CN1530383A - Solid phase polymerization method of polymer - Google Patents
Solid phase polymerization method of polymer Download PDFInfo
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- CN1530383A CN1530383A CNA2004100302328A CN200410030232A CN1530383A CN 1530383 A CN1530383 A CN 1530383A CN A2004100302328 A CNA2004100302328 A CN A2004100302328A CN 200410030232 A CN200410030232 A CN 200410030232A CN 1530383 A CN1530383 A CN 1530383A
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- hot gas
- air channel
- phase polymerization
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Abstract
To provide a solid polymerization method by which a polymer having homogeneous stable quality is obtained in good productivity. The solid polymerization method by heating the powdery polymer by using a hot air-circulating type heating furnace comprises heating the powdery polymer while alternately reversing the direction of the hot air, heating the powdery polymer by using the hot air-circulating type heating furnace having another hot air duct installed in the outside of a hot air duct in which the powdery polymer is left to stand still, or using a separate hot air-circulating type heating furnace having an air duct for cooling, arranged at the periphery of a hot air duct, and cooling the polymer obtained by heating by blowing air into the duct for cooling. (C)2004,JPO&NCIPI.
Description
Technical field
The present invention relates to the method for solid phase polymerization of polymkeric substance.More specifically, the present invention relates to the method for solid phase polymerization of the polymkeric substance of use heat gas circulation type stove.
Background technology
The method of the solid state polymerization by the polyethylene terephthalate, polybutylene terephthalate or the liquid-crystal polyester resin that heat in rare gas element is known, and is rotary drum pattern, fluid bed mode and stirs groove (paddle) pattern as the known pattern that obtains the quality homogeneous polymer.
In addition, same known method places pallet with polymkeric substance in addition, and pallet is inserted in the stove, heats the static polymkeric substance of parking under the state, carries out the method for solid state polymerization.Although these methods provide the quality homogeneous polymer, productivity reduces.A kind of method of solid state polymerization is carried out (JP 05-287080 A) in the pallet of heat transfer unit (HTU) is housed.
Yet, rotary drum pattern, fluid bed mode and stir the apparatus structure complexity of trough pattern, cost an arm and a leg, in addition, polymkeric substance remains in this device easily, and changing product kind time-like, can not avoid the pollution of the low amounts of product of manufacturing in service last time, need unpick and wash with thorough cleaning, thereby need a large amount of manpowers.
In addition, polymkeric substance is placed pallet, pallet is inserted in the stove, in the static method of carrying out solid-phase polymerization under the state of parking, when in solid-phase polymerization with a large amount of pallets are static when being placed in the Large Furnace, can obtain the polymkeric substance that quality changes with tray position, even and pallet heat transfer plate is housed, also be not enough to reduce mass discrepancy.
Summary of the invention
The inventor is in order to overcome the problems referred to above, and produce all even stable polymer of the quality with good productivity, carried out a large amount of research, and final the discovery, carry out solid-phase polymerization by the direction that alternately changes hot gas, and the direction of hot gas is a constant in traditional method, reduced temperature distribution, even be parked in the Large Furnace a large amount of pallets are static, also can obtain all even stable polymer of quality, by hot gas air channel outside outside the hot gas air channel, further providing with the heated polymerizable thing, can further suppress temperature distribution, obtain the more all even stable polymer of quality, and, can increase the feeding quantity of each pallet owing to quality of stability, by the cooling air channel that provides around the hot gas air channel is provided, can shorten process of cooling, finally significantly improve productivity, thereby finish the present invention.
In other words, the invention provides the method by the solid-phase polymerization of the polymkeric substance that heats in hot gas circular form stove, wherein polymkeric substance heats by the flow direction that alternately changes hot gas.
The accompanying drawing summary
Fig. 1 is the diagrammatic cross-section of used hot gas circular form stove in the traditional method.
Fig. 2 is the diagrammatic cross-section that is used for the example of hot gas circular form stove of the present invention.(explanation of mark)
1: pallet
2: trailer
3: air-circulating fan
4: well heater
5: temperature sensor
6: the hot gas air channel
7: outer hot gas air channel
8: cooling air channel
9: thermally-insulated body
10: door
11: cooling air intake
12: the cooling air outlet
13: water cooler
14: refrigerant inlet
Specific embodiments
Below will describe the present invention in detail.
Be used for not restriction especially of polymkeric substance of the present invention, can comprise for example polyester, polymeric amide, polyamidoimide, polyimide, polyphenylene sulfide.Polyester preferably wherein.
