TWI427082B - 有機二硫代焦磷酸酯之製造方法 - Google Patents
有機二硫代焦磷酸酯之製造方法 Download PDFInfo
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- methylpyridine
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- 238000000034 method Methods 0.000 title claims description 17
- 238000004519 manufacturing process Methods 0.000 title description 4
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 claims description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 150000000185 1,3-diols Chemical class 0.000 claims description 10
- -1 3-methylpyridine cation Chemical class 0.000 claims description 8
- 239000002585 base Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- CIFZCCWGXMYJEU-UHFFFAOYSA-N dithiodiphosphoric acid Chemical compound OP(O)(=S)OP(O)(O)=S CIFZCCWGXMYJEU-UHFFFAOYSA-N 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 5
- 239000008346 aqueous phase Substances 0.000 claims description 4
- 239000012074 organic phase Substances 0.000 claims description 4
- 125000005997 bromomethyl group Chemical group 0.000 claims description 3
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- 229910001514 alkali metal chloride Inorganic materials 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 239000012458 free base Substances 0.000 claims description 2
- 238000005580 one pot reaction Methods 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 239000002904 solvent Substances 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 229920000151 polyglycol Polymers 0.000 description 2
- 239000010695 polyglycol Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- UENGBOCGGKLVJJ-UHFFFAOYSA-N 2-chloro-1-(2,4-difluorophenyl)ethanone Chemical compound FC1=CC=C(C(=O)CCl)C(F)=C1 UENGBOCGGKLVJJ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 150000007530 organic bases Chemical group 0.000 description 1
- VXTFGYMINLXJPW-UHFFFAOYSA-N phosphinane Chemical compound C1CCPCC1 VXTFGYMINLXJPW-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657109—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms esters of oxyacids of phosphorus in which one or more exocyclic oxygen atoms have been replaced by (a) sulfur atom(s)
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657109—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms esters of oxyacids of phosphorus in which one or more exocyclic oxygen atoms have been replaced by (a) sulfur atom(s)
