CN107159310A - 一种有机磷酸酯催化剂及其制备方法 - Google Patents
一种有机磷酸酯催化剂及其制备方法 Download PDFInfo
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- 150000003014 phosphoric acid esters Chemical class 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
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- 239000007787 solid Substances 0.000 claims abstract description 13
- YYQRGCZGSFRBAM-UHFFFAOYSA-N Triclofos Chemical compound OP(O)(=O)OCC(Cl)(Cl)Cl YYQRGCZGSFRBAM-UHFFFAOYSA-N 0.000 claims abstract description 9
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229960001147 triclofos Drugs 0.000 claims abstract description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 6
- NCCOOTMRZHTROF-UHFFFAOYSA-N ethylphosphanium;bromide Chemical compound [Br-].CC[PH3+] NCCOOTMRZHTROF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011777 magnesium Substances 0.000 claims abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 12
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- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000003480 eluent Substances 0.000 claims description 6
- FRIJBUGBVQZNTB-UHFFFAOYSA-M magnesium;ethane;bromide Chemical compound [Mg+2].[Br-].[CH2-]C FRIJBUGBVQZNTB-UHFFFAOYSA-M 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 claims 1
- 229910001623 magnesium bromide Inorganic materials 0.000 claims 1
- 150000001718 carbodiimides Chemical class 0.000 abstract description 8
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- 229910019142 PO4 Inorganic materials 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 150000004857 phospholes Chemical class 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- -1 phosphorus series compound Chemical class 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
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- WHRNULOCNSKMGB-UHFFFAOYSA-N tetrahydrofuran thf Chemical compound C1CCOC1.C1CCOC1 WHRNULOCNSKMGB-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
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- 229910052785 arsenic Inorganic materials 0.000 description 2
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- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- JRIGVWDKYXCHMG-UHFFFAOYSA-N (5-arsoroso-2-hydroxyphenyl)azanium;chloride Chemical compound Cl.NC1=CC([As]=O)=CC=C1O JRIGVWDKYXCHMG-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- 229920013683 Celanese Polymers 0.000 description 1
