CN100532397C - Polymerization apparatus and method for producing polymer - Google Patents
Polymerization apparatus and method for producing polymer Download PDFInfo
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- CN100532397C CN100532397C CNB2005800281269A CN200580028126A CN100532397C CN 100532397 C CN100532397 C CN 100532397C CN B2005800281269 A CNB2005800281269 A CN B2005800281269A CN 200580028126 A CN200580028126 A CN 200580028126A CN 100532397 C CN100532397 C CN 100532397C
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0053—Details of the reactor
- B01J19/0066—Stirrers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
- B01J19/1806—Stationary reactors having moving elements inside resulting in a turbulent flow of the reactants, such as in centrifugal-type reactors, or having a high Reynolds-number
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00002—Chemical plants
- B01J2219/00027—Process aspects
- B01J2219/0004—Processes in series
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
- B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
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Abstract
A polymerization apparatus is characterized by comprising a mixing tank wherein a liquid mixture is prepared by mixing a monomer and a polymerization initiator, a polymerization pot wherein the monomer is polymerized by heating the liquid mixture, a feed pipe for supplying the liquid mixture from the mixing tank to the polymerization pot, and a temperature-regulating means for regulating the temperature of the liquid mixture in the feed pipe. A method for producing a polymer wherein a liquid mixture prepared by mixing a monomer and a polymerization initiator in a mixing tank is supplied to a polymerization pot through a feed pipe and the monomer is polymerized by heating the liquid mixture in the polymerization pot is characterized in that the temperature of the liquid mixture in the feed pipe is maintained within a range of 15-30 DEG C.
Description
Technical field
The method for producing polymer that the present invention relates to a kind of poly-unit and used this device.
Background technology
As the method that obtains vinyl polymer by the polymerization vinyl monomer, known have a solution polymerization process.As the poly-unit that can be used for solution polymerization, have the tempering tank of mixing vinyl monomer, solvent and polymerization starter usually and carry out vinyl monomer polymeric polymeric kettle by tempering tank through the mixed solution of supply-pipe supply by heating.In solution polymerization process, there are mixing in polymeric kettle, heated solvent, alkene monomer and polymerization starter to carry out polymeric intermittence type polymerization method, and in polymeric kettle, drop into solvent in advance, and under specified temperature, to polymeric kettle, splash into the mixture of supplying with alkene monomer and polymerization starter and carry out polymeric and splash into the formula polymerization from tempering tank.The former can be used as the method that obtains the higher molecular polymkeric substance.In addition, the latter can be used as when accessing low molecule multipolymer, also can obtain the method that more even multipolymer is formed in the vinyl copolymer that is made of multiple alkene monomer unit.Yet, use aforementioned poly-unit and, can produce following inconvenience by splashing into the formula polymeric kettle when carrying out solution polymerization.
In this poly-unit, owing to be positioned at the inboard on polymeric kettle top near the supply-pipe outlet, so its heat because of polymeric kettle inside is heated.So in the solution polymerization of using this poly-unit, vinyl monomer is to be supplied in the polymeric kettle with polymerization starter blended state.Therefore, the part of vinyl monomer begins polymerization owing to being heated near the pipe the supply-pipe outlet, and in supply-pipe generation vinyl polymer and formed glass cullet (cullet), and when using multiple alkene monomer, generate mostly and form inhomogenous multipolymer.When producing glass cullet, produce in the filtration operation after polymerization and stop up, or, in the coating that with polymeric liquid or this polymers soln is raw material, produce muddy removing fully under the situation of glass cullet by filtering operation.In addition, if a large amount of the generation formed inhomogenous multipolymer, then copolymer solution becomes muddy, or being in the coating of raw material with this polymers soln, produces the coating defects of point-like sometimes.This phenomenon especially many comprise alkene monomer with hydroxyl or have carboxylic acid group's alkene monomer and the situation of derivative under significantly occur.
In addition, when using the solid state polymerization starter, wait under the state of temperature step-down in the winter time, the mixed solution that flows through supply-pipe turned cold before arriving polymeric kettle, and polymerization starter is separated out.The polymerization starter of separating out is deposited in the supply-pipe, has just stopped up supply-pipe soon.
Especially, owing to be acrylic coating when use resin, in order to reduce quantity of solvent, need the polymkeric substance of lower molecular weight, and need to improve polymerization starter concentration thus, thereby 2 kinds of top rough sledding occur easily at vinyl polymer.