The example of polyester comprises: such as phenyl ester between polyethylene terephthalate, polybutylene terephthalate, poly terephthalic acid, poly-m-phthalic acid to phenyl ester, poly terephthalic acid-1, the polyester of 4-hexanaphthene dimethyl ester etc.; The polyester that obtains by for example aromatics hydroxyl carboxylic acid of P-hydroxybenzoic acid, 2-hydroxyl-6-naphthoic acid etc.; In addition, by above listed compound with such as terephthalic acid, m-phthalic acid, 2, the aromatic dicarboxylic acid of 6-naphthalic acid etc. and such as quinhydrones, Resorcinol, 4,4 '-dihydroxybiphenyl, 2, the liquid crystal polyester that the aromatic hydroxy compound of 6-dihydroxy naphthalene etc. obtains.
Be used for the form that polymkeric substance of the present invention can be powder or pellet, and median size is generally powder or the pellet of the about 10mm of about 0.05-.
Fig. 1 is the diagrammatic cross-section of used hot gas circular form stove in the traditional method.(A) being longitudinally sectional view, is along horizontal sectional view (B).After opening door (10), push in the hot gas circular form stove being loaded with the trailer (2) that contains the pallet (1) that will carry out the polymkeric substance of solid-phase polymerization, and the static hot gas air channel (6) that places.Provide electric heater (4), temperature sensor (5), air-circulating fan (3) and cooling with water cooler (13) on top, cover thermally-insulated body (9) on every side.
When the size of hot gas circular form stove hour, obtain the polymkeric substance of little inhomogeneous quality, and when the many big pallet of static placement, the ununiformity of polymer quality is not fully suppressed.
On the contrary, Fig. 2 is the diagrammatic cross-section that is used for the example of hot gas circular form stove of the present invention.(A) being longitudinally sectional view, is along horizontal sectional view (B).After opening door (10), the trailer (2) that is loaded with the pallet (1) that contains polymkeric substance is pushed in the hot gas circular form stove, and the static hot gas air channel that places.The temperature sensor (5) and the air-circulating fan (3) of electric heater (4), well heater front and back are provided on top.Provide another hot gas air channel (7) at outside, the hot gas air channel (6) of static placement polymkeric substance (among this figure about part and bottom).The entrance and exit of the hot gas in this hot gas air channel (7) is connected with the hot gas air channel (6) of static placement polymkeric substance, yet hot gas air channel (7) are spaced, and does not allow hot gas to flow out and enters.In addition, provide cooling air channel (8) on every side in the hot gas air channel, and cooling air channel is not connected with the hot gas air channel.Cover with lagging material (9) around this cooling air channel.In cooling, air is blown into by cooling air intake (11), and discharges from cooling air outlet (12).
For pallet is placed stove, can adopt the fixed shelf, yet, from the viewpoint of operability and productivity, preferably use 1-10 the trailer that can carry about 20-200 pallet, make the pallet can disposable taking-up and put into.
The present invention is for quantity, the pallet shape of stove interpolymer, and the not concrete qualification of the shape of trailer shelf layer.
Wanting the industrial consumption of polymeric polymkeric substance in single job is the about 3000kg of about 200-.Preferred polymer loading is the about 1-10kg of each pallet, and the preferred thickness of powder is about 10-200mm on the pallet, when adding powder, does not preferably produce the temperature difference between pallet inside and surface.
Can adopt electric heater or heating agent heater heats.Preferably use electric heater,, and reduced equipment cost because this moment need be such as the device of heating agent coil pipe etc.
The heating of polymkeric substance is undertaken by the direction that alternately changes hot gas.Be about 10-60 minute the pitch time of conversion, preferably about 20-40 minute.When conversion need be carried out with the constant interval time, just change usually with the constant interval time.
After the conversion of the flow direction of hot gas, make the heat output of well heater keep constant immediately, and do not change with output before the conversion.The stage of constant output is generally about 5-10 minute.Because have the temperature difference between the hot gas before and after the well heater, if do not change under this condition, the output of well heater will obviously increase, it is unstable that temperature control can become.For fear of this problem, the output before the conversion is kept constant, after conversion, reach approximate design temperature up to the temperature of controlled temperature sensor.By this measure,, also can obtain the hot gas of approximately constant temperature even the direction of hot gas is changed.
According to the difference of type of polymer etc., the heating of polymkeric substance is carried out a few hours usually by tens of hours after with the nitrogen purging furnace air.
Cool off after having heated.In order to cool off, air is blown in the cooling air channel on every side of hot gas air channel.Under situation by the heating agent heating, can adopt heating agent is changed into refrigerant and carries out the refrigerative method, more effective is that air is blown in the cooling air channel.By refrigerant is used in combination with blowing, can further shorten cooling time.
The air purge process furnace is used in the cooling back, takes out the polymkeric substance with solid state polymerization then.
Embodiment
Below will list embodiments of the invention, but not limit the scope of the invention.Physicals among the embodiment is measured according to following method.
