KR100334466B1 - Novel process of purification for crude o-chloro-p-toluidine and process of preparation for o-chloro-p-toluidine-5-sulfonic acid using the purified o-chloro-p-toluidine - Google Patents
Novel process of purification for crude o-chloro-p-toluidine and process of preparation for o-chloro-p-toluidine-5-sulfonic acid using the purified o-chloro-p-toluidine Download PDFInfo
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- RQKFYFNZSHWXAW-UHFFFAOYSA-N 3-chloro-p-toluidine Chemical compound CC1=CC=C(N)C=C1Cl RQKFYFNZSHWXAW-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title claims abstract description 44
- 238000000746 purification Methods 0.000 title claims description 10
- 238000002360 preparation method Methods 0.000 title description 7
- AKOPUPHRJSONOI-UHFFFAOYSA-N 5-amino-4-chloro-2-methylbenzenesulfonic acid Chemical compound CC1=CC(Cl)=C(N)C=C1S(O)(=O)=O AKOPUPHRJSONOI-UHFFFAOYSA-N 0.000 title 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001914 filtration Methods 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 239000000706 filtrate Substances 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000006227 byproduct Substances 0.000 claims abstract description 5
- 239000000047 product Substances 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 30
- 238000001816 cooling Methods 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 3
- 239000011343 solid material Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract description 9
- 238000004064 recycling Methods 0.000 abstract description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 abstract 1
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 22
- 235000019441 ethanol Nutrition 0.000 description 10
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- IBSQPLPBRSHTTG-UHFFFAOYSA-N 1-chloro-2-methylbenzene Chemical compound CC1=CC=CC=C1Cl IBSQPLPBRSHTTG-UHFFFAOYSA-N 0.000 description 1
- PLVBBUUBVVJOIB-UHFFFAOYSA-N 2,5-dichloro-4-methylaniline Chemical compound CC1=CC(Cl)=C(N)C=C1Cl PLVBBUUBVVJOIB-UHFFFAOYSA-N 0.000 description 1
- AYVZXDFCFQSWJD-UHFFFAOYSA-N 2,6-dichloro-3-methylaniline Chemical compound CC1=CC=C(Cl)C(N)=C1Cl AYVZXDFCFQSWJD-UHFFFAOYSA-N 0.000 description 1
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 description 1
- HPSCXFOQUFPEPE-UHFFFAOYSA-N 2-chloro-5-methylaniline Chemical compound CC1=CC=C(Cl)C(N)=C1 HPSCXFOQUFPEPE-UHFFFAOYSA-N 0.000 description 1
- GTEUMCIATAHZFK-UHFFFAOYSA-N 3,5-dichloro-4-methylaniline Chemical compound CC1=C(Cl)C=C(N)C=C1Cl GTEUMCIATAHZFK-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methyl-N-phenylamine Natural products CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B63/00—Purification; Separation; Stabilisation; Use of additives
- C07B63/04—Use of additives
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
본발명은 (i) 반응기 내에 저품위 액상 OCPT(o-클로로-p-톨루이딘) 10중량부를 투입하고 C1-C5알콜 40 - 55 중량부를 가하여 25 - 35분간 교반하는 단계;(ii) 반응기에 황산 5 - 10 중량부를 3 - 5 시간 동안 가하는 단계; (iii) 1 - 3 시간 동안 방치시킨 후 반응물을 여과하는 단계; 및 (iv) 여과 후 얻은 생성물을 상기 알콜로 수회 세척 및 건조시키는 단계를 포함하는 OCPT의 정제방법, 정제된 OCPT 의 황산염으로부터 용매법 및 무용매법에 의해 OCPT-5-설폰산을 제조하는 방법, 및 OCPT 황산염 제조시에 부생하는 여액을 재활용하여 OCPT-5-설폰산을 제조하는 방법에 관한 것이다.The present invention comprises the steps of (i) 10 parts by weight of low-grade liquid OCPT (o-chloro-p-toluidine) in the reactor and adding 40-55 parts by weight of C 1 -C 5 alcohol and stirring for 25-35 minutes; (ii) to the reactor Adding 5-10 parts by weight of sulfuric acid for 3-5 hours; (iii) filtering the reaction after leaving for 1-3 hours; And (iv) washing and drying the product obtained after filtration several times with the alcohol, a method for preparing OCPT-5-sulfonic acid by solvent and solvent-free method from sulfates of purified OCPT, And it relates to a method for producing OCPT-5-sulfonic acid by recycling the by-product filtrate in the manufacture of OCPT sulfate.