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- IKWTVSLWAPBBKU-UHFFFAOYSA-N a1010_sial Chemical compound O=[As]O[As]=O IKWTVSLWAPBBKU-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- AOPRFYAPABFRPU-UHFFFAOYSA-N amino(imino)methanesulfonic acid Chemical compound NC(=N)S(O)(=O)=O AOPRFYAPABFRPU-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 229910000413 arsenic oxide Inorganic materials 0.000 description 1
- 229960002594 arsenic trioxide Drugs 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
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- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 230000001955 cumulated effect Effects 0.000 description 1
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- 125000000623 heterocyclic group Chemical group 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
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- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
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- 239000003607 modifier Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229950008475 oxophenarsine Drugs 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- RVZJVYCTFGOEHX-UHFFFAOYSA-N phosphetane Chemical compound C1CPC1 RVZJVYCTFGOEHX-UHFFFAOYSA-N 0.000 description 1
- GWLJTAJEHRYMCA-UHFFFAOYSA-N phospholane Chemical compound C1CCPC1 GWLJTAJEHRYMCA-UHFFFAOYSA-N 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0255—Phosphorus containing compounds
- B01J31/0267—Phosphines or phosphonium compounds, i.e. phosphorus bonded to at least one carbon atom, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, the other atoms bonded to phosphorus being either carbon or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C267/00—Carbodiimides
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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
- C07F9/6568—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 atoms as the only ring hetero atoms
- C07F9/65685—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 atoms as the only ring hetero atoms the ring phosphorus atom being part of a phosphine oxide or thioxide
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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- Y02P20/584—Recycling of catalysts
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Abstract
本发明公开了一种有机磷酸酯催化剂及其制备方法,该催化剂结构式如下:
