TW461914B - Derivatized Rhodamine dye, its copolymer and the treating industrial waters with said copolymer - Google Patents
Derivatized Rhodamine dye, its copolymer and the treating industrial waters with said copolymer Download PDFInfo
- Publication number
- TW461914B TW461914B TW086110148A TW86110148A TW461914B TW 461914 B TW461914 B TW 461914B TW 086110148 A TW086110148 A TW 086110148A TW 86110148 A TW86110148 A TW 86110148A TW 461914 B TW461914 B TW 461914B
- Authority
- TW
- Taiwan
- Prior art keywords
- ester
- rhodamine
- copolymer
- scope
- patent application
- Prior art date
Links
- 229920001577 copolymer Polymers 0.000 title claims abstract description 14
- 239000008235 industrial water Substances 0.000 title claims abstract description 6
- 239000001022 rhodamine dye Substances 0.000 title 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical class [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims abstract description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- 229920000642 polymer Polymers 0.000 claims description 44
- 229940043267 rhodamine b Drugs 0.000 claims description 24
- -1 alkyl propionate Chemical compound 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 15
- 150000002148 esters Chemical class 0.000 claims description 11
- 238000001514 detection method Methods 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 238000010526 radical polymerization reaction Methods 0.000 claims description 8
- 238000011049 filling Methods 0.000 claims description 7
- 230000002079 cooperative effect Effects 0.000 claims description 4
- 150000001721 carbon Chemical group 0.000 claims description 3
- 229920001114 fluorescent copolymer Polymers 0.000 claims 2
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 claims 1
- YIOJGTBNHQAVBO-UHFFFAOYSA-N dimethyl-bis(prop-2-enyl)azanium Chemical compound C=CC[N+](C)(C)CC=C YIOJGTBNHQAVBO-UHFFFAOYSA-N 0.000 claims 1
- QVKOLZOAOSNSHQ-UHFFFAOYSA-N prop-1-ene;prop-2-enoic acid Chemical compound CC=C.OC(=O)C=C QVKOLZOAOSNSHQ-UHFFFAOYSA-N 0.000 claims 1
- 235000021419 vinegar Nutrition 0.000 claims 1
- 239000000052 vinegar Substances 0.000 claims 1
- 125000005250 alkyl acrylate group Chemical group 0.000 abstract description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 abstract 2
- 235000019270 ammonium chloride Nutrition 0.000 abstract 1
- 125000004432 carbon atom Chemical group C* 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 25
- 239000000178 monomer Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 description 14
- 239000000047 product Substances 0.000 description 12