Description
본 발명은 o-클로로-p-톨루이딘(OCPT)화합물의 새로운 정제 방법 및 이를 이용한 OCPT-5-설폰산의 합성방법에 관한 것으로서, 보다 상세하게는 저품위 OCPT를 황산염 형태로 정제시키는 방법 및, 이 염으로부터 OCPT-5-설폰산을 제조하는 방법에 관한 것이다.The present invention relates to a novel purification method of o-chloro-p-toluidine (OCPT) compound and a method for synthesizing OCPT-5-sulfonic acid using the same, and more particularly, a method for purifying low-grade OCPT in the form of sulfate, and A method for preparing OCPT-5-sulfonic acid from salts.
OCPT-5-설폰산은 아조계 적색 안료의 핵심적 원료 중의 하나로서, 적색 색상이 선명하여 적색 잉크, 페인트 등의 원재료로서 널리 사용되고 있다. 현재, OCPT-5-설폰산은 OCPT를 진한 황산과 반응시켜 제조되며, 고품위 OCPT로부터 OCPT-5-설폰산을 제조하는 경우, 순도 및 수율이 우수한 반면 원료인 OCPT의 가격이 비싸서 OCPT-5-설폰산의 제조단가가 높아지는 단점이 있고, 한편, 저품위 OCPT로부터 OCPT-5-설폰산을 제조하는 경우, 제조단가는 내려가는 반면에 순도 및 수율이 떨어지는 단점이 있다. 당업계에서는, 저품위 OCPT 및 고품위 OCPT를 1 : 1 등의 적정한 비율로 섞어서 OCPT-5-설폰산을 제조하는 방법이 널리 행해지는 바, 이 방법에 따를 경우에도 OCPT-5-설폰산의 순도가 고품위 OCPT로부터의 OCPT-5-설폰산 제조시보다 떨어져서 우수한 품질을 얻기 힘들고, 제조단가 또한 저품위 OCPT를 이용한 경우보다 높다는 문제점이 있다.OCPT-5-sulfonic acid is one of the core raw materials of azo red pigment, and its red color is vivid, so it is widely used as a raw material of red ink, paint and the like. At present, OCPT-5-sulfonic acid is prepared by reacting OCPT with concentrated sulfuric acid. When OCPT-5-sulfonic acid is produced from high-quality OCPT, the purity and yield are excellent, but the price of OCPT, a raw material, is high. There is a disadvantage in that the production cost of phonic acid is increased, on the other hand, in the case of manufacturing OCPT-5-sulfonic acid from low-grade OCPT, the production cost is lowered, while the purity and yield are low. In the art, a method of producing OCPT-5-sulfonic acid by mixing low-grade OCPT and high-grade OCPT in an appropriate ratio of 1: 1, etc. is widely performed, and the purity of OCPT-5-sulfonic acid is also followed according to this method. There is a problem in that it is difficult to obtain excellent quality from the production of OCPT-5-sulfonic acid from high quality OCPT, and the manufacturing cost is also higher than that of low quality OCPT.
본 발명은 상기의 몇 가지 문제점을 해결하기 위한 것으로서, 저품위의 OCPT를 저비용의 간단한 공정에 의해 고순도로 정제하고, 정제된 OCPT염으로부터 고순도의 o-클로로-p-톨루이딘(OCPT)-5-설폰산을 제조함으로써, 고품위 OCPT로부터 OCPT-5-설폰산을 제조하는 방법과 대등하거나 또는 더욱 우수한 순도의 OCPT-5-설폰산 제조하는 방법을 제공하고자 한다. 또한, OCPT의 정제시 부생하는 여액도 재활용하여 OCPT-5-설폰산을 제조하는 방법을 제공하고자 한다.The present invention is to solve some of the above problems, the low-grade OCPT is purified by a low cost simple process, high-purity o-chloro-p-toluidine (OCPT) -5-sulfur from the purified OCPT salt By preparing phonic acid, it is intended to provide a method for producing OCPT-5-sulfonic acid of equivalent or better purity than the process for producing OCPT-5-sulfonic acid from high quality OCPT. In addition, to provide a method for producing OCPT-5-sulfonic acid by recycling the by-product filtrate during the purification of OCPT.
본 발명은 o-클로로-p-톨루이딘(OCPT)화합물의 새로운 정제 방법 및 이를 이용한 OCPT-5-설폰산의 합성방법에 관한 것이다.The present invention relates to a novel purification method of o-chloro-p-toluidine (OCPT) compound and a method for synthesizing OCPT-5-sulfonic acid using the same.
