CN1534053A - Solid phase polymerizing method of powdery polymer - Google Patents
Solid phase polymerizing method of powdery polymer Download PDFInfo
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- CN1534053A CN1534053A CNA2004100399889A CN200410039988A CN1534053A CN 1534053 A CN1534053 A CN 1534053A CN A2004100399889 A CNA2004100399889 A CN A2004100399889A CN 200410039988 A CN200410039988 A CN 200410039988A CN 1534053 A CN1534053 A CN 1534053A
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- polymkeric substance
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Abstract
The method for polymerizing a powdery polymer such as a polyester, polyamide, polyamideimide and polyphenylene sulfide in a solid phase by heating with a hot-air circulation-type furnace, comprises the steps of thermally fusing a part of the powdery polymer by adjusting the temperature of the hot air in the range from a temperature lower than the fluidizing temperature by 10[deg.]C to a temperature higher than that by 20[deg.]C, and then heat the polymer with hot air increased in velocity.
Description
[technical field]
The present invention relates to the solid phase polymerization method of powder shaped polymkeric substance, the more detailed method that relates to the solid state polymerization that uses hot air circulation type stove of saying.
[background technology]
People have known the method that in rare gas element polyethylene terephthalate, polybutylene terephthalate or liquid crystalline polyester resin carry out solid state polymerization, and in order to reduce the deviation of polymer quality, the crowd knows rotary drum mode, fluidized-bed mode or oar formula.Yet complex structure that these modes are not only installed and price height, and the inner easy residual goods of device are unavoidably sneaked into a spot of preceding kind when switching kind, in addition, and for thorough cleaning must be cleaned labour that need be very big in dismounting.
In addition, know also polymkeric substance put into the disc type charging tray that these materials are stacked into column plate insert in the process furnace, polymer powder under static state carries out the method (for example, with reference to Patent Document 1) of solid state polymerization.
[Patent Document 1]
Specially permit communique No. 3087430
Yet, the powder shaped polymkeric substance is added on the charging tray, insert the method for carrying out solid state polymerization in the process furnace, though be that apparatus structure is fairly simple, switch the good method of kind etc. easily, the powder polymkeric substance disperses when improving the wind speed between charging tray, lose from the unrestrained back of charging tray, this polymkeric substance produces thermal ageing simultaneously, secondly, sneaks into the problem in next batch of material.And the temperature distribution in the stove becomes big when reducing wind speed, the problem that has the quality of solid state polymerization resulting product to reduce.
[summary of the invention]
Present inventors are in order to solve such problem, for workmanship expeditiously evenly and stable polymer, Yan Jiu result repeatedly, discovery is by after making the thermal welding of powder shaped polymer moieties, the speed that improves hot blast heats, polymkeric substance can not disperse and improve wind speed between charging tray, and the temperature distribution in the stove can be little as a result, can obtain quality evenly and stable polymer, in addition, because temperature distribution diminishes, the feeding quantity of each charging tray is increased, thereby finished the present invention.
Be that the present invention is the method for solid phase polymerization of powder polymkeric substance, it is characterized in that the speed that improves hot blast heats after using hot air circulation type stove heating powder shaped polymkeric substance to carry out in the method for solid state polymerization, making the thermal welding of powder shaped polymer moieties.
It is even that method of the present invention obtains quality, and the thermal ageing polymkeric substance is sneaked into the method for few solid state polymerization polymkeric substance, provides the good method for solid phase polymerization of industrial high efficiency production.
Below, explain the present invention.
The polymkeric substance that uses as the present invention does not have particular determination, for example, can enumerate polyester, polymeric amide, polyamidoimide, polyimide, polyphenylene sulfide etc., wherein preferably uses polyester.
Here, polyester, for example, can enumerate polybutylene terephthalate, phenyl ester between poly terephthalic acid, poly-m-phthalic acid is to phenyl ester, poly terephthalic acid-1, the polyester of 4-hexanaphthene dimethyl ester etc., the polyester that makes by the aromatic hydroxy-carboxylic of right-hydroxy-benzoic acid or 2-hydroxyl-6-naphthoic acid etc., in addition, also have these and terephthalic acid, m-phthalic acid, 2, the aromatic dicarboxylic acid and the Resorcinol of 6-naphthalene dicarboxylic acids etc., Resorcinol, 4,4 '-dihydroxybiphenyl, 2, the liquid crystalline polyester that the aromatic hydroxy compound of 6-dihydroxy naphthlene etc. makes etc.
In addition, the polymer powder that the present invention uses does not have particular restriction to particle diameter, uses the polymer powder about median size 0.05-5mm usually.
[description of drawings]
Fig. 1 is the sectional view of the column plate type hot air circulation type stove of pattern the present invention use.
Fig. 2 represents the hot blast temperature among the embodiment and the graphic representation of polymer flow temperature.
