PL224151B1 - Methacrylic photochromic homopolymers containing derivatives of 4-amino-N-(4-methylpyrimidin-2-yl) benzenesulfonamide and method for obtaining them - Google Patents
Methacrylic photochromic homopolymers containing derivatives of 4-amino-N-(4-methylpyrimidin-2-yl) benzenesulfonamide and method for obtaining themInfo
- Publication number
- PL224151B1 PL224151B1 PL411791A PL41179115A PL224151B1 PL 224151 B1 PL224151 B1 PL 224151B1 PL 411791 A PL411791 A PL 411791A PL 41179115 A PL41179115 A PL 41179115A PL 224151 B1 PL224151 B1 PL 224151B1
- Authority
- PL
- Poland
- Prior art keywords
- ethyl
- methylpyrimidin
- phenyl
- azo
- sulfamoyl
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 24
- 229920001519 homopolymer Polymers 0.000 title claims description 20
- 125000005395 methacrylic acid group Chemical group 0.000 title claims description 9
- QPPBRPIAZZHUNT-PBZDKDNVSA-N 4-amino-n-(4-methylpyrimidin-2-yl)benzenesulfonamide Chemical class CC1=CC=NC(NS(=O)(=O)[13C]=2[13CH]=[13CH][13C](N)=[13CH][13CH]=2)=N1 QPPBRPIAZZHUNT-PBZDKDNVSA-N 0.000 title description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- -1 4-methylpyrimidin-2-yl Chemical group 0.000 claims description 15
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 13
- 239000003999 initiator Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 230000015271 coagulation Effects 0.000 claims description 6
- 238000005345 coagulation Methods 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical group CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 239000012451 post-reaction mixture Substances 0.000 claims 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- LVILGAOSPDLNRM-UHFFFAOYSA-N 4-methylpyrimidine Chemical class CC1=CC=NC=N1 LVILGAOSPDLNRM-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 description 1
- KHBQMWCZKVMBLN-UHFFFAOYSA-N Benzenesulfonamide Chemical compound NS(=O)(=O)C1=CC=CC=C1 KHBQMWCZKVMBLN-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Substances N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- 230000010365 information processing Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical class COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- Optical Record Carriers And Manufacture Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
Przedmiotem wynalazku są fotochromowe homopolimery metakrylowe zawierające pochodne 4-amino-N-(4-metylopirymidyn-2-ilo)benzenosulfonamidu znajdujące zastosowanie w optycznym przetwarzaniu i magazynowaniu informacji oraz w optyce nieliniowej.The subject of the invention are photochromic methacrylic homopolymers containing 4-amino-N- (4-methylpyrimidin-2-yl) benzenesulfonamide derivatives for use in optical information processing and storage as well as in nonlinear optics.
Przedmiotem wynalazku jest również sposób otrzymywania fotochromowych homopolimerów metakrylowych, zawierających pochodne 4-amino-N-(4-metylopirymidyn-2-ilo)benzenosulfonamidu.The subject of the invention is also a method of obtaining photochromic methacrylic homopolymers containing 4-amino-N- (4-methylpyrimidin-2-yl) benzenesulfonamide derivatives.
Z polskiego opisu patentowego PL 213155 znane są homopolimery metakrylowe, które zawierają w strukturze meru grupę 4-benzonitrylową, 4-N-(5-metyloizoksazol-3-ilo)benzenosulfonamidową lub 4-N-(4,6-dimetylopirymidyn-2-ilo)benzenosulfonamidową oraz sposób ich wytwarzania, polegający na wolnorodnikowej polimeryzacji w rozpuszczalniku. Opisane związki charakteryzują się absorpcją w zakresie 440-450 nm.From the Polish patent description PL 213155 there are known methacrylic homopolymers which contain in the structure of the mer a 4-benzonitrile, 4-N- (5-methylisoxazol-3-yl) benzenesulfonamide or 4-N- (4,6-dimethylpyrimidin-2-yl) group ) benzenesulfonamide and the method of their production, which is based on free radical polymerization in a solvent. The described compounds are characterized by absorption in the range of 440-450 nm.