본 발명의 첫 번째 양상은, (i) 반응기 내에 저품위 액상 OCPT(o-클로로-p-톨루이딘) 10중량부를 투입하고 C1-C5알콜 40 - 55 중량부를 가하여 25 - 35분간 교반하는 단계; (ii) 반응기에 황산 5 - 10 중량부를 3 - 5 시간 동안 가하는 단계; (iii) 1 - 3 시간 동안 방치시킨 후 반응물을 여과하는 단계; 및 (iv) 여과 후 얻은 고형 물질을 상기 알콜로 수회 세척 및 건조시키는 단계를 포함하는 OCPT의정제방법이다.The first aspect of the present invention comprises the steps of: (i) adding 10 parts by weight of low-grade liquid OCPT (o-chloro-p-toluidine) into the reactor and adding 40-55 parts by weight of C 1 -C 5 alcohol to stir for 25 to 35 minutes; (ii) adding 5-10 parts by weight of sulfuric acid to the reactor for 3-5 hours; (iii) filtering the reaction after leaving for 1-3 hours; And (iv) washing and drying the solid material obtained after the filtration several times with the alcohol.
현재 시판되는 저품위 OCPT는 OCPT(순도: 약 96.8%) 이외에, o-클로로톨루엔, p-톨루이딘, 2-클로로-5-메틸 아닐린, 2-클로로-4-니트로-톨루엔, 3-브로모-4-메틸아닐린, 2,5-디클로로-4-메틸아닐린, 2,6-디클로로-3-메틸아닐린, 3,5-디클로로-4-메틸아닐린 등의 불순물을 포함한다.본 발명의 용어에서 사용된 저품위 OCPT란 OCPT함량이 97.0%이하이고, 다양한 불순물을 함유하는 OCPT를 말한다. 또한 불순물의 예는 상기 기재의 예와 같다.Low-grade OCPTs currently available are o-chlorotoluene, p-toluidine, 2-chloro-5-methyl aniline, 2-chloro-4-nitro-toluene, 3-bromo-4, in addition to OCPT (purity: about 96.8%). Impurities such as -methylaniline, 2,5-dichloro-4-methylaniline, 2,6-dichloro-3-methylaniline, 3,5-dichloro-4-methylaniline, and the like. Low-grade OCPT refers to OCPT containing less than 97.0% of OCPT and containing various impurities. In addition, the example of an impurity is the same as the example of the said description.
반응용매로 사용되는 C1-C5알콜 중, 이소프로필알콜(IPA)은 상대적으로 인화성이 낮고, 경제적이어서 특히 바람직하다.Of the C 1 -C 5 alcohols used as the reaction solvent, isopropyl alcohol (IPA) is particularly preferred because it is relatively inflammable and economical.
반응용매인 알콜은 47-48 중량부를 가하는 것이 바람직하다.It is preferable to add 47-48 parts by weight of the alcohol which is the reaction solvent.
황산은 7 중량부 만큼을 4시간에 걸쳐 적하하는 것이 바람직하다.It is preferable to add dropwise sulfuric acid over 4 hours by 7 parts by weight.
여과 후 얻은 고형물질은 OCPT의 황산염으로서, OCPT-5-설폰산의 제조에 사용할 수 있고, 여과 후 남은 여액 또한 OCPT-5-설폰산의 제조에 재활용할 수 있다.The solid obtained after filtration is the sulfate of OCPT, which can be used for the preparation of OCPT-5-sulfonic acid, and the filtrate remaining after filtration can also be recycled for the production of OCPT-5-sulfonic acid.
본 발명의 두 번째 양상은, (i) 상기한 OCPT의 정제방법으로 얻은 OCPT 염 10 중량부를 반응기 내에 투입하고 물 1.3 - 1.5 중량부를 가한 후 25 - 35 분간 교반하는 단계; (ii) 황산 1.7 - 2.1 중량부를 1 - 3 시간 동안 가하는 단계; (iii) 140 - 160℃에서 1 - 3 시간동안 용해시킨 후 반응기에 진공을 거는 단계; (iv) 165 - 175℃, 600 - 750 mmHg 의 감압하에서 2 - 4 시간동안 반응시키는 단계; (v) 195 - 205℃, 600 - 750 mmHg 의 감압하에서 14 - 16 시간동안 반응시키는 단계; (vi) 165 - 175℃, 600 - 750 mmHg 의 감압하에서 3 - 5 시간동안 반응시키는 단계; 및 (vii) 미반응의 OCPT양이 0.32중량% 이하가 될 때 열원을 차단하고 5- 8 시간동안 냉각시키는 단계를 포함하는 OCPT-5-설폰산의 제조 방법이다.The second aspect of the present invention comprises the steps of: (i) adding 10 parts by weight of the OCPT salt obtained by the method for purifying OCPT into the reactor, adding 1.3-1.5 parts by weight of water, and then stirring it for 25-35 minutes; (ii) adding 1.7-2.1 parts of sulfuric acid for 1-3 hours; (iii) dissolving at 140-160 ° C. for 1-3 hours and then vacuuming the reactor; (iv) reaction at 165-175 ° C., 600-750 mmHg under reduced pressure for 2-4 hours; (v) reacting at 195-205 ° C. under a reduced pressure of 600-750 mmHg for 14-16 hours; (vi) 165-175 ° C., reaction under reduced pressure of 600-750 mmHg for 3-5 hours; And (vii) blocking the heat source and cooling for 5-8 hours when the amount of unreacted OCPT is 0.32% by weight or less.