In addition, as preventing that the monomer in the supply-pipe from carrying out the polymeric method, known have a method (for example, patent documentation 1 and patent documentation 2) that vinyl monomer and polymerization starter is supplied to polymeric kettle respectively.
Yet, when vinyl monomer and polymerization starter are supplied to polymeric kettle by supply-pipe respectively, because they directly have been fed into the solvent cut of polymeric kettle separately in advance, therefore contact need is for a long time in polymeric kettle vinyl monomer and polymerization starter, and the part of polymerization starter is decomposed and was lost efficacy before this, the polymerization starter useless such problem that becomes.
Patent documentation 1: the spy opens clear 63-30334 communique
Patent documentation 2: the spy opens the 2002-167411 communique
Summary of the invention
Therefore, the object of the invention is to provide the poly-unit that can not generate polymkeric substance in a kind of supply-pipe set between from the tempering tank to the polymeric kettle or separate out polymerization starter, and can stablize the method for producing polymer that preparation does not have the polymers soln that impurity sneaks into.
That is to say, poly-unit of the present invention is characterised in that, have: the tempering tank that monomer and polymerization starter is mixed with mixed solution, heating mixed solution and carry out the polymeric kettle of monomer polymerization, in polymeric kettle, supply with the supply-pipe of tempering tank mixed solution, regulate the temperature equipment of mixeding liquid temperature in the supply-pipe.
In addition, method for producing polymer of the present invention, be by supply-pipe will be in tempering tank the mixed solution for preparing of mix monomer and polymerization starter be supplied in the polymeric kettle, and in polymeric kettle heating mixed solution and carry out the method for producing polymer of monomer polymerization, it is characterized in that, the temperature of mixed solution in the supply-pipe is remained in 15-30 ℃ the scope.
According to poly-unit of the present invention, between from the tempering tank to the polymeric kettle, in the set supply-pipe, can suppress to generate polymkeric substance or separate out polymerization starter.In addition, according to method for producing polymer of the present invention, can stablize the polymers soln that preparation does not have impurity to sneak into.The present invention is particularly useful for making the acrylic coating resin.
Description of drawings
[Fig. 1] is the brief configuration figure of an example of expression poly-unit of the present invention.
[Fig. 2] is near the amplification profile the outlet of mixed solution supply-pipe in Fig. 1 poly-unit.
Nomenclature
10 poly-units
12 tempering tanks
14 polymeric kettles
32 mixed solution supply-pipes
40 overflow pipes (register)
Embodiment
Below, explain the present invention.
Fig. 1 is the brief configuration figure of an example of expression poly-unit of the present invention.These poly-unit 10 basic comprisings are as follows, have: mix and the temporary storage monomer, the tempering tank 12 of solvent and polymerization starter, carry out the polymeric kettle 14 of monomer polymerization by the mixed solution of tempering tank 12 supplies by heating, store the supply groove 16 of polymerization starter solution, supply with monomer to tempering tank 12, the raw material supplying pipe 30 of solvent, the mixed solution supply-pipe 32 of mixed solution in polymeric kettle 14 supply tempering tanks 12, the polymers soln take-off pipe 34 of the polymers soln that taking-up prepares in polymeric kettle 14, the polymerization starter supply-pipe 36 of the polymerization starter solution in polymeric kettle 14 supply grooves 16, coaxial setting and around the overflow pipe 40 (register) of mixed solution supply-pipe 32, supply with the water service pipe 42 of water and the water shoot 44 of drainage water from overflow pipe 40 to overflow pipe 40.
Tempering tank 12 has groove body 60, stirs the paddle 62 of its internal liquid, makes paddle motor rotating 64, supplies with the inlet 65 of polymerization starter and the register 66 of regulating tank main body 60 internal temperatures.As tempering tank 12, can use those used tempering tanks in solution polymerization device in the past.
Mixed solution supply-pipe 32 and overflow pipe 40 (register) are two sleeve pipes as shown in Figure 2, and interior pipe is mixed solution supply-pipe 32, and outer tube is an overflow pipe 40.By in overflow pipe 40, flowing through the water of regulating excess temperature, just the mixeding liquid temperature that flows through mixed solution supply-pipe 32 can be adjusted to specified temperature.