- 239000000700 radioactive tracer Substances 0.000 description 12
- 239000000701 coagulant Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007850 fluorescent dye Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ADFXKUOMJKEIND-UHFFFAOYSA-N 1,3-dicyclohexylurea Chemical compound C1CCCCC1NC(=O)NC1CCCCC1 ADFXKUOMJKEIND-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015271 coagulation Effects 0.000 description 3
- 238000005345 coagulation Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000004809 thin layer chromatography Methods 0.000 description 3
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000000502 dialysis Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241001417516 Haemulidae Species 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 101150031658 Nacc1 gene Proteins 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 210000000078 claw Anatomy 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001917 fluorescence detection Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 150000007857 hydrazones Chemical class 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 238000011005 laboratory method Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B69/00—Dyes not provided for by a single group of this subclass
- C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
- C09B69/103—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing a diaryl- or triarylmethane dye
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B69/00—Dyes not provided for by a single group of this subclass
- C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Pathology (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Physics & Mathematics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
Description
4 6 19 14 Λ7 Β7 五 、發明説明( 經濟部中央標準局員工消費合作社印製 ijj背景 1·發明領域 本發明係有關若丹明B(Rohdamine Β),其被改質含有 乙埽基且其併入基聚合反應化合物,諸如,二烯丙基二甲 基録氣化物(DADMAC)聚合物。 2.習知技術之描述 技術上之進步已能經濟而實際地檢測廢水流出物内聚 合物凝固劑之殘留量。 凝固劑結果之知識具有數優點: 1) 檢測處理過水之殘質, 2) 控制凝固劑之添加,及 3) 闡明凝固作用之機構。 此能較佳控制此等凝固劑之劑量且減少造成污 染之此等聚合物,檢測水溶性聚合物凝固劑之普遍 方法已有,其摻合小量之螢光染劑且利用混合物之 螢光性決定水溶液系統内之聚合物濃度。 此方法已達某些成功,但其具限制。於此用螢光染料 與聚合物凝固劑之簡單摻合物中,其問題為染劑本身與其 它組份(諸如,顆粒)結合。其後之染料螢光測試無法提 供聚合物凝固劑之位置。最近方法已共價地改質染料,如 此其能藉由化學反應被併人聚合物内。因染料與凝固劑係 物理性附接,檢測染料亦檢測凝固劑聚合物。雖然此方法 已符合某些成功’經濟性上重要的是染料需於低漢度輕易 被檢測之。特別地,現無法獲得—種其内化學結合之榮光
I- HH 1--1 I f *I (請先閱讀背面之注意事項存填寫本頁)
