CN116888188A - Polymer production system and polymer production method - Google Patents
Polymer production system and polymer production method Download PDFInfo
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- CN116888188A CN116888188A CN202280014130.3A CN202280014130A CN116888188A CN 116888188 A CN116888188 A CN 116888188A CN 202280014130 A CN202280014130 A CN 202280014130A CN 116888188 A CN116888188 A CN 116888188A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 150
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 113
- 239000012530 fluid Substances 0.000 claims abstract description 465
- 230000001603 reducing effect Effects 0.000 claims abstract description 313
- 238000002156 mixing Methods 0.000 claims abstract description 132
- 150000001875 compounds Chemical class 0.000 claims abstract description 57
- 230000002708 enhancing effect Effects 0.000 claims abstract description 3
- 229920005575 poly(amic acid) Polymers 0.000 claims description 52
- 238000006243 chemical reaction Methods 0.000 claims description 48
- 238000005259 measurement Methods 0.000 claims description 46
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 27
- 239000002253 acid Substances 0.000 claims description 26
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 15
- 238000005304 joining Methods 0.000 claims description 14
- 229920001721 polyimide Polymers 0.000 claims description 12
- 239000004642 Polyimide Substances 0.000 claims description 10
- 238000012644 addition polymerization Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 238000002835 absorbance Methods 0.000 claims description 6
- 230000014759 maintenance of location Effects 0.000 claims description 4
- 238000002441 X-ray diffraction Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 125000004427 diamine group Chemical group 0.000 claims 2
- 239000007788 liquid Substances 0.000 description 62
- 238000009826 distribution Methods 0.000 description 41
- 238000003756 stirring Methods 0.000 description 26
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 24
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- 239000002904 solvent Substances 0.000 description 18
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- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 2
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- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
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- 239000005456 alcohol based solvent Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- YKNMIGJJXKBHJE-UHFFFAOYSA-N (3-aminophenyl)-(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=CC(N)=C1 YKNMIGJJXKBHJE-UHFFFAOYSA-N 0.000 description 1
- LRMDXTVKVHKWEK-UHFFFAOYSA-N 1,2-diaminoanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=C(N)C(N)=CC=C3C(=O)C2=C1 LRMDXTVKVHKWEK-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- FBMQNRKSAWNXBT-UHFFFAOYSA-N 1,4-diaminoanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(N)=CC=C2N FBMQNRKSAWNXBT-UHFFFAOYSA-N 0.000 description 1
- RLYCRLGLCUXUPO-UHFFFAOYSA-N 2,6-diaminotoluene Chemical compound CC1=C(N)C=CC=C1N RLYCRLGLCUXUPO-UHFFFAOYSA-N 0.000 description 1
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 description 1
- OLQWMCSSZKNOLQ-UHFFFAOYSA-N 3-(2,5-dioxooxolan-3-yl)oxolane-2,5-dione Chemical compound O=C1OC(=O)CC1C1C(=O)OC(=O)C1 OLQWMCSSZKNOLQ-UHFFFAOYSA-N 0.000 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 1
- FUJGQJMITCJTFA-UHFFFAOYSA-N 3-[3-(2,3-dicarboxyphenoxy)phenoxy]phthalic acid Chemical compound OC(=O)C1=CC=CC(OC=2C=C(OC=3C(=C(C(O)=O)C=CC=3)C(O)=O)C=CC=2)=C1C(O)=O FUJGQJMITCJTFA-UHFFFAOYSA-N 0.000 description 1
- KHDSXXRHWXXXBY-UHFFFAOYSA-N 3-[4-(2,3-dicarboxyphenoxy)phenoxy]phthalic acid Chemical compound OC(=O)C1=CC=CC(OC=2C=CC(OC=3C(=C(C(O)=O)C=CC=3)C(O)=O)=CC=2)=C1C(O)=O KHDSXXRHWXXXBY-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- ZWQOXRDNGHWDBS-UHFFFAOYSA-N 4-(2-phenylphenoxy)aniline Chemical group C1=CC(N)=CC=C1OC1=CC=CC=C1C1=CC=CC=C1 ZWQOXRDNGHWDBS-UHFFFAOYSA-N 0.000 description 1
- KHYXYOGWAIYVBD-UHFFFAOYSA-N 4-(4-propylphenoxy)aniline Chemical compound C1=CC(CCC)=CC=C1OC1=CC=C(N)C=C1 KHYXYOGWAIYVBD-UHFFFAOYSA-N 0.000 description 1
- ZWUBBMDHSZDNTA-UHFFFAOYSA-N 4-Chloro-meta-phenylenediamine Chemical compound NC1=CC=C(Cl)C(N)=C1 ZWUBBMDHSZDNTA-UHFFFAOYSA-N 0.000 description 1
- YGYCECQIOXZODZ-UHFFFAOYSA-N 4415-87-6 Chemical compound O=C1OC(=O)C2C1C1C(=O)OC(=O)C12 YGYCECQIOXZODZ-UHFFFAOYSA-N 0.000 description 1
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000005700 Putrescine Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- OYTKINVCDFNREN-UHFFFAOYSA-N amifampridine Chemical compound NC1=CC=NC=C1N OYTKINVCDFNREN-UHFFFAOYSA-N 0.000 description 1
- 229960004012 amifampridine Drugs 0.000 description 1
- MRSWDOKCESOYBI-UHFFFAOYSA-N anthracene-2,3,6,7-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=C2C=C(C=C(C(C(=O)O)=C3)C(O)=O)C3=CC2=C1 MRSWDOKCESOYBI-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- JUNWLZAGQLJVLR-UHFFFAOYSA-J calcium diphosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])(=O)OP([O-])([O-])=O JUNWLZAGQLJVLR-UHFFFAOYSA-J 0.000 description 1
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 1
- 229940043256 calcium pyrophosphate Drugs 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
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- 238000010276 construction Methods 0.000 description 1
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- SSJXIUAHEKJCMH-UHFFFAOYSA-N cyclohexane-1,2-diamine Chemical compound NC1CCCCC1N SSJXIUAHEKJCMH-UHFFFAOYSA-N 0.000 description 1
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 235000019821 dicalcium diphosphate Nutrition 0.000 description 1
- 235000019700 dicalcium phosphate Nutrition 0.000 description 1
- RBMTXFLUVLIQGN-UHFFFAOYSA-N dodecane-1,10-diamine Chemical compound CCC(N)CCCCCCCCCN RBMTXFLUVLIQGN-UHFFFAOYSA-N 0.000 description 1
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
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- KADGVXXDDWDKBX-UHFFFAOYSA-N naphthalene-1,2,4,5-tetracarboxylic acid Chemical compound OC(=O)C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC(C(O)=O)=C21 KADGVXXDDWDKBX-UHFFFAOYSA-N 0.000 description 1
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- JGGWKXMPICYBKC-UHFFFAOYSA-N phenanthrene-1,8,9,10-tetracarboxylic acid Chemical compound C1=CC=C(C(O)=O)C2=C(C(O)=O)C(C(O)=O)=C3C(C(=O)O)=CC=CC3=C21 JGGWKXMPICYBKC-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- JRDBISOHUUQXHE-UHFFFAOYSA-N pyridine-2,3,5,6-tetracarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)N=C1C(O)=O JRDBISOHUUQXHE-UHFFFAOYSA-N 0.000 description 1
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- LUEGQDUCMILDOJ-UHFFFAOYSA-N thiophene-2,3,4,5-tetracarboxylic acid Chemical compound OC(=O)C=1SC(C(O)=O)=C(C(O)=O)C=1C(O)=O LUEGQDUCMILDOJ-UHFFFAOYSA-N 0.000 description 1
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Abstract
The polymer production system (1) is provided with: a1 st supply unit (112) for supplying A1 st fluid (A1) containing A1 st polymerizable compound; a2 nd supply unit (122) for supplying A2 nd fluid (A2) containing A2 nd polymerizable compound; a1 st junction (J1) that joins the 1 st fluid (A1) and the 2 nd fluid (A2) to generate A1 st joined fluid (B); a1 st tubular mixing section (20) disposed downstream of the 1 st junction section (J1), the 1 st tubular mixing section (20) enhancing mixing of the 1 st junction fluid (B) in the radial direction to generate a1 st tubular mixed fluid (C); and a1 st variation reducing unit (30) connected to the 1 st tubular mixing unit, wherein the 1 st variation reducing unit (30) generates the 1 st generated fluid (D) by reducing the viscosity variation in the axial direction of the 1 st tubular mixing fluid (C).
Description
Technical Field
The present invention relates to a polymer production system and a polymer production method. In detail, the present invention relates to a polymer production system capable of continuously producing a polymer and a polymer production method using the polymer production system.
Background
Conventionally, as a method for producing a polymer such as polyamide acid (polyamide acid), for example, a method is known in which a1 st fluid and a2 nd fluid are mixed in a mixing tank and the mixed fluids are further mixed by a tubular pipe-type mixer (for example, refer to patent document 1). In the pipe mixer, the mixed fluid is passed through by driving a pump, and the mixed fluid is stirred while moving along the axial direction of the pipe.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 62-214912
Disclosure of Invention
Problems to be solved by the invention
In the tube mixer, homogenization is performed by mixing in the radial direction of the tube, but the viscosity variation of the mixed fluid generated in the axial direction of the tube is maintained because the residence time distribution in the tube mixer is small. Since the mixing ratio of the raw materials needs to be precisely adjusted as the polymer to be produced becomes higher in the addition polymerization reaction, it is difficult to continuously obtain a polymer having a high viscosity of 1000poise or more in a state of stable viscosity, for example, although a polymer having a low viscosity can be stably obtained in the addition polymerization reaction by a tube mixer. In a polymer whose viscosity varies with time, there is a problem that a film having a constant thickness cannot be obtained when the polymer is formed into a film. In order to solve this problem, it is considered to provide a stirring tank or the like downstream of the pipe mixer to eliminate the viscosity fluctuation, but this increases the equipment cost, and besides, there is a problem that the polymer solution is involved in bubbles and it is necessary to perform deaeration before film formation.
As a result of intensive studies to solve the above problems, it has been found that, conventionally, in order to reduce the time required and the loss of the product, the residence time in the liquid feed line for transporting the produced polymer is preferably short, but the viscosity of the produced polymer can be greatly reduced with time by deliberately providing a site with a long residence time in the liquid feed line for the polymer, and the present invention has been completed.
The purpose of the present invention is to provide a polymer production system and a production method that can continuously and stably obtain a desired polymer with little viscosity fluctuation over time. Another object of the present invention is to provide a polymer production system and a production method capable of reducing the overproof rate by reducing the fluctuation range of the properties of the produced polymer in the continuous polymer production process.
Solution for solving the problem
The following embodiments are included in specific means for solving the above-described problems.
A polymer production system for producing a polymer from a 1 st fluid and a 2 nd fluid, wherein the 1 st fluid contains a 1 st polymerizable compound, the 1 st polymerizable compound has addition polymerization, the 2 nd fluid contains a 2 nd polymerizable compound, the 2 nd polymerizable compound has addition polymerization, and the 1 st polymerizable compound is addition polymerized, and the polymer production system comprises: a 1 st supply unit configured to supply the 1 st fluid; a 2 nd supply unit configured to supply the 2 nd fluid; a 1 st junction that joins the 1 st fluid and the 2 nd fluid to generate a 1 st joined fluid; a 1 st tubular mixing section disposed downstream of the 1 st joining section, the 1 st tubular mixing section enhancing mixing of the 1 st joining fluid in a radial direction to generate a 1 st tubular mixed fluid; and a 1 st variation reducing unit which is disposed downstream of the 1 st tubular mixing unit, wherein the 1 st variation reducing unit generates the 1 st generated fluid by reducing variation in the properties of the 1 st tubular mixing fluid in the axial direction.
The polymer production system according to claim 1, wherein the polymer production system further comprises a 1 st measurement unit that obtains 1 st reaction information on a physical quantity and/or a composition of one or more of the 1 st merged fluid, the 1 st tube mixed fluid, and the 1 st produced fluid.
The polymer production system according to < 3 >, wherein the 1 st measuring section has 1 or more devices selected from the group consisting of a viscometer, a thermometer, a pressure gauge, a pump pressure gauge, an absorbance gauge, an infrared spectrometer, a near infrared spectrometer, a densitometer, a color difference gauge, a refractive index gauge, a spectrophotometer, a conductivity gauge, a turbidity gauge, an ultrasonic sensor, and a fluorescent X-ray analysis device.
The polymer production system according to claim 2, further comprising a 1 st temperature adjustment unit for adjusting a temperature of one or more of the 1 st fluid, the 2 nd fluid, the 1 st combined fluid, the 1 st tube mixed fluid, and the 1 st produced fluid.
The polymer production system according to any one of < 1 > - < 4 >, wherein the 1 st fluctuation reducing section is constituted of 1 or more tubular members, and a total value of average residence times of the tubular members is 7 minutes or more.
The polymer production system according to any one of < 1 > - < 4 >, wherein the 1 st variation reducing section is a pipe having an average residence time of the fluid flowing therein of 7 minutes or longer.
