for continuous reaction, the retention time of the second kettle is 2.15h, after the first kettle material is fed into the second kettle, the vinyl acetate monomer is further consumed along with the extension of the reaction time, the polymerization rate is gradually improved, and a mixture (polymerization rate 60% and polymerization degree 1550) containing unreacted vinyl acetate monomer and Binzhou Kano 17-99 polyvinyl acetate is obtained for standby;
s2, rectifying a mixture containing unreacted vinyl acetate monomer and the Binzhou Keno 17-99 polyvinyl acetate to remove the monomer, adding the mixture containing unreacted vinyl acetate monomer and the Binzhou Keno 17-99 polyvinyl acetate into a tower, blowing methanol gas from the bottom of the tower (adding methanol, gasifying and recycling gas to blow the methanol gas phase through a reboiler) to enable unreacted vinyl acetate monomer, methanol and a small amount of water and impurities to be distilled out from the top of the tower, condensing the mixture through a first tower condenser and then entering a distillation tank, wherein a part of distillate is fed as a second tower, and the other part of distillate is used as a first tower reflux liquid, and the tower still is used for obtaining the Binzhou Keno 17-99 polyvinyl acetate without vinyl acetate, and then feeding the mixture into a tank field lattice resin tank for alcoholysis working procedure after being regulated to a certain temperature through a cooling plate; the polyvinyl alcohol model obtained by alcoholysis of the polyvinyl acetate of the Kaono 17-99 in the coast state is PVA17-99 in the Kaono state.
Specific parameters for the production of keno 17-99 polyvinyl acetate using initiator t-butyl peroxyneodecanoate solution are shown in table 1.
Example 5
A conventional 20-99 polyvinyl acetate production method comprises the following steps:
s1, preheating vinyl acetate monomer and 17% methanol from a preheater to 56 ℃, sequentially adding the vinyl acetate monomer and the 17% methanol into a polymerization kettle, pumping an initiator tert-butyl peroxyneodecanoate solution with the concentration of 0.5% out of a liquid outlet pipeline of the preheater through an initiator pump, and directly adding the initiator tert-butyl peroxyneodecanoate solution into the polymerization kettle, wherein the addition rate of the initiator tert-butyl peroxyneodecanoate solution is 0.0056%; after the raw materials are subjected to preliminary reaction in a kettle, the residence time of the first kettle is 2.25h, the materials in the first kettle are sent into a second kettle for continuous reaction, the residence time of the second kettle is 2.25h, after the materials in the first kettle are sent into the second kettle, the vinyl acetate monomer is further consumed along with the extension of the reaction time, the polymerization rate is gradually improved, and a mixture (the polymerization rate is 53 percent and the polymerization degree is 2130) containing unreacted vinyl acetate monomer and 20-99 polyvinyl acetate is obtained for standby;
s2, rectifying a mixture containing unreacted vinyl acetate monomer and 20-99 polyvinyl acetate to remove the monomer, adding the mixture containing the unreacted vinyl acetate monomer and 20-99 polyvinyl acetate into a tower, blowing methanol gas (adding methanol to gasify through a reboiler and recycling gas to blow methanol gas phase) from the bottom of the tower, distilling the unreacted vinyl acetate monomer, the methanol and a small amount of water and impurities from the top of the tower, condensing the mixture through a tower condenser, feeding a distillate part serving as a second tower, partially serving as a first tower reflux liquid, obtaining 20-99 polyvinyl acetate without the vinyl acetate at the bottom of the tower, regulating the temperature through a cooling plate, and then feeding the mixture into a tank lattice resin tank for alcoholysis working procedures; the polyvinyl alcohol model obtained by alcoholysis of 20-99 polyvinyl acetate is PVA20-99.
Specific parameters for the production of conventional 20-99 polyvinyl acetate using initiator t-butyl peroxyneodecanoate solution are shown in Table 1.