In addition, as shown in Figure 2, overflow pipe 40 is around the outlet of mixed solution supply-pipe 32 until the mixed solution supply-pipe 32 that is positioned at polymeric kettle 14 upper inner, and in the exit of mixed solution supply-pipe 32, the end face of overflow pipe 40 is sealed.
In addition, the two telescopic end faces that formed by mixed solution supply-pipe 32 and overflow pipe 40 preferably tilt with respect to tubular axis as shown in Figure 2.By two box face are tilted, arrive two box face and flow out and make, and then form big drop and drop down onto the polymeric kettle from two sleeve pipe front ends from the effusive mixed solution of mixed solution supply-pipe 32 outlets.This tilt angle alpha is preferably 30-60 °.
Under two box face and the orthogonal situation of tubular axis, the mixed solution that comes out from mixed solution supply-pipe 32 directly forms the little spittle and disperses out polymeric kettle 14, on the inwall of the polymeric kettle 14 that mixed solution exposes attached to polymeric kettle 14 inner liquid levels 20 tops and the paddle 72b of paddle 72 topmosts, and polymerization takes place herein, or generation vinyl polymer, because this polymkeric substance is insoluble to solvent, therefore form glass cullet, or when using multiple alkene monomer, generate a large amount of inhomogenous multipolymers of forming.When producing glass cullet, in the filtration procedure after polymerization, the generation possibility of jamming is arranged.In addition, if in filtering operation, can't eliminate glass cullet fully, then be easy to generate muddiness in the coating as raw material with polymeric liquid or this polymers soln.In addition, if produce a lot of inhomogenous multipolymers of forming, then formed the polymers soln muddiness, or become the reason that in the coating that with this polymers soln is raw material, produces the point-like coating defects.
In addition, the position of mixed solution supply-pipe 32 in polymeric kettle 14, between polymeric kettle 14 inwalls and paddle 72b, preferably mixed solution roughly can be splashed into position intermediate, so that the mixed solution that splashes into is not attached on the topmost paddle 72b of the polymeric kettle 14 that exposed above the liquid level 20 and paddle 72 in polymeric kettle 14.
Below, the method for producing polymer that uses poly-unit 10 is described.
At first, in polymeric kettle 14, drop into solvent, polymeric kettle 14 inside are heated to specified temperature by register 76.
In addition, in tempering tank 12, supply with monomer and solvent by raw material supplying pipe 30, and from the 65 input polymerization starters that enter the mouth.In tempering tank 12, fully stir and mix monomer, solvent and polymerization starter, and resulting mixed solution temporary storage is got up.
Then, beginning flows into to be adjusted to the water of specified temperature in overflow pipe 40.Supplying with water in overflow pipe 40 finishes until solution polymerization.
Then, on one side temperature in the controlled polymerization still 14, by mixed solution supply-pipe 32 the splash into speed of the mixed solution in the tempering tank 12 with regulation is splashed in the polymeric kettle 14 on one side, carry out solution polymerization.After mixed solution splashes into end, as required, add polymerization starter by supplying with groove 16 by polymerization starter supply-pipe 36.
After solution polymerization is finished, filter operation from the bottom of polymeric kettle 14 through strainer 78, and take out polymers soln by polymers soln take-off pipe 34.
Control is supplied to the water yield and temperature thereof in the overflow pipe 40, so that the mixeding liquid temperature in the mixed solution supply-pipe 32 remains in 15-30 ℃ the scope.Specifically be that the water yield that is supplied to supply-pipe is preferably 25-50L/min, more preferably 30-40L/min.In addition, the temperature of supply water is preferably 15-30 ℃, more preferably 18-25 ℃.
If the temperature of mixed solution is less than 15 ℃ in the mixed solution supply-pipe 32, when using the solid state polymerization starter, just flow through mixed solution cooling before arriving polymeric kettle 14 of mixed solution supply-pipe 32, separating out of polymerization starter might be taken place so.On the other hand, if mixeding liquid temperature surpasses 30 ℃ in the mixed solution supply-pipe 32, then possible monomer generation polymerization generates glass cullet, perhaps generates a lot of inhomogenous multipolymers of forming.
As monomer, when the preparation vinyl polymer, can use various vinyl monomers.In addition, when the preparation acrylic resin, can use various methacrylic esters and/or acrylate, and be used in combination with other vinyl polymer as required.
