CN1429244A - Process for producing acrylic polymer - Google Patents
Process for producing acrylic polymer Download PDFInfo
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- CN1429244A CN1429244A CN 01809681 CN01809681A CN1429244A CN 1429244 A CN1429244 A CN 1429244A CN 01809681 CN01809681 CN 01809681 CN 01809681 A CN01809681 A CN 01809681A CN 1429244 A CN1429244 A CN 1429244A
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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Abstract
A process for producing a powder which is excellent in powder properties such as handleability, flowability, and antiblocking property, has excellent redispersibility during melt-kneading together with other resin(s), and is reduced in fish-eye generation. The process comprises spraying an emulsion polymerization latex containing an acrylic polymer as the main component in a drying chamber, simultaneously introducing a drying gas thereinto through an inlet of the drying chamber to dry the latex and thereby form a powder of the acrylic polymer, and collecting the powder through an outlet of the drying chamber. In this process, the spraying of the latex is conducted with a spray nozzle, the temperature of the gas around the inlet of the drying chamber is regulated to below 200 DEG C, and the temperature of the gas around the outlet of the drying chamber is regulated to a temperature lower than the temperature higher by 30 DEG C than the minimum film-forming temperature of the emulsion polymerization latex. Thus, a powder having excellent performances is obtained.
Description
Technical field
The present invention relates to make the method for acrylic polymer powder by the emulsion polymerization latex that with the acrylic polymer is main component, specifically, relate to the manufacture method that can obtain the acrylic polymer of powder characteristics powder good and that redispersibility is good with other resin melting mixing time the such as flowability.
The application is the application according to the patent application (patent application 2000-149069 number) that proposes to Japan, and the content of this Japanese publication record is put down in writing wherein as the part of specification sheets of the present invention.
Background technology
Usually adopt the emulsion polymerization manufacturing as the employed acrylic polymer of the properties-correcting agent of various plastics such as polyvinyl chloride (PVC) RESINS.And the acrylic polymer behind the emulsion polymerization finally is used for and other resin melting mixing, makes Powder Recovery by the emulsion polymerization latex behind the emulsion polymerization (below abbreviate " latex " as).
As by the method for such latex, the directly spray-drying process of spraying drying latex in hot blast is arranged with the Powder Recovery acrylic polymer.
And, in the aforesaid propylene based polymer powder that obtains like this (below, abbreviate " powder " sometimes as), for as properties-correcting agent, require following powder property.
(1) operability, flowability, the resistance to blocking in the powder operating process is good.(below, these characteristics are called " powder characteristics ")
Dispersiveness during (2) with other resin melting mixing such as polyvinyl chloride (PVC) RESINS (below, be called " redispersibility ") is good, seldom produce come from properties-correcting agent do not disperse the fish eyes shape defective that thing forms (below, be called " flake ").
The powder characteristics of above-mentioned (1) is that the particle diameter of powder is more little, and the structure of powder is thick more poor more, and in contrast, the redispersibility of above-mentioned (2) then is that the particle diameter of powder is more little and structure powder is thick more good more.
Therefore, in order to be met the powder that has the phase cross-demand like this, must control moisture eliminator operating condition.
For example, opening the method for putting down in writing in the flat 8-169914 communique the spy is: carrying out in the spray-dired method having carried out back catalytic latex with initiator, setting the temperature out of moisture eliminator with the second-order transition temperature of polymkeric substance (below be called " Tg ") as benchmark.
Yet, in the method because the latex spray method is used rotating disk, thereby exist the particle diameter of resulting powder little, the problem of mobile difference.And, when using this rotating disk to reclaim the big powder of powder diameter, make fine powder, meal all increase and make size-grade distribution become extremely wide easily, its result often causes powder property to reduce.
In addition, because the Tg of polymkeric substance is set the temperature out of moisture eliminator as benchmark, can not control the correct powdery structure of powder, there is bad this class problem of powder characteristics and redispersibility in its result.Even when using the average Tg (apparent Tg) of powder particle, this situation also is same.
When with Tg being benchmark setting temperature out like this, can not correctly control the reason of powdery structure can think: in the acrylic polymer powder of making recently, owing to require multiple performance as properties-correcting agent, thereby its structure mostly is multi-ply construction, and the Tg of such multi-layer structure material can not specifically determine usually.
