TWI835457B - Method for preparing high molecular weight cycloaliphatic polycarbonate - Google Patents
Method for preparing high molecular weight cycloaliphatic polycarbonate Download PDFInfo
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- TWI835457B TWI835457B TW111147474A TW111147474A TWI835457B TW I835457 B TWI835457 B TW I835457B TW 111147474 A TW111147474 A TW 111147474A TW 111147474 A TW111147474 A TW 111147474A TW I835457 B TWI835457 B TW I835457B
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- propane
- hydroxycyclohexyl
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- 239000004417 polycarbonate Substances 0.000 title claims abstract description 37
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 14
- CDBAMNGURPMUTG-UHFFFAOYSA-N 4-[2-(4-hydroxycyclohexyl)propan-2-yl]cyclohexan-1-ol Chemical compound C1CC(O)CCC1C(C)(C)C1CCC(O)CC1 CDBAMNGURPMUTG-UHFFFAOYSA-N 0.000 claims abstract description 85
- 239000002904 solvent Substances 0.000 claims abstract description 81
- 239000000203 mixture Substances 0.000 claims abstract description 45
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000011259 mixed solution Substances 0.000 claims abstract description 36
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 150000007530 organic bases Chemical class 0.000 claims abstract description 19
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 62
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 48
- 238000002360 preparation method Methods 0.000 claims description 48
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 44
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical group CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 38
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 33
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 31
- 125000002723 alicyclic group Chemical group 0.000 claims description 27
- 239000002131 composite material Substances 0.000 claims description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 22
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 18
- 238000006068 polycondensation reaction Methods 0.000 claims description 17
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 12
- DMEDNTFWIHCBRK-UHFFFAOYSA-N 1,3-dichloro-2-methylbenzene Chemical compound CC1=C(Cl)C=CC=C1Cl DMEDNTFWIHCBRK-UHFFFAOYSA-N 0.000 claims description 10
- RYMMNSVHOKXTNN-UHFFFAOYSA-N 1,3-dichloro-5-methyl-benzene Natural products CC1=CC(Cl)=CC(Cl)=C1 RYMMNSVHOKXTNN-UHFFFAOYSA-N 0.000 claims description 10
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical group ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 10
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- 239000001294 propane Substances 0.000 claims description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000001953 recrystallisation Methods 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- JLYXXMFPNIAWKQ-GNIYUCBRSA-N gamma-hexachlorocyclohexane Chemical compound Cl[C@H]1[C@H](Cl)[C@@H](Cl)[C@@H](Cl)[C@H](Cl)[C@H]1Cl JLYXXMFPNIAWKQ-GNIYUCBRSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229960002809 lindane Drugs 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 claims description 2
- 238000006317 isomerization reaction Methods 0.000 claims 1
- 239000003426 co-catalyst Substances 0.000 abstract 1
- 238000006482 condensation reaction Methods 0.000 abstract 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 48
- 239000000047 product Substances 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 15
- 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 14
- 238000004458 analytical method Methods 0.000 description 13
- JEGMWWXJUXDNJN-UHFFFAOYSA-N 3-methylpiperidine Chemical compound CC1CCCNC1 JEGMWWXJUXDNJN-UHFFFAOYSA-N 0.000 description 8
- 238000005259 measurement Methods 0.000 description 7
- UZOFELREXGAFOI-UHFFFAOYSA-N 4-methylpiperidine Chemical compound CC1CCNCC1 UZOFELREXGAFOI-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- -1 hydroxycyclohexyl Chemical group 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 150000003927 aminopyridines Chemical class 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 229940127554 medical product Drugs 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- LAYPMCGIWDGYKX-UHFFFAOYSA-N trichloromethyl hydrogen carbonate Chemical compound OC(=O)OC(Cl)(Cl)Cl LAYPMCGIWDGYKX-UHFFFAOYSA-N 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- YVPZFPKENDZQEJ-UHFFFAOYSA-N 4-propylcyclohexan-1-ol Chemical compound CCCC1CCC(O)CC1 YVPZFPKENDZQEJ-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003965 capillary gas chromatography Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 239000012084 conversion product Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 210000000750 endocrine system Anatomy 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- VYMDGNCVAMGZFE-UHFFFAOYSA-N phenylbutazonum Chemical compound O=C1C(CCCC)C(=O)N(C=2C=CC=CC=2)N1C1=CC=CC=C1 VYMDGNCVAMGZFE-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
Abstract
Description
本發明係關於一種聚碳酸酯之製備方法，尤其係關於一種高分子量脂環族聚碳酸酯之製備方法。 The present invention relates to a method for preparing polycarbonate, in particular to a method for preparing high molecular weight alicyclic polycarbonate.
聚碳酸酯(PC)是一種綜合性能優良的工程塑膠，其具有耐高溫、高透明、高強度、耐衝擊及高熱阻等特性，廣泛應用於食品包裝、醫療器械、建築建材、電子電腦、汽車、航太航空及光學等領域，其中，雙酚A(BPA)型之芳香族聚碳酸酯最為普遍。 Polycarbonate (PC) is an engineering plastic with excellent comprehensive properties. It has the characteristics of high temperature resistance, high transparency, high strength, impact resistance and high thermal resistance. It is widely used in food packaging, medical equipment, construction materials, electronic computers, automobiles, etc. , aerospace, optics and other fields, among which bisphenol A (BPA) type aromatic polycarbonate is the most common.
然而，該芳香族聚碳酸酯具有苯環結構，故製得之聚碳酸酯無法耐紫外光照射；又，雙酚A型芳香族聚碳酸酯所殘留之雙酚A單體(BPA，2,2-雙(4-羥基苯基)丙烷)尚有干擾內分泌系統或導致雌性早熟之環境賀爾蒙等問題。因此，開發其他單體替代雙酚A之研究係備受關注。特別是氫化雙酚A(HBPA，2,2-雙(4-羥基環己基)丙烷)，其結構與雙酚A單體相似且不具苯環結構，係替代雙酚A之理想單體，但目前國內外對工業製備脂環族聚碳酸酯之技術仍還未有任何具體報導。 However, the aromatic polycarbonate has a benzene ring structure, so the polycarbonate produced cannot withstand ultraviolet light irradiation; in addition, the residual bisphenol A monomer (BPA, 2, 2-bis(4-hydroxyphenyl)propane) also has environmental hormone problems such as interfering with the endocrine system or causing premature puberty in females. Therefore, research on developing other monomers to replace bisphenol A has attracted much attention. In particular, hydrogenated bisphenol A (HBPA, 2,2-bis(4-hydroxycyclohexyl)propane) has a structure similar to bisphenol A monomer and does not have a benzene ring structure. It is an ideal monomer to replace bisphenol A, but At present, there are still no specific reports on the technology for industrial preparation of alicyclic polycarbonate at home and abroad.
依據文獻，關於脂環族聚碳酸酯之合成方法，可分為光氣法及非光氣法(例如，酯交換法)。惟，光氣法所使用之光氣具有高危險性且不易取得；而非光氣法係須在高溫低壓下進行，其反應條件相較光氣法更為嚴苛。此外，先前技術所製之脂環族聚碳酸酯的分子量較低，故而難以取代原聚碳酸酯材料的應用。有鑑於此，有必要提出一種有效生產高分子量脂環族聚碳酸酯之製備方法，以解決上述先前技術所存在的問題。 According to the literature, the synthesis method of alicyclic polycarbonate can be divided into phosgene method and non-phosgene method (for example, transesterification method). However, the phosgene used in the phosgene method is highly dangerous and difficult to obtain; the non-phosgene method must be carried out under high temperature and low pressure, and its reaction conditions are more stringent than the phosgene method. In addition, the alicyclic polycarbonate produced in the prior art has a low molecular weight, so it is difficult to replace the original polycarbonate material in application. In view of this, it is necessary to propose a preparation method for effectively producing high molecular weight alicyclic polycarbonate to solve the above-mentioned problems existing in the prior art.