Example 6
A conventional 26-99 polyvinyl acetate production method, which comprises the following steps:
s1, preheating vinyl acetate monomer and 10% methanol from a preheater to 56 ℃, sequentially adding the vinyl acetate monomer and the 10% methanol into a polymerization kettle, pumping an initiator tert-butyl peroxyneodecanoate solution with the concentration of 0.5% out of a liquid outlet pipeline of the preheater through an initiator pump, and directly adding the initiator tert-butyl peroxyneodecanoate solution into the polymerization kettle, wherein the addition rate of the initiator tert-butyl peroxyneodecanoate solution is 0.0015%; after the raw materials are subjected to preliminary reaction in a kettle, the residence time of the first kettle is 2.59 hours, the materials in the first kettle are sent into a second kettle for continuous reaction, the residence time of the second kettle is 2.59 hours, after the materials in the first kettle are sent into the second kettle, the vinyl acetate monomer is further consumed along with the extension of the reaction time, the polymerization rate is gradually improved, and a mixture (the polymerization rate is 35 percent and the polymerization degree is 3000) containing unreacted vinyl acetate monomer and 26-99 polyvinyl acetate is obtained for standby;
s2, rectifying a mixture containing unreacted vinyl acetate monomer and 26-99 polyvinyl acetate to remove the monomer, adding the mixture containing the unreacted vinyl acetate monomer and 26-99 polyvinyl acetate into a tower, blowing methanol gas (adding methanol to gasify through a reboiler and recycling gas to blow methanol gas phase) from the bottom of the tower, distilling the unreacted vinyl acetate monomer, the methanol and a small amount of water and impurities from the top of the tower, condensing the mixture through a tower condenser, feeding a distillate part serving as a second tower, partially serving as a first tower reflux liquid, obtaining 26-99 polyvinyl acetate without the vinyl acetate at the bottom of the tower, regulating the temperature through a cooling plate, and then feeding the mixture into a tank lattice resin tank for alcoholysis working procedures; the polyvinyl alcohol model obtained by alcoholysis of 26-99 polyvinyl acetate is PVA26-99.
Specific parameters for the production of conventional 26-99 polyvinyl acetate using initiator t-butyl peroxyneodecanoate solution are shown in Table 1.
Example 7
A method for producing conventional 05-99 polyvinyl acetate, which comprises the following steps:
s1, preheating vinyl acetate monomer and 45% methanol from a preheater to 56 ℃, sequentially adding the vinyl acetate monomer and the 45% methanol into a polymerization kettle, pumping an initiator tert-butyl peroxyneodecanoate solution with the concentration of 0.5% out of a liquid outlet pipeline of the preheater through an initiator pump, and directly adding the initiator tert-butyl peroxyneodecanoate solution into the polymerization kettle, wherein the addition rate of the initiator tert-butyl peroxyneodecanoate solution is 0.0621%; after the raw materials are subjected to preliminary reaction in a kettle, the residence time of the first kettle is 2.50h, the materials in the first kettle are sent into a second kettle for continuous reaction, the residence time of the second kettle is 2.50h, after the materials in the first kettle are sent into the second kettle, the vinyl acetate monomer is further consumed along with the extension of the reaction time, the polymerization rate is gradually improved, and a mixture (the polymerization rate is 90 percent and the polymerization degree is 400) containing unreacted vinyl acetate monomer and 05-99 polyvinyl acetate is obtained for standby;
s2, rectifying a mixture containing unreacted vinyl acetate monomer and 05-99 polyvinyl acetate to remove the monomer, adding the mixture containing the unreacted vinyl acetate monomer and 05-99 polyvinyl acetate into a tower, blowing methanol gas (adding methanol to gasify through a reboiler and recycling gas to blow methanol gas phase) from the bottom of the tower, distilling the unreacted vinyl acetate monomer, the methanol and a small amount of water and impurities from the top of the tower, condensing the mixture through a tower condenser, feeding a distillate part serving as a second tower, partially serving as a first tower reflux liquid, obtaining 05-99 polyvinyl acetate without the vinyl acetate at the bottom of the tower, regulating the temperature through a cooling plate, and then feeding the mixture into a tank lattice resin tank for alcoholysis working procedures; the polyvinyl alcohol model obtained by alcoholysis of the 05-99 polyvinyl acetate is PVA05-99.