- C07F9/657136—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms esters of oxyacids of phosphorus in which one or more exocyclic oxygen atoms have been replaced by (a) sulfur atom(s) the molecule containing more than one cyclic phosphorus atom
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
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Description
本發明係關於一種用於製造式I有機二硫代焦磷酸酯之改良方法：
其中R1、R2、R3、R4和R5獨立地為氫、C1-4烷基、氯甲基或溴甲基。
在此及下文，C1-4烷基應瞭解係意謂任何具有一至四個碳原子之直鏈或支鏈烷基，尤其是甲基、乙基、丙基、異丙基、丁基、異丁基、第二丁基及第三丁基。
式I化合物以作為聚合物用阻燃劑著稱，特別是在紡織品應用方面，參見例如NL 7508884 A。
已知用於製造式I有機二硫代焦磷酸酯之方法涉及1,3-二醇與硫代磷醯氯(PSCl3)反應得到2氯-2硫基-1,3,2-二氧雜磷(phosphorinane)中間物，將其分離，然後與鹼金屬或鹼土金屬的氧化物、氫氧化物，碳酸鹽或碳酸氫鹽(最佳為氧化鈣)在三級有機鹼存在下反應(CH 625 806)或與水反應(NL 7508884 A)。先前技術方法需要不同的溶劑或溶劑混合物以供中間物2氯-2硫基-1,3,2-二氧雜磷
之該二個反應步驟及分離之用。此外，當在第二步驟中使用氧化鈣時，此造成氯化鈣的形成，其必須要被分離除去。
本發明之一目的是要提供用於製造式I有機二硫代焦磷酸酯之簡化方法，其不需要不同的溶劑，且不會造成有機鹽形成為副產物。
根據本發明，此目的已經藉由申請專利範圍第1項中所界定之方法達成。申請人已發現式I之有機二硫代焦磷酸酯可藉由包括下列步驟的方法製得：
其中R1、R2、R3、R4和R5獨立地為氫、C1-4烷基、氯甲基或溴甲基，(i)使式II之1,3-二醇反應：
其中R1、R2、R3、R4和R5係如上文所定義，以獲得式III之2-氯-2-硫基-1,3,2-二氧雜磷
其中R1、R2、R3、R4和R5係如上文所定義，以及(ii)將2-氯-2-硫基-1,3,2-二氧雜磷(III)在鹼存在下以水部分地水解，以獲得對應的二硫代焦磷酸酯(I)，其中3-甲基吡啶同時用在步驟(i)和(ii)中作為有機溶劑和作為鹼。
作為溶劑，3-甲基吡啶可單獨使用或以與其他溶劑的混合物使用。在本發明方法之一個較佳具體實例中，3-甲基吡啶係在二步驟中用作唯一的溶劑。
亦在本發明範圍內的是單獨或與其他鹼組合使用3-甲基吡啶。在一個較佳具體實例中，3-甲基吡啶係在二步驟中用作唯一的鹼。
在一個特佳具體實例中，二反應步驟係以一鍋(one-pot)反應進行而未分離2-氯-2-硫基-1,3,2-二氧雜磷 中間物(III)。
在一個甚至更佳的具體實例中，在步驟(i)中，係將硫代磷醯氯緩慢地加到1,3-二醇(II)於3-甲基吡啶之溶液中，而在步驟(ii)中，係將水緩慢地加到在步驟(i)中獲得的反應混合物中。令人驚訝地發現到，有可能藉由在硫代磷醯氯的添加完成之前開始添加水而縮短本發明之方法。因此，有可能讓步驟(i)和(ii)至少有部分係同時發生，因為2-氯-2-硫基-1,3,2-二氧雜磷中間物(III)的水解在所有1,3-二醇起
始物(II)反應之前便開始。水的添加可在已經添加一半、三分之一或甚至更少的硫代磷醯氯之後開始進行。
在一個尤佳具體實例中，式I、II和III中之R1、R4和R5在每次出現時為氫原子，而R2和R3皆為甲基。
步驟(i)和(ii)有利地係在-10℃與100℃之間，較佳20℃與100℃之間或40℃與80℃之間反應溫度下進行。若二步驟係分開進行，則在第一個步驟中的溫度較佳係在20℃與50℃之間，而在第二個步驟中則在50℃與60℃之間。若硫代磷醯氯和水係同時添加或在重疊的時段添加，則反應較佳係在20℃至50℃開始而在50℃至60℃完成。由於反應放熱，反應溫度的增加至少有部分可藉由利用反應熱達成。
二反應步驟皆可在相對較濃的溶液中進行，較佳為每莫耳1,3-二醇(II)或硫代磷醯氯使用5莫耳與10莫耳之間的3-甲基吡啶。由於每莫耳硫代磷醯氯需要3莫耳3-甲基吡啶作為鹼來結合步驟(i)中形成的氯化氫(2莫耳HCl)和步驟(ii)中形成的氯化氫(1莫耳HCl)，其餘2莫耳與7莫耳之間量可當作溶劑的3甲基吡啶非常地少。視溫度，尤其是步驟(ii)中的溫度，以及用作溶劑之3-甲基吡啶的量而定，氯化3-甲基吡啶陽離子係以固體或液體(亦即熔體或濃溶液)形式獲得。
在步驟(ii)之後所獲得反應混合物的處理可以簡單方式進行如下：添加一定量足以溶解在反應步驟(i)和(ii)中形成之氯化3-甲基吡啶陽離子的水，並藉由過濾分離出二硫代
焦磷酸酯(I)。若氯化3-甲基吡啶陽離子係以液體形成獲得，則該處理可藉由在添加水之前過濾出產物而進一步簡化。