W polskim opisie patentowym PL 203037 przedstawiono chromoforowe homopolimery metakrylowe zawierające w łańcuchu bocznym ugrupowanie diazenylowe. Istotą opisanej metody jest sprzęganie soli diazoniowej z niechromoforowym homopoli[2-metyloakrylanem 2-{alkilo(fenylo)amino}etylu] w środowisku mieszaniny rozpuszczalników organicznych: dioksanu, kwasu octowego i kwasu propionowego, w obecności octanu sodowego. Stosując opisaną metodę otrzymano homopolimery z wydajnością 75-82%, które charakteryzują się absorpcją w zakresie 442-486 nm.Polish patent specification PL 203037 describes chromophore methacrylic homopolymers containing a diazenyl group in the side chain. The essence of the described method is the coupling of the diazonium salt with non-chromophore homopoly [2-methylacrylate 2- {alkyl (phenyl) amino} ethyl] in a mixture of organic solvents: dioxane, acetic acid and propionic acid in the presence of sodium acetate. Using the described method, homopolymers were obtained with the efficiency of 75-82%, which are characterized by absorption in the range of 442-486 nm.
W publikacji K.Sadagopan, A.S. Rekha, D.Ratna, A.B. Samui Journal of Applied Polymer Science 104 (2007) 3497-3504 opisano syntezę metakrylowych kopolimerów zawierających pochodną p-anizydyny lub 4-nitroaniliny. Opisane przez autorów polimery otrzymywane są na drodze kopolimeryzacji azo-monomeru z metakrylanem metylu, w środowisku N-dimetyloformamidu oraz w obecności inicjatora rodnikowego w postaci 2,2'-azobis(izobutyronitrylu). W celu wytrącenia produktu, mieszanina poreakcyjna wylewana jest do metanolu. Stosując powyższy sposób syntezy otrzymano kopolimery z wydajnością 75-85%. Uzyskane w pracy kopolimery wykazują absorpcję w zakresie 356-377 nm.In the publication of K. Sadagopan, A.S. Rekha, D. Ratna, A.B. Samui Journal of Applied Polymer Science 104 (2007) 3497-3504 describes the synthesis of methacrylic copolymers containing a derivative of p-anisidine or 4-nitroaniline. The polymers described by the authors are obtained by copolymerization of azo-monomer with methyl methacrylate in N-dimethylformamide medium and in the presence of a radical initiator in the form of 2,2'-azobis (isobutyronitrile). In order to precipitate the product, the reaction mixture is poured into methanol. Using the above synthesis method, the copolymers were obtained in a yield of 75-85%. The copolymers obtained in the work show an absorption in the range of 356-377 nm.
Dotychczas nie zostały w literaturze opisane fotochromowe homopolimery metakrylowe zawierające pochodne 4-amino-N-(6-metylopirymidyn-2-ilo)benzenosulfonamidu oraz sposób ich otrzymywania.Until now, photochromic methacrylic homopolymers containing 4-amino-N- (6-methylpyrimidin-2-yl) benzenesulfonamide derivatives and the method of their preparation have not been described in the literature.
Istotą rozwiązania według wynalazku są fotochromowe homopolimery metakrylowe o wzorze ogólnym 1, w którym R oznacza grupę metylową lub etylową, n oznacza liczbę merów 2-metyloprop-2-enianu 2-[4-[(E)-[4-[(4-metylopirymidyn-2-ilo)sulfamoilo]fenylo]azo]-N-metylo-anilino]etylu lub 2-metyloprop-2-enianu 2-[4-[(E)-[4-[(4-metylopirymidyn-2-ilo)sulfamoilo]fenylo]azo]-N-etylo-anilino]etylu od 1 do 50.The present invention is based on photochromic methacrylic homopolymers of general formula I, in which R is a methyl or ethyl group, n is the number of 2-methylprop-2-enoate units of 2- [4 - [(E) - [4 - [(4- methylpyrimidin-2-yl) sulfamoyl] phenyl] azo] -N-methylanilino] ethyl or 2- [4 - [(E) - [4 - [(4-methylpyrimidin-2-yl) 2-methylprop-2-enoate ) sulfamoyl] phenyl] azo] -N-ethylanilino] ethyl from 1 to 50.