Like this, all excellent powder of redispersibility that obtain the powder characteristics of above-mentioned (1) and (2) is difficult, does not also see the report of the moisture eliminator operating condition of the relevant powder that obtains such performance.
Summary of the invention
The objective of the invention is to: to being that the emulsion polymerization latex of main component carries out spraying drying and produces in the manufacture method of acrylic polymer of acrylic polymer powder with the acrylic polymer, the operating condition of setting moisture eliminator makes the acrylic polymer powder as the properties-correcting agent of various Plastic Resins have following performance, that is: powder characteristics such as operability, flowability, resistance to blocking are good and redispersibility is good, to produce the flake amount few during with other resin melting mixing.
The present inventor furthers investigate the powder characteristics of acrylic polymer and the tremendous influence of redispersibility with the structure of the polymkeric substance that constitutes powder the particle diameter of powder.It found that, by with nozzle latex being sprayed in the moisture eliminator and when controlling the particle diameter of drop of spraying, with the minimum film-forming temperature of latex (below, be called " MFT ") set temperature in the moisture eliminator for benchmark, especially near the temperature the outlet of moisture eliminator, so that improve the powder characteristics and the redispersibility of prepared acrylic polymer simultaneously, thereby finished the present invention.Promptly, the manufacture method of acrylic polymer of the present invention, have: will be that the emulsion polymerization latex of main component is when being sprayed in the moisture eliminator with the acrylic polymer, inlet portion by moisture eliminator feeds the dry gas of using, make above-mentioned latex drying make the acrylic polymer powder, reclaim the operation of this powder by the export department of moisture eliminator, it is characterized in that: carry out the spraying of above-mentioned latex with nozzle, near the above-mentioned moisture eliminator inlet portion drying is decided to be with gas temperature is lower than 200 ℃, and near the drying the dryer export portion is decided to be the temperature that the minimum film-forming temperature that is lower than above-mentioned emulsion polymerization latex adds 30 ℃ with gas temperature.
Embodiment
Below, the present invention will be described in detail.
At first, the used moisture eliminator of the present invention is described.This moisture eliminator has at least: the latex spraying that will be obtained by emulsion polymerization imports the nozzle in the container, and the drying that feeds dry latex of being sprayed is with the inlet portion of gas with as the export department of above-mentioned dry relief outlet with gas and dried powder.And, above-mentioned nozzle is arranged on moisture eliminator top, above-mentioned inlet portion is arranged on moisture eliminator top makes drying contact with the latex of being sprayed with gas, above-mentioned export department is arranged on the bottom, drops to the situation of bottom while employed drying preferably presents to be flowed by the top of moisture eliminator with gas.
In addition, the overall shape of such moisture eliminator is not particularly limited, its capacity also is not particularly limited, the small-scale of using from the laboratory is to all can using on a large scale that industrial production is used.
As above-mentioned nozzle, the preferred pressure that the latex of being sprayed is applied 0.1-20Mpa that uses makes latex can be formed the pressure nozzle of particulate to spray at a high speed by nozzle.Especially preferably make the latex ejection of being sprayed form the pressurization rotation nozzle of rotational flow.
Can spray dried latex with this nozzle, the spray pressure when making latex form particulate by adjustment can be adjusted the particle diameter of resulting powder, makes it have the particle diameter that can obtain desired powder property.Therefore the scope of particle diameter that can obtain desired powder property can suitably be adjusted according to the structure of this polymkeric substance, the MFT of latex etc. owing to also depend on the structure of this polymkeric substance as described later.
Adopt such method, compare, can obtain the big powder of particle diameter with the rotating disk spray pattern that adopts the prior art example.
Near the drying inlet portion of above-mentioned moisture eliminator gas temperature (below, be called " temperature in ") be lower than 190 ℃ for being lower than 200 ℃, being preferably.More than 200 ℃ the time, cause resulting powder surface blocking under warming partly to occur, the redispersibility when making melting mixing reduces, and the generation of flake increases.
Though the lower limit to above-mentioned temperature in is not particularly limited, can it be in certain temperature range by near the temperature dryer export described later portion is suitably set, preferably more than 140 ℃.When above-mentioned temperature in was lower than 140 ℃, dry air quantity with gas increased greatly.
Near the export department of above-mentioned moisture eliminator gas temperature (below, be called " temperature out ") be that the MFT that is lower than above-mentioned latex adds 30 ℃ temperature.