Description
技术领域
本发明涉及有机化合物技术领域,具体涉及一种用于异氰酸酯合成碳化二亚胺的有机磷酸酯催化剂及其制备方法。
背景技术
碳化二亚胺类化合物是非常重要的精细化学品,由于具有累积双键结构,可与含活性氢的化合物进行加成反应。因此,可以用作环氧树脂、涂料、粘合剂等的交联剂,也可用作聚氨酯、聚酯类材料的抗水解剂,作为性能优异的水解稳定剂,不仅适用于聚酯、聚氨酯弹性体,还适用于聚酯纤维,可用于热塑性聚氨酯等聚合物的加工。聚碳化二亚胺具有良好的耐热性、电绝缘性和力学性能,在涂料,粘合剂,高分子改性剂,交联剂中具有广泛的用途。碳化二亚胺制备方法主要有脲和硫脲脱水或硫化氢、硫脲与芳基氰酸酯反应或用次氯酸盐氧化硫脲等方法,但这些方法并不适合合成碳化二亚胺齐聚物和高聚物。直到20世纪70年代不断出现的有机磷催化剂后,开始采用有机磷类催化剂从异氰酸酯合成碳化二亚胺路线成为主流。不仅用于单异氰酸酯合成碳化二亚胺,二异氰酸酯合成聚碳化二亚胺,同时也用于催化合成碳化二亚胺改性异氰酸酯产品。
目前,有机磷类催化剂主要分为高效催化剂(磷杂环类化合物)、低效催化剂(磷酸酯类化合物),金属有机化合物催化剂和聚合物接枝固相催化剂。磷杂环类高效催化剂主要以DuPont公司的杂环戊烯等有机磷系化合物,ICI公司的磷杂环戊烯或磷杂环戊烷类催化剂,BASF公司的磷杂环戊烯及其氧化物作为催化剂,Bayer公司的磷杂环戊烯或磷杂环丁烷的氧化物或硫化物催化剂等为代表。磷酸酯类低效催化剂主要以DuPont公司磷酸酯类、氨基磷酸酯类催化剂,BASF公司的三氯甲基氧化磷催化剂,Celanese公司的有机磷酸盐类催化剂为代表。金属有机化合物催化剂常见如砷类化合物中四烷基砷、三烷基氧化砷等。聚合物接枝固相催化剂主要包括聚合物接枝有机磷固相催化剂和聚合物接枝有机砷固相催化剂。
上述催化剂要么合成工艺复杂,要么生产成本高,或者催化效率低。
发明内容
本发明就是针对上述已有技术存在的不足,提供一种用于异氰酸酯合成碳化二亚胺的有机磷酸酯催化剂及其制备方法。
本发明就是通过以下技术方案实现的。
一种有机磷酸酯催化剂,其特征在于,所述的有机磷酸酯催化剂结构式如下:
一种上述的有机磷酸酯催化剂的制备方法,其特征在于,所述制备方法步骤包括:由三氯化磷、异戊二烯和三氯乙基磷酸酯反应得到中间体1,中间体1与乙基溴化镁反应得到有机磷酸酯催化剂。
根据上述的制备方法,其特征在于,所述三氯化磷、异戊二烯、三氯乙基磷酸酯按摩尔比为1:(3.0‐5.0):(0.3‐0.8),加入到干燥密闭反应瓶中,加热至温度100‐120℃,密闭反应时间40‐50h,冷却至室温,静置分层,将吸取得到的上清液进行旋蒸、干燥,得到中间体1。
根据上述的制备方法,其特征在于,将无水四氢呋喃加入到中间体1中,其中,无水四氢呋喃与中间体1液固比按ml/g计为1.0—3.0:1,冰浴下滴加乙基溴化镁,乙基溴化镁与中间体1液固比按ml/g计为(4.0‐12.0):1,室温反应时间为8‐12h,加入稀盐酸进行淬灭反应,采用甲基叔丁基醚进行萃取,有机相用饱和碳酸氢钠水溶液洗,然后用盐水洗,使用无水硫酸钠进行干燥过滤,旋蒸后,进行层析柱分离提纯,得到有机磷酸酯催化剂。
根据上述的制备方法,其特征在于,进行层析柱分离提纯时,洗脱剂采用石油醚和乙酸乙酯,所述石油醚和乙酸乙酯体积比为10:1。
本发明的有益技术效果,本发明提供了一种有机磷酸酯催化剂及制备方法,该催化剂用于异氰酸酯合成碳化二亚胺齐聚物和高聚物,该催化剂的合成工艺简单易实现,反应条件温和,原料简单,生产成本低。所得催化剂产品为固体,催化效率高,可在低温下实现催化,可循环使用而且不失催化活性。
具体实施方式
下面结合具体实施方式对本发明进行详细说明。
一种有机磷酸酯催化剂,结构式如下:
一种制备有机磷酸酯催化剂的方法步骤包括:由三氯化磷、异戊二烯和三氯乙基磷酸酯反应得到中间体1,中间体1与乙基溴化镁反应得到有机磷酸酯催化剂。具体地,三氯化磷、异戊二烯、三氯乙基磷酸酯摩尔比为1:(3.0‐5.0):(0.3‐0.8),加入到干燥密闭反应瓶中,加热至温度100‐120℃,密闭反应时间40‐50h,反应完毕后,冷却至室温,静置分层,将吸取得到的上清液进行旋蒸、干燥,得到中间体1;将无水四氢呋喃加入到中间体1中,其中,无水四氢呋喃与中间体1液固比按ml/g计为1.0—3.0:1,冰浴下滴加乙基溴化镁,乙基溴化镁与中间体1液固比按ml/g计为(4.0‐12.0):1,室温反应时间为8‐12h,反应体系中有大量白色固体析出,反应完毕后,加入稀盐酸进行淬灭反应,采用甲基叔丁基醚进行萃取,有机相用饱和碳酸氢钠水溶液洗,然后用盐水洗,使用无水硫酸钠进行干燥过滤,旋蒸后,进行层析柱分离提纯,洗脱剂采用石油醚和乙酸乙酯,所述石油醚PE和乙酸乙酯EA体积比为10:1,得到有机磷酸酯催化剂。
实施例1
称取三氯乙基磷酸酯318.0g(1.18mol),三氯化磷413.0g(1.96mol),异戊二烯405.0g(5.89mol),2,6‐二叔丁基‐4‐甲基苯酚BHT 2.1g(9.8mmol)加入到干燥密闭反应瓶中,加热至105℃密闭反应48h。反应完毕后,冷却降温至室温,静置分层,吸取上清液旋蒸干燥,得到中间体1。
称取中间体1 250g,加入无水四氢呋喃THF 500ml,冰浴下滴加乙基溴化镁2000ml(1M in THF),室温反应10h,反应体系中有大量白色固体析出。反应完毕后,加入3M的稀盐酸淬灭反应,用甲基叔丁基醚萃取,有机相用饱和碳酸氢钠水溶液洗,盐水洗,无水硫酸钠干燥过滤,旋蒸后,进行层析柱分离提纯(洗脱剂PE:EA=10:1),得有机磷酸酯催化剂产品53.0g。检测分析:HNMR(400MHz,CDCl3)化学位移(δ):5.48(d,1H),2.23-2.55(m,4H),1.87(m,2H),1.79(s,3H),1.26(m,3H)。