As vinyl monomer, for example can enumerate methacrylic esters such as methyl methacrylate, Jia Jibingxisuanyizhi, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, methacrylic tert-butyl acrylate, methacrylic acid pentyl ester, cyclohexyl methacrylate, methacrylic acid 2-ethylhexyl, methacrylic acid stearyl, lauryl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate; Acrylate such as methyl acrylate, ethyl propenoate, n-butyl acrylate, isobutyl acrylate, 2-EHA, vinylformic acid 2-hydroxy methacrylate, 4-hydroxy acrylate; Alkenyl cyanide compound such as vinyl cyanide, methacrylonitrile; Aromatic series alkene formula compounds such as vinylbenzene; Unsaturated carboxylic acid such as vinylformic acid, methacrylic acid etc.
Polymerization starter as vinyl monomer, for example can enumerate, peroxidation di-isopropyl two carbonic ethers, peroxidation two uncle's hexyls, peroxidation neodecanoic acid tertiary butyl ester, peroxidation PIVALIC ACID CRUDE (25) tertiary butyl ester, peroxidation 2 ethyl hexanoic acid tertiary butyl ester, lauroyl peroxide pivalate, benzoyl peroxide, peroxidation sec.-propyl carbonic acid tertiary butyl ester, peroxidation phenylformic acid tertiary butyl ester, dicumyl peroxide, di-t-butyl peroxide, 1,1 '-di-t-butyl peroxide-3,3, organo-peroxides such as 5-trimethyl-cyclohexane; 2,2 '-azo two (2, the 4-methyl pentane nitrile), 2,2 '-Diisopropyl azodicarboxylate, 2,2 '-azo, two 2-methylbutyronitriles, 1-1 ' azo two (1-cyclohexanenitrile), 2,2 '-azo two azo-compounds such as (2,4, the 4-trimethylpentane).
As solvent, for example can enumerate aromatic hydrocarbonss such as toluene, dimethylbenzene; Alkylol cpds such as Virahol, 1-butanols, isopropylcarbinol; Ester cpds such as vinyl acetic monomer, n-butyl acetate, isobutyl acetate; Ethylene glycol monoethyl ether, propylene glycol monomethyl ether; Ketone compounds such as methylethylketone, mibk, pimelinketone; Aliphatic hydrocarbon such as normal hexane, normal heptane etc.
In above-mentioned poly-unit 10, owing to be provided with overflow pipe 40 (register) around mixed solution supply-pipe 32, therefore polymerization does not take place the mixeding liquid temperature that flows through mixed solution supply-pipe 32 can be adjusted to monomer, the temperature that polymerization starter is not separated out, and can be suppressed at and generate polymkeric substance in the pipe, separate out polymerization starter.
In addition, in using the method for producing polymer of this poly-unit 10, because the mixeding liquid temperature of mixed solution supply-pipe 32 remains on below 30 ℃, generation that therefore can the killer tube interpolymer, and can access the polymers soln that does not have impurity to sneak into.In addition because the mixeding liquid temperature in the mixed solution supply-pipe 32 remains on more than 15 ℃, therefore can killer tube in the separating out of polymerization starter, and can not interrupt preparation, stably prepare polymers soln.
In addition, poly-unit of the present invention is not limited to the device of legend, as long as be provided with the poly-unit of regulating the register of mixeding liquid temperature in the supply-pipe on supply-pipe from the tempering tank mixed solution to polymeric kettle that supply with, then no matter any form is all right.
Embodiment
Below, be described more specifically the present invention by embodiment.
[embodiment 1]
Using poly-unit 10 shown in Figure 1, is to carry out the preparation of acrylic coating with resin under 30 ℃ the condition at temperature.
As tempering tank 12, use the capacity of groove body 60 to be 4.5m
3And groove with paddle 62 and motor 64.The sleeve temperature of tempering tank is made as 25 ℃.As polymeric kettle 14, use the capacity of still main body 70 to be 6m
3And still with paddle 72, motor 74, sleeve (register 76) and strainer 78.As supplying with groove 16, use capacity to be 0.5m
3Groove.
At first, to polymeric kettle 14 in drop into 460kg propylene glycol monomethyl ether and 920kg diformazan benzo stir on one side, by the 500KPa pressurized hot water in the sleeve internal temperature of polymeric kettle 14 is risen to 100 ℃ on one side.