、1T !ν > • ml 1 I · 4 6 19 1 4 經濟部中央標準局員工消費合作社印製 Λ7 B? 五、發明説明(2 ) ~ 木料(其於用於水溶性系統中可適於檢測此等聚合物)之 DADMAC聚合物。 若能以面螢光染料改質聚合物,如此染料變成分子之 邛伤且如此改質之聚合物可以現存螢光檢測技術以ppb 範圍輕易檢測,則此技藝中之進步可被提供達成之。亦重 要的是’用於聚合物改質時,由可得之化學品輕易合成之 木料為穩定且可保持高程度之螢光性。最後,改質聚合物 應具有活性以作為對應相似未改質聚合物之活性之水處理 化學品。 本發明之綜诚 本發明包含經基c2-c6低級烷基丙烯酸酯之若丹明B酯 羥基低級烷基較佳為具有附接至終端碳原子之羥基之線 !生起基低級烧基。於另一較佳實施例中,若丹明B酯為羥 基低級烷基,CVC 4基,其例子為4羥基丁基丙烯酯之若 丹明B酯。重點為烴鏈結含有羥基及丙烯酯基。羥基用於 • 改質若丹明B’而丙烯酯基用於自由基聚合併入作用。 本發明亦包含二烯丙基二甲.基銨氣化物之共聚物,其 含有0.01-2莫耳%之上述型式.之若丹明2酯。注意的是任何 自由基聚合反應方法可併入本發明,只要染料之螢光性被 保持。本發明進一步意欲使用此等聚合物於水處理應用, 諸如,凝固作用,但不限於此。此使聚合物之劑量及殘量 可使用傳統螢光檢測裝置控制並監視之,即使聚合物係以 Ppb範圍存在。 凰-示簡要說明 t請先閲讀背面之注意事項再填寫本頁) 1裝-- _ T____ • n--δn . 本紙張尺度適用中國國家標準 (〇阳)八4規格(210父297公釐) 461914 五 、發明説明( Λ7 B7 經濟部中央標準局員工消費合作社印掣 第1圖顯示若丹明B與4-羥基丁基丙烯酯反應之示意圖 第2圖例示DADMAC與第1圖之改質若丹明b之聚合反 應。 第3圖證明DADMAC—若丹明b共聚物作為凝固劑之能 力且於低劑量時可輕易檢測之。 趋J隹實施例之;fe祕 改質若丹明B及其DADMAC共聚物 若丹明B為已知之螢光染料,其結構如第1圖所示。4-羥基丁基丙烯酯為已知丙烯酯且可購得。雖然此酯較佳, 但可用於實施本發明之其它丙烯酯為2_羥基乙基丙烯酯及 6-¾基己基丙烯g旨等。羥基丙烯酯為期望與若丹明B之羧 酸基於低溫度反應,如於約溫度±24<>c且使用文獻所述一 般合成方法’如,Tetrahedr〇n Letter Νο· 46,第 4745-8,
Pergamon Press, 1978,及 Euro P〇lymer j·第 27冊,Νο.10, 第1045及1048頁。此等文獻之揭示在此被併入參考用。 以丙烯酯改質之若丹明B改質之DADMAC可使用已知 自由基聚合反應技術合成之。此等共聚物可含有〇.〇1至2 莫耳%之改質若丹明B單體(其係以DADMAC為基準)。當然 ,本發明係為單體,且潛在地可以較高量被併入。較佳者 ,螢光單體之量為0.1至丨莫耳%範圍内。改質或示踪之 DADMAC聚合物具有至少〇·3之特黏度(係於3〇艺,lM之 NaN〇3中測量)。對於大部份水處理應用,諸如,凝固作 用,特性黏度需為0.3至〇·9之範圍内。對於某些應用,特 本紙張尺度適用巾_家鮮(CNS )A4&( 210X297公f )— (請先閲讀背面之注意事項再填寫本頁) 裝-----
、1T-1 1 - fn n I ^ I 461914 Λ7 B7 發明説明(4 性黏度可為1.6或更大。當用於處理工業用水時,改質聚 合物之劑量-般係由每百萬為數份至數百,而其係依處理 請 先 閱 讀 背 面 之 注 意 事 項 再 % 本我 頁 * 系統與所用聚合物之特性黏度而定。當作為凝固劑時,劑 量典型上為數ppm至約1〇〇 ppm。 本發明之評估 合成程序.4-經基丁基丙婦酯/若丹明b酯 訂 下列等序被用於在實驗室中製備此材料且係顯示於第 1圖。於100ml之圓底燒瓶(其配製有磁性攪拌棒),添加3 〇〇 克(6.26莫耳)之若丹明;8(97%)及4〇ml之無水二氣甲烷溶劑 。於氮氣下攪拌混合物至若丹明試劑溶解。定量(〇 〇8克 ,0.65莫耳)之4-二甲基胺基咕唆(DMAP)與1.5ml(1.6當量) 之4-羥基丁基丙烯酯(hb a,96%) —起被添加至燒瓶。混 合物被冷卻至〇°C,6.26ml之1,3-二環己基碳二醯亞胺(DCC ’ 1.0M二氯甲貌溶液,1當量)被注入反應燒瓶並擾拌。反 應於0 C保持1/2小時,然後反應被緩慢加溫至室溫,然後 於氮氣下攪拌至隔夜。需注意反應副產物二環己基尿素 (DCU)於添加DCC後短暫地開始自溶液沈澱(約3分鐘)。 經濟部中央標準局員工消費合作社印製 於反應期終結時,二氯甲烷溶劑經由旋轉式蒸發移除 ’反應混合物再次溶於5〇mi之乙腈。不溶解之DCU被濾出 且移除溶劑,產物於真空乾燥之,留下無晶固體,其係可 溶水及大部份極性有機溶劑。產物亦具有格外有效染料之 特性。一些雜質藉由使用乙腈流動相使材料通過矽石凝膠 栓塞(70-270網目)而移除之。於此方法中,1.6克染料被隔 離(分子量=605.19 amu)。薄層色譜分析(TLC)顯示三點存 本紙張尺度適财_家標準(CNS》Α4规格(21()><297公旗) 461914 ---------87 五、發明説明(5 ) — 一 I 在,二點為弱且一點為強。強點係對應於產物。低於產物 點之弱點係對應於未反應若丹明B。於產物上方之弱點係 未知’其可能係因二聚產物。所有點似為螢光性。得最好 刀離之TLC溶劑為異丙醇。NMR分析產生錯合光譜,其顯 示知產物被形成。純度約9〇%。主要雜質為約5%未反應若 丹明B試劑及5%未知化合物。 合成程序;示踪DADMAC聚合物 下列實驗室方法被用於製備含有上述若丹明丙烯酯染 料單體之DADMAC聚合物且顯示於第2圖。於配置攪拌軸 、熱偶、冷凝器、氮氣入口及添加口之25〇1111反應釜内, 添加0.28克(0· 13莫耳%,以單體為基準)之染料單體(約9〇% 純度)及5.16克D.I.水。於此添加80.64克之62〇%之dadmac 單體溶液。混合物被攪拌並以氮氣汽提。18〇克之Nac丨被 加入混合物且反應混合物於水浴中加熱至58它。起始劑溶 液藉由使0.50克V-50起始劑溶於5.00克1)丄水中而製備之。 • lml之此起始劑溶液被注入反應器,且開啟計時器。丄小時 經濟部中央標準局員工消費合作社印t 後,另lml之起始劑溶液被添加至反應器,且於2小時及3 小時記號時再度為之。此時·混合物為非常稠之相。45小 時後,聚合物開始爬上攪拌桿、當計時器達5小時,4〇mi 之D.I·水被加入混合物,然後於5 25小時添加額外17爪1之 水。然後反應溫度升至8(rc,然後保留之lml起始劑溶液 被注入反應器。混合物被保持於g〇 t並授拌1小時。反廡 器自水浴移除,且83克之D.I.水被攪拌添加.混合物被冷 卻,且另一 83克的水被添加至反應器產生15%聚合物溶液 _^___-8- 本紙張尺度適用中國國家標f ( CNS ) A4規格(2丨〇χ297公趙) 一 -~· -_ 461914 .丄 11.