[nomenclature]
1: charging tray, 2: chassis, 3: recirculation blower, 4: temperature sensor, 5: heat-carrier inlet, 6 is used in heating: heat-carrier inlet, 7 is used in cooling: heat exchanger, 8: thermal insulation material, 9: door, 10: hot blast wind-tunnel.
Fig. 1 is the sectional view of the column plate type hot air circulation type stove among the expression the present invention of pattern ground.(A) be that sectional view, (B) are view in transverse section longitudinally.The chassis (2) that is loading the charging tray (1) that is added with the powder shaped polymkeric substance is opened door (9) and is admitted in the hot air circulation type stove, leaves standstill in hot blast wind-tunnel (10).Top is if with the heat exchanger (7) of thermal barrier, temperature sensor (4) and recirculation blower (3), use thermal insulation material (8) to cover on every side.Heat exchanger is provided with heating and uses heat-carrier inlet (6) with heat-carrier inlet (5) and cooling, according to intensification, cooling each inlet is switched.
The shape of column plate does not have particular restriction, and from operation, the production efficiency aspect considers that preferred use can load the about 20-200 of charging tray about 10 of the right chassis 1-that faces left, the mode that concentrated taking-up is put into.Industrial in hot blast circular form stove the about each time 200-3 of charging, 000kg.
In addition, the thickness of powder shaped polymkeric substance is 10-200mm on the about 1-10kg of inlet amount of the powder shaped polymkeric substance of per 1 charging tray, the charging tray, and preferred feedstock makes charging tray inside temperature head not occur with the surface.
Be added with in the hot air circulation type stove of powder shaped polymkeric substance and carry out nitrogen replacement, the limit makes flow of nitrogen gas limit heating carrying out solid state polymerization.The speed of initial inhibition hot blast is low, prevents dispersing of powder shaped polymkeric substance.After heating powder shaped polymkeric substance makes the thermal welding of powder shaped polymer moieties, improve the speed of hot blast, the temperature distribution of dwindling in the stove heats.Therefore, loss and pollution that the powder shaped polymkeric substance disperses and causes polymkeric substance can be prevented, quality can be obtained simultaneously evenly and stable polymer.
The portion of hot welding of powder shaped polymkeric substance is carried out under the temperature of 20 ℃ of the temperature-Gao of low 10 ℃ of the yield temperature of the temperature ratio copolymer that makes hot blast.The yield temperature of polymkeric substance is different according to the polymerization degree of polymkeric substance, utilize heating curve figure to obtain the yield temperature of polymkeric substance, the temperature of hot blast is set made it to become the said temperature scope in advance, the portion of hot welding was insufficient when the temperature of hot blast was too lower than yield temperature, the undue welding of polymkeric substance when too high and bad.The temperature of hot blast for example uses the temperature sensor (4) of Fig. 1 to measure among the present invention.
The speed of hot blast, the speed between charging tray, to make the thermal welding of powder shaped polymer moieties (till) preferred about 0.5-2m/ second, make preferred about 3-8m/ second after the thermal welding of powder shaped polymer moieties.Usually, the pass of the speed of measuring in advance with velocimeter and the rotating speed of recirculation blower is the basis, and the rotating speed of regulating recirculation blower carries out the setting of the hot blast speed between charging tray.
Though depending on resin forms, but usually the hot blast speed between charging tray is about 0.5-2m/ second, make hot blast temperature than the temperature range heating of 20 ℃ of the temperature-Gao of low 10 ℃ of the yield temperature of polymkeric substance about 3-4 hour, after reaching about 270-290 ℃, hot blast speed between charging tray is about 3-8m/ second, and still polymerization was carried out in heating in about 4-6 hour under this certain hot blast temperature.
Utilize Fig. 2 to describe particularly.Fig. 2 represents the hot blast temperature among the embodiment and the graphic representation of polymer flow temperature.Make hot blast temperature be raised to 250 ℃ from 150 ℃ by average 3.8 ℃/minute, be raised to 280 ℃ from 250 ℃, keep certain at 280 ℃ then by average 0.135 ℃/minute.The polymer flow temperature, identical therewith is the value that adds heat determination in addition according to the hot blast temperature graphic representation.Polymerization was carried out in the heating back in about 30-240 minute, the polymer flow temperature rises simultaneously.Heat up and to make hot blast temperature become temperature than 20 ℃ of the temperature-Gao of low 10 ℃ of polymer flow temperature.Be difficult to disperse after the polymkeric substance thermal welding during this time, the speed of the hot blast that raises then heats.
Heating means can be used electric heater, also can use thermal fluid heater, variation to hot blast speed does not have particular restriction yet, the general method that adopts frequency transformer, pole changer the motor of recirculation blower to be carried out speed change, externally establish the method for mechanical transmission, utilize the variable wind shelves to regulate the method for air quantity.