상기한 방법은 OCPT로부터 OCPT-5-설폰산을 제조하는 방법 중 소위 '무용매법'이다.The above-mentioned method is the so-called 'solvent-free method' among the methods for producing OCPT-5-sulfonic acid from OCPT.
상기 단계 (i)에서, OCPT 염 10중량부 당 물 1.4 중량부를 가해 30분간 교반하는 것이 바람직하다.In step (i), it is preferable to add 1.4 parts by weight of water per 10 parts by weight of the OCPT salt and stir for 30 minutes.
상기 단계 (ii)에서, 황산 1.9 중량부를 2시간 동안 가하는 것이 바람직하다.In step (ii), it is preferable to add 1.9 parts by weight of sulfuric acid for 2 hours.
상기 단계 (iii)에서, 150℃에서 2시간 동안 용해시켜 반응기에 진공을 거는 것이 바람직하다.In the step (iii), it is preferable to dissolve at 150 ° C. for 2 hours to apply a vacuum to the reactor.
상기 단계 (iv) 에서, 170 ℃, 650 - 700 mmHg 에서 3 시간동안 반응시키는 것이 바람직하다.In the above step (iv), the reaction is preferably carried out at 170 ° C. and 650-700 mmHg for 3 hours.
상기 단계 (v) 에서, 200 ℃, 650 - 700 mmHg 에서 15 시간동안 반응시키는 것이 바람직하다.In the step (v), it is preferable to react at 200 ° C. at 650-700 mmHg for 15 hours.
상기 단계 (vi) 에서, 170 ℃, 650 - 700 mmHg 에서 4 시간동안 반응시키는 것이 바람직하다.In the above step (vi), it is preferable to react at 170 ° C. at 650-700 mmHg for 4 hours.
상기 단계 (vii)에서, 미반응된 OCPT의 양은 반응기 내의 자유 아민의 양으로 측정된다.In step (vii), the amount of unreacted OCPT is determined by the amount of free amine in the reactor.
본 발명의 세 번째 양상은, (i) 상기한 OCPT의 정제방법으로 얻은 OCPT염 10 중량부를 반응기 내에 투입하고 1,2-디클로로벤젠(ODCB) 40 - 60 중량부를 투입한 후 25 - 35 분간 교반하는 단계; (ii) 황산 1.7 - 2.1 중량부를 2 - 4 시간 동안가하는 단계; (iii) 반응기의 온도를 상승시켜, 170 - 190℃에서 11 - 13 시간동안 계속하여 환류냉각하는 단계; (iv) 반응기를 40 - 60℃로 냉각시키는 단계; 및 (v) 반응물을 보유탱크로 이송시킨 후 데칸터(decanter)로 용매를 분리하고 여과한 다음, 얻은 생성물을 건조시키는 단계를 포함하는 OCPT-5-설폰산의 제조 방법이다.The third aspect of the present invention, (i) 10 parts by weight of the OCPT salt obtained by the above-described OCPT purification method into the reactor and 40-60 parts by weight of 1,2-dichlorobenzene (ODCB) and then stirred for 25 to 35 minutes Doing; (ii) adding 1.7-2.1 parts of sulfuric acid for 2-4 hours; (iii) raising the temperature of the reactor to continue reflux cooling at 170-190 ° C. for 11-13 hours; (iv) cooling the reactor to 40-60 ° C .; And (v) transferring the reactants to a holding tank, separating the solvent with a decanter, filtering, and drying the obtained product.
상기한 방법은 OCPT로부터 OCPT-5-설폰산을 제조하는 방법 중 소위 '용매법'이다.The above method is the so-called 'solvent method' among the methods for producing OCPT-5-sulfonic acid from OCPT.
상기 단계 (i)에서, OCPT염 10 중량부 당 ODCB 50중량부를 투입하여 30분간 교반하는 것이 바람직하다.In step (i), it is preferable to add 50 parts by weight of ODCB per 10 parts by weight of the OCPT salt and stir for 30 minutes.