(1) yield temperature
This temperature is when melt viscosity is 48000 pools, nozzle by internal diameter 1mm, length 10mm, when under the pressure of 10MPa, extruding the resin with the heating of 4 ℃/minute temperature rise rate, the temperature that the CFT-500 type modified version flowing test instrument made from Shimadzu Corp. is measured.When this temperature was low, resin flow was bigger.
(2) anti-scolder whipability
To under the fixed temperature, soaked 60 seconds in the H60A scolder (tin 60%, plumbous 40%) of the small sample (thickness 1.2mm) that JIS K7113 1 (1/2) is shaped, measure the temperature when in moulded parts, observing bubble (foaming).When this temperature was higher, the thermotolerance of resin was better.Reference example (preparation of liquid crystal polyester)
With 1304kg (7238mol) p-acetoxybenzoic acid, 651kg (2408mol) 4,4 '-acetoxyl biphenyl, 300kg (1806mol) terephthalic acid and 100kg (602mol) m-phthalic acid join in the SUS316L polymerization reaction chamber of the 3m3 that has oar type agitator, begin to stir.Subsequently under nitrogen atmosphere with 1 ℃/minute speed with mixture heating up to 300 ℃, remove byproduct acetate simultaneously, and under 300 ℃, keep 60 minutes again.After this seal polymerization reaction chamber, under with the condition of nitrogen with the 0.1MPa pressurization, by the belt cooler cooling, thus extracting resin.The output of this reaction product is 1600kg, productive rate 98%.With its median size that is ground to about 0.4mm, obtain yield temperature and be total aromatic polyester (hereinafter referred to as " prepolymer ") of 250 ℃.
With the degree of crystallinity of polarizing microscope measurement gained prepolymer, with the formation of the anisotropic fusion phase of viewing optics.
Carry out the solid-phase polymerization of prepolymer with above-mentioned hot gas circular form stove (hereinafter referred to as novel stove) shown in Figure 2.The prepolymer of each 6.2kg of obtaining in the reference example is packed in the aluminium pallet, 52 this pallets are placed on the trailer, 3 trailers are pushed in the stove.With nitrogen with 1Nm
3/ minute purging process furnace 25 minutes heats up until 250 ℃ with 3.8 ℃/minute mean rate then, with 0.14 ℃/minute mean rate from 250 ℃ of intensifications until 280 ℃, and under 280 ℃, keeping again 300 minutes under the identical nitrogen gas stream.Begin to cool down from beginning to warm to, the sense of rotation of air-circulating fan was changed once in per 30 minutes, with the direction of transition heat gas.After this in cooling air channel, be blown into air, be cooled to 150 ℃, use the air purge furnace atmosphere then, take out the goods (hereinafter referred to as " prepolymer ") of solid state polymerization.
From near the pallet of the highest section the furnace bottom and lowest segment, and near the pallet of fire door the highest section and lowest segment to the prepolymer sampling, and the yield temperature of measuring prepolymer in the stove distributes.All residue prepolymers are mixed.With Asahi Glass Co., the abrading glass (REV-8) that Ltd. makes mixes in the mixed prepolymer with the amount of 40wt% and is mixed, use then twin screw extruder (PCM-30, Ikegai TekkoK.K. makes) under 390 ℃ with mixture pelleting.The PS40E5ASE type injector made from Nissei Jushi Kogyo K.K. under the metal molding temperature of 400 ℃ barrel zone temperatures and 130 ℃, with the injection moulding of gained particle, and is estimated anti-scolder whipability.The results are shown in table 1.
Undertaken by the method identical, just respectively adorn the 7.5kg prepolymer in the aluminium pallet with embodiment 1.The results are shown in table 1.
Comparative example 1
Undertaken by the method identical with embodiment 1, different is to adopt above-mentioned traditional hot gas circular form stove (hereinafter referred to as " traditional burner ") shown in Figure 1, and heat with constant direction, and the direction of transition heat gas is not cooled off by pass to refrigeration agent in water cooler.The results are shown in table 1.
Comparative example 2
Undertaken by the method identical with embodiment 1, the direction of different is hot gas is not changed and is kept constant.The results are shown in table 1.