The polymer production system according to any one of < 7 > < 1 > - < 4 >, wherein a 1 st tube mixed fluid measurement unit is provided between the 1 st tube type mixing unit and the 1 st variation reducing unit, the 1 st tube mixed fluid measurement unit obtains 1 st tube mixed fluid reaction information concerning a physical quantity and/or a composition of the 1 st tube mixed fluid, and a 1 st generation fluid measurement unit is further provided at or downstream of an outlet of the 1 st variation reducing unit, the 1 st generation fluid measurement unit obtains 1 st generation fluid reaction information concerning a physical quantity and/or a composition of the 1 st generation fluid, and a volume of the 1 st variation reducing unit is 0.5 to 100 times a volume of the 1 st tube type mixing unit.
The polymer production system according to any one of < 1 > - < 4 >, wherein the volume of the 1 st variation reducing section is 5 to 100 times the volume of the 1 st tubular mixing section.
The polymer production system according to any one of < 1 > - < 4 >, wherein the 1 st variation reducing section is a pipe having a residence time of 3 minutes or longer for a fluid passing through a trace having a fastest flow rate.
The polymer production system according to any one of < 1 > - < 4 >, wherein the 1 st variation reducing section is constituted of 1 or more tubular members, the average flow velocity of the fluid flowing inside the tubular members is 0.01m/s or less, and the total length of the tubular members is 0.7m or more.
The polymer production system according to any one of < 1 > - < 10 >, wherein when a 4X cross-sectional area/wet cycle is used as a representative length, the Reynolds number of the fluid flowing in the 1 st variation reducing portion is 2100 or less.
The polymer production system according to < 1 > wherein the 1 st fluctuation reducing section has no driven mixer, and the fluid forms an open channel.
The polymer production system according to < 1 > wherein 10 minutes or more is required from the outflow of the fluid passing through the trace having the fastest flow rate to the outflow of 70% of the fluid simultaneously flowing into the 1 st variation alleviation portion.
The polymer production system according to any one of < 1 > - < 13 >, wherein the 1 st polymerizable compound and the 2 nd polymerizable compound satisfy any one of the following (a) to (c), and polyamide acid is produced as the polymer,
(a) One of the 1 st polymerizable compound and the 2 nd polymerizable compound is tetracarboxylic dianhydride, the other is diamine,
(b) One of the 1 st polymerizable compound and the 2 nd polymerizable compound is an acid anhydride-terminated polyamic acid or an amino-terminated polyamic acid, the other is a diamine or a tetracarboxylic dianhydride,
(c) One of the 1 st polymerizable compound and the 2 nd polymerizable compound is an acid anhydride-terminated polyamic acid or an amino-terminated polyamic acid, and the other is an amino-terminated polyamic acid or an acid anhydride-terminated polyamic acid.
The polymer production system according to < 14 > further comprising an imidizing unit imidizing the produced polyamic acid, wherein polyimide is produced as the polymer.
The polymer manufacturing system according to claim 1, wherein the 1 st measurement unit acquires the 1 st reaction information of any one or more of the 1 st merged fluid, the 1 st tube mixed fluid, and the 1 st generated fluid, and the polymer manufacturing system further includes a control unit that controls any one or more operations selected from the group consisting of supply of the 1 st supply unit, supply of the 2 nd supply unit, and temperature adjustment of the 1 st temperature adjustment unit based on the 1 st reaction information acquired.
The polymer manufacturing system according to claim 1, wherein the 1 st measurement unit acquires the 1 st reaction information of the 1 st mixed fluid and/or the 1 st reaction information of the 1 st tube mixed fluid, and further comprises a control unit that predicts a property of the 1 st generated fluid based on the 1 st reaction information acquired, and controls any one or more operations selected from the group consisting of fluid supply to the 1 st supply unit, fluid supply to the 2 nd supply unit, and temperature adjustment to the 1 st temperature adjustment unit based on the predicted property of the 1 st generated fluid.
A method for producing a polymer, wherein the polymer production system according to any one of < 1 > - < 17 > is used.
A method for producing a polyamic acid solution and/or polyimide, wherein the polymer production system according to any one of < 1 > - < 17 > is used.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a polymer production system and a polymer production method capable of continuously and stably obtaining a desired polymer with less viscosity fluctuation with time can be provided. In addition, it is possible to provide a polymer production system and a production method capable of reducing the overproof rate by providing a mechanism for reducing the fluctuation of the properties of a polymer in the continuous production process of the polymer, which is simple in structure and low in equipment cost.
Drawings
Fig. 1 is a diagram showing a polymer production system according to embodiment 1.
Fig. 2 is a diagram showing a polymer production system according to embodiment 2.
Fig. 3 is a diagram showing a polymer production system according to embodiment 3.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.
Embodiment 1 to embodiment 3 are examples of a polymer production system including a1 st tubular mixing section and a1 st fluctuation reducing section.
Embodiment 1
A polymer production system according to embodiment 1 will be described with reference to fig. 1. Fig. 1 is a diagram showing a polymer production system according to embodiment 1.
First, an outline of the polymer production system 1 in embodiment 1 will be described.
The polymer production system 1 is a production system for producing a polymer using A1 st fluid A1 and A2 nd fluid A2 as raw materials, wherein the 1 st fluid A1 contains A1 st polymerizable compound, the 1 st polymerizable compound has addition polymerization properties, the 2 nd fluid A2 contains A2 nd polymerizable compound, and the 2 nd polymerizable compound has addition polymerization properties. Embodiment 1 is an example of a polymer production system in which a1 st tubular mixing section and a1 st fluctuation reducing section are provided in series.
Here, the 1 st tubular mixing section refers to a tubular mixing section that uniformizes properties in the radial direction while circulating a fluid. The 1 st variation reducing section is a structural section capable of reducing variation in the characteristics in the axial direction by positively generating a residence time distribution using a difference in flow velocity based on the trace in the flow path.
Hereinafter, as an example, the following will be described: one of the 1 st polymerizable compound and the 2 nd polymerizable compound is tetracarboxylic dianhydride, and the other is diamine, and polyamide acid is produced as a polymer. More specifically, the following is explained: the 1 st polymerizable compound contained in the 1 st fluid A1 is tetracarboxylic dianhydride, and the 2 nd polymerizable compound contained in the 2 nd fluid A2 is diamine, and polyamide acid is produced as a polymer.
The tetracarboxylic dianhydride is not particularly limited, and the same materials as those used in the conventional polyimide synthesis can be used. Specific examples of the tetracarboxylic dianhydride include: 3,3',4' -benzophenone tetracarboxylic dianhydride, 3',4' -biphenyl tetracarboxylic dianhydride, 2, 3',4' -biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, 1, 3-bis (2, 3-dicarboxyphenoxy) benzene dianhydride, 1, 4-bis (2, 3-dicarboxyphenoxy) benzene dianhydride, 2, 3',4' -benzophenone tetracarboxylic dianhydride, 2',3,3' -benzophenone tetracarboxylic dianhydride, 2', 3' -biphenyl tetracarboxylic dianhydride, 2', aromatic tetracarboxylic dianhydrides such as 6,6' -biphenyltetracarboxylic dianhydride, naphthalene-1, 2,4, 5-tetracarboxylic dianhydride, anthracene-2, 3,6, 7-tetracarboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, and 2, 2-bis (4-hydroxyphenyl) propane dibenzoate-3, 3',4' -tetracarboxylic dianhydride; aliphatic tetracarboxylic dianhydrides such as butane-1, 2,3, 4-tetracarboxylic dianhydride; alicyclic tetracarboxylic dianhydrides such as cyclobutane-1, 2,3, 4-tetracarboxylic dianhydride; heterocyclic tetracarboxylic dianhydrides such as thiophene-2, 3,4, 5-tetracarboxylic dianhydride and pyridine-2, 3,5, 6-tetracarboxylic dianhydride; etc. The tetracarboxylic dianhydride may be used alone or in combination of two or more.
As the solvent of the 1 st fluid A1, a solvent that dissolves tetracarboxylic dianhydride and polyamic acid can be used. Specific examples of the solvent include: amide solvents such as N, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1, 3-dimethyl-2-imidazolidinone, and acetanilide; cyclic ester solvents such as gamma-butyrolactone; chain ester solvents such as ethyl acetate; ketone solvents such as 2-propanone, 3-pentanone, propanone, methyl ethyl ketone, etc.; ether solvents such as tetrahydrofuran and dioxolane; alcohol solvents such as methanol, ethanol, and isopropanol; aromatic hydrocarbon solvents such as toluene and xylene; etc. Among these, amide solvents, cyclic ester solvents and ether solvents having high solubility of polyamic acid are preferable. The solvent may be used alone or in combination of two or more. For example, the solubility of polyamic acid can be improved by mixing an alcohol solvent having high polarity with a solvent having low solubility of polyamic acid such as acetone, ethyl acetate, methyl ethyl ketone, toluene, xylene, or the like.
The 1 st fluid A1 may contain a small amount of tertiary amine such as trimethylamine and triethylamine, or acetic acid in order to improve the solubility of tetracarboxylic dianhydride or the reactivity with diamine.
The diamine is not particularly limited, and the same materials as those used in the conventional polyimide synthesis can be used. Specific examples of the diamine include: 4,4' -diaminodiphenylmethane, 4' -diaminodiphenyl ether, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 4' -bis (4-aminophenoxy) biphenyl, 1,4' -bis (4-aminophenoxy) benzene, 1,3' -bis (4-aminophenoxy) benzene, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,4' -diaminodiphenyl ether, 4' -diaminodiphenyl sulfone, 3,4' -diaminodiphenyl sulfone aromatic diamines such as 3,3' -diaminodiphenyl sulfone, 4' -methylene-bis (2-chloroaniline), 3' -dimethyl-4, 4' -diaminobiphenyl, 4' -diaminodiphenyl sulfide, 2, 6-diaminotoluene, 2, 4-diaminochlorobenzene, 1, 2-diaminoanthraquinone, 1, 4-diaminoanthraquinone, 3' -diaminobenzophenone, 3,4' -diaminobenzophenone, 4' -diaminobenzophenone, and 4,4' -diaminodibenzene; aliphatic diamines such as 1, 2-diaminoethane, 1, 4-diaminobutane, tetramethylenediamine, and 1, 10-diaminododecane; alicyclic diamines such as 1, 4-diaminocyclohexane, 1, 2-diaminocyclohexane, bis (4-aminocyclohexyl) methane, and 4,4' -diaminodicyclohexylmethane; heterocyclic diamines such as 3, 4-diaminopyridine; etc. The diamine may be used alone or in combination of two or more.
As the solvent of the 2 nd fluid A2, a solvent that dissolves diamine and polyamic acid can be used. Specific examples of the solvent include: amide solvents such as N, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1, 3-dimethyl-2-imidazolidinone, and acetanilide; cyclic ester solvents such as gamma-butyrolactone; chain ester solvents such as ethyl acetate; ketone solvents such as 2-propanone, 3-pentanone, propanone, methyl ethyl ketone, etc.; ether solvents such as tetrahydrofuran and dioxolane; alcohol solvents such as methanol, ethanol, and isopropanol; aromatic hydrocarbon solvents such as toluene and xylene; etc. Among these, amide solvents, cyclic ester solvents and ether solvents having high solubility of polyamic acid are preferable. The solvent may be used alone or in combination of two or more. For example, the solubility of polyamic acid can be improved by mixing an alcohol solvent having high polarity with a solvent having low solubility of polyamic acid such as acetone, ethyl acetate, methyl ethyl ketone, toluene, xylene, or the like.
The 1 st fluid A1 and/or the 2 nd fluid A2 may be dispersed with a filler that becomes a lubricant of the polyimide film. Examples of the lubricant include inorganic particles such as titanium oxide, anhydrous calcium hydrogen phosphate, calcium pyrophosphate, calcium carbonate, silica, alumina, barium sulfate, zirconia, kaolin, talc, clay, and mica, and organic particles containing an acrylic or styrene component. Further, inorganic particles and organic particles added for the purpose of modifying other properties of the polyimide film such as strength and thermal conductivity of the film may be dispersed.
As shown in fig. 1, the polymer production system 1 is configured to mix A1 st fluid A1 and A2 nd fluid A2 as raw materials at A1 st mixing section J1 to generate A1 st mixed fluid B, and to mix the 1 st mixed fluid B at A1 st tubular mixing section 20 to generate A1 st tubular mixed fluid C having the same concentration of each component in the radial direction of the tube. Next, the 1 st variation reducing unit 30 reduces the viscosity variation in the axial direction of the 1 st tube mixed fluid C to obtain the 1 st produced fluid D, thereby producing polyamide acid (polymer) having less viscosity variation with time.
The polymer production system 1 further includes a liquid feed line L connected from the 1 st tank 11 and the 2 nd tank 12 described later to the outlet of the 1 st fluctuation reducing section 30.
The polymerization reaction is performed in either one of the 1 st tubular mixing section 20 and the 1 st variation reducing section 30 or in both of the 1 st tubular mixing section 20 and the 1 st variation reducing section 30. The polymerization reaction may be completely ended at the outlet of the 1 st tubular mixing section 20, or the reaction may not substantially proceed at the outlet of the 1 st tubular mixing section 20, and most of the reaction may proceed at the 1 st variation reducing section 30. The polymerization reaction does not necessarily have to be completed at the outlet of the 1 st fluctuation reducing section 30, and the reaction may be performed in a piping or a buffer tank provided downstream of the 1 st fluctuation reducing section 30. However, in order to obtain a polymer having stable properties, it is preferable to design the polymerization reaction to be completed 80% or more at the outlet of the 1 st variation reducing section 30, and more preferably to design the polymerization reaction to be completed 80% or more at the outlet of the 1 st tubular mixing section 20.