Herein, the MFT of latex can form the minimum temperature of transparent continuous film for latex film forming the time, is the value of representing the Tg on latex particle surface.In addition, MFT is relevant with the sticking power on the latex polymer particles top layer that becomes the powdery structure determinative, also as the index of representing above-mentioned sticking power.
Like this, by being the polymer architecture of the temperature setting may command powder of benchmark with MFT, that is to say characteristics such as the flowability of may command powder and redispersibility.And, even polymkeric substance is multi-ply construction, can control the powder characteristics and the redispersibility of powder too.
Thereby, be lower than the temperature that MFT adds 30 ℃ if the temperature out of moisture eliminator is set at, even, also can obtain the good powder of powder characteristics and redispersibility making when forming different a plurality of latex dryings and making powder.
When said temperature when the MFT of latex adds that 30 ℃ temperature is above because adhesion appears in the surface portion floor of powder, the redispersibility of powder when melting mixing reduced, cause the flake amount that is produced to increase.
In addition, the lower limit of the gas temperature of dryer export is not particularly limited, but preferably is higher than 50 ℃.When being lower than 50 ℃, the drying of powder is insufficient sometimes.
Measuring method as the MFT of above-mentioned latex at first, at the two ends of horizontally disposed aluminium sheet, is provided with heating unit and refrigerating unit as required, makes the temperature of aluminium sheet have thermograde.Secondly, on above-mentioned aluminium sheet with thermograde, the uniform skim of latex is made its drying.Measure again that latex forms the minimum temperature of transparent continuous film and with it as MFT.
The preferable particle size of the powder that obtains with aforesaid condition drying and since also depend on powder the structure etc. of polymkeric substance, thereby cannot treat different things as the same.For example, the low person of Tg (perhaps MFT) owing to powder property is in fact very poor, compares with the high person of glass tansition temperature (or MFT) to be necessary to set particle diameter bigger usually.But, when being preferably 60-300 μ m, 100-200 μ m more preferably.Particle diameter owing to reasons such as micro mist increases, causes operability, flowability, the resistance to blocking of powder to reduce during less than 60 μ m; When particle diameter surpasses 300 μ m, when mixing, then be easy to layering and can not uniform mixing with toner such as polyvinyl chloride (PVC) RESINS.
With acrylic polymer used in above-mentioned manufacture method be the emulsion polymerization latex of main component there is no particular limitation, but preferred MFT is person more than 20 ℃, more preferably MFT is person more than 50 ℃.When MFT is lower than 20 ℃, because of the dryer export temperature dry insufficient below 50 ℃.
Such latex, the propylene of concrete the following stated used is a kind of monomer or two or morely makes its copolymerization, the mixture of seeding polymerization or graft polymerization, these propylene are that monomer is: methyl acrylate, ethyl propenoate, butyl acrylate, propyl acrylate, the 2-ethylhexyl acrylate, the allyl group acrylate, glycidyl acrylate, methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, propyl methacrylate, 2-ethylhexyl methacrylic ester, the allyl methyl acrylate, glycidyl methacrylate, acrylamide, vinyl cyanide etc.In addition, as the monomer beyond the aforesaid propylene system, also can small number of combinations use operable monomer in Emulgating polymers such as vinylbenzene, 2-methyl styrene, 1,3-butadiene, vinyl-acetic ester, vinyl pyridine, be more than the monomer 50 quality % but preferably contain propylene.
In addition, can also use divinylbenzene, 1 simultaneously, the chain-transfer agent of linking agent, thio-alcohol, terebene classes and so on such as 3-dibutene dimethacrylate, allyl methyl acrylate, glycidyl methacrylate.
As the employed polymerization starter of the emulsion polymerization of aforesaid propylene based polymer, there is no particular limitation, but can use redox series initiators as described below, that is: with water-soluble persulphates such as Potassium Persulphate, Sodium Persulfate, ammonium persulphates, organo-peroxides such as di-isopropylbenzene hydroperoxide, p-menthane hydroperoxide, cumine hydroperoxide, t-butyl hydroperoxide are as the redox series initiators of one of composition.
As the used emulsifying agent of the emulsion polymerization of aforesaid propylene based polymer, there is no particular limitation, the following stated material can be used in combination i.e.: an alkali metal salt of senior lipid acid such as disproportionation rosin, oleic acid, stearic acid, sulfonic acid alkali metal salts such as Witco 1298 Soft Acid more than a kind or 2 kinds.