為解決上述之問題，本發明係提供一種高分子量脂環族聚碳酸酯之製備方法，係包括：於第一溶劑、有機鹼催化劑和助催化劑之存在下，使2,2-雙(4-羥基環己基)丙烷之異構體混合物溶解於該第一溶劑中形成混合溶液，且該2,2-雙(4-羥基環己基)丙烷之異構體混合物於該混合溶液中之含量為0.5至1.0體積莫耳濃度，其中，該2,2-雙(4-羥基環己基)丙烷之異構體混合物中的順-反異構體的含量為45mol%以下；以及將溶解於第二溶劑中之雙(三氯甲基)碳酸酯添加至該混合溶液中進行縮聚反應，以製得峰值分子量(Mp)大於12000g/mol之脂環族聚碳酸酯。 In order to solve the above problems, the present invention provides a preparation method of high molecular weight alicyclic polycarbonate, which includes: in the presence of a first solvent, an organic base catalyst and a cocatalyst, 2,2-bis(4- The isomer mixture of hydroxycyclohexyl)propane is dissolved in the first solvent to form a mixed solution, and the content of the isomer mixture of 2,2-bis(4-hydroxycyclohexyl)propane in the mixed solution is 0.5 to a volume molar concentration of 1.0, wherein the content of cis-trans isomers in the isomer mixture of 2,2-bis(4-hydroxycyclohexyl)propane is less than 45 mol%; and will be dissolved in the second solvent The bis(trichloromethyl) carbonate is added to the mixed solution to perform a polycondensation reaction to produce an alicyclic polycarbonate with a peak molecular weight (Mp) greater than 12,000 g/mol.
於本發明的一具體實施態樣中，該製備方法復包括在形成該混合溶液之前，使尚未純化之2,2-雙(4-羥基環己基)丙烷於複合溶劑的存在下，經再結晶形成該2,2-雙(4-羥基環己基)丙烷之異構體混合物，再將該2,2-雙(4-羥基環己基)丙烷之異構體混合物溶解於該第一溶劑中，以形成混合溶液。 In a specific embodiment of the present invention, the preparation method further includes, before forming the mixed solution, recrystallizing unpurified 2,2-bis(4-hydroxycyclohexyl)propane in the presence of a composite solvent. Form the isomer mixture of 2,2-bis(4-hydroxycyclohexyl)propane, and then dissolve the isomer mixture of 2,2-bis(4-hydroxycyclohexyl)propane in the first solvent, to form a mixed solution.
於本發明的一具體實施態樣中，該複合溶劑係使用液態含氯溶劑，且該液態含氯化合物溶劑係選自由二氯甲烷、氯仿、四氯化碳、1,2-二氯乙烷、六氯環己烷及氯苯所組成的群組之其中至少兩種溶劑。 In a specific embodiment of the present invention, the composite solvent is a liquid chlorine-containing solvent, and the liquid chlorine-containing compound solvent is at least two solvents selected from the group consisting of dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, hexachlorocyclohexane and chlorobenzene.
於本發明的一具體實施態樣中，該液態含氯溶劑係包括氯仿及氯苯，且該氯仿及該氯苯之莫耳比為9.9：0.1至7：3。 In a specific implementation of the present invention, the liquid chlorine-containing solvent includes chloroform and chlorobenzene, and the molar ratio of the chloroform and the chlorobenzene is 9.9:0.1 to 7:3.
於本發明的一具體實施態樣中，存在於該複合溶劑中之該尚未純化之2,2-雙(4-羥基環己基)丙烷之濃度為0.05至5g/ml。 In a specific implementation of the present invention, the concentration of the unpurified 2,2-bis(4-hydroxycyclohexyl)propane present in the composite solvent is 0.05 to 5g/ml.
於本發明的一具體實施態樣中，該再結晶包括以1至3hr之時間條件和60至85℃，且最佳為65至75℃之溫度條件於200至800rpm加熱攪拌溶解有該2,2-雙(4-羥基環己基)丙烷之複合溶劑至該複合溶劑回流；靜置該複合溶劑1至8hr，並使該複合溶劑降至室溫；以及過濾該降至室溫之複合溶劑，以分離濾液和富含反-反異構體之2,2-雙(4-羥基環己基)丙烷之異構體混合物。 In a specific embodiment of the present invention, the recrystallization includes heating and stirring at 200 to 800 rpm to dissolve the 2, under a time condition of 1 to 3 hr and a temperature condition of 60 to 85°C, and preferably 65 to 75°C. The composite solvent of 2-bis(4-hydroxycyclohexyl)propane is refluxed to the composite solvent; the composite solvent is allowed to stand for 1 to 8 hours, and the composite solvent is allowed to drop to room temperature; and the composite solvent that is dropped to room temperature is filtered, To separate the filtrate and the isomer mixture of 2,2-bis(4-hydroxycyclohexyl)propane rich in trans-anti isomers.
於本發明的一具體實施態樣中，該2,2-雙(4-羥基環己基)丙烷之異構體混合物中的反-反異構體的含量為45至99mol%。 In a specific implementation of the present invention, the content of the trans-trans isomer in the isomer mixture of 2,2-bis(4-hydroxycyclohexyl)propane is 45 to 99 mol%.
於本發明的一具體實施態樣中，該2,2-雙(4-羥基環己基)丙烷之異構體混合物的順-反異構體的含量為大於0至5mol%。 In a specific implementation of the present invention, the content of cis-trans isomers of the isomer mixture of 2,2-bis(4-hydroxycyclohexyl)propane is greater than 0 to 5 mol%.
於本發明的一具體實施態樣中，經純化再結晶之2,2-雙(4-羥基環己基)丙烷的純度為99%以上。 In a specific implementation of the present invention, the purity of the purified and recrystallized 2,2-bis(4-hydroxycyclohexyl)propane is above 99%.
於本發明的一具體實施態樣中，該第一溶劑係選自由甲苯、二氯甲烷、氯仿、氯苯、己二腈、2,6-二氯甲苯、四氫呋喃及吡啶所組成的群組之其中一種溶劑。較佳地，該第一溶劑係選擇沸點高於60℃且含氯之 溶劑，例如氯仿、氯苯及2,6-二氯甲苯。此外，溶解雙(三氯甲基)碳酸酯之第二溶劑亦同於溶解2,2-雙(4-羥基環己基)丙烷之第一溶劑。例如，可選自由甲苯、二氯甲烷、氯仿、氯苯、己二腈、2,6-二氯甲苯、四氫呋喃及吡啶所組成的群組之其中一種溶劑。此外，本發明中並未添加水性溶劑，以避免影響反應。 In a specific implementation of the present invention, the first solvent is selected from the group consisting of toluene, dichloromethane, chloroform, chlorobenzene, adiponitrile, 2,6-dichlorotoluene, tetrahydrofuran and pyridine. one of the solvents. Preferably, the first solvent is one with a boiling point higher than 60°C and containing chlorine. Solvents such as chloroform, chlorobenzene and 2,6-dichlorotoluene. In addition, the second solvent that dissolves bis(trichloromethyl)carbonate is also the same as the first solvent that dissolves 2,2-bis(4-hydroxycyclohexyl)propane. For example, one solvent selected from the group consisting of toluene, dichloromethane, chloroform, chlorobenzene, adiponitrile, 2,6-dichlorotoluene, tetrahydrofuran and pyridine. In addition, no aqueous solvent is added in the present invention to avoid affecting the reaction.
於本發明的一具體實施態樣中，該有機鹼催化劑係含氮之有機鹼，例如可選自三乙胺、吡啶、3-甲基哌啶、4-甲基哌啶及4-二甲氨基吡啶(DMAP)所組成的群組中之至少一種。較佳地，該有機鹼催化劑為4-二甲氨基吡啶，且該4-二甲氨基吡啶與該雙(三氯甲基)碳酸酯之莫耳比為0.01：1至0.3：1。 In a specific embodiment of the present invention, the organic base catalyst is a nitrogen-containing organic base, for example, it can be selected from the group consisting of triethylamine, pyridine, 3-methylpiperidine, 4-methylpiperidine and 4-dimethyl. At least one of the group consisting of aminopyridine (DMAP). Preferably, the organic base catalyst is 4-dimethylaminopyridine, and the molar ratio of the 4-dimethylaminopyridine to the bis(trichloromethyl)carbonate is 0.01:1 to 0.3:1.