Istotą wynalazku jest również sposób otrzymywania fotochromowych homopolimerów o wzorze 1, w którym R oznacza grupę metylową lub etylową, n oznacza liczbę merów 2-metyloprop-2-enianu 2-[4-[(E)-[4-[(4-metylopirymidyn-2-ilo)sulfamoilo]fenylo]azo]-N-metylo-anilino]etylu lub 2-metyloprop-2-enianu 2-[4-[(E)-[4-[(4-metylopirymidyn-2-ilo)sulfamoilo]fenylo]azo]-N-etylo-anilino]etylu od 1 do 50 polegający na tym, że chromoforowy monomer 2-metyloprop-2-enian 2-[4-[(E)-[4-[(4-metylopirymidyn-2-ilo)sulfamoilo]fenylo]azo]-N-metylo-anilino]etylu lub 2-metyloprop-2-enian 2-[4-[(E)-[4-[(4-metylopirymidyn-2-ilo)sulfamoilo]fenylo]azo]-N-etylo-anilino]etylu rozpuszcza się w rozpuszczalniku organicznym wybranym spośród: tetrahydrofuran lub mieszaniny tetrahydrofuran i γ-butyrolakton o zawartości 70% objętościowych tetrahydrofuranu i poddaje rodnikowej homopolimeryzacji w obecności inicjatora rodnikowego wybranego z grupy: 2,2'-azobis(izobutyronitryl) lub nadtlenek benzoilu, którą prowadzi się w temperaturze z zakresu 60-120°C, w obecności inicjatora rodnikowego i w atmosferze gazu inertnego.The essence of the invention is also the method of obtaining photochromic homopolymers of the formula I, in which R is a methyl or ethyl group, n is the number of 2-methylprop-2-enoate units of 2- [4 - [(E) - [4 - [(4-methylpyrimidines -2-yl) sulfamoyl] phenyl] azo] -N-methylanilino] ethyl or 2- [4 - [(E) - [4 - [(4-methylpyrimidin-2-yl) 2-methylprop-2-enoate sulfamoyl] phenyl] azo] -N-ethyl-anilino] ethyl from 1 to 50 relying on the 2- [4 - [(E) - [4 - [(4-methylpyrimidine) chromophore monomer -2-yl) sulfamoyl] phenyl] azo] -N-methylanilino] ethyl or 2- [4 - [(E) - [4 - [(4-methylpyrimidin-2-yl) 2-methylprop-2-enoate sulfamoyl] phenyl] azo] -N-ethyl-anilino] ethyl is dissolved in an organic solvent selected from: tetrahydrofuran or a mixture of tetrahydrofuran and γ-butyrolactone containing 70% by volume of tetrahydrofuran and subjected to radical homopolymerization in the presence of a radical initiator selected from the group: 2, 2'-azobis (isobutyronitrile) or benzoyl peroxide, which is carried out at a temperature with a range of 60-120 ° C, in the presence of a radical initiator and in an inert gas atmosphere.
Korzystnie stosuje się od 5 do 12% wagowych inicjatora rodnikowego w stosunku do masy monomeru.Preferably, from 5 to 12% by weight of radical initiator, based on the weight of the monomer, is used.
Korzystnie reakcję homopolimeryzacji prowadzi się w atmosferze azotu.Preferably the homopolymerization reaction is carried out under a nitrogen atmosphere.
Korzystnie reakcję homopolimeryzacji prowadzi się w atmosferze argonu.Preferably the homopolymerization reaction is carried out under an argon atmosphere.
Korzystnie reakcję homopolimeryzacji prowadzi się od 48 do 72 godzin.Preferably, the homopolymerization reaction is carried out for 48 to 72 hours.
Korzystnie otrzymane produkty wydziela się przez wytrącenie z wody lub mieszaniny wodno-lodowej.Preferably the products obtained are separated by precipitation from water or an ice-water mixture.