实施例2
称取三氯乙基磷酸酯862.4g(6.0mol),三氯化磷275.5g(2.0mol),异戊二烯1100.2g(16.0mol),2,6‐二叔丁基‐4‐甲基苯酚BHT 3.47g(16.2mmol)加入到干燥密闭反应瓶中,加热至105℃密闭反应48h。反应完毕后,冷却降温至室温,静置分层,吸取上清液旋蒸干燥,得到中间体1。
称取无水四氢呋喃THF 1000ml,加入到中间体1(1000g)中,冰浴下滴加乙基溴化镁4000ml(1M in THF),室温反应8h,反应体系中有大量白色固体析出。反应完毕后,加入3M的稀盐酸淬灭反应,用甲基叔丁基醚萃取,有机相用饱和碳酸氢钠水溶液洗,盐水洗,无水硫酸钠干燥过滤,旋蒸后,进行层析柱分离提纯(洗脱剂PE:EA=10:1),得有机磷酸酯催化剂产品98.0g。检测分析:HNMR(400MHz,CDCl3)化学位移(δ):5.48(d,1H),2.23-2.55(m,4H),1.87(m,2H),1.79(s,3H),1.26(m,3H)。
实施例3
称取三氯乙基磷酸酯242.0g(0.9mol),三氯化磷206.6g(1.50mol),异戊二烯515.7g(7.5mol),2,6‐二叔丁基‐4‐甲基苯酚BHT 1.95g(9.0mmol)加入到干燥密闭反应瓶中,加热至105℃密闭反应48h。反应完毕后,冷却降温至室温,静置分层,吸取上清液旋蒸干燥,得到中间体1。
称取无水四氢呋喃THF 600ml,加入到中间体1(200g)中,冰浴下滴加乙基溴化镁2400ml(1M in THF),室温反应12h,反应体系中有大量白色固体析出。反应完毕后,加入3M的稀盐酸淬灭反应,用甲基叔丁基醚萃取,有机相用饱和碳酸氢钠水溶液洗,盐水洗,无水硫酸钠干燥过滤,旋蒸后,进行层析柱分离提纯(洗脱剂PE:EA=10:1),得有机磷酸酯催化剂产品50.0g。检测分析:HNMR(400MHz,CDCl3)化学位移(δ):5.48(d,1H),2.23-2.55(m,4H),1.87(m,2H),1.79(s,3H),1.26(m,3H)。
以上所述的仅是本发明的较佳实施例,并不局限本发明。应当指出对于本领域的普通技术人员来说,在本发明所提供的技术启示下,还可以做出其它等同改进,均可以实现本发明的目的,都应视为本发明的保护范围。
Claims (5)
1.一种有机磷酸酯催化剂,其特征在于,所述的有机磷酸酯催化剂结构式如下:
2.一种如权利要求1所述的有机磷酸酯催化剂的制备方法,其特征在于,所述制备方法步骤包括:由三氯化磷、异戊二烯和三氯乙基磷酸酯反应得到中间体1,中间体1与乙基溴化镁反应得到有机磷酸酯催化剂。
3.根据权利要求2所述的制备方法,其特征在于,所述三氯化磷、异戊二烯、三氯乙基磷酸酯按摩尔比为1:3.0‐5.0:0.3‐0.8,加入到干燥密闭反应瓶中,加热至温度100‐120℃,密闭反应时间40‐50h,冷却至室温,静置分层,将吸取得到的上清液进行旋蒸、干燥,得到中间体1。
4.根据权利要求2所述的制备方法,其特征在于,将无水四氢呋喃加入到中间体1中,其中,无水四氢呋喃与中间体1液固比按ml/g计为1.0—3.0:1,冰浴下滴加乙基溴化镁,乙基溴化镁与中间体1液固比按ml/g计为4.0‐12.0:1,室温反应时间为8‐12h,加入稀盐酸进行淬灭反应,采用甲基叔丁基醚进行萃取,有机相用饱和碳酸氢钠水溶液洗,然后用盐水洗,使用无水硫酸钠进行干燥过滤,旋蒸后,进行层析柱分离提纯,得到有机磷酸酯催化剂。
5.根据权利要求4所述的制备方法,其特征在于,进行层析柱分离提纯时,洗脱剂采用石油醚和乙酸乙酯,所述石油醚和乙酸乙酯体积比为10:1。
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US4080377A (en) * | 1976-02-19 | 1978-03-21 | Bayer Aktiengesellschaft | Production of cyclic five-membered ring unsaturated phosphine dichlorides |
EP0019224A2 (de) * | 1979-05-16 | 1980-11-26 | Hoechst Aktiengesellschaft | Verfahren zur Herstellung von 1-Halogen-1-oxo-delta 3-phospholenen |
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US4080377A (en) * | 1976-02-19 | 1978-03-21 | Bayer Aktiengesellschaft | Production of cyclic five-membered ring unsaturated phosphine dichlorides |
EP0019224A2 (de) * | 1979-05-16 | 1980-11-26 | Hoechst Aktiengesellschaft | Verfahren zur Herstellung von 1-Halogen-1-oxo-delta 3-phospholenen |
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