Emulsion polymerization method and emulsion polymerization condition to employed latex in the above-mentioned manufacture method are not particularly limited, and can implement by existing known method and condition.
In addition, above-mentioned latex both can be single, also can be the mixture of multiple latex.
Have again,, also can in the latex of spraying, add suitable antioxidant and additive etc. and carry out spraying drying in order to prevent the oxidation in moisture eliminator.
Have again, for powder properties such as the resistance to blocking that improves resulting acrylic polymer powder, loose specific weights, can also add inorganic filling agent such as silicon-dioxide, talcum, lime carbonate and polyacrylic ester, polyvinyl alcohol, polyacrylamide etc. and carry out spraying drying.
In the manufacture method of acrylic polymer of the present invention, by above-mentioned emulsion polymerization latex being sprayed to by in the moisture eliminator of adjusting temperature as mentioned above with above-mentioned nozzle, reclaim from exit portion again after making its drying, just can obtain having the acrylic polymer powder of desired powder energy property.
Have, in the present invention, except the air temperature ranges of regulation spray pattern, moisture eliminator inlet, outlet, there is no particular limitation to spray drying unit, method, condition etc. again.And, as drying gas, though preferred air cheaply also can use rare gas element and air is mixed use with inert gas.
Like this, in the manufacture method of acrylic polymer of the present invention, when using the nozzle spray dried latex, the MFT of latex is controlled temperature in the moisture eliminator as benchmark, thereby when suitably controlling powder diameter, can also control the structure of this polymkeric substance according to the composition of acrylic polymer, to make powder with good powder property.
That is to say, adopt the present invention, powder characteristics such as the operability in the time of can making powder operation, flowability, resistance to blocking and the redispersibility during with other resin melting mixing such as polyvinyl chloride (PVC) RESINS are good, produce the few acrylic polymer powder of flake.
Embodiment
Below, according to embodiment the present invention is described." part " in embodiment, the comparative example is all represented " mass parts " as long as do not add explanation in addition.
Carry out the synthetic of propylene resin composition, behind the minimum film-forming temperature (MFT) of measuring resulting latex, carry out spraying drying, reclaim powder, various rerum naturas are estimated.With dryer export temperature, dryer inlet temperature, evaluation result gathers and is shown in table 1.
Embodiment 1,2 and comparative example 1,2,3
(1) propylene resin composition is synthetic
85 parts of methyl methacrylates, 15 parts of butyl methacrylate, 0.003 part of uncle's lauryl mercaptan, 1.5 parts of alkenyl potassium succinates, deionized waters are joined in the reactor for 190 parts, after replacing with nitrogen, begin to heat up while stir.Thereafter, the temperature in reactor reaches 40 ℃ the moment, the mixture of 2 parts of Potassium Persulphates, 10 parts of deionized waters is joined begin polymerization in the reactor, keeps after 200 minutes, takes out resulting latex from reactor.
(2) mensuration of MFT
Use minimum film-forming temperature determinator (high woods physics and chemistry (strain) system), measure the MFT of above-mentioned latex.
To survey periodic mensuration temperature condition and be set at 20 ℃ of low-temperature end, 180 ℃ of temperature end.Measurement result, the MFT of latex is 85 ℃.
(3) spraying drying
To carry out spraying drying in the above-mentioned latex importing moisture eliminator.As the moisture eliminator of this moment, using the vertical tube part internal diameter is 3.5 meters, and the vertical tube part height is 4 meters, and the tapering height is 2.8 meters a moisture eliminator, uses pressurization nozzle (spray pressure is 2.4Mpa) as spraying plant.
In addition, use air as drying with gas.
Feed speed, the air output of heated air, dryer inlet temperature, the temperature out of latex at this moment are shown in table 1.
(4) evaluation of various rerum naturas
A. powder median size
Use size-grade distribution valuator device, measured the mid-diameter (middle footpath is typically expressed as " D50 ") of quality criteria by Japanese industrial standards (No. the 40th, JIS) regulation.(50% the particle diameter that is equivalent to integration mass distribution curve)
B. powder flowbility
Add 50 gram powder in the loose specific weight determinator that the JIS-K-6721 standard is used, the flow state when taking off plate washer with the appearance method observation is divided into following level Four and estimates.