Next, a specific structure of the polymer production system 1 will be described.
As shown in fig. 1, the polymer production system 1 includes a1 st tank 11, a1 st tank on-off valve 111, a 2 nd tank 12, a 2 nd tank on-off valve 121, a1 st supply pump 112 (1 st supply unit), a 2 nd supply pump 122 (2 nd supply unit), a1 st junction J1, a1 st tubular mixing unit 20, a1 st variation reducing unit 30, a liquid feed line L, and a control unit 200. The liquid feed line L includes a1 st liquid feed portion L1, a 2 nd liquid feed portion L2, a 3 rd liquid feed portion L3, a 4 th liquid feed portion L4, and a 5 th liquid feed portion L5. The polymer production system 1 includes a1 st flow rate measurement unit 113, a 2 nd flow rate measurement unit 123, a1 st pipe mixed fluid measurement unit 222 (1 st measurement unit), and a1 st produced fluid measurement unit 322 (1 st measurement unit).
The 1 st tank 11 contains A1 st fluid A1, and A1 st polymerizable compound is dissolved in the 1 st fluid A1, and the 1 st polymerizable compound has addition polymerization property. In the present embodiment, the 1 st tank 11 contains the 1 st fluid A1 in which tetracarboxylic dianhydride is dissolved. The 1 st fluid A1 contained in the 1 st tank 11 is supplied to the 1 st junction J1 via the 1 st liquid feed portion L1.
The 1 st liquid feeding portion L1 is a line connecting the 1 st tank 11 and the 1 st junction portion J1. Between the 1 st tank 11 and the 1 st junction portion J1 in the 1 st liquid sending portion L1, a1 st tank on-off valve 111, a1 st supply pump 112, and a1 st flow rate measuring portion 113 are arranged in this order from the upstream side toward the downstream side.
The 1 st tank opening/closing valve 111 is disposed in the vicinity of the lower part of the 1 st tank 11 in the 1 st liquid feeding portion L1, and opens and closes the 1 st liquid feeding portion L1 on the upstream side of the 1 st supply pump 112.
The 1 st supply pump 112 supplies the 1 st fluid A1 contained in the 1 st tank 11 to the 1 st junction J1. The 1 st supply pump 112 discharges the 1 st fluid A1 at a predetermined flow rate. For example, the 1 st fluid A1 is supplied by adjusting the 1 st supply pump 112 under conditions such that the polyamic acid having desired properties can be obtained.
In the present embodiment, the 1 st supply pump 112 is constituted by a fixed displacement pump.
In the present embodiment, the 1 st fluid A1 supplied from the 1 st supply pump 112 and the 2 nd fluid A2 supplied from the 2 nd supply pump 122 described later are supplied under control, whereby a polyamic acid having a desired property is obtained. Accordingly, the accuracy of supplying the 1 st fluid A1 and the 2 nd fluid A2 is preferably high, and in the present embodiment, the 1 st supply pump 112 is constituted by a fixed displacement pump, and the 2 nd supply pump 122 described later is also constituted by a fixed displacement pump.
The fixed displacement pump is a positive displacement pump, and a certain amount of fluid is repeatedly delivered with high accuracy. Examples of the fixed displacement pump include an extrusion type reciprocating pump such as a plunger pump, and a rotary pump such as a gear pump having gears.
The 1 st flow rate measuring unit 113 measures the flow rate of the 1 st fluid A1 downstream of the 1 st supply pump 112 in the 1 st liquid feeding unit L1. In the present embodiment, the 1 st flow rate measurement unit 113 is disposed between the 1 st supply pump 112 and the 1 st junction J1. The 1 st flow rate measurement unit 113 outputs the measured flow rate of the 1 st fluid A1 to the control unit 200 described later.
The 2 nd tank 12 contains A2 nd fluid A2, and A2 nd polymerizable compound is dissolved in the 2 nd fluid A2, and the 2 nd polymerizable compound has addition polymerization property and is addition polymerized with the 1 st polymerizable compound. In the present embodiment, the 2 nd tank 12 contains the 2 nd fluid A2 in which diamine is dissolved. The 2 nd fluid A2 contained in the 2 nd tank 12 is supplied to the 1 st junction J1 via the 2 nd liquid feed portion L2.
The 2 nd liquid feeding portion L2 is a line connecting the 2 nd tank 12 and the 1 st junction portion J1. Between the 2 nd tank 12 and the 1 st junction portion J1 in the 2 nd liquid sending portion L2, a2 nd tank on-off valve 121, a2 nd supply pump 122, and a2 nd flow rate measuring portion 123 are arranged in this order from the upstream side toward the downstream side.
The 2 nd tank opening/closing valve 121 is disposed in the vicinity of the lower part of the 2 nd tank 12 in the 2 nd liquid feeding portion L2, and opens and closes the 2 nd liquid feeding portion L2 on the upstream side of the 2 nd supply pump 122.
The 2 nd supply pump 122 supplies the 2 nd fluid A2 contained in the 2 nd tank 12 to the 1 st junction J1. The 2 nd supply pump 122 ejects the 2 nd fluid A2 at a predetermined flow rate. For example, the 2 nd fluid A2 is supplied by adjusting the 2 nd supply pump 122 under conditions such that the polyamic acid having desired properties can be obtained.
In the present embodiment, the 2 nd supply pump 122 is constituted by a fixed displacement pump for the same reason as the 1 st supply pump 112 described above.
The 2 nd flow rate measuring unit 123 measures the flow rate of the 2 nd fluid A2 on the downstream side of the 2 nd supply pump 122 in the 2 nd liquid feeding unit L2. In the present embodiment, the 2 nd flow rate measuring unit 123 is disposed between the 2 nd supply pump 122 and the 1 st junction portion J1. The 2 nd flow rate measuring unit 123 outputs the measured flow rate of the 2 nd fluid A2 to the control unit 200 described later.
The 1 st junction J1 is disposed on the downstream side of the 1 st supply pump 112 and on the downstream side of the 2 nd supply pump 122. The 1 st junction J1 joins the 1 st fluid A1 and the 2 nd fluid A2 to generate A1 st joined fluid B. In the 1 st junction J1, the 1 st fluid A1 and the 2 nd fluid A2 are joined in a state of not being in contact with the gas. The 1 st junction J1 is constituted by a junction valve that joins the 1 st fluid A1 supplied from the 1 st supply pump 112 and the 2 nd fluid A2 supplied from the 2 nd supply pump 122.
The 1 st tubular mixing section 20 is disposed downstream of the 1 st junction section J1. The 1 st tubular mixing section 20 agitates the 1 st merged fluid B in a state where the 1 st merged fluid B is not in contact with the gas, and generates a1 st tubular mixed fluid C by forming a fluid having the same concentration of each component in the radial direction of the tube at the outlet of the 1 st tubular mixing section 20.
The 1 st tubular mixing section 20 includes a tubular reactor composed of a double tube extending in a predetermined direction. The 1 st tubular mixing section 20 includes a 1 st tubular mixing stirring section 21 disposed radially inward and a 1 st tubular mixing temperature adjusting section 22 (1 st temperature adjusting section) disposed radially outward. The 1 st tubular mixing section 20 is formed so that the 1 st joining fluid B circulates at a desired residence time.
The 1 st tubular mixing and stirring section 21 stirs the 1 st mixed fluid B. In the present embodiment, the 1 st tubular mixing and stirring section 21 stirs the 1 st mixed fluid B adjusted to a temperature suitable for the polymerization reaction by the 1 st tubular mixing and temperature adjusting section 22.
The 1 st pipe type mixing and stirring section 21 is configured to include, for example, a static mixer such as a nozzle or an orifice, a driving mixer such as an in-line mixer having a centrifugal pump, a swirl pump, and stirring blades, preferably a static mixer, and more preferably a static mixer. In addition, a tube in which a twisted belt is inserted (see [ fig. 19] of japanese patent application laid-open No. 2003-314982) is preferable because stirring acceleration effect can be obtained similarly to a static mixer, but stirring acceleration effect can be better obtained by a static mixer.
The static mixer is not particularly limited, and examples thereof include Kenics mixer type, sulzer SMV type, sulzer SMX type, tray Hi-mixer type, komax mixer type, lightning mixer type, ross ISG type, bran & tube mixer type and the like. Of these, the Kenics mixer type static mixer is more preferable because it is simple in construction and therefore has no dead space.
The 1 st tubular mixing and temperature adjusting section 22 is a piping section arranged radially outside the 1 st tubular mixing and stirring section 21. The 1 st tubular mixing and temperature adjusting unit 22 adjusts (e.g., cools) the 1 st fluid B flowing through the 1 st tubular mixing and stirring unit 21 to a desired temperature condition. In the 1 st tubular mixing and temperature adjusting section 22, the 1 st combined fluid B is adjusted to a temperature suitable for the polymerization reaction, and flows through the 1 st tubular mixing and stirring section 21.
The generated 1 st tube mixed fluid C is supplied to the 1 st variation reducing portion 30 via the 4 th liquid feeding portion L4.
The 1 st tube mixed fluid measurement unit 222 acquires 1 st tube mixed fluid reaction information (1 st reaction information) concerning the viscosity of the 1 st tube mixed fluid C between the 1 st tube mixing unit 20 and the 1 st variation reducing unit 30 in the 4 st liquid feeding unit L4. Since the polymerization reaction proceeds by stirring in the 1 st tubular mixing and stirring section 21, the viscosity increases, and the viscosity information is effective as reaction information. The 1 st pipe mixed fluid measuring unit 222 outputs the acquired viscosity information of the 1 st pipe mixed fluid C to the control unit 200 described later.
The 1 st tube mixed fluid measurement unit 222 acquires 1 st tube mixed fluid reaction information (1 st reaction information) concerning the temperature of the 1 st tube mixed fluid C between the 1 st tube mixing unit 20 and the 1 st variation reducing unit 30 in the 4 st liquid feeding unit L4. The polymerization reaction is performed by stirring in the 1 st tubular mixing and stirring section 21, but the reaction rate of the polymerization reaction varies depending on the temperature, and therefore, the temperature information is effective as the reaction information. The 1 st pipe mixed fluid measuring unit 222 outputs the acquired temperature information of the 1 st pipe mixed fluid C to the control unit 200 described later.
The 1 st variation reducing section 30 is disposed downstream of the 1 st tubular mixing section 20. The 1 st variation reducing portion 30 is formed of a double pipe, and includes a 1 st variation reducing pipe portion 31 disposed radially inward and a 1 st variation reducing temperature adjusting portion 32 (1 st temperature adjusting portion) disposed radially outward. In the present embodiment, the 1 st variation reducing and temperature adjusting unit 32 adjusts the temperature to a temperature suitable for polymerization reaction of the 1 st tube mixed fluid C.
In the 1 st variation reducing pipe section 31, the viscosity variation in the axial direction of the 1 st pipe mixed fluid C is reduced by the residence time distribution generated by the speed difference in the radial direction when the 1 st pipe mixed fluid C flows in the 1 st variation reducing pipe section 31, and the behavior of the 1 st produced fluid D flowing out is stabilized. For example, in the case of laminar flow within a circular tube, the flow rate of the fluid passing through the center of the tube is the fastest and the residence time is the shortest. On the other hand, the flow rate of the fluid passing through the wall edge is extremely slow, and therefore the residence time is very long. By the difference in the retention time based on the trace, variation in the property in the axial direction can be alleviated.
In order to obtain a sufficient viscosity fluctuation reducing effect in the 1 st fluctuation reducing pipe section 31, the 1 st pipe mixed fluid C preferably flows in a laminar flow in the 1 st fluctuation reducing pipe section 31. In order to flow in laminar flow in the 1 st variation reducing pipe portion 31, when 4×cross-sectional area/wet circumference is used as the representative length d, the reynolds number (ρud/μ) calculated from the viscosity μ, the cross-sectional average flow velocity u, and the density ρ is preferably 2100 or less, and more preferably 0.00001 or more and 1000 or less. In addition, when the solution viscosity is low, the flow guide section is long until the flow progresses, and therefore, the velocity distribution cannot be effectively generated, and therefore, the viscosity of the 1 st pipe mixed fluid C flowing in the 1 st variation reducing pipe portion 31 is preferably high. Specifically, the viscosity of the 1 st pipe mixed fluid C flowing in the 1 st fluctuation reducing pipe section 31 is preferably 0.1poise or more and 100000poise or less, more preferably 1poise or more and 10000poise or less, and still more preferably 5poise or more and 5000poise or less under the temperature conditions at the time of flow.
The 1 st variation reducing pipe section 31 includes a pipe having a sufficiently long average residence time. The average residence time is a value obtained by dividing the volume of the pipe by the volume flow rate of the 1 st pipe mixed fluid C. When the average residence time of the 1 st variation reducing pipe section 31 is long, the stabilizing effect of the viscosity of the 1 st generated fluid D flowing out of the 1 st variation reducing pipe section 31 is large. Accordingly, the larger the variation in the behavior of the 1 st mixed fluid C flowing out from the 1 st tubular mixing section 20 in the axial direction is, the longer the average residence time of the 1 st variation reducing piping section 31 is preferably.