於一具體實施態樣中，該助催化劑係為三乙胺或吡啶。在本發明中，助催化劑不同於有機鹼催化劑。若有機鹼催化劑選自3-甲基哌啶、4-甲基哌啶及4-二甲氨基吡啶(DMAP)所組成的群組中之至少一種，則助催化劑係為三乙胺或吡啶。具體的說，該催化劑/助催化劑之組合係選自三乙胺/吡啶、吡啶/三乙胺、3-甲基哌啶/吡啶、3-甲基哌啶/三乙胺、4-甲基哌啶/吡啶、4-甲基哌啶/三乙胺、4-二甲氨基吡啶/吡啶及4-二甲氨基吡啶/三乙胺所組成的群組之其中一種。於本發明的一具體實施態樣中，該助催化劑與該雙(三氯甲基)碳酸酯之莫耳比為2：1至18：1。於本發明的一具體實施態樣中，該助催化劑為吡啶，且該吡啶與該雙(三氯甲基)碳酸酯之莫耳比為2：1至18：1。 In a specific implementation, the cocatalyst is triethylamine or pyridine. In the present invention, the cocatalyst is different from the organic base catalyst. If the organic base catalyst is selected from at least one of the group consisting of 3-methylpiperidine, 4-methylpiperidine and 4-dimethylaminopyridine (DMAP), the cocatalyst is triethylamine or pyridine. Specifically, the catalyst/cocatalyst combination is selected from triethylamine/pyridine, pyridine/triethylamine, 3-methylpiperidine/pyridine, 3-methylpiperidine/triethylamine, 4-methyl One of the group consisting of piperidine/pyridine, 4-methylpiperidine/triethylamine, 4-dimethylaminopyridine/pyridine and 4-dimethylaminopyridine/triethylamine. In a specific implementation of the present invention, the molar ratio of the cocatalyst and the bis(trichloromethyl)carbonate is 2:1 to 18:1. In a specific implementation of the present invention, the cocatalyst is pyridine, and the molar ratio of the pyridine to the bis(trichloromethyl)carbonate is 2:1 to 18:1.
於本發明的一具體實施態樣中，該第二溶劑係選自由甲苯、二氯甲烷、氯仿、氯苯、己二腈、2,6-二氯甲苯、四氫呋喃及吡啶所組成的群組之其中一種溶劑。 In a specific implementation of the present invention, the second solvent is selected from the group consisting of toluene, dichloromethane, chloroform, chlorobenzene, adiponitrile, 2,6-dichlorotoluene, tetrahydrofuran and pyridine. one of the solvents.
於本發明的一具體實施態樣中，該雙(三氯甲基)碳酸酯係於5至20℃之溫度範圍的條件下分批添加至該混合溶液中 In a specific implementation of the present invention, the bis(trichloromethyl)carbonate is added to the mixed solution in batches under a temperature range of 5 to 20°C.
於本發明的一具體實施態樣中，該雙(三氯甲基)碳酸酯係於10至100rmp之攪拌轉速範圍的條件下分批添加至該混合溶液中。 In a specific implementation of the present invention, the bis(trichloromethyl)carbonate is added to the mixed solution in batches at a stirring speed ranging from 10 to 100 rpm.
於本發明的一具體實施態樣中，以該2,2-雙(4-羥基環己基)丙烷之進料量為10g之基礎計算，該雙(三氯甲基)碳酸酯係以0.15至0.4g/min(克/分鐘)之進料量添加至該混合溶液中。 In a specific implementation of the present invention, based on the calculation based on the feed amount of 2,2-bis(4-hydroxycyclohexyl)propane being 10g, the bis(trichloromethyl)carbonate is from 0.15 to A feed amount of 0.4g/min (grams/minute) was added to the mixed solution.
於本發明的一具體實施態樣中，該2,2-雙(4-羥基環己基)丙烷與該雙(三氯甲基)碳酸酯之莫耳比為1：1至4：1。 In a specific implementation of the present invention, the molar ratio of the 2,2-bis(4-hydroxycyclohexyl)propane and the bis(trichloromethyl)carbonate is 1:1 to 4:1.
於另一具體實施態樣中，該縮聚反應時間為4至24hr。 In another specific implementation, the polycondensation reaction time is 4 to 24 hr.
於一具體實施態樣中，該縮聚反應溫度為15至180℃。 In a specific implementation, the polycondensation reaction temperature is 15 to 180°C.
於一具體實施態樣中，該縮聚反應係於100至600rmp之攪拌轉速範圍的條件下進行。 In a specific implementation, the polycondensation reaction is carried out at a stirring speed ranging from 100 to 600 rpm.
根據本發明，透過液態含氯溶劑及重結晶法(recrystallization method)，使2,2-雙(4-羥基環己基)丙烷純化再結晶以形成其中的順-反異構體的含量為45mol%以下之異構體混合物(isomer mixture)，並透過適量有機鹼催化劑、助催化劑及優化之滴加條件，而能在常壓下進行縮聚反應製得高分子量之聚碳酸酯。 According to the present invention, 2,2-bis(4-hydroxycyclohexyl)propane is purified and recrystallized through a liquid chlorine-containing solvent and a recrystallization method to form a cis-trans isomer content of 45 mol%. The following isomer mixture, through appropriate amounts of organic base catalysts, cocatalysts and optimized dripping conditions, can undergo polycondensation reaction under normal pressure to produce high molecular weight polycarbonate.
此外，透過有機鹼催化劑及助催化劑，使2,2-雙(4-羥基環己基)丙烷溶解度提高，而能有效參與反應。特別是該助催化劑之使用，使有機鹼催化劑之活性得以有效控制，提供後續縮聚時之即時反應性，令混合溶液的製備可於常溫下進行製備，不僅免除反應物析出而造成水解之風險，亦能有利於量化生產。又，透過分批添加反應單體雙(三氯甲基)碳酸酯，使本發明之脂環族聚碳酸酯可於溫和的反應條件下進行製備。 In addition, through the organic base catalyst and cocatalyst, the solubility of 2,2-bis(4-hydroxycyclohexyl)propane is increased, so that it can effectively participate in the reaction. In particular, the use of this cocatalyst allows the activity of the organic base catalyst to be effectively controlled, providing immediate reactivity during subsequent polycondensation, allowing the preparation of the mixed solution to be carried out at room temperature, which not only avoids the risk of hydrolysis caused by the precipitation of reactants, but also It can also be beneficial to quantitative production. Furthermore, by adding the reaction monomer bis(trichloromethyl)carbonate in batches, the alicyclic polycarbonate of the present invention can be prepared under mild reaction conditions.
因本發明之製法具高反應選擇性，故所製之脂環族聚碳酸酯係具有高分子量及高純度之特質，符合食用容器、光學、醫療產品的使用需求，增加其應用價值。 Because the preparation method of the present invention has high reaction selectivity, the alicyclic polycarbonate produced has the characteristics of high molecular weight and high purity, which meets the use requirements of edible containers, optical and medical products, and increases its application value.
以下係藉由特定的具體實施例說明本發明之實施方式，熟習此技藝之人士可由本說明書所揭示之內容輕易地瞭解本發明之優點及功效。本發明亦可藉由其它不同之實施方式加以施行或應用，本說明書中的各項細節亦可基於不同觀點與應用，在不悖離本發明所揭示之精神下賦予不同之修飾與變更。此外，本文所有範圍和值都係包含及可合併的。落在本文中所述的範圍內之任何數值或點，例如任何整數都可以作為最小值或最大值以導出下位範圍等。 The following describes the implementation of the present invention through specific embodiments. Those skilled in the art can easily understand the advantages and effects of the present invention from the content disclosed in this specification. The present invention can also be implemented or applied in other different embodiments. Various details in this specification can also be modified and changed based on different viewpoints and applications without departing from the spirit of the present invention. In addition, all ranges and values herein are inclusive and combinable. Any value or point that falls within the range described in this article, such as any integer, can be used as a minimum or maximum value to derive a lower range, etc.
本發明所述之「2,2-雙(4-羥基環己基)丙烷之異構體混合物」係指包含具有順-順構型之2,2-雙(4-羥基環己基)丙烷、順-反構型之2,2-雙 (4-羥基環己基)丙烷和反-反構型之2,2-雙(4-羥基環己基)丙烷。該順-順構型之2,2-雙(4-羥基環己基)丙烷亦稱為「順-順異構體」；該順-反構型之2,2-雙(4-羥基環己基)丙烷亦稱為「順-反異構體」以及該反-反構型之2,2-雙(4-羥基環己基)丙烷亦稱為「反-反異構體」。 The "isomer mixture of 2,2-bis(4-hydroxycyclohexyl)propane" mentioned in the present invention refers to 2,2-bis(4-hydroxycyclohexyl)propane with cis-cis configuration, cis - Anti-configuration 2,2-double (4-hydroxycyclohexyl)propane and 2,2-bis(4-hydroxycyclohexyl)propane in trans-anti configuration. The cis-cis configuration of 2,2-bis(4-hydroxycyclohexyl)propane is also called the "cis-cis isomer"; the cis-trans configuration of 2,2-bis(4-hydroxycyclohexyl)propane ) Propane is also called the "cis-trans isomer" and the trans-anti configuration of 2,2-bis(4-hydroxycyclohexyl)propane is also called the "anti-trans isomer".