In addition, in tempering tank 12, add 230kg propylene glycol monomethyl ether, 230kg dimethylbenzene, 345kg zinc methacrylate, 345kg zinc oleate methacrylic ester, 207kg methyl methacrylate, 403kg ethyl propenoate and 92kg peroxidation acid tertiary butyl ester, stir, mix, obtain mixed solution.The temperature of mixed solution is 20 ℃.
Beginning flows into 20 ℃ water in overflow pipe 40 with 35L/ minute flow.Supplying with water in overflow pipe 40 finishes until solution polymerization.
Then,, the internal temperature of polymeric kettle 14 is controlled at 100 ℃, on one side the speed of the mixed solution in the tempering tank 12 with 11.9kg/ minute is splashed in the polymeric kettle 14, carry out solution polymerization on one side by adjusting the temperature of pressurized hot water in the sleeve.During splashing into mixed solution to polymeric kettle, the mixeding liquid temperature at supply-pipe exit portion upstream side 30cm place is 20 ℃, and the mixeding liquid temperature of supply-pipe export department office also is 20 ℃.
After mixed solution splashes into end, to polymeric kettle 14, drop into 115kg dimethylbenzene, and the internal temperature of polymeric kettle 14 was kept 1 hour down at 100 ℃ from tempering tank 12.In addition, in supplying with groove 26, add 23kg peroxidation acid tertiary butyl ester and 230kg dimethylbenzene, mix, prepare polymerization starter solution, and its speed with 4.2kg/ minute is splashed into to polymeric kettle 14.After splashing into end,, the internal temperature of polymeric kettle 14 is controlled at 100 ℃, stirred 2 hours on one side on one side by adjusting the pressurized hot water in the sleeve.And then, in polymeric kettle 14, drop into 115kg dimethylbenzene by supplying with groove 26, mix, cool off, and finish reaction.Get liquid by strainer from the bottom of polymeric kettle 14, obtain resin solution.Observe the inside of polymeric kettle 14, confirmed not have dirt especially.
[embodiment 2]
Using the poly-unit 10 identical with embodiment 1, is the preparation of carrying out acrylic coating usefulness resin under 30 ℃ the condition at temperature.
At first, to polymeric kettle 14 in drop into 1744kg vinyl acetic monomer and 92kg n-butyl acetate on one side, and stir, by the 500KPa pressurized hot water in the sleeve internal temperature of polymeric kettle 14 is risen to 80 ℃ on one side.
In addition, in tempering tank 12, add 450kg n-butyl acetate, 1031kg methyl methacrylate, 653kg n-BMA, 481kg 2-hydroxyethyl methacrylate, 103kg 2-hydroxyethyl methacrylate, 23kg methacrylic acid and 34kg2,2 '-Diisopropyl azodicarboxylate, stir, mix, obtain mixed solution.The temperature of mixed solution is 20 ℃.
Beginning flows into 20 ℃ water in overflow pipe 40 with 35L/ minute flow.Supplying with water in overflow pipe 40 finishes until solution polymerization.
Then,, the internal temperature of polymeric kettle 14 is controlled at 80 ℃, on one side the speed of the mixed solution in the tempering tank 12 with 11.6kg/ minute is splashed in the polymeric kettle 14, carry out solution polymerization on one side by adjusting the temperature of pressurized hot water in the sleeve.During splashing into mixed solution to polymeric kettle, the mixeding liquid temperature at supply-pipe exit portion upstream side 30cm place is 20 ℃, and the mixeding liquid temperature of supply-pipe export department office also is 20 ℃.
After mixed solution splashes into end, to polymeric kettle 14, drop into the 80kg vinyl acetic monomer, and the internal temperature of polymeric kettle 14 was kept 1 hour down at 80 ℃ from tempering tank 12.In addition, add 9kg2 in supplying with groove 16,2 '-Diisopropyl azodicarboxylate and 206kg vinyl acetic monomer by being mixed with polymerization starter solution, and splash into its speed with 3.6kg/ minute to polymeric kettle 14.After splashing into end,, the internal temperature of polymeric kettle 14 is controlled at 85 ℃, stirred 2 hours on one side on one side by adjusting the pressurized hot water in the sleeve.In addition, in polymeric kettle 14, drop into the 218kg vinyl acetic monomer, mix, cool off, and finish reaction by supplying with groove 26.Get liquid by strainer from the bottom of polymeric kettle 14, obtain resin solution.Resin solution is water white.