◎ ... fabulous
Zero ... fairly good
△ ... good
* ... bad
C. the evaluation of flake
To be used 8 inches rollers (in 150 ℃) melting mixing after 4 minutes by the resin that batching as described below is formed, and add 2 parts by the above-mentioned acrylic resin powder that obtains, melting mixing be 5 minutes again, cuts tabular resin, makes and estimates the flake test piece.Thereafter, by the rear portion irradiation of resin, be included in the appearance method evaluation flake amount that per unit area produced in the test piece that is made into (individual/16cm2).
Batching is:
100 parts of polyvinyl chloride (PVC) RESINS (n=1300)
Trioctyl trimellitate
(flower Wang Shi Yan (strain) system, trade(brand)name T-80) 80 parts
Ba-Zn type stablizer
(daily output Off ェ ロ (strain) system, trade(brand)name LTL-55) 1.0 parts
Epoxidised soybean oil
(Tokyo Off ァ イ Application (strain) system, trade(brand)name NF-3000) 5.0 parts
2.0 parts of titanium oxide (the former industry of stone (strain) system, trade(brand)name R-830)
0.1 part of carbon black
Embodiment 3,4, comparative example 4
(1) propylene resin composition is synthetic
46 parts of methyl methacrylates, 9 parts of butyl acrylates, 0.01 part of uncle's lauryl mercaptan, 1 part of alkenyl potassium succinate, 190 parts of deionized waters are joined in the reactor, carry out nitrogen replacement after, begin to heat up while stir.Temperature in reactor reaches 40 ℃ the moment, the mixture of 2 parts of Potassium Persulphates, 10 parts of deionized waters joined begin polymerization in the reactor, thereafter, keep after 120 minutes, joining in the reactor, keep after 100 minutes by taking out in the reactor with time of 60 minutes mixture with 37 parts of methyl methacrylates, 8 parts of butyl acrylates.
(2) mensuration of MFT
Measure with the method identical with embodiment 1.The result who measures, the MFT of latex is 72 ℃.
(3) spraying drying
Carry out with the method identical with embodiment 1.Feed speed, the air output of heated air, dryer inlet temperature, the temperature out of latex are shown in table 1.
(4) evaluation of various rerum naturas
Carry out with the method identical with embodiment 1.
Embodiment 5,6, comparative example 5
(1) propylene resin composition is synthetic
1.5 parts of Voranol EP 2001 phosphides, 0.01 part of potassium hydroxide, 200 parts of deionized waters are joined in the reactor, carry out nitrogen replacement after, on one side stir, add 25 parts of methyl methacrylates, 0.03 part of cumine hydroperoxide on one side, begin to heat up., when temperature in reactor reach 50 ℃ the moment again the mixture of 0.3 part sodium formaldehyde sulphoxylate, 10 part deionized waters joined in reactor begin polymerization, kept 100 minutes thereafter., again with 100 minute mixture with 30 part vinylbenzene, 25 part butyl acrylates, 1 part uncle lauryl mercaptan, 0.003 part cumine hydroperoxide join in reactor, kept 120 minutes thereafter., again with 60 minute mixture with 20 part methyl methacrylates, 0.003 part cumine hydroperoxide join in reactor, keep after 100 minutes, by taking out in the reactor thereafter.
(2) mensuration of MFT
Measure with the method identical with embodiment 1.The result who measures, the MFT of latex is 62 ℃.
(3) spraying drying
Carry out with the method identical with embodiment 1.Feed speed, the air output of heated air, dryer inlet temperature, the temperature out of latex are shown in table 1.
(4) evaluation of various rerum naturas
Carry out with the method identical with embodiment 1.
Comparative example 6
Except the moisture eliminator that uses rotating disk spray pattern (revolution is 15000rpm), all the other use the method identical with embodiment 3 to carry out.
As a result, though median size is 50 μ m, can confirm that micro mist, meal increase, the mobile reduction.
Comparative example 7
In order to make particle diameter with the rotating disk spray pattern is powder about 100 μ m, and except revolution was 6500rpm, all the other used the method identical with comparative example 4 to carry out.As a result, undried drop is attached on the wall, the latex of spraying all can not be reclaimed as dried powder.