本發明所述之「富含反-反異構體之2,2-雙(4-羥基環己基)丙烷之異構體混合物」係指該2,2-雙(4-羥基環己基)丙烷之異構體混合物中之反-反異構體含量大於50mol%，或介於50至99mol%，例如，50、55、60、65、70、75、80、85、90、95、96、97、98、99mol%。 The "isomer mixture of 2,2-bis(4-hydroxycyclohexyl)propane rich in trans-trans isomers" mentioned in the present invention refers to the 2,2-bis(4-hydroxycyclohexyl)propane The anti-anti isomer content in the isomer mixture is greater than 50 mol%, or between 50 and 99 mol%, for example, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, 99mol%.
本發明所述之「富含順-反異構體之2,2-雙(4-羥基環己基)丙烷之異構體混合物」係指該2,2-雙(4-羥基環己基)丙烷之異構體混合物中之順-反異構體含量大於50mol%，或介於50至99mol%，例如，50、55、60、65、70、75、80、85、90、95、96、97、98、99mol%。 The "isomer mixture of 2,2-bis(4-hydroxycyclohexyl)propane rich in cis-trans isomers" mentioned in the present invention refers to the 2,2-bis(4-hydroxycyclohexyl)propane The cis-trans isomer content in the isomer mixture is greater than 50 mol%, or between 50 and 99 mol%, for example, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, 99mol%.
依據本發明，係提供一種高分子量脂環族聚碳酸酯之製備方法，係包括：於第一溶劑、有機鹼催化劑和助催化劑之存在下，使該2,2-雙(4-羥基環己基)丙烷之異構體混合物溶解於該第一溶劑中形成混合溶液，且該2,2-雙(4-羥基環己基)丙烷之異構體混合物於該混合溶液中之含量為0.5至1.0體積莫耳濃度，其中，該2,2-雙(4-羥基環己基)丙烷之異構體混合物中的順-反異構體的含量為45mol%以下；以及將溶解於第二溶劑中之雙(三氯甲基)碳酸酯添加至該混合溶液中進行縮聚反應，以製得具下式(I)之脂環族聚碳酸酯，其中，n為大於40， According to the present invention, a method for preparing high molecular weight alicyclic polycarbonate is provided, which includes: in the presence of a first solvent, an organic base catalyst and a cocatalyst, the 2,2-bis(4-hydroxycyclohexyl) ) The isomer mixture of propane is dissolved in the first solvent to form a mixed solution, and the content of the isomer mixture of 2,2-bis(4-hydroxycyclohexyl)propane in the mixed solution is 0.5 to 1.0 volume Molar concentration, wherein the content of cis-trans isomers in the isomer mixture of 2,2-bis(4-hydroxycyclohexyl)propane is less than 45 mol%; and the bis(4-hydroxycyclohexyl)propane will be dissolved in the second solvent (Trichloromethyl) carbonate is added to the mixed solution to perform a polycondensation reaction to prepare an alicyclic polycarbonate with the following formula (I), wherein n is greater than 40,
透過上述之製備方法，所製之脂環族聚碳酸酯的峰值分子量(Mp)可大於12000g/mol；於一具體實施態樣中，n為40至280，例如，n為40、50、60、70、80、90、100、110、120、130、140、150、160、170、180、190、200、210、220、230、240、250、260、270或280。 Through the above preparation method, the peak molecular weight (Mp) of the prepared alicyclic polycarbonate can be greater than 12000g/mol; in a specific implementation, n is 40 to 280, for example, n is 40, 50, 60 , 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270 or 280.
於本發明之實施例中，本發明製法所用的反應裝置復包括一攪拌裝置，例如為一攪拌釜式反應器。於一具體實施態樣中，該攪拌裝置係可選自旋漿式攪拌器、渦輪式攪拌器、槳式攪拌器、錨式攪拌器、折葉式攪拌器、側入式攪拌器、推進式攪拌器、磁力加熱式攪拌器或螺帶式攪拌器。 In embodiments of the present invention, the reaction device used in the preparation method of the present invention further includes a stirring device, such as a stirred tank reactor. In a specific implementation, the mixing device can be a rotating paddle mixer, a turbine mixer, a paddle mixer, an anchor mixer, a hinged blade mixer, a side-entry mixer, or a propeller mixer. Stirrer, magnetically heated stirrer or ribbon stirrer.
於本發明的一具體實施態樣中，該製備方法復包括在形成該混合溶液之前，使尚未純化之2,2-雙(4-羥基環己基)丙烷於複合溶劑的存在下，經再結晶形成該2,2-雙(4-羥基環己基)丙烷之異構體混合物，再將該2,2-雙(4-羥基環己基)丙烷之異構體混合物溶解於該第一溶劑中，以形成混合溶液。 In a specific embodiment of the present invention, the preparation method further includes, before forming the mixed solution, recrystallizing unpurified 2,2-bis(4-hydroxycyclohexyl)propane in the presence of a composite solvent. Form the isomer mixture of 2,2-bis(4-hydroxycyclohexyl)propane, and then dissolve the isomer mixture of 2,2-bis(4-hydroxycyclohexyl)propane in the first solvent, to form a mixed solution.
於本發明的一具體實施態樣中，該複合溶劑係使用液態含氯溶劑，且該液態含氯化合物溶劑係選自由二氯甲烷、氯仿、四氯化碳、1,2-二氯乙烷、六氯環己烷及氯苯所組成的群組之其中至少兩種溶劑。 In a specific implementation of the present invention, the composite solvent uses a liquid chlorine-containing solvent, and the liquid chlorine-containing compound solvent is selected from dichloromethane, chloroform, carbon tetrachloride, and 1,2-dichloroethane. At least two solvents from the group consisting of hexachlorocyclohexane and chlorobenzene.
於本發明的一具體實施態樣中，該液態含氯溶劑係包括氯仿及氯苯，且該氯仿及該氯苯之莫耳比為9.9：0.1至7：3，較佳為9.5：0.5至7.5：2.5。於其他實施態樣中，該氯仿及該氯苯之莫耳比可為9.9：0.1、9.7：0.3、9.5：0.5、9.4：0.6、9.3：0.7、9.2：0.8、9.1：0.9、9：1、8.9：1.1、8.8：1.2、8.7：1.3、8.6：1.4、8.5：1.5、8.4：1.6、8.3：1.7、8.2：1.8、8.1：1.9、8：2、7.9：2.1、7.8：2.2、7.7：2.3、7.6：2.4、7.5：2.5、7.3：2.7或7：3。 In a specific implementation of the present invention, the liquid chlorine-containing solvent includes chloroform and chlorobenzene, and the molar ratio of the chloroform and the chlorobenzene is 9.9:0.1 to 7:3, preferably 9.5:0.5 to 7:3. 7.5: 2.5. In other embodiments, the molar ratio of the chloroform and the chlorobenzene can be 9.9:0.1, 9.7:0.3, 9.5:0.5, 9.4:0.6, 9.3:0.7, 9.2:0.8, 9.1:0.9, 9:1 , 8.9: 1.1, 8.8: 1.2, 8.7: 1.3, 8.6: 1.4, 8.5: 1.5, 8.4: 1.6, 8.3: 1.7, 8.2: 1.8, 8.1: 1.9, 8: 2, 7.9: 2.1, 7.8: 2.2, 7.7 :2.3, 7.6:2.4, 7.5:2.5, 7.3:2.7 or 7:3.
於本發明的一具體實施態樣中，存在於該複合溶劑中之該尚未純化之2,2-雙(4-羥基環己基)丙烷之濃度為0.05至5g/ml。於其他實施態樣中，存在於該複合溶劑中之該尚未純化之2,2-雙(4-羥基環己基)丙烷之濃度可為0.05、0.06、0.07、0.08、0.09、0.1、0.2、0.3、0.4、0.5、0.6、0.7、0.8、0.9、1、1.1、1.2、1.3、1.4、1.5、1.6、1.7、1.8、1.9、2、2.1、2.2、2.3、2.4、2.5、2.6、2.7、2.8、2.9、3、3.5、4、4.5或5g/ml。 In a specific implementation of the present invention, the concentration of the unpurified 2,2-bis(4-hydroxycyclohexyl)propane present in the composite solvent is 0.05 to 5g/ml. In other embodiments, the concentration of the unpurified 2,2-bis(4-hydroxycyclohexyl)propane present in the composite solvent may be 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.2, 0.3 ,0.4,0.5,0.6,0.7,0.8,0.9,1,1.1,1.2,1.3,1.4,1.5,1.6,1.7,1.8,1.9,2,2.1,2.2,2.3,2.4,2.5,2.6,2.7,2.8 , 2.9, 3, 3.5, 4, 4.5 or 5g/ml.