五、發明說明(6 ) -—_H-£kJ 第86110148號專利申請案說明書修正頁修正日期:89年6月 性深粉紅色材料、 下列程序被用於描述聚合物_。B_r〇〇kfield黏.度使用_ #2轉 軸(速率為12)而獲得之。特性黏度(LV.)於1%聚合物溶液( 其係由6.67克聚合物產物、50ml之2M NaCCh、lml之1M乙 酸鈉溶液製備,且以100ml D.I.水稀釋)取得之。透析實驗 使用12,000〜14,000Mw切片膜施行之。使用標準技術。聚 合物產物被沈澱且藉由添加少量產物至大體積丙酮而隔離 之。所形成之凝膠被隔離且溶於小量曱醇。任何不可溶之 固體被濾掉,用醇聚合物溶液添加至大體積丙酮。沈澱之 . . .. . 聚合物被收集,清洗且於真空下乾燥。染料單體以0.13莫 耳%(以DADMAC單體為基準,且假設染料單體純度90%)或 0.08重量%產物被併入染料。染料约99%併入聚合物被達成 . . . . 之。示踪聚DADMAC之總聚合物固體於15%測量。合成之 示踪聚合物具有第I表所示特徵》 _ 第I表
示踪之聚DADMAC 聚DADMAC 外觀: 深紅/粉紅色 清淅之白色 布魯克菲爾德黏度: 1363 cps 990 cps I.V.: 1.0dL/g 1.03 dL/g pH : 4.85 4.68 重量平均分子量: 890,000 475,000 數平均分子量: 70,000 32,000 聚分散性: 12.7 14.8 聚合物固體: 15%(理論值) 14.97 本紙張尺度適用中,國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製
> ' — 111 — — — 一SJIIIIIIII — I _ ^ — — — —Γιιι— — — — — — — — — — i I 1 I I 461914 Λ7 B7 五、發明説明(7 ) 除顏色外,示踪之聚dadmac具有相似於未示踪之聚 DADMAC之性質。聚DADMAC染料併入被分析測定之。聚 合物於沈澱及清洗後保留顏色。聚合物亦被置於12,000〜 14,000透析膜且48小時後以d.i.水透析之。僅小量顏色被 觀察通過膜。膜内材料為鮮粉紅色。比較實驗被為之,其 中’染料單體與未示踪聚dadmac摻合。於此情況中,& 貫 際上所有染料似忽通過膜而將未示踪聚合物留於後。分才斤 顯示在示踪聚合物中約9pprn之殘留示踪單體。 檢測限制 基於許多原因較低檢測限制為所期望的。較低 檢測限制使配方人員於新產物中使用較低染料量。 為控制之用,染料示踪分子需無需改變產物性質而 檢測之。最後,對於示踪聚合物檢測,染料分子螢 光敏感性愈尚,檢測限制愈低。最後一點對於回應· 處理過水中聚合物殘質之問題非常重要。螢光敏感 性被定義成: 經濟部中央標準局員工消費合作社印裝 (請先閲讀背面之注意事唄再填寫本頁j 、-p 螢光敏感性=消光係數X量子產率。由第π表顯示 改質之若丹明具有比若丹明B為高之螢光敏感性。藉 由改質右丹明B,吾#獲得優於若丹明b之二明顯優 點:高螢光敏感性及將染料併入自由基聚合反應内 之月b力。對於示踪聚dadmac,檢測限制使用標準 螢光技術測定為50ppb。其可低至lOppb。 10- 本紙張尺度適家標) A4規格(2丨〇x297,gy 五、 Α7 —〜一一 _ B? 、發明説明(8 ) 第Π表 ----- 吸收峰 消光係數 (1-莫耳/公分) 相對量子 產率* 明 Β 555 110.000 0.62(絕餅佶、 改質之若丹明B -------- 示踪之 540 5R5 88,500 0.96
經濟部中央標準局員工消費合作社印製 因若丹明B改質聚合物係藉自由基聚合反應經丙烯酯 與碳苯基部份之化學反應而形成之,逆向水解反應會移除 染料部份。因此,丙烯酯基對水解之穩定性非常重要。改 質若丹明B丙烯酯單體被送至潛在水解條件,且使用色譜 術檢測自由若丹明B(殘質及自水解而得)、單體及任何其 它水解產物。結果顯示於PH 7於低單體濃度時,於室溫^ 未曝光下,28天後約15-2〇%之示踪單體被水解。但是,高 單體濃度⑽G ppm)溶液赠在室溫且未曝光下敎高達* 星期’ m㈣附接至聚合物時染料單體水解速率會較慢, 其係由於可能之空間限制。 示踪聚合物活性 祕煉廠之通氣盆流出之廢水被用於活性測試。第3 圖顯示示踪聚DADMAC具活性。此& „ 此結果證實化學示踪聚 DADMAC不會抑制凝固力。活认 佑性於 NTU(Nephrolytic
Turbidity Units)測量。 -11- 本紙張尺度適用中國國家標準(CMS ) A4規格(210X 297公您) (請先閱讀背面之注意事項再填寫本頁) 裝.