Specifically, for example, when the newtonian fluid flows in laminar flow in the 1 st variation reducing pipe section 31 which is a straight pipe having a circular cross section, the variation in viscosity at the outlet of the 1 st variation reducing pipe section 31 is reduced by 56% when the average residence time of the 1 st variation reducing pipe section 31 is 3 minutes, the variation in viscosity is reduced by 74% when the average residence time is 7 minutes, and the variation in viscosity is reduced by 81% when the average residence time is 11 minutes. Here, the reduction of the viscosity fluctuation refers to a ratio in which the difference between the maximum value and the minimum value of the viscosity at the outlet of the 1 st fluctuation reducing piping section 31 is reduced with respect to the difference between the maximum value and the minimum value of the viscosity at the inlet of the 1 st fluctuation reducing piping section 31.
In fig. 1, the structure is shown in which only 1 st variation reducing pipe section 31 is provided, but the 1 st variation reducing pipe section 31 may be a structure in which two or more tubular members are connected by a joint or the like. In this case, the total value of the average residence time of the two or more tubular members constituting the 1 st fluctuation reducing piping section 31 is preferably 7 minutes or more. The longer the average residence time of the 1 st fluctuation reducing pipe section 31, the greater the effect of reducing the viscosity fluctuation, but in order to suppress the loss of the produced polymer to a small extent, the total value of the average residence time is preferably 300 minutes or less.
The fluid flowing through the 1 st variation reducing pipe portion 31 is not limited to the newtonian fluid, but in the case of the non-newtonian fluid, the velocity distribution changes under the influence of shear, and the residence time distribution is different, so that the rate of decrease in viscosity variation is different from that in the case of the newtonian fluid. Therefore, when designing the average residence time of the 1 st variation reducing pipe section 31, it is preferable to consider the flow of the fluid flowing in the 1 st variation reducing pipe section 31. For example, in the case of a pseudoplastic fluid having a smaller residence time distribution than a newtonian fluid, the average residence time of the 1 st variation reducing pipe section 31 is preferably made longer.
In the 1 st variation alleviation piping section 31, the variation with a shorter period than the average residence time can be alleviated, but the variation with a longer period than the average residence time is difficult to alleviate. Therefore, it is preferable that the average residence time of the 1 st fluctuation reducing piping section 31 is sufficiently longer than the average fluctuation period of the 1 st pipe mixed fluid C which may occur at the outlet of the 1 st pipe type mixing section 20. The average fluctuation period as referred to herein is an average time from when the viscosity of the 1 st tube mixed fluid C at the outlet of the 1 st tube type mixing section 20 reaches the maximum value to when the viscosity reaches the minimum value once and then reaches the maximum value again. The average residence time of the 1 st fluctuation reducing pipe section 31 is preferably 1 time or more, more preferably 2 times or more the average fluctuation period of the 1 st pipe mixed fluid C at the outlet of the 1 st pipe type mixing section 20.
In order to provide the 1 st variation reducing pipe section 31 with an appropriate average residence time in response to the viscosity variation of the 1 st pipe mixed fluid C, the volume of the 1 st variation reducing pipe section 31 is preferably 0.5 to 100 times, more preferably 5 to 100 times the volume of the 1 st pipe mixed stirring section 20.
Further, since the 1 st fluctuation reducing pipe section 31 reduces the viscosity fluctuation by the distribution of the residence time based on the difference in flow velocity, the flow velocity is extremely slow at the pipe wall side, and thus, by designing the residence time of the fluid passing through the trace having the highest flow velocity to be sufficiently long, a sufficient viscosity fluctuation reducing effect can be obtained. The trace with the fastest flow rate is the trace that always passes through the center of the cross section, for example, in the case of laminar flow in a circular tube. When the trace particles and the colorant are placed in the entire cross section of the inlet of the 1 st variation reducing pipe section 31, the time required for the trace particles and the colorant to initially flow out from the outlet of the 1 st variation reducing pipe section 31 is substantially equal to the residence time of the fluid passing through the trace having the fastest flow velocity. Specifically, for example, when the newton fluid flows in laminar flow in the 1 st variation reducing pipe section 31 which is a straight pipe having a circular cross section, the variation in viscosity at the outlet of the 1 st variation reducing pipe section 31 is reduced by 72% when the residence time of the fluid passing through the trace having the fastest flow velocity is 3 minutes. In the 1 st variation reducing pipe section 31, the longer the residence time of the fluid passing through the trace having the highest flow velocity is, the greater the effect of reducing the viscosity variation is, but in order to suppress the loss of the produced polymer to be small, the total value of the residence times of the fluid passing through the trace having the highest flow velocity is more preferably 150 minutes or less.
If the average residence time of the 1 st variation reducing pipe section 31 is the same, the stabilizing effect of the viscosity of the 1 st produced fluid D is the same regardless of the cross-sectional area and length of the 1 st variation reducing pipe section 31 and the flow rate of the 1 st pipe mixed fluid C flowing in the 1 st variation reducing pipe section 31. However, when the 1 st fluctuation reducing pipe section 31 has a small cross-sectional area and a long length, the 1 st pipe mixed fluid C has a large pressure loss when flowing through the 1 st fluctuation reducing pipe section 31, and therefore, a pipe having a high pressure resistance is required, and the equipment cost is high. Therefore, it is preferable to increase the cross-sectional area of the 1 st variation reducing pipe section 31 to some extent and to shorten the length. Specifically, the cross-sectional average flow velocity is preferably set to be 0.01m/s or less and the length is set to be 0.7m or more, more preferably 0.00001m/s or more and 0.003m/s or less and the length is set to be 0.7m or more and 60m or less. Here, the average flow rate of the cross section is a value obtained by dividing the volume flow rate of the 1 st pipe mixed fluid C by the cross section area of the 1 st fluctuation reducing pipe section 31. In the case where the 1 st variation reducing pipe section 31 is configured by connecting two or more tubular members with a joint or the like, the total value of the lengths of the two or more tubular members is 0.7m or more and 60m or less.
As the 1 st variation reducing pipe portion 31, a hollow cylindrical pipe is preferably used in order to reduce the equipment cost. However, the shape of the 1 st variation reducing pipe section 31 is not particularly limited as long as it is a shape that generates a distribution in the residence time by the velocity distribution in the cross-sectional direction when the 1 st pipe mixed fluid C flows. Specifically, a structure may be provided inside, a pipe bent by a bend or the like may be used, or a cross section may be other than a circular shape. Further, a valve, a sensor, or the like may be provided in the middle of the 1 st fluctuation reducing pipe section 31.
In order to obtain the 1 st generated fluid D containing no bubbles, the 1 st fluctuation reducing pipe section 31 is preferably transported in a state where the fluid is not in contact with the gas. However, the present invention is not limited to this, and if the air bubbles are not involved in the 1 st pipe mixed fluid C, a gas phase may be present in the 1 st variation reducing pipe portion 31.
The 1 st variation reducing pipe section 31 is provided between the 1 st pipe mixed fluid measuring section 222 and the 1 st generated fluid measuring section 322. The 1 st variation reducing pipe portion 31 is preferably a cylindrical pipe having the same inner diameter size in a range from an upstream end to a downstream end in the flow direction of the 1 st pipe mixed fluid C. The length of the 1 st variation reducing pipe section 31 is preferably 5 to 1000 times the inner diameter. The inner diameter of the 1 st fluctuation reducing pipe section 31 is preferably 0.5 to 10 times the inner diameter of the 4 th liquid feeding section L4 located upstream. In addition, in the 1 st variation reducing pipe section 31, the 1 st pipe mixed fluid C flows in a state where it is filled in the internal space of the 1 st variation reducing pipe section 31, and therefore, the difference in flow velocity of the 1 st pipe mixed fluid C in the radial direction is large.
The 1 st variation reducing and temperature adjusting portion 32 is a pipe portion arranged radially outside the 1 st variation reducing pipe portion 31. The 1 st variation reducing and temperature adjusting unit 32 adjusts (e.g., cools) the 1 st pipe mixed fluid C flowing through the 1 st variation reducing pipe unit 31 to a desired temperature condition. In the 1 st variation reducing and temperature adjusting section 32, the 1 st tube mixed fluid C is adjusted to a temperature suitable for polymerization reaction, and flows through the 1 st variation reducing and temperature adjusting section 31.
In the above-described 1 st tubular mixing section 20 and 1 st variation reducing section 30, the 1 st tubular mixing section 20 is arranged in the preceding stage, and the 1 st variation reducing section 30 is arranged in the following stage, whereby, when there is a variation in viscosity in the axial direction of the pipe in the 1 st tubular mixing section 20 in the preceding stage, the variation in viscosity in the axial direction of the pipe can be greatly reduced in the 1 st variation reducing section 30 in the following stage.
For example, when a viscosity variation in the axial direction of the pipe is generated in the generated fluid due to a variation in the ratio of the 1 st fluid A1 to the 2 nd fluid A2, it is difficult to generate a radial velocity distribution in the 1 st tubular mixing section 20 having a structure for stirring therein, and the viscosity variation in the axial direction of the pipe of the mixed fluid cannot be eliminated. In contrast, by disposing the 1 st tubular mixing section 20 in the preceding stage and disposing the 1 st variation reducing section 30 in the subsequent stage, the 1 st variation reducing section 30 in the subsequent stage delivers the liquid with a distribution in residence time after the radial properties are made uniform by the 1 st tubular mixing section 20 in the preceding stage, and thus the viscosity variation in the axial direction of the tube of the 1 st mixed fluid C, which cannot be eliminated in the 1 st tubular mixing section 20 in the preceding stage, can be greatly reduced in the 1 st variation reducing section 30 in the subsequent stage.
The 1 st generated fluid measurement unit 322 is located at or downstream of the outlet of the 1 st variation reducing unit 30, and acquires 1 st generated fluid reaction information (1 st reaction information) concerning the viscosity of the 1 st generated fluid D in the 5 th liquid feeding unit L5. Since the viscosity increases by the progress of the polymerization reaction, the viscosity information is effective as reaction information. The 1 st generated fluid measurement unit 322 outputs the acquired viscosity information of the 1 st generated fluid to the control unit 200 described later.
The 1 st generated fluid measurement unit 322 also acquires 1 st generated fluid reaction information (1 st reaction information) concerning the temperature of the 1 st generated fluid D in the 5 th liquid feeding unit L5. The reaction rate of the polymerization reaction varies depending on the temperature, and therefore, the temperature information is effective as the reaction information. The 1 st generated fluid measurement unit 322 outputs the acquired temperature information of the 1 st generated fluid to the control unit 200 described later.
The 1 st tube mixed fluid measurement unit 222 and the 1 st generated fluid measurement unit 322 according to the present embodiment are examples of measurement units that acquire reaction information on physical quantities and/or compositions of one or more fluids of the 1 st tube mixed fluid C and the 1 st generated fluid D.
The measurement unit is not limited to the 1 st tube mixed fluid measurement unit 222 and the 1 st generation fluid measurement unit 322 (types of physical quantities and/or compositions, measurement methods) of the present embodiment. The measuring unit may have, for example, 1 or two or more devices selected from the group consisting of a viscometer, a thermometer, a manometer, a pump pressure meter, an absorbance meter, an infrared spectrometer, a near infrared spectrometer, a densitometer, a color difference meter, a refractive index meter, a spectrophotometer, a conductivity meter, a turbidity meter, and a fluorescent X-ray analysis device. The measurement unit acquires 1 or more types of reaction information concerning the physical quantity and/or composition of the measurement object, and outputs the acquired reaction information to the control unit 200 described later.
A buffer tank (not shown) may be provided downstream of the 5 th liquid feed line L5 to accommodate the 1 st generated fluid D. The buffer tank is a tank for accommodating a raw material fluid when polyimide is produced by imidizing polyamide acid as a polymer, for example.
In the case where the polymer production system 1 in the present embodiment produces polyimide, the polymer production system 1 further includes an imidization unit for imidizing the polyamic acid. The imidizing unit (not shown) imidizes the polyamic acid by, for example, a thermal imidizing method of thermal dehydration ring closure, a chemical imidizing method using a dehydrating agent and an imidizing accelerator, or the like.
In the case of producing polyimide in the polymer production system 1, the buffer tank may not be provided, and the liquid may be supplied from the 1 st fluctuation reducing section 30 to the imidizing section. However, it is more preferable to temporarily house the polyamic acid in a buffer tank.
The control unit 200 is described. The 1 st supply pump 112, the 2 nd supply pump 122, the 1 st pipe type mixed temperature adjusting portion 22, the 1 st variation reducing temperature adjusting portion 32, the 1 st flow measuring portion 113, the 2 nd flow measuring portion 123, the 1 st pipe mixed fluid measuring portion 222, and the 1 st generated fluid measuring portion 322 are electrically connected to the control portion 200. In this specification, control lines from the control unit 200 to the pumps, the temperature adjusting units, and the measuring units are not shown.
The control unit 200 controls the supply pumps 112 and 122 based on the flow values measured by the flow measuring units 113 and 123.