상기 단계 (ii)에서, 황산 1.9 중량부를 3시간 동안 적하하는 것이 바람직하다.In the step (ii), 1.9 parts by weight of sulfuric acid is preferably added dropwise for 3 hours.
상기 단계 (iii)에서, 180-182℃에서 12시간 동안 반응시키는 것이 바람직하다.In the step (iii), it is preferable to react for 12 hours at 180-182 ℃.
상기 단계 (iv)에서, 반응기 온도를 약 50℃로 냉각시키는 것이 바람직하다.In step (iv) above, it is preferred to cool the reactor temperature to about 50 ° C.
본 발명의 네 번째 양상은, (i) 상기한 OCPT의 정제시 부생하는 여액을 회수하여 처리탱크로 이송하는 단계; (ii) 여액 10 중량부를 활성탄 0.2 - 0.4 중량부로 처리한 후, 이를 반응기로 이송하는 단계; (iii) 반응기에 과량으로 들어 있는 황산에 대응하여 OCPT 0.6 - 0.8 중량부를 투입하는 단계; (iv) 반응기 온도를 100 - 130℃로 올려서 OCPT 정제시 사용된 알콜을 증류시켜 알콜을 회수하는 단계; (v) 반응기에 OCDB 7 - 9 중량부를 투입하고, 115 - 125℃를 유지해서 알콜을 추가로 증류 및 회수하고, 다시 OCDB 10 - 14 중량부를 추가 투입하고 25-35분간 교반하는단계; (vi) 반응기의 온도를 상승시켜, 170 - 190℃에서 11 - 13 시간동안 계속하여 환류냉각하는 단계; (vii) 반응기를 40 - 60℃로 냉각시키는 단계; 및 (viii) 반응물을 보유탱크로 이송시킨 후 데칸터(decanter)로 용매를 분리하고 여과한 다음, 얻은 생성물을 건조시키는 단계를 포함하는 OCPT-5-설폰산의 제조 방법이다.A fourth aspect of the present invention includes the steps of: (i) recovering the by-product filtrate upon purification of the OCPT and transporting it to a treatment tank; (ii) treating 10 parts by weight of the filtrate with 0.2-0.4 parts by weight of activated carbon and then transferring it to the reactor; (iii) adding 0.6-0.8 parts by weight of OCPT in response to excess sulfuric acid in the reactor; (iv) raising the reactor temperature to 100-130 ° C. to distill the alcohol used in OCPT purification to recover the alcohol; (v) adding 7-9 parts by weight of OCDB to the reactor, maintaining the temperature at 115-125 ° C. to further distill and recover the alcohol, and further adding 10-14 parts by weight of OCDB and stirring for 25-35 minutes; (vi) raising the temperature of the reactor to continue reflux cooling at 170-190 ° C. for 11-13 hours; (vii) cooling the reactor to 40-60 ° C .; And (viii) transferring the reactants to a holding tank, separating the solvent with a decanter, filtering, and drying the obtained product.
본 발명은 저품위 OCPT의 정제시 부생하는 여액도 재활용하여 OCPT-5-설폰산의 제조에 재활용된다는 점에서 경제적인 잇점이 있다.The present invention is economically advantageous in that the by-product filtrate is also recycled in the production of OCPT-5-sulfonic acid by regeneration of low-grade OCPT.
상기 단계(ii)에서, 여액 10중량부 당 활성탄 0.3 중량부를 사용하는 것이 바람직하다.In step (ii), it is preferable to use 0.3 parts by weight of activated carbon per 10 parts by weight of the filtrate.
상기 단계(iii)에서, OCPT를 0.7 중량부 투입하는 것이 바람직하다.In the step (iii), it is preferable to add 0.7 parts by weight of OCPT.
상기 단계(iv)에서, 반응기 온도는 120℃인 것이 바람직하다.In step (iv), the reactor temperature is preferably 120 ° C.
상기 단계 (v)에서, OCDB는 처음에 8중량부 투입하여 알콜을 회수하고, 이후 다시 12중량부를 투입하여 알콜을 회수하는 것이 바람직하다.In the step (v), OCDB is initially added 8 parts by weight to recover the alcohol, then 12 parts by weight is preferably added to recover the alcohol.
상기 단계 (vi)에서, 180-182℃에서 12시간 동안 반응시키고, 이후 50℃로 냉각시키는 것이 바람직하다.In the above step (vi), it is preferable to react at 180-182 ° C. for 12 hours, and then cool to 50 ° C.
본 발명은 본발명의 보호범위를 제한하지 않는 다음 실시예에 의해 더욱 상세히 설명된다.The invention is illustrated in more detail by the following examples which do not limit the scope of protection of the present invention.