、1T
Claims (1)
- 461914H8 (:8砰 1)8 89· 6 · 19 : 經濟部智慧財產局員工消脅合作社印製 六、申請專利範圍, 第8611 0148號專利申請案案申請專利範圍修正本 修正日期:89年06月 1. 一種經基C2_C6低級烧基丙烤酸酯之若丹明b酯。 2·如申請專利範圍第1項之若丹明B酯,其中該羥基低級 烧基為具有附接至終端碳原子之羥基之線性經基低級 烧基。 3. 如申請專利範圍第1項之若丹明8酯,其中該羥基低烷 基為C2-C4烷基。 4. 一種4-經基丁基丙婦醋之若:丹明b酯。 5. —種二烯丙基二甲基銨氣化物之共聚物,其含有〇〇1 〜2莫耳。/〇之申請專利範圍第·)項之若丹明B酯。 6 _如申请專利範圍第5項之共聚物,其中該若丹明B酯為 申請專利範圍第2項之酯。 7_如申睛專利範圍第5項之共聚物,其中該若丹明B酯為 申請專利範圍第3項之酯。 . . . ... . . ..... - 8. 如申請專利範圍第5項之共聚物,其中該若丹明日酯為 申請專利範爵第4項之酯。 9. 一種以勞光共聚物來處理工業水用之方法,其係.用以控 制並監測該共聚物的劑量與存在,該方法包含 (a) 將使螢光共聚物加入該工業用水中,其中該榮光共 聚物是由二稀丙基二甲基鞍氣化物與經基〇2_^6低 級烧基丙烯酸酯之若丹明B酯起自由基聚合反應而 形成的;以及 (b) 利用螢光檢測方式來監測在該工業用水中的榮光共 1 '· ·12- (請先閱讀背面之注意事項再填寫本頁) 訂· --線丨 本紙張尺度過用节國國冢標準(CNS)A4規格(210 X 297公釐) 461914 A8 B8 C8 Ό8 六、申請專利範圍 ’: * V % 聚物。 1 0.如申請專利範圍第9項之方法’其中該酯係為一其羥基 連接至低級從基之終端碳原子的線性羥基低級烷基。 11. 如申請專利範圍第9項之方法,其中該羥基低級烷基係 為C2-C4烧基。 12. 如申請專利範圍第9項之方法 0.01-2莫耳百分比之該酯。 1 3,如申請專利範圍第9項之方法 基丙烯酯之若丹明B酯。 其中該螢光共聚物含有 其中該S旨係為4-羥基丁 .(請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 -In I ^ a·— βββ il·— ^1- n n n· tfn fl^i n I J^i n -UK n n· n II IV n n tn n ../t_ i ^ -13- 本紙張尺度適用I:國國、家標準(CNS)A4規格(210 X 297公釐)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/682,497 US5772894A (en) | 1996-07-17 | 1996-07-17 | Derivatized rhodamine dye and its copolymers |
Publications (1)
Publication Number | Publication Date |
---|---|
TW461914B true TW461914B (en) | 2001-11-01 |
Family
ID=24739964
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW086110148A TW461914B (en) | 1996-07-17 | 1997-07-17 | Derivatized Rhodamine dye, its copolymer and the treating industrial waters with said copolymer |
Country Status (17)
Country | Link |
---|---|
US (3) | US5772894A (zh) |
EP (1) | EP0912639B1 (zh) |
JP (1) | JP2000514855A (zh) |
KR (1) | KR20000023793A (zh) |
AR (1) | AR008259A1 (zh) |
AT (1) | ATE206735T1 (zh) |
AU (1) | AU718403B2 (zh) |
BR (1) | BR9710307A (zh) |
CA (1) | CA2210556A1 (zh) |
DE (1) | DE69707289T2 (zh) |
DK (1) | DK0912639T3 (zh) |
ES (1) | ES2164365T3 (zh) |
NO (1) | NO310516B1 (zh) |
NZ (1) | NZ333402A (zh) |
TW (1) | TW461914B (zh) |
WO (1) | WO1998002492A1 (zh) |
ZA (1) | ZA976218B (zh) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI467329B (zh) * | 2012-01-30 | 2015-01-01 | Jsr Corp | 著色劑、著色組成物、彩色濾光片及顯示元件 |
TWI615433B (zh) * | 2013-02-15 | 2018-02-21 | 和光純藥工業股份有限公司 | 聚合物、化合物、著色組成物及彩色濾光片用著色組成物 |
TWI705979B (zh) * | 2014-07-03 | 2020-10-01 | 日商富士軟片和光純藥股份有限公司 | 接枝聚合物、樹脂著色物、其製造方法以及含有該樹脂著色物的樹脂組成物 |
Families Citing this family (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU5935300A (en) * | 1999-07-22 | 2001-02-13 | Nalco Chemical Company | Fluorescent water-soluble polymers |
GB9920774D0 (en) | 1999-09-03 | 1999-11-03 | Avecia Ltd | Polymer |
US6727372B2 (en) | 2000-08-07 | 2004-04-27 | Eastman Chemical Company | Colorant compounds containing copolymerizable vinyl groups |
EP1739135A3 (en) * | 2000-08-07 | 2008-12-10 | Eastman Chemical Company | Colorant compounds containing copolymerizable vinyl groups |