The control unit 200 controls the 1 st supply pump 112 and/or the 2 nd supply pump 122, for example, so that the mass ratio of the 1 st polymerizable compound contained in the 1 st fluid A1 to the 2 nd polymerizable compound contained in the 2 nd fluid A2 is controlled within a predetermined range. The mass ratio is set to, for example, a polyamic acid that can obtain desired properties. The control unit 200 controls the temperature conditions of the 1 st tubular mixing temperature control unit 22 and/or the 1 st fluctuation reducing temperature control unit 32, for example, to control the reaction rate of the polymerization reaction within a predetermined range.
The control unit 200 controls any one or more of the supply of the 1 st supply pump 112, the supply of the 2 nd supply pump 122, the temperature adjustment of the 1 st pipe type mixed temperature adjusting unit 22, and the temperature adjustment of the 1 st fluctuation reducing temperature adjusting unit 32 based on the 1 st reaction information acquired by the 1 st pipe mixed fluid measuring unit 222 and/or the 1 st generated fluid measuring unit 322.
Next, the operation of the polymer production system 1 (polyamic acid production system) in embodiment 1 will be described.
First, in the polymer production system 1, the 1 st supply pump 112 supplies the 1 st fluid A1 and the 2 nd supply pump 122 supplies the 2 nd fluid A2 by starting the operation. Here, the discharge flows of the 1 st supply pump 112 and the 2 nd supply pump 122 are controlled by the control unit 200 so that the 1 st fluid A1 and the 2 nd fluid A2 are supplied at a desired ratio. Thereby, the 1 st fluid A1 and the 2 nd fluid A2 are supplied to the 1 st junction J1. In the 1 st junction J1, the 1 st fluid A1 supplied from the 1 st supply pump 112 and the 2 nd fluid A2 supplied from the 2 nd supply pump 122 are joined and mixed to generate A1 st joined fluid B.
By the supply operation of the 1 st supply pump 112 and the 2 nd supply pump 122, the 1 st fluid B generated in the 1 st junction J1 is transported in the 3 rd liquid feeding portion L3 and supplied to the 1 st tubular mixing portion 20.
In the 1 st tube type mixing section 20, the 1 st mixed fluid B is stirred so that the properties such as the concentration are not uniform in the radial direction) to the same extent in the radial direction, thereby generating the 1 st tube mixed fluid C. When the 1 st tubular mixing section 20 is a static mixer such as a static mixer, the 1 st mixed fluid B is stirred only by passing the liquid. Here, in the 1 st tubular mixing section 20, the 1 st joining fluid B moves in the axial direction of the pipe without generating a large velocity distribution, and therefore, when there is a viscosity variation of the 1 st joining fluid B in the axial direction of the pipe, the variation cannot be eliminated.
The 1 st tube mixed fluid C generated in the 1 st tube type mixing section 20 is transported in the 4 th liquid feeding section L4 and supplied to the 1 st variation reducing section 30.
In the 1 st variation reducing section 30, the 1 st tube mixed fluid C is flowed in, and the liquid is continuously fed in a state where the residence time of the 1 st tube mixed fluid C is distributed by the velocity distribution in the radial direction. This can greatly reduce the viscosity variation in the axial direction of the tube of the 1 st tube mixed fluid C, which cannot be eliminated in the 1 st tube mixing section 20 in the preceding stage, in the 1 st variation reducing section 30 in the following stage. Thus, a desired polymer can be continuously and stably obtained.
Here, in the middle of the operation of the polymer manufacturing system 1, the 1 st pipe mixed fluid measurement unit 222 and the 1 st generated fluid measurement unit 322 acquire viscosity information (measurement step).
The control unit 200 controls the supply pumps 112 and 122 and the temperature adjusting units 22 and 32 based on the viscosity information (1 st reaction information) obtained by the 1 st pipe mixed fluid measuring unit 222 and/or the 1 st generated fluid measuring unit 322 (control step). Thus, polyamic acid having desired properties (temperature and viscosity) can be obtained.
When the distribution of the residence time of the 1 st tube mixed fluid C in the 1 st fluctuation reducing section 30 is known, the 1 st viscosity information is acquired by the 1 st tube mixed fluid measuring section 222 (measuring step), whereby the change with time of the viscosity of the 1 st generated fluid D at the outlet of the 1 st fluctuation reducing section 30 can be predicted (predicting step). The supply pumps 112 and 122 and the temperature adjusting portions 22 and 32 may be controlled based on the viscosity thus predicted (control step). For example, when the hagen-poiseuille flow is formed in the laminar flow in the 1 st variation reducing unit 30, the flow velocity distribution in the radial direction can be calculated, and thus the residence time distribution can be obtained. Thus, when the time-moving average obtained by weighting the residence time distribution is calculated for the viscosity of the 1 st tube mixed fluid C acquired by the 1 st tube mixed fluid measuring unit 222, a predicted value of the viscosity of the 1 st generated fluid D at the outlet of the 1 st fluctuation reducing unit 30 can be obtained.
When the residence time of the 1 st tube mixed fluid C in the 1 st fluctuation reducing section 30 is not clearly distributed, the change with time of the viscosity at the inlet of the 1 st fluctuation reducing section 30 and the change with time of the viscosity at the outlet of the 1 st fluctuation reducing section 30 may be measured once, and the effect of reducing the viscosity fluctuation by the 1 st fluctuation reducing section 30 may be modeled based on the result, thereby predicting the change of the viscosity of the 1 st generated fluid D. In modeling, for example, a first-order delay function or the like can be used.
When the operating conditions are controlled based on the viscosity information obtained by the 1 st pipe mixed fluid measuring section 222, which varies greatly, there is a risk of hunting. On the other hand, when the operating conditions are controlled based on the viscosity information obtained by the 1 st generation fluid measurement unit 322, oscillations are less likely to occur due to stable viscosity, but time is wasted and hence the standard is likely to be exceeded. Accordingly, it is effective to predict the viscosity of the 1 st generated fluid D at the outlet of the 1 st fluctuation reducing section 30 based on the viscosity information acquired by the 1 st pipe mixed fluid measuring section 222, and to control the viscosity based on the viscosity information.
In addition, in the middle of the operation of the polymer manufacturing system 1, the 1 st tube mixed fluid measurement unit 222 and the 1 st generated fluid measurement unit 322 acquire temperature information (measurement step).
The control unit 200 controls the temperature adjustment conditions (control step) of the 1 st pipe type mixed temperature adjusting unit 22 and/or the 1 st variation reducing temperature adjusting unit 32 based on the temperature information (1 st reaction information) acquired by the 1 st pipe mixed fluid measuring unit 222 and/or the 1 st generated fluid measuring unit 322. Thus, polyamic acid having desired properties (temperature and viscosity) can be obtained.
The following effects are achieved by the polymer production system 1 according to the present embodiment.
The polymer production system 1 includes: a1 st supply pump 112 that supplies A1 st fluid A1 containing A1 st polymerizable compound; a2 nd supply pump 122 that supplies A2 nd fluid A2 containing A2 nd polymerizable compound; a1 st junction J1 that joins 1 st fluid A1 and 2 nd fluid A2 to generate 1 st joined fluid B; a1 st tubular mixing section 20 disposed downstream of the 1 st junction section J1, the 1 st tubular mixing section 20 stirring the 1 st junction fluid B to homogenize the radial viscosity fluctuation, thereby generating a1 st tubular mixed fluid C; and a1 st variation reducing unit 30 disposed downstream of the 1 st tubular mixing unit 20, wherein the 1 st variation reducing unit 30 reduces variation in properties of the 1 st tubular mixed fluid C in the axial direction to generate the 1 st generated fluid D.
In the present invention, since the 1 st tube mixed fluid C mixed in the 1 st tube type mixing section 20 arranged in the preceding stage is homogenized in the axial direction in the 1 st variation alleviation section 30 arranged in the subsequent stage, the viscosity variation in the axial direction of the tube of the 1 st tube mixed fluid C, which cannot be eliminated in the 1 st tube type mixing section 20 in the preceding stage, can be eliminated in the 1 st variation alleviation section 30 in the subsequent stage, and the polymer solution can be continuously and stably obtained.
In particular, in the case of producing a polymer having a high viscosity, since the pressure loss when a solution having a high viscosity passes through a tube mixer is large, a high discharge pressure is required for a pump, and the quantitative property of the liquid feed is poor, and therefore, it is difficult to obtain a polymer having a stable viscosity only by the tube mixer. Thus, the present invention is particularly effective in the case of producing a polymer having a high viscosity of 1000poise or more, for example.
In the polymer production system 1, any one or more of the supply of the 1 st supply pump 112, the supply of the 2 nd supply pump 122, the temperature adjustment of the 1 st tube type mixing temperature adjusting section 22, and the temperature adjustment of the 1 st fluctuation reducing temperature adjusting section 32 is controlled based on the 1 st reaction information acquired by the 1 st tube mixed fluid measuring section 222 and/or the 1 st generated fluid measuring section 322. Thus, a polymer having desired properties (temperature, viscosity) can be obtained.
In the present embodiment, the following is explained: one of the 1 st polymerizable compound and the 2 nd polymerizable compound is tetracarboxylic dianhydride, and the other is diamine, and polyamide acid is produced as a polymer, but the present invention is not limited thereto.
For example, a polyamide acid may be produced by using either one of the 1 st polymerizable compound and the 2 nd polymerizable compound as an acid anhydride-terminated polyamide acid (prepolymer) or an amino-terminated polyamide acid (prepolymer) and the other one as a diamine or tetracarboxylic dianhydride. In this case, when one of the 1 st polymerizable compound and the 2 nd polymerizable compound is an acid anhydride-terminated polyamic acid, the other is a diamine. In addition, when one of the 1 st polymerizable compound and the 2 nd polymerizable compound is an amino-terminal polyamic acid, the other is a tetracarboxylic dianhydride.
For example, the polymer may be produced by using either one of the 1 st polymerizable compound and the 2 nd polymerizable compound as an acid anhydride-terminated polyamic acid or an amino-terminated polyamic acid, and the other one as an amino-terminated polyamic acid or an acid anhydride-terminated polyamic acid. In this case, when one of the 1 st polymerizable compound and the 2 nd polymerizable compound is an acid anhydride-terminated polyamic acid, the other is an amino-terminated polyamic acid.
< embodiment 2 >
The polymer production system in embodiment 2 is described with reference to fig. 2. Fig. 2 is a diagram showing a polymer production system according to embodiment 2. The same reference numerals are given to the same components as those of embodiment 1.
The 1 st variation reducing section 30 of the present embodiment is disposed downstream of the 1 st tubular mixing section 20. The 1 st fluctuation reducing section 30 includes a cylindrical 1 st fluctuation reducing tank 31a having no stirrer, and a 1 st fluctuation reducing temperature adjusting section 32 (1 st temperature adjusting section) disposed outside the 1 st fluctuation reducing tank 31 a. In the present embodiment, the 1 st pipe mixed fluid C is adjusted to a temperature suitable for the polymerization reaction by the 1 st fluctuation reducing and temperature adjusting section 32.
In the 1 st variation reducing tank 31a, the viscosity variation in the axial direction (the flow direction of the fluid) of the 1 st tube mixed fluid C is reduced by the residence time distribution caused by the velocity difference between the vertical direction and the horizontal direction, and the behavior of the 1 st produced fluid D flowing out is stabilized, whereby the variation in the behavior of the 1 st tube mixed fluid C in the axial direction can be reduced.
In the 1 st variation reducing tank 31a, an open channel is formed, the 1 st tube mixed fluid C flows in from the upper part in the vertical direction, and the 1 st generated fluid D flows out from the lower part. Since the 1 st variation reducing tank 31a is set to be an open channel, the pressure on the inflow side of the 1 st tube mixed fluid C becomes the pressure of the gas phase portion, and therefore, the discharge pressure of the 1 st supply pump 112 and the discharge pressure of the 2 nd supply pump 122 can be reduced compared with the case where the 1 st tube mixed portion 20 is followed by a pipe, which is excellent in this point. The gas phase portion can be maintained at a constant pressure by an inert gas or the like.
The shape of the 1 st variation reducing tank 31a is not particularly limited, but is preferably a structure in which a dead space is not easily generated, and more preferably a cylindrical tank. If the ratio (L/D) of the diameter D to the height L of the cylindrical tank is too small, the fluid does not flow sufficiently in the horizontal direction, and short-pass tends to occur easily, so that the L/D is preferably 0.5 or more. On the other hand, if the L/D is too large, it is difficult to install the device, and therefore, the L/D is preferably 10 or less. Therefore, it is preferably 0.5 to 10.
The inlet of the 1 st variation reducing tank 31a may be provided on the wall surface or may be an insertion tube. In the case of the insertion tube, it is preferable that the inflow port is provided so as to be held in the liquid surface or so as to flow the fluid along the wall surface, thereby preventing air bubbles from being mixed. The outflow port of the 1 st fluctuation reducing tank 31a is preferably provided at a position where the entire outflow port is immersed in the liquid, so as to prevent air bubbles from being mixed.
The inflow rate of the 1 st tube mixed fluid C into the 1 st fluctuation reducing tank 31a is preferably controlled to be the same as the outflow rate of the 1 st produced fluid D, but may be varied. For example, the outflow speed of the 1 st generated fluid D may be controlled so that the liquid level of the 1 st fluctuation reducing tank 31a is within a predetermined range.