Can see that by these results embodiment 1-6 can obtain mobile and the high powder of redispersibility.By comparison, can also see that the temperature in the moisture eliminator is taken among the comparative example 1-5 outside the temperature range of the present invention regulation, the redispersibility of powder is all very poor.In addition, in the comparative example 6 of spraying with rotating disk, the flowability of powder is also very poor, and, similarly use the rotating disk spray pattern, in the comparative example of setting particle diameter bigger 7, then can not reclaim powder.
Adopt aforesaid the present invention, the acrylic polymer powder that redispersibility is good, the flake generation is few in the time of can obtaining the good and melting mixing of powder characteristics such as operability, flowability, resistance to blocking.
The good acrylic polymer powder of such powder characteristics suits as processability enhancers such as the anti-impact modifier of polyvinyl chloride (PVC) RESINS, polystyrene, polycarbonate, ABS resin, acrylic resin, other various engineering plastics etc., lubricants.
The present invention can implement with other various ways in the scope that does not exceed its spirit or principal character.Therefore, the above embodiments only only be in every respect example and, can not be as determinate explanation.Protection scope of the present invention is not subjected to any constraint of specification sheets text by the described scope decision of claims.And then, belong to claims protection domain equivalent modification or the change all within the scope of the invention.
| Embodiment | Comparative example | ||||||||||||
| ????1 | ????2 | ????3 | ????4 | ????5 | ????6 | ????1 | ????2 | ????3 | ????4 | ????5 | ????6 | ????7 | |
| Minimum film-forming temperature (℃) | ????85 | ????85 | ????72 | ????72 | ????62 | ????62 | ????85 | ????85 | ????85 | ????72 | ????62 | ????72 | ????62 |
| Latex feed speed (kg/hr) | ????45 | ????45 | ????50 | ????50 | ????55 | ????55 | ????45 | ????45 | ????31 | ????50 | ????55 | ????50 | ????55 |
| Heated air air output (Nm 3/hr) | ???850 | ????800 | ????800 | ????850 | ????900 | ????900 | ????1200 | ????1100 | ????850 | ????1000 | ????1000 | ????810 | ????1000 |
| Dryer inlet temperature (℃) | ???160 | ????185 | ????160 | ????185 | ????160 | ????185 | ????195 | ????205 | ????195 | ????205 | ????205 | ????160 | ????205 |
| The dryer export temperature (℃) | ???70 | ????80 | ????60 | ????80 | ????60 | ????80 | ????120 | ????120 | ????120 | ????103 | ????100 | ????60 | ????100 |
| Median size D50 (μ m) | ???95 | ????102 | ????85 | ????91 | ????110 | ????106 | ????96 | ????98 | ????101 | ????88 | ????118 | ????50 | ????(100) |
| Mobile | ???○ | ????○ | ????○ | ????○ | ????◎ | ????◎ | ????○ | ????○ | ????○ | ????○ | ????◎ | ????× | ??????- |
| Fish-eye number is (individual/16cm 2) | ??65 | ????90 | ????5 | ????18 | ????2 | ????10 | ????1051 | ????1210 | ????1120 | ????285 | ????120 | ????25 | ??????- |
Claims (6)
1, a kind of manufacture method of acrylic polymer, this method has following operation: when will be sprayed in the moisture eliminator as the emulsion polymerization latex of main component with acrylic polymer, feed the dry gas of using from the inlet portion of moisture eliminator, make above-mentioned latex drying make the acrylic polymer powder, export department by moisture eliminator reclaims this powder again, it is characterized in that: carry out the spraying of above-mentioned latex with nozzle, near the above-mentioned moisture eliminator inlet portion drying is set at gas temperature is lower than 200 ℃, and near the drying the export department of moisture eliminator is set at the temperature that the minimum film-forming temperature that is lower than above-mentioned emulsion polymerization latex adds 30 ℃ with gas temperature.
2, the manufacture method of acrylic polymer according to claim 1 is characterized in that: near the drying gas temperature the above-mentioned moisture eliminator inlet portion is for being lower than 190 ℃.
3, the manufacture method of propylene series copolymer according to claim 2 is characterized in that: near the drying gas temperature the above-mentioned moisture eliminator inlet portion is 140 ℃-190 ℃.
4, the manufacture method of propylene series copolymer according to claim 1 is characterized in that: near the temperature the export department of above-mentioned moisture eliminator is that the minimum film-forming temperature that is lower than above-mentioned emulsion polymerization latex adds 20 ℃ temperature.