<실시예 1: OCPT의 정제> Example 1 Purification of OCPT
실시예 1-1Example 1-1
OCPT를 96.8 중량% 함유하는 중국산 조 OCPT 200g(1.367 mol)을 3구 플라스크(2L) 반응기에 투입하고, IPA 1200 ml를 가해 30분간 교반한 후, 97 % 황산 138.25 g(1.367 mol)을 4시간 동안에 적가장치로 적하하고, 이를 2시간 방치시켰다. 이후, 반응생성물을 여과하고, 여과된 반응생성물을 IPA 150 ml로 2회 세척한 후, 건조하여 순도 99.58 %의 OCPT황산염 235.94 g(수율 = 80.92 중량%)을 얻었다.200 g (1.367 mol) of crude Chinese OCPT containing 96.8% by weight of OCPT was added to a three-necked flask (2 L) reactor, 1200 ml of IPA was added thereto, followed by stirring for 30 minutes, followed by 138.25 g (1.367 mol) of 97% sulfuric acid for 4 hours. Was dropped into the dropping apparatus and left for 2 hours. Thereafter, the reaction product was filtered, and the filtered reaction product was washed twice with 150 ml of IPA, followed by drying to obtain 235.94 g (yield = 80.92 wt%) of OCPT sulfate having a purity of 99.58%.
실시예 1-2Example 1-2
IPA 대신 에틸 알콜을 사용한다는 점을 제외하고는 실시예 1-1에서와 동일한 공정을 행하여, 순도 99.59%의 OCPT 황산염 209.94 g(수율 = 72.00 중량%)을 얻었다.The same process as in Example 1-1 was carried out except that ethyl alcohol was used instead of IPA, to obtain 209.94 g (yield = 72.00 wt%) of OCPT sulfate having a purity of 99.59%.
실시예 1-3Example 1-3
IPA를 800ml 사용한다는 점을 제외하고는 실시예 1-1에서와 동일한 공정을 행하여, 순도 99.52%의 OCPT 황산염 211.51 g(수율 = 72.54 중량%)을 얻었다.The same process as in Example 1-1 was carried out except that 800 ml of IPA was used, to obtain 211.51 g of OCPT sulfate having a purity of 99.52% (yield = 72.54 wt%).
실시예 1-4Example 1-4
황산을 69.13g(0.68 mol) 사용한다는 점을 제외하고는 실시예 1-1에서와 동일한 공정을 행하여, 순도 99.41%의 OCPT 황산염 247.65 g(수율 = 84.94 중량%)을 얻었다.The same process as in Example 1-1 was carried out except that 69.13 g (0.68 mol) of sulfuric acid was used to obtain 247.65 g (yield = 84.94% by weight) of OCPT sulfate having a purity of 99.41%.
<실시예 2: OCPT황산염으로부터 무용매법에 의한 OCPT-5-설폰산의 제조> Example 2 Preparation of OCPT-5-Sulfonic Acid from the OCPT Sulfate by Solventless Method
4구 플라스크(1L) 반응기에 실시예 1-1에서 제조한 OCPT 염 235.94 g과 물 32 g을 가하여 30분간 교반한 후, 황산 44.82 g을 2시간 동안에 적가장치로 적하하고, 150℃로 승온시킨 후 반응기에 진공을 걸었다. 이후, 170℃로 다시 승온하고, 650-700 mmHg에서 3시간 동안 유지시켰다. 그리고 다시 승온하여 200℃, 650-700mmHg에서 15시간 반응시키고, 같은 압력에서 반응온도를 170℃로 강하하고 4시간동안 계속 반응시켰다. 이후, 반응기 내 미반응 OCPT 함량이 0.32 중량% 이하가 될 때, 열원을 차단하고 6시간동안 냉각시켜, 순도가 98.4 %이고, 엷은 분홍색을 띤 백색 결정물인 OCPT-5-설폰산 249.18 g (수율 = 80.92 중량%)를 얻었다.235.94 g of the OCPT salt prepared in Example 1-1 and 32 g of water were added to a four-necked flask (1 L) reactor, followed by stirring for 30 minutes, and 44.82 g of sulfuric acid was added dropwise thereto over 2 hours, and the temperature was increased to 150 ° C. After the vacuum was put into the reactor. The temperature was then raised to 170 ° C. again and maintained at 650-700 mmHg for 3 hours. Then, the mixture was heated up again and reacted at 200 ° C. and 650-700 mmHg for 15 hours. At the same pressure, the reaction temperature was lowered to 170 ° C. and continued for 4 hours. Then, when the unreacted OCPT content in the reactor is 0.32% by weight or less, the heat source is blocked and cooled for 6 hours to give 249.18 g of OCPT-5-sulfonic acid, which is 98.4% pure and pale pinkish white crystals (yield) = 80.92 wt%).