[embodiment]
Below, enumerate embodiments of the invention, but the present invention is not limited by these.In addition, each rerum natura among the embodiment is the value that adopts following method to measure.
(1) yield temperature
Yield temperature is to use the high-order formula flow test machine CFT-500 type of Shimadzu Seisakusho Ltd.'s system.Adopt 4 ℃/minute the heat-up rate heating resin under the 10MPa pressure when the nozzle of internal diameter 1mm, long 10mm is extruded, melt viscosity shows the temperature in 48, the 000 pool moment.This temperature low flow more is big more.
(2) anti-scolding tin whipability
JIS K7113 1 (1/2) model reduced specimen (thick 1.2mm) was flooded for 60 seconds in the H60 of design temperature A scolding tin (tin 60%, plumbous 40%), measure the moulding product and go up the blistered temperature of appearance.Temperature is high more to show that the thermotolerance of resin is good more.
Reference example
(manufacturing of liquid crystal polyester)
P-acetoxy-benzoic acid 1,304kg (7,238 moles), 4,4 '-diacetoxy biphenyl 651kg (2,408 moles), terephthalic acid 300kg (1,806 mole), m-phthalic acid 100kg (602 moles) are added to the 3m that has paddle stirrer
3The polymeric kettle of SUS 316L system in.
Under nitrogen environment atmosphere, adopt 1 ℃/minute speed.The acetic acid limit that by-product was stirred, removed on the limit is warmed up to 300 ℃ from 180 ℃, keeps 60 minutes at 300 ℃ again.Then, airtight polymeric kettle, with nitrogen pressure under the state of 0.1MPa, the limit is extracted with the belt cooler limit.The output of this reactant is 1, and the 600kg yield is 98%.Product is ground into median size 0.4mm.Make the Wholly aromatic polyester (to call prepolymer in the following text) of 250 ℃ of yield temperatures.With polarizing microscope the resin of gained is measured liquid crystal liquid crystal property, result's judgement is formed with optically anisotropic fusion phase.
Embodiment 1
The column plate type hot air circulation type stove that uses Fig. 2 to represent advances the solid state polymerization of prepolymer.In the charging tray of aluminum, respectively fill the prepolymer 6.2kg that the above-mentioned reference example makes, on chassis, load 52 these charging trays of dish, 3 chassis are added in the hot air circulation type stove.Press 1Nm to hot blast circular form stove
3/ component blowed nitrogen replacement after 25 minutes.Blow nitrogen equally and hot blast is raised to 250 ℃ from 150 ℃, hot blast is raised to 280 ℃ from 250 ℃, kept 300 minutes at 280 ℃ again by about 0.14 ℃/minute heat-up rate by average 3.8 ℃ of/minute intensification speed.Begin to 280 ℃ from intensification, regulating the recirculation blower rotating speed, to make the wind speed between charging tray be 1.5m/ second, and making this wind speed after arriving 280 ℃ is 4m/ second.Then, thermal barrier is switched to cold side and be cooled to 150 ℃.Then, carry out the taking-up of solid polymer (to call the high-quality polymkeric substance in the following text) with behind the air displacement furnace interior.Taken a sample by the epimere of the epimere in the stove, hypomere and reveal, hypomere, the yield temperature of measuring high-quality polymkeric substance in the stove distributes, and remaining high-quality polymkeric substance is all carried out blending.High-quality polymkeric substance to blending cooperates Asahi Glass system milled glass (REV-8) 40 weight %, mixes the back and uses twin screw extruder (pond shellfish ironworker corporate system PCM-30), carries out granulation at 390 ℃.Use day smart resin system PS40E5ASE of an industrial type injection moulding machine, under 400 ℃ of barrel temperatures, 130 ℃ of conditions of die temperature, the pellet of gained is carried out injection molding, estimate anti-scolding tin whipability.Evaluation result is shown in table 1.
Embodiment 2
Except respectively fill prepolymer 7.5kg in the aluminum charging tray, other carry out similarly to Example 1.Evaluation result is shown in table 1.
Comparative example 1
Except not changing the rotating speed of recirculation blower, make 280 ℃ after, the wind speed between charging tray still is 1.5m/ beyond second, other carry out similarly to Example 1.Evaluation result is shown in table 1.
Comparative example 2
Except the rotating speed of setting recirculation blower makes wind speed between the beginning charging tray is 4.0m/ second, and other carry out similarly to Example 1.Evaluation result is shown in table 1.