於本發明的一具體實施態樣中，該再結晶包括以1至3hr之時間條件和60至85℃，且最佳為65至75℃之溫度條件於200至800rpm加熱攪拌溶解有該2,2-雙(4-羥基環己基)丙烷之複合溶劑至該複合溶劑回流；靜置該複合溶劑1至8hr，並使該複合溶劑降至室溫；以及過濾該降至室溫之複合溶劑，以分離濾液和富含反-反異構體之2,2-雙(4-羥基環己基)丙烷之異構體混合物。於其他具體實施態樣中，攪拌轉速範圍可為400至600rpm。於其他實施態樣中，可經由60、65、70、75、80或85℃之溫度，1、1.5、2、2.5或3hr之時間，以及200、250、300、350、400、400、410、420、430、440、450、460、470、480、490、500、510、520、 530、540、550、560、570、580、590、600、650、700、750或800rpm之攪拌轉速下，加熱攪拌溶解有該2,2-雙(4-羥基環己基)丙烷之複合溶劑至該複合溶劑回流。 In a specific embodiment of the present invention, the recrystallization includes heating and stirring at 200 to 800 rpm to dissolve the 2, under a time condition of 1 to 3 hr and a temperature condition of 60 to 85°C, and preferably 65 to 75°C. The composite solvent of 2-bis(4-hydroxycyclohexyl)propane is refluxed to the composite solvent; the composite solvent is allowed to stand for 1 to 8 hours, and the composite solvent is allowed to drop to room temperature; and the composite solvent that is dropped to room temperature is filtered, To separate the filtrate and the isomer mixture of 2,2-bis(4-hydroxycyclohexyl)propane rich in trans-anti isomers. In other specific implementations, the stirring speed may range from 400 to 600 rpm. In other embodiments, the temperature can be 60, 65, 70, 75, 80 or 85°C, the time of 1, 1.5, 2, 2.5 or 3 hr, and 200, 250, 300, 350, 400, 400, 410 ,420,430,440,450,460,470,480,490,500,510,520, At a stirring speed of 530, 540, 550, 560, 570, 580, 590, 600, 650, 700, 750 or 800 rpm, heat and stir the composite solvent containing the 2,2-bis(4-hydroxycyclohexyl)propane to The composite solvent was refluxed.
於本發明的一具體實施態樣中，係於自加熱回流起，靜置該複合溶劑1至8hr(小時)。於其他實施態樣中，可靜置1、1.5、2、2.5、3、3.5、4、4.5、5、5.5、6、6.5、7、7.5、8hr。 In a specific embodiment of the present invention, the composite solvent is allowed to stand for 1 to 8 hours after being heated to reflux. In other embodiments, it can be left to stand for 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, or 8 hours.
於本發明的一具體實施態樣中，該2,2-雙(4-羥基環己基)丙烷之異構體混合物中的反-反異構體的含量為45至99mol%。於其他實施態樣中，該反-反構型之2,2-雙(4-羥基環己基)丙烷之含量為45、49、50、55、60、64、65、70、75、80、85、87、88、89、90、91、91.5、92、92.5、93、93.5、94、94.5、95、95.5、96、96.5、97、97.5、98、98.5或99mol%。 In a specific implementation of the present invention, the content of the trans-trans isomer in the isomer mixture of 2,2-bis(4-hydroxycyclohexyl)propane is 45 to 99 mol%. In other embodiments, the content of the anti-anti configuration of 2,2-bis(4-hydroxycyclohexyl)propane is 45, 49, 50, 55, 60, 64, 65, 70, 75, 80, 85, 87, 88, 89, 90, 91, 91.5, 92, 92.5, 93, 93.5, 94, 94.5, 95, 95.5, 96, 96.5, 97, 97.5, 98, 98.5 or 99mol%.
於本發明的一具體實施態樣中，該2,2-雙(4-羥基環己基)丙烷之異構體混合物的順-反異構體的含量為大於0至45mol%以下。例如大於0、1、1.1、1.2、1.3、1.4、1.5、1.6、1.7、1.8、1.9、2、2.5、3、3.5、4、4.5、5、10、20、30、32、40、44或45mol%。於其他實施態樣中，該2,2-雙(4-羥基環己基)丙烷之異構體混合物的順-反異構體的含量為大於0至5mol%。例如：大於0、1、1.1、1.2、1.3、1.4、1.5、1.6、1.7、1.8、1.9、2、2.5、3、3.5、4、4.5或5mol%。 In a specific implementation of the present invention, the content of cis-trans isomers of the isomer mixture of 2,2-bis(4-hydroxycyclohexyl)propane is greater than 0 and less than 45 mol%. For example, greater than 0, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.5, 3, 3.5, 4, 4.5, 5, 10, 20, 30, 32, 40, 44 or 45mol%. In other embodiments, the cis-trans isomer content of the isomer mixture of 2,2-bis(4-hydroxycyclohexyl)propane is greater than 0 to 5 mol%. For example: greater than 0, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.5, 3, 3.5, 4, 4.5 or 5 mol%.
於本發明的一具體實施態樣中，經純化再結晶之2,2-雙(4-羥基環己基)丙烷的純度為99%以上，例如：99、99.1、99.2、99.3、99.4、99.5、99.6、99.7、99.8或99.9%。 In a specific implementation of the present invention, the purity of the purified and recrystallized 2,2-bis(4-hydroxycyclohexyl)propane is more than 99%, such as: 99, 99.1, 99.2, 99.3, 99.4, 99.5, 99.6, 99.7, 99.8 or 99.9%.
於本發明的一具體實施態樣中，該第一溶劑係選自由甲苯、二氯甲烷、氯仿、氯苯、己二腈、2,6-二氯甲苯、四氫呋喃及吡啶所組成的群組之其中一種溶劑。較佳地，該第一溶劑係選擇沸點高於60℃且含氯之溶劑，例如氯仿、氯苯及2,6-二氯甲苯。此外，溶解雙(三氯甲基)碳酸酯之第二溶劑亦同於溶解2,2-雙(4-羥基環己基)丙烷之第一溶劑。例如，可選自由甲苯、二氯甲烷、氯仿、氯苯、己二腈、2,6-二氯甲苯、四氫呋喃及吡啶所組成的群組之其中一種溶劑。此外，本發明中並未添加水性溶劑，以避免影響反應。 In a specific implementation of the present invention, the first solvent is selected from the group consisting of toluene, dichloromethane, chloroform, chlorobenzene, adiponitrile, 2,6-dichlorotoluene, tetrahydrofuran and pyridine. one of the solvents. Preferably, the first solvent is a solvent with a boiling point higher than 60°C and containing chlorine, such as chloroform, chlorobenzene and 2,6-dichlorotoluene. In addition, the second solvent that dissolves bis(trichloromethyl)carbonate is also the same as the first solvent that dissolves 2,2-bis(4-hydroxycyclohexyl)propane. For example, one solvent selected from the group consisting of toluene, dichloromethane, chloroform, chlorobenzene, adiponitrile, 2,6-dichlorotoluene, tetrahydrofuran and pyridine. In addition, no aqueous solvent is added in the present invention to avoid affecting the reaction.
於本發明的一具體實施態樣中，該有機鹼催化劑係含氮之有機鹼，例如可選自三乙胺、吡啶、3-甲基哌啶、4-甲基哌啶及4-二甲氨基吡啶(DMAP)所組成的群組中之至少一種。較佳地，該有機鹼催化劑為4-二甲氨基吡啶，且該4-二甲氨基吡啶與該雙(三氯甲基)碳酸酯之莫耳比為0.01：1至0.3：1。於其他實施態樣中，該4-二甲氨基吡啶與該雙(三氯甲基)碳酸酯之莫耳比可為0.05：1、0.1：1、0.15：1、0.2：1或0.25：1。 In a specific embodiment of the present invention, the organic base catalyst is a nitrogen-containing organic base, for example, it can be selected from the group consisting of triethylamine, pyridine, 3-methylpiperidine, 4-methylpiperidine and 4-dimethyl. At least one of the group consisting of aminopyridine (DMAP). Preferably, the organic base catalyst is 4-dimethylaminopyridine, and the molar ratio of the 4-dimethylaminopyridine to the bis(trichloromethyl)carbonate is 0.01:1 to 0.3:1. In other embodiments, the molar ratio of the 4-dimethylaminopyridine and the bis(trichloromethyl)carbonate can be 0.05:1, 0.1:1, 0.15:1, 0.2:1 or 0.25:1 .