<실시예 3: OCPT황산염으로부터 용매법에 의한 OCPT-5-설폰산의 제조> Example 3 Preparation of OCPT-5-Sulfonic Acid from Solvent Method from OCPT Sulfate
3구 플라스크 반응기(1L)에 실시예 1-1에서 제조한 OCPT 염 200 g(1.367 mol ) 및 1,2-디클로로벤젠(ODCB) 500ml를 가하여 30분간 교반한 후, 황산 10.71 g을 3시간 동안에 적가장치로 적하하였다. 이후, 반응기의 온도를 180 ℃로 상승시켜 12시간 동안 계속하여 환류냉각(Reflux)하였다. 이후, 반응기를 50 ℃로 냉각하고 반응생성물을 여과하고 건조시켜 순도 98.4%이고, 회색분말상인 OCPT-5-설폰산 249.18 g (수율 = 80.92 중량 %)을 얻었다.200 g (1.367 mol) of OCPT salt prepared in Example 1-1 and 500 ml of 1,2-dichlorobenzene (ODCB) were added to a three-necked flask reactor (1 L), followed by stirring for 30 minutes, followed by 10.71 g of sulfuric acid for 3 hours. It was dripped by the dropping apparatus. Thereafter, the temperature of the reactor was raised to 180 ° C. and reflux was continued for 12 hours. The reactor was then cooled to 50 ° C. and the reaction product was filtered and dried to give 249.18 g of OCPT-5-sulfonic acid with a purity of 98.4% (gray yield) (yield = 80.92% by weight).
<실시예 4: OCPT정제시 부생하는 여액으로부터 용매법에 의한 OCPT-5-설폰산 제조> Example 4 Preparation of OCPT-5-Sulfonic Acid by Solvent Method from Filtrate by-produced in OCPT Purification
실시예 1-1에서 여과 후 생긴 여액 445 ml를 14 g의 활성탄으로 처리하고, 이 여액을 3구 플라스크 반응기(1L)로 이송하였다. 그리고 과량으로 들어있는 황산(100 중량%, 14.85 g)과 대응하도록 OCPT 21.44 g을 반응기에 추가투입하고, 반응기 온도를 90 ℃정도로 올려 IPA를 약 200 ml를 회수하였다. 여기에 계속해서 1,2-디클로로벤젠(ODCB) 200 ml을 추가하고 90 ℃로 유지하여, IPA 240 ml를 추가로 회수하였다. 이후, ODCB 300 ml를 더 투입하고, 반응기의 온도를 180 ℃로 상승시키고, 12시간 동안 계속하여 환류냉각(Reflux)하였다. 이후, 반응기를 교반하면서 50 ℃로 냉각하고, 반응생성물을 여과하고 건조시켜, 순도 98.1%인 회색분말상의 OCPT-5-설폰산 53.98 g을 얻었다.In Example 1-1, 445 ml of the filtrate formed after filtration were treated with 14 g of activated carbon, and the filtrate was transferred to a three-necked flask reactor (1 L). In addition, 21.44 g of OCPT was added to the reactor to correspond to excess sulfuric acid (100 wt%, 14.85 g), and the reactor temperature was raised to about 90 ° C. to recover about 200 ml of IPA. Subsequently, 200 ml of 1,2-dichlorobenzene (ODCB) was added and maintained at 90 ° C. to further recover 240 ml of IPA. Thereafter, 300 ml of ODCB was further added, the temperature of the reactor was raised to 180 ° C., and reflux was continued for 12 hours. Thereafter, the reactor was cooled to 50 DEG C while stirring, and the reaction product was filtered and dried to obtain 53.98 g of OCPT-5-sulfonic acid in gray powder having a purity of 98.1%.