[comparative example 1]
As poly-unit, use except that overflow pipe 40 is not set, all identical poly-unit with embodiment 1, and under the condition identical, carry out the preparation of acrylic coating similarly to Example 1 with resin with embodiment 1.In addition, the temperature of mixed solution is 20 ℃ in the tempering tank.In addition, splash into mixed solution in polymeric kettle during, the mixeding liquid temperature at supply-pipe exit portion upstream side 30cm place is 20 ℃, but the mixeding liquid temperature of supply-pipe export department office has risen to 80 ℃.
[comparative example 2]
As poly-unit, use except that overflow pipe 40 is not set, all identical poly-unit with embodiment 1, and under the condition identical with embodiment 2 and embodiment 2 carry out the preparation of acrylic coating equally with resin.In addition, the temperature of mixed solution is 20 ℃ in the tempering tank.In addition, splash into mixed solution in polymeric kettle during, the mixeding liquid temperature at supply-pipe exit portion upstream side 30cm place is 20 ℃, but the mixeding liquid temperature of supply-pipe export department office has risen to 60 ℃.
The resin solution that obtains has a bit muddy.
[embodiment 3]
Use the poly-unit 10 identical, and be the preparation of carrying out acrylic coating usefulness resin under 5 ℃ the condition at temperature with embodiment 1.
At first, to polymeric kettle 14 in drop into 752kg dimethylbenzene and 460kg vinyl acetic monomer on one side, and stir, by the 500KPa pressurized hot water in the sleeve internal temperature of polymeric kettle 14 is risen to 130 ℃ on one side.
In addition, in tempering tank 12, add 230kg vinylbenzene, 1237kg n-BMA, 115kg methacrylic acid stearyl, 285kg 2-hydroxyethyl methacrylate, 400kg vinylformic acid 2-hydroxy methacrylate, 32kg methacrylic acid, 81kg2,2 '-Diisopropyl azodicarboxylate, 46kg peroxidation acid tertiary butyl ester, stir, mix, obtain mixed solution.The temperature of mixed solution is 20 ℃ in the tempering tank.
Beginning flows into 20 ℃ water in overflow pipe 40 with 35L/ minute flow.Supplying with water in overflow pipe 40 finishes until solution polymerization.
Then,, the internal temperature of polymeric kettle 14 is controlled at 130 ℃, on one side the speed of the mixed solution in the tempering tank 12 with 10.1kg/ minute is splashed in the polymeric kettle 14, carry out solution polymerization on one side by adjusting the temperature of pressurized hot water in the sleeve.Splash into mixed solution in polymeric kettle during, the mixeding liquid temperature at supply-pipe exit portion upstream side 30cm place is 20 ℃, and the mixeding liquid temperature of supply-pipe export department office also is 20 ℃.
After mixed solution splashes into end, to polymeric kettle 14, drop into 56kg dimethylbenzene, and the internal temperature of polymeric kettle 14 was kept 1 hour down at 130 ℃ from tempering tank 12.In addition, the internal temperature of polymeric kettle 14 is reduced to 115 ℃ on one side, and polymeric kettle 14 internal temperatures are controlled at 115 ℃, in supplying with groove 16, add 12kg2 on one side, 2 '-Diisopropyl azodicarboxylate and 165kg dimethylbenzene, by being mixed with polymerization starter solution, and its speed with 1.5kg/ minute is splashed into to polymeric kettle 14.After splashing into end, adjust the pressurized hot water in the sleeve, and stirred 2 hours.In addition, in polymeric kettle 14, drop into 100kg dimethylbenzene, mix, cool off, and finish reaction by supplying with groove 26.Get liquid by strainer from the bottom of polymeric kettle 14, obtain resin solution.Resin solution is water white.
Observe to take out polymeric kettle 14 and mixed solution supply-pipe 32 behind the resin solution, owing to heated mixed solution supply-pipe 32 with 20 ℃ water, so confirmed in mixed solution supply-pipe 32 2,2 '-Diisopropyl azodicarboxylate is not separated out.