於一具體實施態樣中，該助催化劑係為三乙胺或吡啶。在本發明中，助催化劑不同於有機鹼催化劑。若有機鹼催化劑選自3-甲基哌啶、4-甲基哌啶及4-二甲氨基吡啶(DMAP)所組成的群組中之至少一種，則助催化劑係為三乙胺或吡啶。具體的說，該催化劑/助催化劑之組合係選自三乙胺/吡啶、吡啶/三乙胺、3-甲基哌啶/吡啶、3-甲基哌啶/三乙胺、4-甲基哌啶/吡啶、4-甲基哌啶/三乙胺、4-二甲氨基吡啶/吡啶及4-二甲氨基吡啶/三乙胺所組成的群組之其中一種。於本發明的一具體實施態樣中，該助催化劑與該雙(三氯甲基)碳酸酯之莫耳比為2：1至18：1。於本發明的一 具體實施態樣中，該助催化劑為吡啶，且該吡啶與該雙(三氯甲基)碳酸酯之莫耳比為2：1至18：1。換言之，助催化劑的用量會大於有機鹼催化劑。於其他實施態樣中，該助催化劑與該雙(三氯甲基)碳酸酯之莫耳比可為3：1、4：1、5：1、6：1、7：1、8：1、9：1、10：1、11：1、12：1、13：1、14：1、15：1、16：1或17：1。 In a specific implementation, the cocatalyst is triethylamine or pyridine. In the present invention, the cocatalyst is different from the organic base catalyst. If the organic base catalyst is selected from at least one of the group consisting of 3-methylpiperidine, 4-methylpiperidine and 4-dimethylaminopyridine (DMAP), the cocatalyst is triethylamine or pyridine. Specifically, the catalyst/cocatalyst combination is selected from triethylamine/pyridine, pyridine/triethylamine, 3-methylpiperidine/pyridine, 3-methylpiperidine/triethylamine, 4-methyl One of the group consisting of piperidine/pyridine, 4-methylpiperidine/triethylamine, 4-dimethylaminopyridine/pyridine and 4-dimethylaminopyridine/triethylamine. In a specific implementation of the present invention, the molar ratio of the cocatalyst and the bis(trichloromethyl)carbonate is 2:1 to 18:1. to one of the present invention In a specific implementation, the cocatalyst is pyridine, and the molar ratio of the pyridine to the bis(trichloromethyl)carbonate is 2:1 to 18:1. In other words, the amount of cocatalyst will be greater than that of organic base catalyst. In other embodiments, the molar ratio of the cocatalyst to the bis(trichloromethyl)carbonate can be 3:1, 4:1, 5:1, 6:1, 7:1, or 8:1 , 9:1, 10:1, 11:1, 12:1, 13:1, 14:1, 15:1, 16:1 or 17:1.
於本發明的一具體實施態樣中，該第二溶劑係選自由甲苯、二氯甲烷、氯仿、氯苯、己二腈、2,6-二氯甲苯、四氫呋喃及吡啶所組成的群組之其中一種溶劑。 In a specific implementation of the present invention, the second solvent is selected from the group consisting of toluene, dichloromethane, chloroform, chlorobenzene, adiponitrile, 2,6-dichlorotoluene, tetrahydrofuran and pyridine. one of the solvents.
於本發明的一具體實施態樣中，該雙(三氯甲基)碳酸酯係於5至20℃之溫度範圍的條件下分批添加至該混合溶液中。於其他實施態樣中，該雙(三氯甲基)碳酸酯可於5、6、7、8、9.5、10、10.5、11、11.5、12、12.5、13、13.5、14、14.5、15、15.5、16、17、18、19或20℃之溫度的條件下分批添加至該混合溶液中。 In a specific implementation of the present invention, the bis(trichloromethyl)carbonate is added to the mixed solution in batches under a temperature range of 5 to 20°C. In other embodiments, the bis(trichloromethyl) carbonate can be at 5, 6, 7, 8, 9.5, 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14, 14.5, 15 , 15.5, 16, 17, 18, 19 or 20℃ temperature conditions were added to the mixed solution in batches.
於本發明的一具體實施態樣中，該雙(三氯甲基)碳酸酯係於10至100rmp之攪拌轉速範圍的條件下分批添加至該混合溶液中。於其他實施態樣中，該雙(三氯甲基)碳酸酯可於10、15、20、25、30、35、40、45、50、55、60、65、70、75、80、85、90、95、100之攪拌轉速的條件下分批添加至該混合溶液中。 In a specific implementation of the present invention, the bis(trichloromethyl)carbonate is added to the mixed solution in batches at a stirring speed ranging from 10 to 100 rpm. In other embodiments, the bis(trichloromethyl) carbonate can be at 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85 , 90, 95, 100 stirring speed conditions were added to the mixed solution in batches.
於本發明的一具體實施態樣中，以2,2-雙(4-羥基環己基)丙烷之進料量為10g之基礎計算，該雙(三氯甲基)碳酸酯係以0.15至0.4g/min(克/分鐘)之進料量添加至該混合溶液中。於其他實施態樣中，該雙(三氯甲基)碳酸酯之進料量可為0.15、0.2、0.25、0.3、0.35或0.4g/min。 具體而言，該雙(三氯甲基)碳酸酯係溶解在第二溶劑中形成雙(三氯甲基)碳酸酯溶液，並分批緩慢添加於該混合溶液中。該雙(三氯甲基)碳酸酯的進料量係指雙(三氯甲基)碳酸酯溶液中的雙(三氯甲基)碳酸酯量。 In a specific implementation of the present invention, based on the calculation based on the feed amount of 2,2-bis(4-hydroxycyclohexyl)propane being 10g, the bis(trichloromethyl)carbonate is 0.15 to 0.4 A feed amount of g/min (grams/minute) was added to the mixed solution. In other embodiments, the feeding amount of bis(trichloromethyl)carbonate can be 0.15, 0.2, 0.25, 0.3, 0.35 or 0.4g/min. Specifically, the bis(trichloromethyl)carbonate is dissolved in the second solvent to form a bis(trichloromethyl)carbonate solution, and is slowly added to the mixed solution in batches. The feeding amount of bis(trichloromethyl)carbonate refers to the amount of bis(trichloromethyl)carbonate in the bis(trichloromethyl)carbonate solution.
於本發明的一具體實施態樣中，該2,2-雙(4-羥基環己基)丙烷與該雙(三氯甲基)碳酸酯之莫耳比為1：1至4：1。於其他實施態樣中，該2,2-雙(4-羥基環己基)丙烷與該雙(三氯甲基)碳酸酯之莫耳比可為1.5：1、2：1、2.5：1、2.7：1、3：1、3.2：1、3.5：1或3.7：1。 In a specific embodiment of the present invention, the molar ratio of the 2,2-bis(4-hydroxycyclohexyl)propane to the bis(trichloromethyl)carbonate is 1:1 to 4:1. In other embodiments, the molar ratio of the 2,2-bis(4-hydroxycyclohexyl)propane to the bis(trichloromethyl)carbonate may be 1.5:1, 2:1, 2.5:1, 2.7:1, 3:1, 3.2:1, 3.5:1 or 3.7:1.
於另一具體實施態樣中，該縮聚反應時間為4至24hr，例如：4、5、6、7、8、9、10、11、12、13、14、15、16、17、18、19、20、21、22、23或24hr。 In another specific implementation, the polycondensation reaction time is 4 to 24 hr, for example: 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23 or 24hr.
於一具體實施態樣中，該縮聚反應溫度為15至180℃，例如：15、20、30、40、50、60、70、80、90、100、110、120、130、140、150、160、170或180℃。 In a specific implementation, the polycondensation reaction temperature is 15 to 180°C, for example: 15, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170 or 180℃.
於一具體實施態樣中，該縮聚反應係於100至600rmp之攪拌轉速範圍的條件下進行，例如：100、110、120、130、140、150、160、170、180、190、200、210、220、230、240、250、260、270、280、290、300、310、320、330、340、350、360、370、380、390、400、410、420、430、440、450、460、470、480、490、500、550或600rmp。 In a specific implementation, the polycondensation reaction is carried out under a stirring speed range of 100 to 600 rpm, for example: 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210 ,220,230,240,250,260,270,280,290,300,310,320,330,340,350,360,370,380,390,400,410,420,430,440,450,460 , 470, 480, 490, 500, 550 or 600rmp.