US20030049850A1 (en) * | 2001-09-12 | 2003-03-13 | Golden Josh H. | Enhanced detection of metal plating additives |
DE602004013316T2 (de) | 2003-06-25 | 2009-05-14 | Rhodia Chimie | Verfahren zur stimulierung einer ölbohrung durch verwendung verschiedener ablagerungsinhibitoren |
KR101151932B1 (ko) | 2004-04-08 | 2012-06-01 | 다우 아그로사이언시즈 엘엘씨 | 살충성 n-치환된 설폭시민 |
FR2887892B1 (fr) * | 2005-07-04 | 2007-09-07 | Biomerieux Sa | Polymeres fluorescents en solution aqueuse et procede de preparation de polymeres fluorescents solubles en solution aqueuse |
TW201309635A (zh) | 2006-02-10 | 2013-03-01 | Dow Agrosciences Llc | 殺蟲性之n-取代(6-鹵烷基吡啶-3-基)烷基磺醯亞胺(二) |
US7932091B2 (en) * | 2006-07-18 | 2011-04-26 | Prochemtech International, Inc. | Colorant tracer for cooling water treatment formulations |
MX2009002302A (es) | 2006-09-01 | 2009-03-13 | Dow Agrosciences Llc | Sulfoximinas de (2-sustituido-1,3-tiazol) alquilo n-sustituidas insecticidas. |
TWI387585B (zh) | 2006-09-01 | 2013-03-01 | Dow Agrosciences Llc | 殺蟲性之n-取代(雜芳基)烷基烴基硫亞胺 |
TWI395737B (zh) | 2006-11-08 | 2013-05-11 | Dow Agrosciences Llc | 作為殺蟲劑之雜芳基(取代的)烷基n-取代的磺醯亞胺 |
US7883898B2 (en) * | 2007-05-07 | 2011-02-08 | General Electric Company | Method and apparatus for measuring pH of low alkalinity solutions |
US20080295581A1 (en) * | 2007-05-31 | 2008-12-04 | General Electric Company | Method for the determination of aqueous polymer concentration in water systems |
CN102015911B (zh) * | 2008-01-17 | 2015-11-25 | 巴斯夫欧洲公司 | 聚合毛发染料 |
AU2009222174B2 (en) | 2008-03-03 | 2013-02-28 | Corteva Agriscience Llc | Pesticides |
US8535644B2 (en) * | 2008-10-10 | 2013-09-17 | Massachusetts Institute Of Technology | Tunable hydrogel microparticles |
US8343771B2 (en) | 2011-01-12 | 2013-01-01 | General Electric Company | Methods of using cyanine dyes for the detection of analytes |
JP5710550B2 (ja) * | 2011-06-17 | 2015-04-30 | 富士フイルム株式会社 | 重合・発色性組成物およびそれに用いる化合物 |
US20130233804A1 (en) * | 2012-03-09 | 2013-09-12 | Yanjiao Xie | Application of fluorescent dyes to trace and quantify chemical dosage in industrial wastewater |
KR101361679B1 (ko) * | 2012-03-30 | 2014-02-12 | (주)경인양행 | 크산텐계 자색 염료 화합물, 이를 포함하는 컬러필터용 착색 수지 조성물 및 이를 이용한 컬러필터 |
US10139385B2 (en) * | 2013-08-12 | 2018-11-27 | Ecolab Usa Inc. | Method of tracing chemical quantities using encapsulated fluorescent dyes |
JP6520935B2 (ja) * | 2014-05-30 | 2019-05-29 | 富士フイルム和光純薬株式会社 | トリフェニルメタン系着色組成物 |
WO2016149471A1 (en) * | 2015-03-17 | 2016-09-22 | Ecolab Usa Inc. | Fluorescent polymers for water treatment |
CN106046246B (zh) * | 2016-05-23 | 2018-05-25 | 陶伟珍 | 重金属检测传感材料及其制备方法与应用 |
CN106008796B (zh) * | 2016-05-30 | 2018-01-02 | 金宝丽科技(苏州)有限公司 | 一种汞离子探针片材的制备方法 |
JPWO2019044872A1 (ja) * | 2017-08-31 | 2020-10-08 | 富士フイルム和光純薬株式会社 | ローダミン連結化合物 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1141147A (en) * | 1964-12-22 | 1969-01-29 | Dainichiseika Color Chem | Fluorescent copolymers |