When the liquid surface is low, the gas phase may be entrained in the outflow port, and therefore, it is preferable that the amount of the 1 st pipe mixed fluid C in the 1 st fluctuation reducing tank 31a is two or more of the volumes of the 1 st fluctuation reducing tank 31 a. When the liquid surface is high, the flow in the 1 st variation reducing tank 31a may change from the open channel flow to the pipe flow or a transition state between the open channel flow and the pipe flow, and thus, the pressure variation in the 1 st variation reducing tank 31a may occur, and therefore, the amount of the 1 st pipe mixed fluid C in the 1 st variation reducing tank 31a is preferably 8 or less of the volume of the 1 st variation reducing tank 31 a. Therefore, the amount of the 1 st pipe mixed fluid C in the 1 st fluctuation reducing tank 31a is preferably controlled to be two to 8 in the volume of the 1 st fluctuation reducing tank 31 a.
When the 1 st variation reducing tank 31a is a cylindrical tank, the angle between the central axis and the installation surface is preferably 75 ° or less in order to reduce the risk of air bubbles being trapped. On the other hand, if the angle is too small, the liquid surface is slowly updated, and therefore, the angle between the central axis of the 1 st fluctuation reducing tank 31a and the installation surface is preferably 45 ° or more. Therefore, the angle between the central axis of the 1 st fluctuation reducing tank 31a and the installation surface is preferably 45 ° to 75 °.
The 1 st fluctuation reducing tank 31a is configured so that the average retention time is sufficiently long. The average residence time is a value obtained by dividing the volume of the solution in the 1 st fluctuation reducing tank 31a by the volume flow rate of the 1 st tube mixed fluid C. When the average residence time of the 1 st variation reducing tank 31a is long, the stabilizing effect of the viscosity of the 1 st produced fluid D flowing out of the 1 st variation reducing tank 31a is large. Accordingly, the larger the variation in the behavior of the 1 st mixed fluid C flowing out of the 1 st tubular mixing section 20 in the axial direction is, the longer the average residence time of the 1 st variation alleviation tank 31a is preferably. The residence time is preferably 3 minutes or more, more preferably 7 minutes or more, and still more preferably 10 minutes or more. The longer the average residence time of the 1 st fluctuation reducing tank 31a, the greater the effect of reducing the viscosity fluctuation, but in order to suppress the loss of the produced polymer to a small extent, the total value of the average residence time is more preferably 300 minutes or less.
In order to provide the 1 st variation reducing tank 31a with an appropriate average residence time in response to the viscosity variation of the 1 st tube mixed fluid C, the volume of the solution in the 1 st variation reducing tank 31a is preferably 0.5 to 100 times, more preferably 5 to 100 times the volume of the 1 st tube mixing and stirring section 20.
The shape of the 1 st variation reducing tank 31a is not particularly limited. Specifically, the structure may be provided inside. Further, a sensor or the like may be provided in the 1 st variation reducing tank 31 a.
Since the inside of the 1 st variation reducing tank 31a is an open channel, the 1 st tube mixed fluid C flowing in from the inlet located on the upper side makes a difference in the flow velocity of the 1 st tube mixed fluid C in the vertical direction and the horizontal direction in the 1 st variation reducing tank 31a, and makes a difference in the residence time in the 1 st variation reducing tank 31a, the variation in the behavior of the 1 st variation reducing tank 31a in the axial direction can be reduced.
The 1 st variation reducing and temperature adjusting unit 32 adjusts (e.g., cools) the 1 st pipe mixed fluid C flowing through the 1 st variation reducing tank 31a to a desired temperature condition.
In the above-described 1 st tubular mixing section 20 and 1 st variation reducing section 30, the 1 st tubular mixing section 20 is arranged in the preceding stage, and the 1 st variation reducing section 30 is arranged in the following stage, whereby, when there is a variation in viscosity in the axial direction of the pipe in the 1 st tubular mixing section 20 in the preceding stage, the variation in viscosity in the axial direction of the pipe can be greatly reduced in the 1 st variation reducing section 30 in the following stage.
Next, the operation of the polymer production system 1 (polyamic acid production system) according to embodiment 2 will be described.
In the 1 st variation reducing section 30, the 1 st tube mixed fluid C is flowed in, and the liquid is continuously fed in a state where the residence time of the 1 st tube mixed fluid C is distributed by the residence time distribution generated by the velocity difference between the vertical direction and the horizontal direction. This can greatly reduce the viscosity variation in the axial direction of the tube of the 1 st tube mixed fluid C, which cannot be eliminated in the 1 st tube mixing section 20 in the preceding stage, in the 1 st variation reducing section 30 in the following stage. Thus, a desired polymer can be continuously and stably obtained.
Embodiment 3
A polymer production system in embodiment 3 is described with reference to fig. 3. Fig. 3 is a diagram showing a polymer production system according to embodiment 3. The same reference numerals are given to the same components as those in embodiment 1 and embodiment 2.
The 1 st variation reducing section 30 of the present embodiment is disposed downstream of the 1 st tubular mixing section 20, and is designed such that the fluid flowing into the 1 st variation reducing section 30 simultaneously flows out of the 1 st variation reducing section 30 with a long time difference by a large residence time distribution. Specifically, the residence time distribution is designed to take 10 minutes or longer from the outflow of the fluid passing through the trace having the highest flow velocity to the outflow of 70% of the fluid simultaneously flowing into the 1 st fluctuation reducing section 30. By this large residence time distribution, the homogenization of the 1 st tube mixed fluid C in the axial direction is promoted, and the 1 st produced fluid D having less viscosity variation with time can be obtained.
The trace having the fastest flow rate is, for example, a trace through which the trace particles and the colorant initially flow out from the outlet of the 1 st fluctuation reducing section 30 when the trace particles and the colorant are placed in the entire cross section of the inlet of the 1 st fluctuation reducing section 30. In addition, "10 minutes or more is required from the time when the fluid flowing through the trace having the fastest flow rate flows out to the time when 70% of the fluid flowing simultaneously into the 1 st variation reducing section 30 flows out" means that, for example, 10 minutes or more is required from the time when the tracer and the colorant initially flow out to the time when the tracer and the colorant flow out from the outlet of the 1 st variation reducing section 30 to the time when the tracer and the colorant are put into the entire cross section of the inlet of the 1 st variation reducing section 30. In this case, the evaluation can be performed by a turbidimeter, a absorptiometer, or the like.
The larger the residence time distribution of the 1 st tube mixed fluid C in the 1 st fluctuation reducing section 30, the larger the viscosity fluctuation reducing effect. However, if the residence time distribution is too large, a large apparatus is required, and the facility cost becomes expensive, so that the 1 st fluctuation reducing section 30 is preferably designed so as to achieve an appropriate residence time distribution. Specifically, it is more preferable that the flow rate be 360 minutes or less from the outflow of the fluid through the trace having the fastest flow rate to the outflow of 70% of the fluid simultaneously flowing into the 1 st fluctuation reducing section 30.
As a structure of the 1 st variation reducing portion 30 for making the residence time distribution large, for example, a structure in which the 1 st tube mixed fluid C is branched into a plurality of flow paths having different residence times and then joined is given. In this case, the 1 st variation reducing portion 30 includes a 1 st variation reducing branching portion J2 (1 st branching portion) for branching the fluid flowing into the plurality of channels and a 1 st variation reducing joining portion J3 (2 nd joining portion) for joining the fluids flowing through the plurality of channels on the downstream side in the flow direction of the fluid in each of the plurality of channels branched by the 1 st variation reducing branching portion J2.
In the configuration shown in fig. 3, the 1 st variation reducing section 30 is configured to distribute the 1 st pipe mixed fluid C to two flow paths having different residence times in the 1 st variation reducing branching section J2 (1 st branching section), and to merge the 1 st mixed fluid C into 1 st flow path again in the 1 st variation reducing merging section J3 (2 nd merging section). The two flow paths of the 1 st variation reducing section 30 are formed of double pipes, and include a 1 st variation reducing pipe section 31 and a 2 nd variation reducing pipe section 33 arranged radially inward, and a 1 st variation reducing temperature adjusting section 32 (1 st temperature adjusting section) and a 2 nd variation reducing temperature adjusting section 34 (1 st temperature adjusting section) arranged radially outward. In the present embodiment, the 1 st pipe mixed fluid C is adjusted to a temperature suitable for the polymerization reaction by the 1 st variation reducing and temperature adjusting unit 32 and the 2 nd variation reducing and temperature adjusting unit 34.
The shape of the piping constituting the 1 st variation reducing section 30 is not particularly limited. For example, as described above, the 1 st variation reducing portion may be configured to have a 1 st branching portion for branching the fluid flowing therein into two or more different flow paths and a 1 st variation reducing and converging portion (2 nd converging portion) for converging the branched flow paths again, may have a structure therein, may use a pipe bent by a bend or the like, and may have a cross section other than a circular shape. Further, a valve, a sensor, or the like may be provided in the middle of the 1 st fluctuation reducing pipe section 31. Further, two or more channels having different residence times may be formed by partitioning the inside of 1 pipe with a partition or the like.
In the 1 st variation reducing section 30, the residence time distribution may be generated by using a speed difference in the radial direction in the same flow path, in addition to the residence time distribution generated by the combination of flow paths having different residence times. For example, in the case of laminar flow within a circular tube, the flow rate of the fluid passing through the center of the tube is the fastest and the residence time is the shortest. On the other hand, the flow rate of the fluid passing through the wall edge is extremely slow, and therefore the residence time is very long. Such a difference in residence time due to the trace can alleviate variation in the characteristics in the axial direction even in 1 flow path.
In order to obtain a sufficient viscosity fluctuation reducing effect by the speed difference in the radial direction in the same flow path, the 1 st pipe mixed fluid C more preferably flows in a laminar flow in the pipe. In order to flow in laminar flow in the 1 st variation reducing pipe section 31 and/or the 2 nd variation reducing pipe section 33, when the 4×cross-sectional area/wet cycle is used as the representative length d, the reynolds number (ρud/μ) calculated from the viscosity μ, the cross-sectional average flow velocity u, and the density ρ is preferably 2100 or less, and more preferably 0.00001 or more and 1000 or less. In addition, when the solution viscosity is low, since the flow guide section is long until the flow progresses, the velocity distribution cannot be effectively generated, and therefore, it is preferable that the viscosity of the 1 st pipe mixed fluid C flowing in the 1 st variation reducing pipe section 31 and/or the 2 nd variation reducing pipe section 33 is high. Specifically, the viscosity of the 1 st pipe mixed fluid C flowing in the 1 st variation reducing pipe section 31 and/or the 2 nd variation reducing pipe section 33 is preferably 0.1poise or more and 100000poise or less, more preferably 1poise or more and 10000poise or less, and still more preferably 5poise or more and 5000poise or less under the temperature conditions at the time of circulation.
Fig. 3 shows an example in which the 1 st fluctuation reducing section 30 is constituted by two channels having different residence times, but the present invention is not limited to this. As described above, if a residence time distribution of 10 minutes or more is required from the outflow of the fluid passing through the trace having the highest flow velocity to the outflow of 70% of the fluid simultaneously flowing into the 1 st variation reducing section 30 due to the velocity difference in the radial direction in 1 flow path, the 1 st variation reducing section 30 may be constituted by only 1 pipe without including the branching section and the joining section. On the other hand, in the case where the inside of the 1 st fluctuation reducing section 30 flows in a turbulent flow or the difference in speed in the radial direction is small due to the influence of the structure in the inside, the 1 st fluctuation reducing section 30 may be configured to branch into 3 or more pipes in order to positively generate the residence time distribution.
In the 1 st fluctuation reducing piping section 31 and the 2 nd fluctuation reducing piping section 33, the fluctuation can be reduced if the period is shorter than the average residence time, but the fluctuation is difficult to reduce if the period is longer than the average residence time. Therefore, it is preferable that the total value of the average residence time of the 1 st variation reducing pipe section 31 and the 2 nd variation reducing pipe section 33 is made sufficiently longer than the average variation period of the 1 st pipe mixed fluid C which may occur at the outlet of the 1 st pipe type mixing section 20. The average residence time referred to herein is a value obtained by dividing the total volume of the flow paths by the volume flow rate of the 1 st tube mixed fluid C. The average fluctuation period is an average value of the time from when the viscosity of the 1 st tube mixed fluid C at the outlet of the 1 st tube type mixing section 20 reaches the maximum value to when the viscosity reaches the minimum value once and reaches the maximum value again. The total value of the average residence time of the 1 st variation reducing pipe section 31 and the 2 nd variation reducing pipe section 33 is preferably 1 time or more, more preferably 2 times or more the average variation period of the 1 st tube mixed fluid C at the outlet of the 1 st tube mixing section 20.
In order to provide the 1 st variation reducing pipe section 31 and the 2 nd variation reducing pipe section 33 with an appropriate average retention time in response to the viscosity variation of the 1 st pipe mixed fluid C, the total value of the volumes of the 1 st variation reducing pipe section 31 and the 2 nd variation reducing pipe section 33 is preferably 0.5 to 100 times the volume of the 1 st pipe type mixed stirring section 20.