Table 1
| Embodiment 1 | Embodiment 2 | Comparative example 1 | Comparative example 2 | ||
| A charging tray-wind speed (m/ second) | ～280℃ | 1.5 | ?1.5 | ?1.5 | ?4.0 |
| 280℃～ | 4.0 | ?4.0 | ?1.5 | ?4.0 | |
| Inlet amount | The kg/ charging tray | 6.2 | ?7.5 | ?6.2 | ?6.2 |
| The kg/ stove | 967 | ?1,170 | ?967 | ?967 | |
| Output | The kg/ stove | 956 | ?1,158 | ?956 | ?935 |
| Productive rate | ％ | 98.9 | ?99.0 | ?98.9 | ?96.7 |
| Treatment time (branch) | The charging displacement | 55 | ?55 | ?55 | ?55 |
| Heat up | 580 | ?580 | ?580 | ?580 | |
| | 120 | ?120 | ?120 | ?120 | |
| Air displacement | 10 | ?10 | ?10 | ?10 | |
| Take out | 30 | ?30 | ?30 | ?30 | |
| Add up to | 795 | ?795 | ?795 | ?795 | |
| Production efficiency | T/ day | 1.73 | ?2.10 | ?1.73 | ?1.69 |
| The yield temperature distribution (℃) | Epimere in the stove | 328 | ?328 | ?328 | ?328 |
| Hypomere in the stove | 327 | ?326 | ?326 | ?326 | |
| The reveal epimere | 326 | ?323 | ?322 | ?327 | |
| The reveal hypomere | 325 | ?322 | ?320 | ?325 | |
| Temperature head | 3 | ?6 | ?8 | ?3 | |
| Anti-scolding tin whipability | ℃ | 310 | ?300 | ?290 | ?310 |
The constant comparative example 1 of embodiment 1 that the back improves hot blast speed and intensification after heat wind speed degree that heats up is compared, and under the situation of same treatment amount, the yield temperature of high-quality polymkeric substance distributes from 8 ℃ and is raised to 3 ℃, and anti-in addition scolding tin whipability also increases substantially.Even the situation current downflow temperature distribution that embodiment 2 treatment capacities increase also is 6 ℃, anti-scolding tin whipability also improves than the out-of-date methods of comparative example 1.Do not consider interparticle thermal welding on the other hand, from the occasion of the comparative example 2 that begins to improve hot blast speed at first, the whipability of temperature distribution and anti-scolding tin is good similarly to Example 1 result, but polymer powder disperses because of hot blast causes and produces about 2% loss.The polymkeric substance that is dispersed in the stove pollutes in addition, might sneak into to burn polymkeric substance in producing next batch of material, must remove the polymkeric substance that disperses by thorough cleaning.
Can make than little, the stay-in-grade polymkeric substance of temperature distribution in the method stove in the past on high efficiency ground according to the present invention.
Claims (6)
1. the method for solid phase polymerization of powder shaped polymkeric substance is characterized in that the speed that improves hot blast heats after using hot air circulation type stove heating powder shaped polymkeric substance to carry out in the method for solid state polymerization, making the thermal welding of powder shaped polymer moieties.
2. the described method of claim 1 is characterized in that hot air circulation type stove is the hot air circulation type stove of column plate type.
3. the described method of claim 1, the median size that it is characterized in that the powder shaped polymkeric substance is 0.05-5mm.
4. the described method of claim 1 is characterized in that the temperature of hot blast makes the thermal welding of powder shaped polymer moieties in the temperature range of hanging down 20 ℃ of 10 ℃-Gao than the yield temperature of polymkeric substance.
5. the described method of claim 1 is characterized in that making till the thermal welding of powder shaped body polymer moieties and thereafter hot blast speed, and the speed between charging tray is respectively 0.5-2m/ second and 3-8m/ second.
6. the described method of claim 1 is characterized in that the powder shaped polymkeric substance is selected from least a kind in polyester, polymeric amide, polyamidoimide, polyimide and the polyphenylene sulfide.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP80083/2003 | 2003-03-24 | ||
| JP2003080083A JP4085202B2 (en) | 2003-03-24 | 2003-03-24 | Solid phase polymerization method for powdered polymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1534053A true CN1534053A (en) | 2004-10-06 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2004100399889A Pending CN1534053A (en) | 2003-03-24 | 2004-03-22 | Solid phase polymerizing method of powdery polymer |
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| Country | Link |
|---|---|
| JP (1) | JP4085202B2 (en) |
| CN (1) | CN1534053A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107636044A (en) * | 2014-12-18 | 2018-01-26 | 罗地亚经营管理公司 | method for producing aromatic polyimide |
-
2003
- 2003-03-24 JP JP2003080083A patent/JP4085202B2/en not_active Expired - Fee Related
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2004
- 2004-03-22 CN CNA2004100399889A patent/CN1534053A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107636044A (en) * | 2014-12-18 | 2018-01-26 | 罗地亚经营管理公司 | method for producing aromatic polyimide |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4085202B2 (en) | 2008-05-14 |
| JP2004285247A (en) | 2004-10-14 |
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