US4654378A (en) * | 1984-05-02 | 1987-03-31 | Calgon Corporation | Process for the manufacture of high solids, free-flowing, granular poly(dimethyldiallyl ammonium chloride) |
GB8512937D0 (en) * | 1985-05-22 | 1985-06-26 | Allied Colloids Ltd | Water treatment |
GB8531118D0 (en) * | 1985-12-18 | 1986-01-29 | Allied Colloids Ltd | Copolymers |
US4826606A (en) * | 1987-05-06 | 1989-05-02 | General Chemical Corporation | Manufacture and use of polymer modified aluminum hydroxide and basic aluminum sulfate |
EP0573762A2 (de) * | 1992-05-11 | 1993-12-15 | BASF Aktiengesellschaft | Rhodaminderivate |
US5846682A (en) * | 1993-03-02 | 1998-12-08 | Showa Denko K.K. | Light decolorizable recording material, ink and toner |
ES2096531B1 (es) * | 1995-07-14 | 1997-12-16 | Consejo Superior Investigacion | Matrices polimericas solidas conteniendo rodaminas y su utilizacion en laseres. |
-
1996
- 1996-07-17 US US08/682,497 patent/US5772894A/en not_active Expired - Fee Related
-
1997
- 1997-07-11 DK DK97936958T patent/DK0912639T3/da active
- 1997-07-11 AT AT97936958T patent/ATE206735T1/de not_active IP Right Cessation
- 1997-07-11 WO PCT/US1997/012024 patent/WO1998002492A1/en not_active Application Discontinuation
- 1997-07-11 AU AU39589/97A patent/AU718403B2/en not_active Ceased
- 1997-07-11 DE DE69707289T patent/DE69707289T2/de not_active Expired - Fee Related
- 1997-07-11 ES ES97936958T patent/ES2164365T3/es not_active Expired - Lifetime
- 1997-07-11 NZ NZ333402A patent/NZ333402A/xx unknown
- 1997-07-11 EP EP97936958A patent/EP0912639B1/en not_active Expired - Lifetime
- 1997-07-11 JP JP10506145A patent/JP2000514855A/ja active Pending
- 1997-07-11 BR BR9710307A patent/BR9710307A/pt not_active Application Discontinuation
- 1997-07-14 ZA ZA9706218A patent/ZA976218B/xx unknown
- 1997-07-16 AR ARP970103191A patent/AR008259A1/es not_active Application Discontinuation
- 1997-07-16 CA CA002210556A patent/CA2210556A1/en not_active Abandoned
- 1997-07-17 TW TW086110148A patent/TW461914B/zh not_active IP Right Cessation
- 1997-11-21 US US08/975,886 patent/US5808103A/en not_active Expired - Fee Related
-
1998
- 1998-06-12 US US09/094,546 patent/US5998632A/en not_active Expired - Fee Related
-
1999
- 1999-01-15 KR KR1019997000275A patent/KR20000023793A/ko not_active Application Discontinuation
- 1999-01-15 NO NO19990197A patent/NO310516B1/no not_active IP Right Cessation
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI467329B (zh) * | 2012-01-30 | 2015-01-01 | Jsr Corp | 著色劑、著色組成物、彩色濾光片及顯示元件 |
TWI615433B (zh) * | 2013-02-15 | 2018-02-21 | 和光純藥工業股份有限公司 | 聚合物、化合物、著色組成物及彩色濾光片用著色組成物 |
TWI705979B (zh) * | 2014-07-03 | 2020-10-01 | 日商富士軟片和光純藥股份有限公司 | 接枝聚合物、樹脂著色物、其製造方法以及含有該樹脂著色物的樹脂組成物 |
Also Published As
Publication number | Publication date |
---|---|
JP2000514855A (ja) | 2000-11-07 |