於本發明之實施例中，於縮聚反應後，由於反應過程形成黏稠之副產物係為轉化不完全之生成物，不利於其反應產物的後端應用，故須選取不溶該上述具式(I)之脂環族聚碳酸酯且對副產物及未反應之2,2-雙(4-羥基環己基)丙烷具溶解性之溶劑，使本發明之製品自反應混合物中沉 澱析出。所述之不溶該具式(I)之脂環族聚碳酸酯之溶劑係為醇類溶劑，其中，又尤以甲醇為佳。 In the embodiments of the present invention, after the polycondensation reaction, since the viscous by-products formed during the reaction are incomplete conversion products, which is not conducive to the back-end application of the reaction products, it is necessary to select insoluble compounds of the above formula (I ) alicyclic polycarbonate and a solvent that is soluble in by-products and unreacted 2,2-bis(4-hydroxycyclohexyl)propane, so that the product of the present invention can be precipitated from the reaction mixture. Precipitate. The solvent that is insoluble in the alicyclic polycarbonate of formula (I) is an alcohol solvent, and among them, methanol is particularly preferred.
以下透過具體實施例對本發明之特點與功效做進一步詳細說明，但不因實施例說明限制本發明之範疇。 The characteristics and effects of the present invention will be further described in detail below through specific examples, but the scope of the present invention will not be limited by the examples.
製備例1Preparation Example 1
將100g含有7%順-順構型、44%順-反構型和49%反-反構型的2,2-雙(4-羥基環己基)丙烷(HBPA)(購自Wako)、810ml氯仿、90ml氯苯置於配有機械攪拌器、冷凝管及進料漏斗之2L三頸瓶中形成一混合溶液。 100g of 2,2-bis(4-hydroxycyclohexyl)propane (HBPA) (purchased from Wako) containing 7% cis-cis configuration, 44% cis-trans configuration and 49% trans-anti configuration, 810ml Chloroform and 90 ml of chlorobenzene were placed in a 2L three-neck flask equipped with a mechanical stirrer, condenser tube and feeding funnel to form a mixed solution.
接著，將該混合溶液於室溫下將攪拌轉速設定至400rpm進行攪拌，接著以2hr之時間條件及75℃之溫度條件加熱回流並冷卻至室溫，於室溫靜置4hr，經減壓抽濾後取濾餅45g，得到經純化再結晶之2,2-雙(4-羥基環己基)丙烷異構體混合物產物。 Then, the mixed solution was stirred at room temperature by setting the stirring speed to 400 rpm, then heated to reflux under a time condition of 2 hr and a temperature condition of 75°C, cooled to room temperature, left to stand at room temperature for 4 hr, and vacuumed under reduced pressure. After filtration, 45 g of the filter cake was taken to obtain a purified and recrystallized 2,2-bis(4-hydroxycyclohexyl)propane isomer mixture product.
使用毛細管氣相層析儀(GC，Shimadzu GC-2010 Plus)分析所製之2,2-雙(4-羥基環己基)丙烷異構體混合物產物，量測其純度、熔點與異構體混合物中順-順異構體、順-反異構體及反-反異構體之含量比例，並將結果紀錄於表1。製備例1的異構體混合物中順-順異構體、順-反異構體及反-反異構體之含量比例為0：2：98。 Capillary gas chromatography (GC, Shimadzu GC-2010 Plus) was used to analyze the prepared 2,2-bis(4-hydroxycyclohexyl)propane isomer mixture product, and its purity, melting point and isomer mixture were measured. The content ratio of cis-cis isomer, cis-trans isomer and trans-trans isomer, and the results are recorded in Table 1. The content ratio of cis-cis isomer, cis-trans isomer and trans-trans isomer in the isomer mixture of Preparation Example 1 is 0:2:98.
製備例2Preparation Example 2
將100g含有15%順-順構型、53%順-反構型和32%反-反構型之2,2-雙(4-羥基環己基)丙烷(HBPA)(購自CPDC)、810ml氯仿、 90ml氯苯置於配有機械攪拌器、冷凝管及進料漏斗之2L三頸瓶中形成一混合溶液。 100g of 2,2-bis(4-hydroxycyclohexyl)propane (HBPA) (purchased from CPDC) containing 15% cis-cis configuration, 53% cis-trans configuration and 32% trans-anti configuration, 810ml Chloroform, 90ml of chlorobenzene was placed in a 2L three-neck flask equipped with a mechanical stirrer, condenser tube and feeding funnel to form a mixed solution.
接著，將該混合溶液於室溫下將攪拌轉速設定至400rpm進行攪拌，接著以2hr之時間條件及75℃之溫度條件加熱回流並冷卻至室溫，於室溫靜置4hr，經減壓抽濾後取濾餅29g，得到經純化再結晶之2,2-雙(4-羥基環己基)丙烷異構體混合物產物，其分析方法係與製備例1相同。製備例2的異構體混合物中順-順異構體、順-反異構體及反-反異構體之含量比例為0：5：95。 Then, the mixed solution was stirred at room temperature by setting the stirring speed to 400 rpm, then heated to reflux under a time condition of 2 hr and a temperature condition of 75°C, cooled to room temperature, left to stand at room temperature for 4 hr, and vacuumed under reduced pressure. After filtration, 29 g of the filter cake was taken to obtain a purified and recrystallized 2,2-bis(4-hydroxycyclohexyl)propane isomer mixture product. The analysis method was the same as Preparation Example 1. The content ratio of cis-cis isomer, cis-trans isomer and trans-trans isomer in the isomer mixture of Preparation Example 2 is 0:5:95.
製備例3Preparation Example 3
將該製備例1之混合溶液置於另一2L三頸瓶中，於室溫下將攪拌轉速設定至650rpm進行攪拌，靜置16hr，經減壓抽濾後取濾餅37g，得到2,2-雙(4-羥基環己基)丙烷(HBPA)異構體混合物產物，其分析方法係與製備例1相同。製備例3的異構體混合物中順-順異構體、順-反異構體及反-反異構體之含量比例為1：97：2。 Place the mixed solution of Preparation Example 1 into another 2L three-necked flask, set the stirring speed to 650rpm for stirring at room temperature, and let it stand for 16 hours. After filtering under reduced pressure, take out 37g of the filter cake to obtain 2,2 - Bis(4-hydroxycyclohexyl)propane (HBPA) isomer mixture product, its analysis method is the same as Preparation Example 1. The content ratio of cis-cis isomer, cis-trans isomer and trans-trans isomer in the isomer mixture of Preparation Example 3 is 1:97:2.
實施例1Example 1
將10g的製備例1所製經純化再結晶之2,2-雙(4-羥基環己基)丙烷(HBPA)異構體混合物、25ml的反應溶劑氯苯、9.32克的助催化劑(Co-cat)吡啶及0.26g的有機鹼催化劑(Org-cat)4-二甲氨基吡啶(DMAP)置於配有機械攪拌器、冷凝管及進料漏斗之三頸瓶中形成一混合溶液，並於常溫常壓條件(25℃，1atm)下進行攪拌，其中，該混合溶液中之2,2-雙(4-羥基環己基)丙烷含量為0.95M。 10 g of the purified and recrystallized 2,2-bis(4-hydroxycyclohexyl)propane (HBPA) isomer mixture prepared in Preparation Example 1, 25 ml of the reaction solvent chlorobenzene, and 9.32 g of the cocatalyst (Co-cat ) Pyridine and 0.26g of organic base catalyst (Org-cat) 4-dimethylaminopyridine (DMAP) are placed in a three-necked flask equipped with a mechanical stirrer, condenser tube and feeding funnel to form a mixed solution, and placed at room temperature Stir under normal pressure conditions (25°C, 1 atm), where the content of 2,2-bis(4-hydroxycyclohexyl)propane in the mixed solution is 0.95M.
接著，進行滴加和攪拌製程。將溫度調整於10℃之溫度條件，並將10g雙(三氯甲基)碳酸酯(BTC)溶解於20ml的氯苯中，配製一雙(三氯甲基)碳酸酯溶液，由滴液漏斗將該雙(三氯甲基)碳酸酯溶液以10℃之滴加溫度及50rmp之攪拌速度於30分鐘內以0.2g/min之滴加速度緩慢滴加至該混合溶液中，接著在120℃之溫度及550rpm之攪拌轉速的條件下進行縮聚反應12小時。待縮聚反應完成後，將甲醇加入上述反應溶液中，經抽氣、過濾、乾燥後，獲得一白色的脂環族聚碳酸酯(HPC)製品。 Next, the dropping and stirring process is carried out. Adjust the temperature to 10°C and dissolve 10g of bis(trichloromethyl)carbonate (BTC) in 20ml of chlorobenzene to prepare a solution of bis(trichloromethyl)carbonate from a dropping funnel. The bis(trichloromethyl)carbonate solution was slowly dropped into the mixed solution at a dropping temperature of 10°C and a stirring speed of 50rmp within 30 minutes at a dropping speed of 0.2g/min, and then at 120°C. The polycondensation reaction was carried out for 12 hours under the conditions of temperature and stirring speed of 550 rpm. After the polycondensation reaction is completed, methanol is added to the above reaction solution, and after vacuuming, filtering, and drying, a white alicyclic polycarbonate (HPC) product is obtained.