In order to obtain the 1 st generated fluid D containing no bubbles, the 1 st variation reducing pipe section 31 and the 2 nd variation reducing pipe section 33 are preferably transported in a state where the fluid is not in contact with the gas. However, the present invention is not limited to this, and if the air bubbles are not involved in the 1 st pipe mixed fluid C, a gas phase may be present in the 1 st variation reducing pipe section 31 and/or the 2 nd variation reducing pipe section 33.
In the structure of fig. 1 in which the 1 st pipe mixed fluid C is branched into two flow paths having different residence times and then joined, the 1 st pipe mixed fluid C flowing into the 1 st variation reducing section 30 is distributed to the 1 st variation reducing pipe section 31 and the 2 nd variation reducing pipe section 33 at the 1 st variation reducing branching section J2. The 1 st pipe mixed fluid C distributed in the 1 st variation reducing branching portion J2 flows toward the 1 st variation reducing joining portion J3 in the 1 st variation reducing piping portion 31 and the 2 nd variation reducing piping portion 33, joins the 1 st variation reducing joining portion J3, and flows out of the 1 st variation reducing portion 30.
The 1 st variation reducing and temperature adjusting portion 32 and the 2 nd variation reducing and temperature adjusting portion 34 are pipe portions disposed radially outward of the 1 st variation reducing pipe portion 31 and radially outward of the 2 nd variation reducing pipe portion 33, respectively, and adjust (e.g., cool) the 1 st pipe mixed fluid C flowing inside to a desired temperature condition. In these temperature adjusting sections, the 1 st pipe mixed fluid C is adjusted to a temperature suitable for polymerization reaction, and flows through the 1 st variation reducing pipe section 31 and the 2 nd variation reducing pipe section 33.
When the 1 st pipe mixed fluid C is not distributed to the plurality of flow paths constituting the 1 st variation reducing section 30 at the respective desired flow rates due to the influence of the difference in pressure loss or the like, 1 or more pumps may be provided in the 1 st variation reducing section 30 so that the flow rate of the 1 st pipe mixed fluid C flowing in each flow path can be adjusted. The 1 st pipe mixed fluid C may be distributed to the respective channels at a desired flow rate by providing 1 or more back pressure valves and valves capable of adjusting the opening degree in the 1 st fluctuation reducing section 30 to adjust the pressure loss.
In the above-described 1 st tubular mixing section 20 and 1 st variation reducing section 30, the 1 st tubular mixing section 20 is arranged in the preceding stage, and the 1 st variation reducing section 30 is arranged in the following stage, whereby, when there is a variation in viscosity in the axial direction of the pipe in the 1 st tubular mixing section 20 in the preceding stage, the variation in viscosity in the axial direction of the pipe can be greatly reduced in the 1 st variation reducing section 30 in the following stage.
Next, the operation of the polymer production system 1 (polyamic acid production system) in embodiment 3 will be described.
In the 1 st variation reducing section 30, the 1 st tube mixed fluid C is flowed in, and the liquid is continuously fed in a state where the residence time of the 1 st tube mixed fluid C is distributed by the velocity distribution in the radial direction and/or the effect of branching into flow paths having different residence times. This can greatly reduce the viscosity variation in the axial direction of the tube of the 1 st tube mixed fluid C, which cannot be eliminated in the 1 st tube mixing section 20 in the preceding stage, in the 1 st variation reducing section 30 in the following stage. Thus, a desired polymer can be continuously and stably obtained.
Here, in the middle of the operation of the polymer manufacturing system 1, the 1 st pipe mixed fluid measurement unit 222 and the 1 st generated fluid measurement unit 322 acquire viscosity information (measurement step).
The control unit 200 controls the supply pumps 112 and 122 and the temperature adjusting units 22, 32, and 34 based on the viscosity information (1 st reaction information) obtained by the 1 st pipe mixed fluid measuring unit 222 and/or the 1 st generated fluid measuring unit 322 (control step). Thus, polyamic acid having desired properties (temperature and viscosity) can be obtained.
When the distribution of the residence time of the 1 st tube mixed fluid C in the 1 st fluctuation reducing section 30 is known, the 1 st viscosity information is acquired by the 1 st tube mixed fluid measuring section 222 (measuring step), whereby the change with time of the viscosity of the 1 st generated fluid D at the outlet of the 1 st fluctuation reducing section 30 can be predicted (predicting step). The supply pumps 112 and 122 and the temperature adjusting units 22, 32, and 34 may be controlled based on the viscosity thus predicted (control step). For example, when the hagen-poiseuille flow is formed in the laminar flow in the 1 st variation reducing unit 30, the flow velocity distribution in the radial direction can be calculated, and thus the residence time distribution can be obtained. Thus, when a time-moving average weighted by the residence time distribution is calculated from the viscosity of the 1 st pipe mixed fluid C acquired by the 1 st pipe mixed fluid measuring unit 222, a predicted value of the viscosity of the 1 st generated fluid D at the outlet of the 1 st fluctuation reducing unit 30 can be obtained. In the case where the 1 st variation reducing unit 30 has a structure in which two or more flow paths are branched, the average of the residence time distribution of each flow path weighted by the flow rate ratio of each flow path may be considered.
In the polymer production system 1, any one or more operations of the supply of the 1 st supply pump 112, the supply of the 2 nd supply pump 122, the temperature adjustment of the 1 st tubular mixing temperature adjusting section 22, the temperature adjustment of the 1 st fluctuation reducing temperature adjusting section 32, and the temperature adjustment of the 2 nd fluctuation reducing temperature adjusting section 34 are controlled based on the 1 st reaction information acquired by the 1 st tubular mixing fluid measuring section 222 and/or the 1 st production fluid measuring section 322. Thus, a polymer having desired properties (temperature, viscosity) can be obtained.
< modification >
Although the above description has been given of 3 embodiments, the present invention is not limited to the above embodiments, and includes modifications and improvements within the scope of achieving the object of the present invention.
For example, in the above embodiment, the fluid is mixed in the 1 st pipe type mixing section and the 1 st variation reducing section. However, the present invention is not limited thereto. A 1-stage or multi-stage tubular mixing section and/or a variation reducing section may be provided further downstream in the structure of the above embodiment. In embodiment 3, the 1 st flow path is merged into 1 st flow path at the 1 st variation-moderating merging portion J3, but the present invention is not limited thereto, and for example, the 1 st pipe mixed fluid C divided into a plurality of flow paths may be independently flowed into a buffer tank or the like provided downstream.
In the present embodiment, the description has been given of the case where the 1 st tubular mixing section 20 is constituted by a double pipe of the 1 st tubular mixing stirring section 21 and the 1 st temperature adjusting section 22, but the present invention is not limited thereto. For example, the 1 st tubular type mixing section 20 may be constituted by only a single tube of the 1 st tubular type mixing and stirring section 21, and the 1 st tubular type mixing and stirring section 21 may be immersed in the temperature-adjusting liquid.
In the above embodiment, the polymer production system for producing polyamide acid or polyimide was described, but the produced polymer is not limited thereto. For example, the polymer production system may be a system for producing a polymer using an addition polymerizable monomer such as a urethane monomer or an epoxy monomer. In the above-described embodiment, the example of reducing the time-dependent viscosity fluctuation by the 1 st fluctuation reducing section 30 has been described, but the property of being able to reduce the fluctuation is not limited to the viscosity, and the time-dependent viscosity fluctuation of other physical properties may be reduced by the 1 st fluctuation reducing section 30 even when the time-dependent viscosity fluctuation occurs.
In the above embodiment, the viscosity measurement unit acquires the viscosity information on the viscosity of the 1 st tube mixed fluid C and the 1 st produced fluid D, and controls the supply amount of the fluid and/or the temperature condition of the mixing based on the acquired viscosity information, but the present invention is not limited thereto. For example, absorbance information on absorbance of the 1 st tube mixed fluid C and the 1 st produced fluid D may be acquired, and the supply amount of the fluid and/or the temperature condition of the mixture may be controlled based on the acquired absorbance information.
In the above embodiment, the example in which the parts of the polymer production system are connected by the 1 st liquid feed line L1, the 2 nd liquid feed line L2, the 3 rd liquid feed line L3, the 4 th liquid feed line L4, and the 5 th liquid feed line L5 has been shown, but the present invention is not limited thereto. For example, the outlet of the 1 st pipe type mixing section 20 and the inlet of the 1 st fluctuation reducing section 30 may be directly connected without the 4 th liquid feed line L4.
In the above embodiment, the method of controlling the temperature of the 1 st tubular mixing section 20 and the temperature of the 1 st fluctuation reducing section 30 has been described, but the present invention is not limited thereto. For example, the temperature adjusting portion of the 1 st pipe type mixing portion 20 and/or the temperature adjusting portion of the 1 st fluctuation reducing portion 30 are not necessarily required, and the temperature adjusting portion may be provided at any one or more of the 1 st junction J1, the 1 st liquid feed line L1, the 2 nd liquid feed line L2, the 3 rd liquid feed line L3, the 4 th liquid feed line L4, and the 5 th liquid feed line L5.
Examples
The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
Example 1 >
In example 1, a polyamic acid was produced using a polymer production system 1 having a structure as shown in fig. 1. The 1 st tank 11 contains A1 st fluid A1, wherein the 1 st fluid A1 is obtained by dissolving an acid anhydride-terminated polyamic acid obtained by a reaction between 4,4' -diaminodiphenyl ether and pyromellitic dianhydride in N, N-dimethylformamide. In addition, A2 nd fluid A2 is contained in the 2 nd tank 12, and the 2 nd fluid A2 is obtained by dissolving p-phenylenediamine in N, N-dimethylformamide.
First, in the 1 st junction J1, the 1 st fluid A1 supplied from the 1 st supply pump 112 and the 2 nd fluid A2 supplied from the 2 nd supply pump 122 are joined and mixed to generate A1 st joined fluid B. Next, in the 1 st tubular mixing section 20, the 1 st mixed fluid B is stirred in a state where the 1 st mixed fluid B does not contact the gas, and the 1 st tubular mixed fluid C having no property unevenness in the radial direction of the tube flows out from the outlet of the 1 st tubular mixing section 20.
More specifically, as the 1 st tubular mixing section 20, a Kenics mixer type static mixer (inner diameter 8mm, length 670 mm) was used, and the 1 st mixed fluid B was stirred in a state where the 1 st mixed fluid B was not in contact with the gas. The total value of the amounts of the 1 st supply pump 112 and the 2 nd supply pump 122 was 1.0cc/s, and the ratio of the supply of the raw materials was adjusted by these pumps, whereby a polymer solution having a desired viscosity was obtained. At the outlet of the 1 st tube type mixing section 20, the polymerization reaction was completed to obtain a1 st tube mixed fluid having the same properties in the radial direction, but a viscosity change was generated in which the difference between the maximum value and the minimum value of the viscosity was about 400poise, as measured by an online viscometer. The average value of the viscosities of the 1 st tube mixed fluid C was 2100poise.
As the 1 st variation reducing portion 30, a hollow cylindrical tube having an inner diameter of 30mm and a length of 900mm was used. The 1 st tube mixed fluid C flowing out of the 1 st tube mixing section 20 was flowed into the 1 st variation reducing section 30 at a volume flow rate of 1.0 cc/s. By the flow velocity distribution generated in the 1 st variation reducing section 30, the 1 st mixed fluid C was mixed in the axial direction, and the 1 st produced fluid D having a viscosity average value of 2100poise and reduced in viscosity variation was discharged from the outlet of the 1 st variation reducing section 30. The difference between the maximum and minimum viscosities of the 1 st produced fluid D was about 80poise, as measured by an online viscometer. Thus, it is understood that by providing the 1 st variation reducing portion 30, the viscosity variation with time of the fluid at the outlet of the 1 st tubular mixing portion 20 can be greatly reduced.
Example 2 >
In example 2, a polyamic acid was produced using the polymer production system 1 having the structure shown in fig. 2. The 1 st tank 11 contains A1 st fluid A1, wherein the 1 st fluid A1 is obtained by dissolving an acid anhydride-terminated polyamic acid obtained by a reaction between 4,4' -diaminodiphenyl ether and pyromellitic dianhydride in N, N-dimethylformamide. In addition, A2 nd fluid A2 is contained in the 2 nd tank 12, and the 2 nd fluid A2 is obtained by dissolving p-phenylenediamine in N, N-dimethylformamide.
First, in the 1 st junction J1, the 1 st fluid A1 supplied from the 1 st supply pump 112 and the 2 nd fluid A2 supplied from the 2 nd supply pump 122 are joined and mixed to generate A1 st joined fluid B. Next, in the 1 st tubular mixing section 20, the 1 st mixed fluid B is stirred in a state where the 1 st mixed fluid B does not contact the gas, and the 1 st tubular mixed fluid C having no property unevenness in the radial direction of the tube flows out from the outlet of the 1 st tubular mixing section 20.