Table 1
| Embodiment | Comparative example | ||||
| ????1 | ????2 | ??1 | ??2 | ||
| The type of hot gas circular form stove | Novel stove | Novel stove | Traditional burner | Novel stove | |
| The direction of hot gas | Conversion | Conversion | A direction | A direction | |
| Feeding quantity | The Kg/ dish | ????6.2 | ????7.5 | ??6.2 | ??6.2 |
| The Kg/ stove | ????967 | ????1170 | ??967 | ??967 | |
| Output | The Kg/ stove | ????956 | ????1158 | ??956 | ??956 |
| Treatment time (minute) | Charging is replaced | ????55 | ????55 | ??55 | ??55 |
| Heat up | ????580 | ????580 | ??580 | ??580 | |
| Cooling | ????90 | ????90 | ??120 | ??90 | |
| Air purge | ????10 | ????10 | ??10 | ??10 | |
| Get material | ????30 | ????30 | ??30 | ??30 | |
| Add up to | ????765 | ????765 | ??795 | ??765 | |
| Productivity | Ton/sky | ????1.80 | ????2.18 | ??1.73 | ??1.80 |
| The yield temperature distribution (℃) | The high section in bottom | ????327 | ????327 | ??328 | ??328 |
| The low section in bottom | ????327 | ????326 | ??326 | ??326 | |
| High section of nearly door | ????326 | ????324 | ??322 | ??324 | |
| The low section of nearly door | ????325 | ????324 | ??320 | ??323 | |
| The temperature difference | ????2 | ????3 | ??8 | ??5 | |
| Anti-scolder whipability | ??(℃) | ????320 | ????320 | ??290 | ??300 |
In the contrast of embodiment 1 and comparative example 1, the distribution of the yield temperature of prepolymer is improved to 2 ℃ from 8 ℃, and anti-scolder whipability also is significantly improved under the same treatment amount.Equally under the situation of the embodiment 2 that treatment capacity increases, anti-scolder whipability is suitable with embodiment 1, yield temperature be distributed as 3 ℃, this is more much better than traditional method.
Comparative example 2 has shown the influence that hot gas is not changed.Because the influence in air channel, yield temperature distribute and anti-scolder whipability all the traditional method than comparative example 1 is good, yet with the situation of the hot gas conversion of embodiment 1 relatively, the degree that embodiment 2 improves is deficiency still.
Consider the influence of cooling air channel, shown in embodiment 1 and comparative example 1, shortened to 90 minute from 120 minutes cooling time.
According to the present invention, compare with traditional method, temperature distribution reduces in the stove, but the workmanship stable polymer, and obtain good productivity.
Claims (5)
1, the method for solid phase polymerization of polymkeric substance, it is by heating in hot gas circular form stove, and wherein polymkeric substance heats by replacing the transition heat gas flow direction.
2, according to the method for solid phase polymerization of claim 1, wherein conversion interval is about 60 minutes of about 10-.
3, according to the method for solid phase polymerization of claim 1, wherein after the conversion of hot gas flow direction, make at once well heater add thermal output keep with conversion before constant.
4, according to the method for solid phase polymerization of claim 1, hot gas air channel outside wherein hot gas circular form stove has outside comprising the hot gas air channel of the powdery polymer that is placed in one.
5, according to the method for solid phase polymerization of claim 1, wherein hot gas circular form stove has cooling air channel on every side in the hot gas air channel, after the heating air is blown into cooling air channel with cooling polymer.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14542/2003 | 2003-01-23 | ||
| JP14542/03 | 2003-01-23 | ||
| JP2003014542A JP3690390B2 (en) | 2003-01-23 | 2003-01-23 | Solid phase polymerization method of powdery polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1530383A true CN1530383A (en) | 2004-09-22 |
| CN100344673C CN100344673C (en) | 2007-10-24 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100302328A Expired - Fee Related CN100344673C (en) | 2003-01-23 | 2004-01-21 | Solid phase polymerization method of polymer |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP3690390B2 (en) |
| CN (1) | CN100344673C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5726610B2 (en) * | 2011-04-15 | 2015-06-03 | Ｊｘ日鉱日石エネルギー株式会社 | Method for producing liquid crystalline polyester |
| JP6309778B2 (en) * | 2014-02-12 | 2018-04-11 | ユニチカ株式会社 | Polyamideimide production method and polyamideimide |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1063196C (en) * | 1996-02-09 | 2001-03-14 | 中国纺织大学 | Preparing method for super high molecular weight polyester |
| JP4320800B2 (en) * | 1998-07-06 | 2009-08-26 | 東レ株式会社 | Method and apparatus for continuous processing of thermoplastic materials |
| US6235390B1 (en) * | 1998-11-03 | 2001-05-22 | E. I. Du Pont De Nemours And Company | High RV filaments, and apparatus and processes for making high RV flake and the filaments |
| JP3418915B2 (en) * | 1999-02-01 | 2003-06-23 | 株式会社大阪冷研 | Method for producing polyethylene terephthalate resin for bottles from recovered PET bottles by solid state polymerization |
-
2003
- 2003-01-23 JP JP2003014542A patent/JP3690390B2/en not_active Expired - Fee Related
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2004
- 2004-01-21 CN CNB2004100302328A patent/CN100344673C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2004224913A (en) | 2004-08-12 |
| CN100344673C (en) | 2007-10-24 |
| JP3690390B2 (en) | 2005-08-31 |
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Granted publication date: 20071024 Termination date: 20180121 |