將上述製品進行分子量測定。使用凝膠滲透層析儀(GPC，Waters，1515 System)偵測製品之峰值分子量，其中，操作條件如下：(1)流動相：1.0ml/min，THF；(2)檢測器型號：Waters 2414折射率偵測器，檢測溫度：40℃；(3)用於GPC檢測製品之濃度：10mg/ml；(4)進樣量：3μL；(5)層析柱型號：Phenogel 00H-0442-K0、00H-0443-K0、00H-0444-K0。其結果如表1所示，經分子量測定分析後，所製之脂環族聚碳酸酯製品的峰值分子量為62,812。 The above products were subjected to molecular weight measurement. Use gel permeation chromatography (GPC, Waters, 1515 System) to detect the peak molecular weight of the product. The operating conditions are as follows: (1) Mobile phase: 1.0ml/min, THF; (2) Detector model: Waters 2414 Refractive index detector, detection temperature: 40℃; (3) Concentration for GPC detection products: 10mg/ml; (4) Injection volume: 3μL; (5) Chromatography column model: Phenogel 00H-0442-K0 , 00H-0443-K0, 00H-0444-K0. The results are shown in Table 1. After molecular weight measurement and analysis, the peak molecular weight of the prepared alicyclic polycarbonate product was 62,812.
實施例2Example 2
脂環族聚碳酸酯之製備及分析方法係與實施例1相同，惟異動該製備例1所製之HBPA為製備例2所製經純化再結晶之HBPA，以獲得一白色的HPC製品。其結果如表1所示，經分子量測定分析後，所製之HPC製品的峰值分子量為49,535。 The preparation and analysis methods of alicyclic polycarbonate are the same as those in Example 1, except that the HBPA prepared in Preparation Example 1 is the purified and recrystallized HBPA prepared in Preparation Example 2 to obtain a white HPC product. The results are shown in Table 1. After molecular weight measurement and analysis, the peak molecular weight of the prepared HPC product was 49,535.
實施例3Example 3
脂環族聚碳酸酯之製備及分析方法係與實施例1相同，惟異動該製備例1所製之HBPA為購自Chemiway的HBPA，其異構體混合物中順-順異構體、順-反異構體及反-反異構體之含量比例為4：32：64，以獲得一白色的HPC製品。其結果如表1所示，經分子量測定分析後，所製之HPC製品的峰值分子量為21,921。 The preparation and analysis methods of alicyclic polycarbonate are the same as those in Example 1, except that the HBPA prepared in Preparation Example 1 is HBPA purchased from Chemiway. In its isomer mixture, cis-cis isomers, cis-cis isomers, and cis-cis isomers. The content ratio of anti-isomer and anti-anti-isomer is 4:32:64 to obtain a white HPC product. The results are shown in Table 1. After molecular weight measurement and analysis, the peak molecular weight of the prepared HPC product was 21,921.
實施例4Example 4
脂環族聚碳酸酯之製備及分析方法係與實施例1相同，惟異動該製備例1所製之HBPA為購自Wako的HBPA，其異構體混合物中順-順異構體、順-反異構體及反-反異構體之含量比例為7：44：49，以獲得一白色的HPC製品。其結果如表1所示，經分子量測定分析後，所製之HPC製品的峰值分子量為16,678。 The preparation and analysis methods of alicyclic polycarbonate are the same as those in Example 1, except that the HBPA prepared in Preparation Example 1 is HBPA purchased from Wako. In its isomer mixture, cis-cis isomer, cis-cis isomer, The content ratio of anti-isomer and anti-anti-isomer is 7:44:49 to obtain a white HPC product. The results are shown in Table 1. After molecular weight measurement and analysis, the peak molecular weight of the prepared HPC product was 16,678.
比較例1Comparative example 1
脂環族聚碳酸酯之製備及分析方法係與實施例1相同，惟異動該製備例1所製之HBPA為購自CPDC的HBPA，其異構體混合物中順-順異構體、順-反異構體及反-反異構體之含量比例為15：53：32，以獲得一白色的HPC製品。其結果如表1所示，經分子量測定分析後，所製之HPC製品的峰值分子量為9,425。 The preparation and analysis methods of alicyclic polycarbonate are the same as those in Example 1, except that the HBPA prepared in Preparation Example 1 is HBPA purchased from CPDC. In its isomer mixture, cis-cis isomer, cis-cis isomer, The content ratio of anti-isomer and anti-anti-isomer is 15:53:32 to obtain a white HPC product. The results are shown in Table 1. After molecular weight measurement and analysis, the peak molecular weight of the prepared HPC product was 9,425.
比較例2Comparative example 2
脂環族聚碳酸酯之製備及分析方法係與實施例1相同，惟異動該製備例1所製之HBPA為製備例3所製之HBPA，以獲得一白色的HPC製品。其結果如表1所示，經分子量測定分析後，所製之HPC製品的峰值分子量為1,276。 The preparation and analysis methods of alicyclic polycarbonate are the same as those in Example 1, except that the HBPA prepared in Preparation Example 1 is the HBPA prepared in Preparation Example 3 to obtain a white HPC product. The results are shown in Table 1. After molecular weight measurement and analysis, the peak molecular weight of the prepared HPC product was 1,276.
如表1結果所示，與比較例1和比較例2所製之脂環族聚碳酸酯之峰值分子量(Mp)相比；本發明實施例1至實施例4的2,2-雙(4-羥基環己基)丙烷，藉由含有小於45mol%之順-反異構體或大於45mol%之反-反異構體，可使所製之脂環族聚碳酸酯具有大於12000g/mol之峰值分子量(Mp)。 As shown in the results in Table 1, compared with the peak molecular weight (Mp) of the alicyclic polycarbonate produced in Comparative Example 1 and Comparative Example 2; the 2,2-bis(4 -Hydroxycyclohexyl)propane, by containing less than 45 mol% of cis-trans isomers or greater than 45 mol% of trans-trans isomers, can make the alicyclic polycarbonate have a peak value greater than 12000g/mol Molecular weight (Mp).
綜上所述，本發明係透過調整異構體之組成及比例，例如，使2,2-雙(4-羥基環己基)丙烷之異構體混合物中的順-反異構體的含量為45mol%以下，並在有機鹼催化劑及助催化劑之存在下先進行預反應，使2,2-雙(4-羥基環己基)丙烷溶解度提高，而能有效參與反應，並結合反應單體雙(三氯甲基)碳酸酯之使用，使本發明之脂環族聚碳酸酯可於溫和的反應條件下進行製備。因此，本發明藉由具高反應選擇性之製備方法，使所製之脂環族聚碳酸酯係具有高分子量及高純度之特質，符合食用容器、光學、醫療產品的使用需求，增加其應用價值。 To sum up, the present invention adjusts the composition and proportion of isomers, for example, so that the content of cis-trans isomers in the isomer mixture of 2,2-bis(4-hydroxycyclohexyl)propane is 45 mol% or less, and carry out pre-reaction in the presence of organic base catalyst and cocatalyst to increase the solubility of 2,2-bis(4-hydroxycyclohexyl)propane and effectively participate in the reaction, and combine the reaction monomer bis( The use of trichloromethyl carbonate allows the alicyclic polycarbonate of the present invention to be prepared under mild reaction conditions. Therefore, through the preparation method with high reaction selectivity, the alicyclic polycarbonate produced in the present invention has the characteristics of high molecular weight and high purity, which meets the use requirements of edible containers, optical and medical products, and increases its application value.
上述實施例僅為例示性說明，而非用於限制本發明。任何熟習此項技藝之人士均可在不違背本發明之精神及範疇下，對上述實施例進行修飾與改變。因此，本發明之權利保護範圍係由本發明所附之申請專利範圍所定義，只要不影響本發明之效果及實施目的，應涵蓋於此公開技術內容中。 The above embodiments are only illustrative and not intended to limit the present invention. Anyone skilled in the art can make modifications and changes to the above embodiments without departing from the spirit and scope of the invention. Therefore, the scope of rights protection of the present invention is defined by the scope of the patent application attached to the present invention. As long as it does not affect the effect and implementation purpose of the present invention, it should be covered by this disclosed technical content.
Claims (17)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| TWI835457B true TWI835457B (en) | 2024-03-11 |
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