AU718403B2 (en) | 2000-04-13 |
EP0912639B1 (en) | 2001-10-10 |
US5998632A (en) | 1999-12-07 |
DK0912639T3 (da) | 2002-02-11 |
DE69707289T2 (de) | 2002-07-18 |
ATE206735T1 (de) | 2001-10-15 |
ZA976218B (en) | 1998-03-03 |
US5808103A (en) | 1998-09-15 |
WO1998002492A1 (en) | 1998-01-22 |
CA2210556A1 (en) | 1998-01-17 |
EP0912639A1 (en) | 1999-05-06 |
AU3958997A (en) | 1998-02-09 |
NO990197D0 (no) | 1999-01-15 |
AR008259A1 (es) | 1999-12-29 |
BR9710307A (pt) | 1999-08-17 |
NZ333402A (en) | 2000-03-27 |
KR20000023793A (ko) | 2000-04-25 |
DE69707289D1 (de) | 2001-11-15 |
US5772894A (en) | 1998-06-30 |
NO310516B1 (no) | 2001-07-16 |
ES2164365T3 (es) | 2002-02-16 |
NO990197L (no) | 1999-03-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
TW461914B (en) | Derivatized Rhodamine dye, its copolymer and the treating industrial waters with said copolymer | |
Klier et al. | Self-associating networks of poly (methacrylic acid-g-ethylene glycol) | |
JPH02105809A (ja) | 水溶性カチオンポリマー分散液の製造方法 | |
CN112375191B (zh) | 嵌段共聚物及其制备方法和应用 | |
Abu-Thabit et al. | Phosphonobetaine/sulfur dioxide copolymer by Butler’s cyclopolymerization process | |
Abdelaal et al. | Modification and characterization of polyacrylic acid for metal ion recovery | |
JP3439214B2 (ja) | ビニルピリジンおよびアセトキシスチレンから誘導された両性コポリマー | |
KR20220115564A (ko) | 신규 설포베타인 단량체, 이의 제조 방법, 및 이의 용도 | |
EP0225596A2 (en) | Method of producing sulfomethyl polyacrylamide polymers and sulfomethylamide unit containing polymers | |
US3823100A (en) | Polysaccharide based flocculants | |
US2875162A (en) | Vinylphenyl aliphatic aminocarboxylic acid polymers | |
JPS61138607A (ja) | カチオン性水溶性重合体の重合方法 | |
JPS5814425B2 (ja) | 不飽和第3級アミンまたはその第4級アンモニウム塩の安定化法 | |
JPH03203916A (ja) | 3―メタクリロイルオキシ―2―ヒドロキシプロピルトリメチルアンモニウムクロリドモノマーとビニルモノマーのコポリマー | |
Shafa-Amry et al. | Synthesis and chelation properties of Mannich polymers derived from piperazine and some hydroxy benzaldoximes | |
US3235493A (en) | Process for clarifying suspensions | |
Park et al. | Graft polymerization of acrylic acid onto corn starch in aqueous isopropanol solution | |
CN116239720B (zh) | 具有双重碱基面识别Hg2+的温敏性线性高分子材料及其制备方法 | |
WO2003087170A1 (en) | Polyacrylamide hydrogels | |
US3297734A (en) | Purification of sulfonated monomers | |
US4066522A (en) | Process for the production of high molecular weight acrylamide polymers | |
El-Mossalamy et al. | Novel Complexes of Copper with modified grafted cellulose copolymer and its application | |
Biagiotti et al. | Esterification of poly (γ-glutamic acid)(γ-PGA) mediated by its tetrabutylammonium salt | |
US4777218A (en) | Cationic nitrogen acrylamide polymers | |
US4354907A (en) | Radiation polymerization of cationic monomer in aqueous alcohol |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
GD4A | Issue of patent certificate for granted invention patent | ||
MM4A | Annulment or lapse of patent due to non-payment of fees |