[comparative example 3]
As poly-unit, use except that overflow pipe 40 is not set, all identical poly-unit with embodiment 3, and be under 5 ℃ the condition at temperature and embodiment 3 carries out the preparation of acrylic coating with resin equally.In addition, the temperature of mixed solution is 20 ℃ in the tempering tank.In addition, splash into mixed solution in polymeric kettle during, the mixeding liquid temperature at supply-pipe exit portion upstream side 30cm place is 20 ℃, but the mixeding liquid temperature of supply-pipe export department office is 5 ℃.In this system, because water of no use 20 ℃ heating mixed solution supply-pipe 32, so mixed solution supply-pipe 32 is because 2, separating out of 2 '-Diisopropyl azodicarboxylate and stopping up, and fail to finish polymerization.
Industrial utilizability
Because polyplant of the present invention and method for producing polymer can gather to resulting by inhibition of impurities Sneak in the compound solution, therefore eliminated the muddiness of the coating take this polymer solution as raw material, and When this coating of coating, suppressed the generation of point-like coating defects.
Claims (2)
1, a kind of poly-unit is characterized in that, has:
Monomer and polymerization starter are mixed with the tempering tank of mixed solution,
In polymeric kettle, supply with the supply-pipe of tempering tank mixed solution,
The mixed solution that heating is supplied with by supply-pipe carries out the polymeric kettle of monomer polymerization,
Be used to regulate the temperature equipment of the interior mixeding liquid temperature of supply-pipe to 15-30 ℃ scope.
2, a kind of method for producing polymer, be by supply-pipe will be in tempering tank the mixed solution for preparing of mix monomer and polymerization starter be supplied in the polymeric kettle, and in polymeric kettle heating mixed solution and carry out the method for producing polymer of monomer polymerization, it is characterized in that, the temperature of mixed solution in the supply-pipe is remained in 15-30 ℃ the scope.
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| JP188108/2004 | 2004-06-25 | ||
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| JP2008050461A (en) * | 2006-08-24 | 2008-03-06 | Mitsubishi Rayon Co Ltd | Production method for polymer, polymer and resist composition |
| JP5820354B2 (en) * | 2012-08-24 | 2015-11-24 | 三菱レイヨン株式会社 | Method for producing polymer and method for producing resist composition |
| PL2765149T3 (en) | 2013-02-06 | 2019-06-28 | Uhde Inventa-Fischer Gmbh | Method for the production of a titanium containing catalyst, titanium containing catalyst, method for the production of polyester and polyester |
| SI2772305T1 (en) * | 2013-02-27 | 2018-04-30 | Uhde Inventa-Fischer Gmbh | Polymerisation device and method and device for producing thermoplastic polymers |
| JP2014196512A (en) * | 2014-07-14 | 2014-10-16 | 三菱レイヨン株式会社 | Production method for polymer, and production method for resist composition |
| JP6443971B2 (en) * | 2014-09-30 | 2018-12-26 | 株式会社日本触媒 | Method for producing thermoplastic resin |
| JP6812642B2 (en) * | 2016-03-01 | 2021-01-13 | 三菱ケミカル株式会社 | Manufacturing method of aqueous dispersion |
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| JPH08183809A (en) * | 1994-12-28 | 1996-07-16 | Mitsui Petrochem Ind Ltd | Feed of solid catalyst into olefin polymerizer and nozzle |
| JP3937111B2 (en) * | 1997-03-04 | 2007-06-27 | 三菱瓦斯化学株式会社 | Method for producing polymer |
| US6252016B1 (en) * | 1997-12-19 | 2001-06-26 | Rohm And Haas Company | Continuous polymerization in a non-cylindrical channel with temperature control |
| JP3434225B2 (en) * | 1998-11-27 | 2003-08-04 | 三菱レイヨン株式会社 | Method for producing methacrylic polymer |
| JP3934489B2 (en) * | 2002-06-12 | 2007-06-20 | 株式会社日本触媒 | Method and apparatus for producing (meth) acrylic acid polymer |
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| CN101006102A (en) | 2007-07-25 |
| JP5249514B2 (en) | 2013-07-31 |
| CN101481430B (en) | 2011-05-04 |
| WO2006001113A1 (en) | 2006-01-05 |
| JPWO2006001113A1 (en) | 2008-04-17 |
| JP2013100560A (en) | 2013-05-23 |
| CN101481430A (en) | 2009-07-15 |
| JP5590425B2 (en) | 2014-09-17 |
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