Specific parameters for the production of conventional 05-99 polyvinyl acetate using initiator t-butyl peroxyneodecanoate solution are shown in Table 1.
Comparative example 1
A conventional 17-99 polyvinyl acetate production method is the same as in example 3, except that azobisisobutyronitrile is used as an initiator, the concentration of azobisisobutyronitrile is 1.2%, the addition rate is 0.035%, and specific parameters are shown in Table 1.
Comparative example 2
A method for producing the polyvinyl acetate 17-99 of Kano in coastal state is the same as in example 4, except that azobisisobutyronitrile is used as an initiator, the concentration of the azobisisobutyronitrile is 1.2%, the addition rate is 0.0425%, and specific parameters are shown in Table 1.
Comparative example 3
A conventional 20-99 polyvinyl acetate production method was the same as in example 5, except that azobisisobutyronitrile was used as the initiator, the azobisisobutyronitrile concentration was 1.2%, the addition rate was 0.018%, and specific parameters are shown in Table 1.
Comparative example 4
A conventional 26-99 polyvinyl acetate production method is the same as in example 6, except that azobisisobutyronitrile is used as an initiator, the concentration of azobisisobutyronitrile is 1.2%, the addition rate is 0.0066%, and specific parameters are shown in Table 1.
TABLE 1
As can be seen from Table 1, under the same vinyl acetate monomer feeding condition, the same type of polyvinyl acetate is produced, compared with azodiisobutyronitrile, the tert-butyl peroxyneodecanoate solution of the initiator provided by the invention is reduced by 3-4 times in the use amount of the initiator, so that the effect of higher initiation efficiency is realized under the same initiator use amount condition, and the capability of producing more types of polyvinyl acetate is provided; the internal quality of the produced polyvinyl acetate is analyzed, the product reaches the standard at one time, and the polymerization rate and the polymerization process are stable, so that the quality standard is met, and the quality is stable.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (7)
1. A process for producing polyvinyl acetate, comprising the steps of:
preheating vinyl acetate monomer and methanol to 55-57 ℃, sequentially adding the vinyl acetate monomer and the methanol into a reaction kettle, and then adding an initiator to perform polyaddition reaction for 4.2-5.2h; separating unreacted vinyl acetate monomer after stopping the reaction and recovering; the slurry after separating vinyl acetate monomer is polyvinyl acetate;
the preparation method of the initiator comprises the following steps: taking out the tert-butyl peroxyneodecanoate stock solution stored at the temperature of less than or equal to minus 15 ℃, mixing the stock solution with methanol at the temperature of less than or equal to 0 ℃ for 120min, and obtaining the uniformly dispersed tert-butyl peroxyneodecanoate solution with the concentration of 0.5 percent.
2. The method for producing polyvinyl acetate according to claim 1, wherein the polymerization degree of the polyvinyl acetate is 400 to 3000.
3. The method for producing polyvinyl acetate according to claim 1, wherein the ratio of methanol is 10% -45%, the ratio of methanol is the percentage of the mass of methanol to the total mass of methanol and vinyl acetate monomer, and the calculation formula is
4. The method for producing polyvinyl acetate according to claim 1, wherein the addition rate of the initiator is 0.0015% -0.01%, the addition rate of the initiator is a percentage of the mass of the initiator to the mass of the vinyl acetate monomer, and the calculation formula is
5. The method for producing polyvinyl acetate according to claim 1, wherein the concentration of the tert-butyl peroxyneodecanoate stock solution is not less than 92%.
6. The method for producing polyvinyl acetate according to claim 1, wherein the concentration of methanol is 99.8%.
7. The production method of polyvinyl acetate according to claim 1, wherein the mass ratio of the tert-butyl peroxyneodecanoate stock solution to the methanol is 20kg:4203kg.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202311721948.1A CN117624423A (en) | 2023-12-14 | 2023-12-14 | Production method of polyvinyl acetate |
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| CN202311721948.1A CN117624423A (en) | 2023-12-14 | 2023-12-14 | Production method of polyvinyl acetate |
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