<비교예 1: 저품위 OCPT로부터 용매법에 의한 OCPT-5-설폰산 제조> Comparative Example 1: Preparation of OCPT-5-Sulfonic Acid from Solvent OCPT by Solvent Method
4구 플라스크 반응기(1L)에 저품위 OCPT 30g(0.206ml) 및 1,2-디클로로벤젠 (ODCB) 600ml을 투입하고, 반응기를 10분간 교반하였다. 그리고, 97% 황산21.4 g(0.217mol)을 20분에 걸쳐 적하하였다. 이후, 승온시켜 180℃에서 12시간동안 계속 환류냉각하였다. 이후, 50℃로 냉각하고 여과한 다음, 이를 140℃에서 12시간 건조시켜, 순도 96.8 %인 회색분말상의 OCPT-5-설폰산 44.8g(수율 = 98.3 중량%)을 얻었다.30 g (0.206 ml) of low-grade OCPT and 600 ml of 1,2-dichlorobenzene (ODCB) were added to a four-necked flask reactor (1 L), and the reactor was stirred for 10 minutes. And 21.4 g (0.217 mol) of 97% sulfuric acid was dripped over 20 minutes. Thereafter, the temperature was raised to reflux cooling at 180 ° C. for 12 hours. Thereafter, the mixture was cooled to 50 ° C., filtered, and dried at 140 ° C. for 12 hours to obtain 44.8 g (yield = 98.3 wt%) of OCPT-5-sulfonic acid on gray powder having a purity of 96.8%.
<비교예 2: 고순도 OCPT로부터 OCPT-5-설폰산 제조(용매법)> Comparative Example 2: Preparation of OCPT-5-Sulfonic Acid from High Purity OCPT (Solvent Method)
4구 플라스크 반응기(1L)에, OCPT를 99.77% 함유하는 시판되는 독일산 OCPT 30g(0.206ml) 및 1,2-디클로로벤젠(ODCB) 600ml을 투입하고 반응기를 10분간 교반하였다. 그리고, 97% 황산 21.4g(0.217mol)을 20분에 걸쳐 적하하였다. 이후, 승온시켜 180℃에서 12시간동안 계속하여 환류냉각 하였다. 그리고, 50℃로 냉각시키고 여과한 다음, 이를 140℃에서 12시간 건조하여, 순도 98.0 %의 OCPT-5-설폰산 44.8g(수율 98.3 중량%)을 얻었다.Into a four-necked flask reactor (1 L), 30 g (0.206 ml) of commercially available German OCPT containing 99.77% of OCPT and 600 ml of 1,2-dichlorobenzene (ODCB) were charged and the reactor was stirred for 10 minutes. And 21.4 g (0.217 mol) of 97% sulfuric acid was dripped over 20 minutes. Thereafter, the temperature was raised to reflux cooling at 180 ° C. for 12 hours. Then, the mixture was cooled to 50 ° C., filtered, and dried at 140 ° C. for 12 hours to obtain 44.8 g (98.3% by weight) of OCPT-5-sulfonic acid having a purity of 98.0%.
비교예 1의 결과를 실시예 3의 결과와 비교해 보면, 본 방법에 따라서 저품위의 조 OCPT를 정제한 후에 OCPT-5-설폰산을 제조하는 방법에서는 생성물인 OCPT-5-설폰산의 순도가 98.1 %였고, 저품위의 조 OCPT로부터 직접 OCPT-5-설폰산을 제조하는 종래의 방법에 의하면 OCPT-5-설폰산의 순도가 96.8%이므로, 본원방법에 따른 OCPT 정제 및 정제된 OCPT로부터 OCPT-5-설폰산을 제조하는 방법이 OCPT-5-설폰산의 순도면에서 종래 기술보다 우수함을 알 수 있다.Comparing the results of Comparative Example 1 with the results of Example 3, in the method for preparing OCPT-5-sulfonic acid after purifying crude OCPT of low quality according to the present method, the purity of the product, OCPT-5-sulfonic acid, was 98.1. %, And according to the conventional method for preparing OCPT-5-sulfonic acid directly from low-quality crude OCPT, the purity of OCPT-5-sulfonic acid is 96.8%, and thus OCPT-5 from OCPT purified and purified OCPT according to the present method. It can be seen that the method for preparing sulfonic acid is superior to the prior art in terms of purity of OCPT-5-sulfonic acid.
또한, 비교예 2의 결과를 실시예 2 및 3의 결과와 비교해 보면, 본 방법에 따라서 저품위의 조 OCPT로부터 이를 정제시킨 후에 OCPT-5-설폰산을 제조하여 얻은 OCPT-5-설폰산의 순도(98.1 및 98.4 %)는, 고순도 OCPT로부터 OCPT-5-설폰산을 제조하여 얻은 OCPT-5-설폰산의 순도(98.0%)와 대등하거나 더욱 우수함을 알 수 있다.Also, comparing the results of Comparative Example 2 with the results of Examples 2 and 3, the purity of OCPT-5-sulfonic acid obtained by preparing OCPT-5-sulfonic acid after purifying it from crude OCPT of low quality according to the present method (98.1 and 98.4%) can be seen to be comparable or better than the purity (98.0%) of OCPT-5-sulfonic acid obtained by preparing OCPT-5-sulfonic acid from high purity OCPT.
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