More specifically, A1 st fluid A1 and A2 nd fluid A2 were mixed by joining each other using a Kenics mixer type static mixer (inner diameter 8mm, length 670 mm), and A1 st joined fluid B was produced, and the total value of the amounts of the 1 st fluid A1 and the 2 nd fluid A2 was 1.0cc/s. Next, in the 1 st tubular mixing section 20, the 1 st mixed fluid B is stirred in a state where the 1 st mixed fluid B is not in contact with the gas, and a1 st tubular mixed fluid C having no property unevenness in the radial direction of the tube is obtained from the outlet of the 1 st tubular mixing section 20. At the outlet of the 1 st tube type mixing section 20, the polymerization reaction was completed to obtain a1 st tube mixed fluid C having the same degree of properties in the radial direction, but a viscosity change was generated in which the difference between the maximum value and the minimum value of the viscosity was 800poise, as measured by an in-line viscometer. The average value of the viscosities of the 1 st tube mixed fluid C was 1800poise.
As the 1 st variation reducing tank 31a of the 1 st variation reducing section 30, a cylindrical tank having an inner diameter of 80mm and a capacity of 500ml was used, and the central axis of the cylindrical tank was set at 60 ° with respect to the setting surface. A part of the 1 st tube mixed fluid C flowing out of the 1 st tube mixed portion 20 is flowed into the 1 st variation reducing tank 31a from the upper portion thereof at a volume flow rate of 0.2 cc/s. The 1 st generated fluid D is discharged from the bottom of the 1 st fluctuation reducing tank 31a at the same flow rate. The average residence time in the 1 st fluctuation reducing tank 31a was 11min.
By the flow velocity distribution generated in the 1 st variation reducing tank 31a, the 1 st mixed fluid C is mixed in the axial direction, and the 1 st produced fluid D having an average viscosity of 1800poise and less viscosity variation flows out from the outlet of the 1 st variation reducing tank 31 a. The difference between the maximum and minimum viscosities of the 1 st produced fluid D was 40poise, as measured by an in-line viscometer. Thus, by providing the 1 st variation reducing portion 30, the viscosity variation with time of the fluid at the outlet of the 1 st tubular mixing portion 20 is greatly reduced.
Example 3 >
In example 3, a polyamic acid was produced using the polymer production system 1 having the structure shown in fig. 3. The 1 st tank 11 contains A1 st fluid A1, wherein the 1 st fluid A1 is obtained by dissolving an acid anhydride-terminated polyamic acid obtained by a reaction between 4,4' -diaminodiphenyl ether and pyromellitic dianhydride in N, N-dimethylformamide. In addition, A2 nd fluid A2 is contained in the 2 nd tank 12, and the 2 nd fluid A2 is obtained by dissolving p-phenylenediamine in N, N-dimethylformamide.
First, in the 1 st junction J1, the 1 st fluid A1 supplied from the 1 st supply pump 112 and the 2 nd fluid A2 supplied from the 2 nd supply pump 122 are joined and mixed to generate A1 st joined fluid B. Next, in the 1 st tubular mixing section 20, the 1 st mixed fluid B is stirred in a state where the 1 st mixed fluid B does not contact the gas, and the 1 st tubular mixed fluid C having no property unevenness in the radial direction of the tube flows out from the outlet of the 1 st tubular mixing section 20.
More specifically, as the 1 st tubular mixing section 20, a Kenics mixer type static mixer (inner diameter 8mm, length 670 mm) was used, and the 1 st mixed fluid B was stirred in a state where the 1 st mixed fluid B was not in contact with the gas. The total value of the amounts of the 1 st supply pump 112 and the 2 nd supply pump 122 was 1.0cc/s, and the ratio of the supply of the raw materials was adjusted by these pumps, whereby a polymer solution having a desired viscosity was obtained. At the outlet of the 1 st tube type mixing section 20, the polymerization reaction was completed to obtain a1 st tube mixed fluid having the same properties in the radial direction, but a viscosity change was generated in which the difference between the maximum value and the minimum value of the viscosity was about 400poise, as measured by an online viscometer. The average value of the viscosities of the 1 st tube mixed fluid C was 2100poise.
As the 1 st variation reducing portion 30, a hollow cylindrical pipe having an inner diameter of 30mm and a length of 1000mm was used for the 1 st variation reducing piping portion 31, and a hollow cylindrical pipe having an inner diameter of 20mm and a length of 200mm was used for the 2 nd variation reducing piping portion 33, and it took 13 minutes from the outflow of the fluid passing through the trace having the highest flow velocity to the outflow of 70% of the fluid simultaneously flowing into the 1 st variation reducing portion 30. The 1 st tube mixed fluid C flowing out of the 1 st tube mixing section 20 was flowed into the 1 st variation reducing section 30 at a volume flow rate of 1.0 cc/s. By the residence time distribution generated in the 1 st variation reducing section 30, the 1 st mixed fluid C was mixed in the axial direction, and the 1 st produced fluid D having a viscosity average value of 2100poise and less viscosity variation was discharged from the outlet of the 1 st variation reducing section 30. The difference between the maximum and minimum viscosities of the 1 st produced fluid D was about 80poise, as measured by an online viscometer. Thus, it is understood that by providing the 1 st variation reducing portion 30, the viscosity variation with time of the fluid at the outlet of the 1 st tubular mixing portion 20 can be greatly reduced.
Description of the reference numerals
1. A polymer manufacturing system; 11. tank 1; 12. tank 2; 20. a1 st tubular mixing section; 21. a1 st tubular mixing and stirring part; 22. a1 st tube type mixed temperature adjusting part (1 st temperature adjusting part); 30. a1 st variation alleviation unit; 31. a1 st fluctuation reducing piping section; 31a, 1 st variation alleviation tank; 32. a1 st variation-alleviation temperature-adjustment unit (1 st temperature-adjustment unit); 33. a2 nd variation reducing piping section; 34. a2 nd variation-alleviation temperature-adjustment unit (1 st temperature-adjustment unit); 111. tank 1 on-off valve; 112. a1 st supply pump (1 st supply unit); 113. a1 st flow rate measurement unit; 121. 2 nd tank on-off valve; 122. a2 nd supply pump (2 nd supply unit); 123. a2 nd flow rate measurement unit; 200. a control unit; 222. a1 st tube mixed fluid measuring section (1 st measuring section); 322. a2 nd generation fluid measurement unit (1 st measurement unit); a1, fluid 1; a2, fluid 2; B. confluent fluid 1; C. tube 1 mixes the fluid; D. 1 st generation of fluid; l, liquid feeding pipeline; l1, the 1 st liquid feeding pipeline; l2, the 2 nd liquid feeding pipeline; l3, 3 rd liquid feeding pipeline; l4, 4 th liquid feeding pipeline; l5, 5 th liquid feeding pipeline; j1, 1 st junction; j2, the 1 st variation alleviation branching portion (1 st branching portion); j3, 2 nd variation-moderating junction (2 nd junction).
Claims (19)
1. A polymer production system for producing a polymer from a 1 st fluid and a 2 nd fluid as raw materials, wherein the 1 st fluid contains a 1 st polymerizable compound, the 1 st polymerizable compound has addition polymerization, the 2 nd fluid contains a 2 nd polymerizable compound, the 2 nd polymerizable compound has addition polymerization, and the 1 st polymerizable compound is addition polymerized,
the polymer production system comprises:
a 1 st supply unit configured to supply the 1 st fluid;
a 2 nd supply unit configured to supply the 2 nd fluid;
a 1 st junction that joins the 1 st fluid and the 2 nd fluid to generate a 1 st joined fluid;
a 1 st tubular mixing section disposed downstream of the 1 st joining section, the 1 st tubular mixing section enhancing mixing of the 1 st joining fluid in a radial direction to generate a 1 st tubular mixed fluid; and
and a 1 st variation reducing unit which is disposed downstream of the 1 st tubular mixing unit, wherein the 1 st variation reducing unit generates the 1 st generated fluid by reducing variation in the properties of the 1 st tubular mixing fluid in the axial direction.
2. The polymer manufacturing system according to claim 1, wherein,
the polymer production system further includes a 1 st measurement unit that obtains 1 st reaction information on a physical quantity and/or composition of any one or more of the 1 st merged fluid, the 1 st tube mixed fluid, and the 1 st produced fluid.
3. The polymer manufacturing system according to claim 2, wherein,
the 1 st measuring unit has 1 or more devices selected from the group consisting of a viscometer, a thermometer, a manometer, a pump pressure meter, an absorbance meter, an infrared spectrometer, a near infrared spectrometer, a densitometer, a color difference meter, a refractive index meter, a spectrophotometer, a conductivity meter, a turbidity meter, an ultrasonic sensor, and a fluorescent X-ray analysis device.
4. The polymer manufacturing system according to claim 2, wherein,
the polymer production system further includes a 1 st temperature adjustment unit for adjusting the temperature of at least one of the 1 st fluid, the 2 nd fluid, the 1 st combined fluid, the 1 st pipe mixed fluid, and the 1 st produced fluid.
5. The polymer production system according to any one of claim 1 to 4, wherein,
the 1 st variation reducing section is a pipe having an average retention time of the fluid flowing therein of 3 minutes or longer.
6. The polymer production system according to any one of claim 1 to 4, wherein,
the 1 st variation reducing section is composed of 1 or more tubular members,
the total value of the average residence time of the tubular members is 7 minutes or more.
7. The polymer production system according to any one of claim 1 to 4, wherein,
a 1 st-tube mixed fluid measuring unit that acquires 1 st-tube mixed fluid reaction information on a physical quantity and/or composition of the 1 st-tube mixed fluid is provided between the 1 st-tube mixed unit and the 1 st variation reducing unit,
a 1 st generated fluid measuring unit that obtains 1 st generated fluid reaction information on the physical quantity and/or composition of the 1 st generated fluid is further provided at or downstream of the outlet of the 1 st variation reducing unit,
the volume of the 1 st variation reducing section is 0.5 to 100 times the volume of the 1 st tubular mixing section.
8. The polymer production system according to any one of claim 1 to 4, wherein,
the volume of the 1 st variation reducing section is 5 to 100 times the volume of the 1 st tubular mixing section.
9. The polymer production system according to any one of claim 1 to 4, wherein,
the 1 st variation reducing section is a pipe having a residence time of 3 minutes or longer for a fluid passing through a trace having the fastest flow rate.
10. The polymer production system according to any one of claim 1 to 4, wherein,
The 1 st variation reducing section is composed of 1 or more tubular members,
the average flow velocity of the fluid flowing inside the tubular member is 0.01m/s or less,
the total value of the lengths of the tubular members is 0.7m or more.
11. The polymer production system according to any one of claims 1 to 10, wherein,
when 4×cross-sectional area/wet circumference is used as the representative length, the reynolds number of the fluid flowing in the 1 st variation reducing portion is 2100 or less.
12. The polymer manufacturing system of claim 1, wherein,
the 1 st variation reducing section does not have a driving type stirrer, and the fluid forms an open channel.
13. The polymer manufacturing system of claim 1, wherein,
it takes 10 minutes or more from the outflow of the fluid passing through the trace having the fastest flow rate to the outflow of 70% of the fluid simultaneously flowing into the 1 st variation reducing section.
14. The polymer production system according to any one of claims 1 to 13, wherein,
the 1 st polymerizable compound and the 2 nd polymerizable compound satisfy any one of the following (a) to (c), and a polyamic acid is produced as the polymer,
(a) One of the 1 st polymerizable compound and the 2 nd polymerizable compound is tetracarboxylic dianhydride, the other is diamine,
(b) One of the 1 st polymerizable compound and the 2 nd polymerizable compound is an acid anhydride-terminated polyamic acid or an amino-terminated polyamic acid, the other is a diamine or a tetracarboxylic dianhydride,
(c) One of the 1 st polymerizable compound and the 2 nd polymerizable compound is an acid anhydride-terminated polyamic acid or an amino-terminated polyamic acid, and the other is an amino-terminated polyamic acid or an acid anhydride-terminated polyamic acid.
15. The polymer manufacturing system of claim 14, wherein,
the polymer production system further comprises an imidization unit for imidizing the produced polyamic acid, and polyimide is produced as the polymer.
16. The polymer manufacturing system of claim 4, wherein,
the 1 st measurement unit obtains the 1 st reaction information of one or more fluids selected from the 1 st merged fluid, the 1 st tube mixed fluid, and the 1 st generated fluid,
the polymer production system further includes a control unit that controls any one or more operations selected from the group consisting of supply of the fluid from the 1 st supply unit, supply of the fluid from the 2 nd supply unit, and adjustment of the temperature of the 1 st temperature adjustment unit, based on the 1 st reaction information obtained.
17. The polymer manufacturing system of claim 4, wherein,
the 1 st measuring part obtains the 1 st reaction information of the 1 st combined fluid and/or the 1 st reaction information of the 1 st pipe mixed fluid,
the polymer production system further includes a control unit that predicts the property of the 1 st produced fluid based on the 1 st reaction information obtained, and controls any one or more operations selected from the group consisting of the supply of the 1 st supply unit, the supply of the 2 nd supply unit, and the temperature adjustment of the 1 st temperature adjustment unit based on the predicted property of the 1 st produced fluid.
18. A process for producing a polymer, wherein,
use of the polymer manufacturing system of any one of claims 1 to 17.
19. A process for producing a polyamic acid solution and/or polyimide, wherein,
use of the polymer manufacturing system of any one of claims 1 to 17.
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| PCT/JP2022/010836 WO2022196554A1 (en) | 2021-03-18 | 2022-03-11 | Polymer production system and polymer production method |
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