在過濾之後，有利地係將二硫代焦磷酸酯用水洗滌以除去殘餘的3-甲基吡啶和氯化3-甲基吡啶陽離子。已發現洗滌程序可藉由將界面活性劑添加到洗滌水中來促進。較佳的界面活性劑為諸如三乙醇胺聚乙二醇醚之非離子界面活性劑。適合的化合物為市面上可以例如商標Stokomin®(Bozzetto GmbH,Krefeld,Germany)得到者。
在一個較佳具體實例中，係將3-甲基吡啶從濾液回收並循環。
更佳而言，該回收係進行如下：將水和鹼金屬氫氧化物，最佳為氫氧化鈉，加到濾液中，以便從反應步驟(i)和(ii)中形成的氯化3-甲基吡啶陽離子釋放出3-甲基吡啶自由鹼，藉此形成含有溶解鹼金屬氯化物的水相及包含3-甲基吡啶和一些溶解水的有機相。將水相分離除去並藉由有機相之精餾獲得實質上純的3-甲基吡啶，於此將回收的3-甲基吡啶與累積在精餾管柱頂部的溶解水(本身或為與3甲基吡啶之共沸混合物)。在使用3甲基吡啶作為唯一溶劑時，此回收暨循環程序尤其容易。
以下非限制性實施例說明本發明之方法。
在1L攪拌的反應器中裝入3-甲基吡啶(600克，6.44莫耳)和2,2二甲基-1,3丙二醇(104.5克，1莫耳)。將混合物溫熱到45℃，並於4小時期間添加硫代磷醯氯(PSCl3，98%，172.9克，1莫耳)，同時不讓溫度超過50℃。在另30分鐘之後，於45-50℃逐滴添加水(9.5克，0.53莫耳)。然後將混合物溫熱到60℃並保持在該溫度下15小時。然後添加水(160克)以溶解在反應中形成的氯化3-甲基吡啶陽離子。將產物藉過濾分離出來，用水洗滌數次並抽乾。為幫助除去殘餘的3-甲基吡啶，0.015wt.%，將Stokomin® MI 07界面活性劑(三乙醇胺參烷基聚乙二醇醚)加到洗滌水中。
產率：75%。
在1L攪拌的反應器中裝入3-甲基吡啶(600克，6.44莫耳)和2,2二甲基-1,3丙二醇(105.2克， 1莫耳)。將混合物溫熱到50℃，並於3小時期間添加硫代磷醯氯(PSCl3，167.5克， 1莫耳)，同時不讓溫度超過50℃。在硫代磷醯氯添加開始之後一小時，開始為時5.5小時的連續添加水(9.2克，0.51莫耳)，然後在硫代磷醯氯添加完成之後，將溫度在1小時內增高到60℃。在水添加完成之後，於60℃持續攪拌過夜(約16小時)。然後在約2分
鐘內添加水(180克)以溶解在反應中形成的氯化3-甲基吡啶陽離子。將產物藉過濾分離出來並以濾液洗滌。
產量：222克潮濕產物，含量(HPLC分析)：66.1%，相當於84.6%產率。
Claims (4)
- 一種製造式I之有機二硫代焦磷酸酯之方法，
- 如申請專利範圍第1項之方法，其中R1、R4和R5在每次出現時為氫原子，而R2和R3皆為甲基。
- 如申請專利範圍第1項之方法，其中，在藉由過濾分離出二硫代焦磷酸酯(I)之後，將3-甲基吡啶從濾液回收並循環。
- 如申請專利範圍第3項之方法，其中該3-甲基吡啶回收包括下列步驟：將水和鹼金屬氫氧化物加到濾液中，以便從反應步驟(i)和(ii)中形成的氯化3-甲基吡啶陽離子釋放出3-甲基吡啶自由鹼，如此形成含有溶解鹼金屬氯化物的水相及含有3-甲基吡啶與溶解水的有機相；將水相分離除去；以及精餾該有機相，以獲得實質上純的3-甲基吡啶。
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| CN109705390A (zh) * | 2018-12-29 | 2019-05-03 | 南京师范大学 | 一种无卤环状焦磷酸酯在制备阻燃硬质聚氨酯泡沫塑料中的应用 |
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| US5948930A (en) * | 1997-09-11 | 1999-09-07 | Bayer Corporation | Process for preparing O-alkyl, O-alkylphosphorochloridothioates |
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| CH603674A5 (en) * | 1975-05-16 | 1978-08-31 | Sandoz Ag | Derivs of bis (2-(oxo or thiono)-1,3,2-dioxaphosphorinanyl)oxide |
| US5948930A (en) * | 1997-09-11 | 1999-09-07 | Bayer Corporation | Process for preparing O-alkyl, O-alkylphosphorochloridothioates |
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| US8324418B2 (en) | 2012-12-04 |
| HK1159639A1 (en) | 2012-08-03 |
| CN102186870B (zh) | 2014-03-19 |
| EA201100660A1 (ru) | 2011-12-30 |
| CN102186870A (zh) | 2011-09-14 |
| TW201016719A (en) | 2010-05-01 |
| KR20110091699A (ko) | 2011-08-12 |
| EA017760B1 (ru) | 2013-02-28 |
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