5, the manufacture method of acrylic polymer according to claim 1 is characterized in that: the minimum film-forming temperature of above-mentioned latex is more than 20 ℃.
6, the manufacture method of acrylic polymer according to claim 5 is characterized in that: the minimum film-forming temperature of above-mentioned latex is more than 50 ℃.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP149069/00 | 2000-05-19 | ||
| JP149069/2000 | 2000-05-19 | ||
| JP2000149069A JP2001329067A (en) | 2000-05-19 | 2000-05-19 | Manufacturing method of acrylic polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1429244A true CN1429244A (en) | 2003-07-09 |
| CN100341924C CN100341924C (en) | 2007-10-10 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB018096816A Expired - Lifetime CN100341924C (en) | 2000-05-19 | 2001-05-18 | Process for producing acrylic polymer |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP2001329067A (en) |
| CN (1) | CN100341924C (en) |
| WO (1) | WO2001088021A1 (en) |
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| CN1235948C (en) * | 2001-05-17 | 2006-01-11 | 三菱丽阳株式会社 | Method for mfg. polymer particles |
| JP3621396B2 (en) * | 2002-10-18 | 2005-02-16 | 三菱レイヨン株式会社 | Polymer latex spray drying equipment |
| CN100357006C (en) * | 2002-11-29 | 2007-12-26 | 三菱丽阳株式会社 | Process for reclaiming polymer |
| JP4964466B2 (en) * | 2003-09-26 | 2012-06-27 | 三井化学株式会社 | Spherical composite composition and method for producing spherical composite composition |
| EP1724299B1 (en) * | 2004-02-16 | 2011-05-18 | Mitsubishi Rayon Co., Ltd. | Modifier for resin and resin composition using the same and formed article |
| KR101306804B1 (en) * | 2008-11-18 | 2013-09-10 | 에스케이플래닛 주식회사 | A electronic paper particle and method for manufacturing thereof |
| BR112013021510B1 (en) * | 2011-02-28 | 2020-09-24 | Basf Se | PROCESS FOR THE PRODUCTION OF POWDER COATING COMPOSITIONS AND THE USE OF A POLYMER POWDER |
| US8865250B2 (en) * | 2011-02-28 | 2014-10-21 | Basf Se | Production of pulverulent coating compositions for stable protective coatings for pharmaceutical dosage forms |
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| DE3702997A1 (en) * | 1987-02-02 | 1988-08-11 | Roehm Gmbh | METHOD FOR PRODUCING A REDISPERGABLE PLASTIC POWDER |
| DE3807543A1 (en) * | 1988-03-08 | 1989-09-21 | Roehm Gmbh | METHOD FOR PRODUCING SPRAY-DRYED EMULSION POLYMERISATES |
| JPH04145131A (en) * | 1990-10-04 | 1992-05-19 | Japan Synthetic Rubber Co Ltd | Production of hollow polymer particle |
| KR0159947B1 (en) * | 1991-03-12 | 1998-11-16 | 마사아키 오카와라 | Two-fluid pressure nozzle of upward injection type spray dryer using the nozzle and method for control of droplet diameter in the nozzle |
| CN1035238C (en) * | 1992-08-20 | 1997-06-25 | 大川原化工机株式会社 | Prilling apparatus with atomizing drying units |
| DE4320220A1 (en) * | 1993-06-18 | 1994-12-22 | Basf Ag | Use of polymers I which contain copolymerized special monoethylenically unsaturated sulfonic acids as auxiliaries in the spray drying of aqueous dispersions of polymers II |
| JPH08134224A (en) * | 1994-11-15 | 1996-05-28 | Mitsubishi Rayon Co Ltd | Redispersible resin |
| JPH08231729A (en) * | 1995-02-22 | 1996-09-10 | Mitsubishi Rayon Co Ltd | Production of re-dispersible resin and same obtained by it |
-
2000
- 2000-05-19 JP JP2000149069A patent/JP2001329067A/en active Pending
-
2001
- 2001-05-18 CN CNB018096816A patent/CN100341924C/en not_active Expired - Lifetime
- 2001-05-18 WO PCT/JP2001/004153 patent/WO2001088021A1/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| WO2001088021A1 (en) | 2001-11-22 |
| JP2001329067A (en) | 2001-11-27 |
| CN100341924C (en) | 2007-10-10 |
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