Korzystnie do przyspieszenia koagulacji osadu homopolimeru wytrąconego z mieszaniny poreakcyjnej stosuje się chlorek sodu.Preferably sodium chloride is used to accelerate the coagulation of the homopolymer precipitate precipitated from the reaction mixture.
Korzystnie do przyspieszenia koagulacji osadu homopolimeru wytrąconego z mieszaniny poreakcyjnej stosuje się chlorek amonu.Preferably, ammonium chloride is used to accelerate the coagulation of the homopolymer precipitate precipitated from the reaction mixture.
PL 224 151 B1PL 224 151 B1
Przedmiot wynalazku przedstawiony jest w przykładach wytwarzania fotochromowych homopolimerów metakrylowych.The subject of the invention is illustrated in the examples of the preparation of photochromic methacrylic homopolymers.
P r z y k ł a d 1P r z k ł a d 1
Sposób wytwarzania poli(2-metyloprop-2-enianu 2-[4-[(E)-[4-[(4-metylopirymidyn-2-ilo)sulfamoilo]fenylo]azo]-N-metylo-anilino]etylu) o wzorze 1, w którym R oznacza podstawnik metylowy -CH3 3 Method for producing 2- [4 - [(E) - [4 - [(4-methylpyrimidin-2-yl) sulfamoyl] phenyl] azo] -N-methylanilino] ethyl poly (2-methylprop-2-enate) with Formula 1 wherein R is methyl -CH 3 3
W kolbie okrągłodennej o pojemności 50 cm3 umieszcza się 0,5 g (1,0 mmol) 2-metyloprop-2-enianu 2-[4-[(E)-[4-[(4-metylopirymidyn-2-ilo)sulfamoilo]fenylo]azo]-N-metylo-anilino]etylu i rozpusz33 cza się w mieszaninie 7 cm tetrahydrofuranu i 3 cm γ-butyrolaktonu. Kolbę łączy się z chłodnicą zwrotną i przedmuchuje argonem. Następnie dodaje się 0,025 g inicjatora 2,2'-azobis(izobutyronitrylu) (5% wagowych w stosunku do masy monomeru) i ponownie przedmuchuje się argonem. Mieszaninę ogrzewa się w temperaturze 60°C przez 72 godziny przy ciągłym mieszaniu. Po tym czasie zawartość 3 kolby ochładza się do temperatury pokojowej, wylewa do 100 cm3 wody destylowanej. Zawiesinę wytrąconego homopolimeru pozostawia się w chłodziarce na 24 godziny w celu koagulacji osadu. Efektywność koagulacji osadu można zwiększyć poprzez dodatek chlorku sodu. Osad homopolimeru odsącza się na lejku ze spiekiem, pod zmniejszonym ciśnieniem, przemywa kilkukrotnie wodą destylowaną i suszy w temperaturze 45°C. Wydajność produktu otrzymanego tą metodą wynosi 85%.A round bottom flask with a capacity of 50 cm 3 is placed 0.5 g (1.0 mmol) of 2-methylprop-2-enoate 2- [4 - [(E) - [4 - [(4-methyl-pyrimidin-2-yl) sulfamoyl] phenyl] azo] -N-methylanilino] ethyl and dissolved in a mixture of 7 cm tetrahydrofuran and 3 cm γ-butyrolactone. The flask is connected to a reflux condenser and purged with argon. Then 0.025 g of 2,2'-azobis (isobutyronitrile) initiator (5 wt% based on the weight of the monomer) is added and argon is flushed again. The mixture is heated at 60 ° C for 72 hours with constant stirring. After this time, the contents of the 3 flask are cooled to room temperature, poured into 100 cm 3 of distilled water. The homopolymer suspension is left in the refrigerator for 24 hours to coagulate the precipitate. The effectiveness of sludge coagulation can be increased by adding sodium chloride. The homopolymer precipitate is filtered off on a fritted funnel under reduced pressure, washed several times with distilled water and dried at 45 ° C. The yield of the product obtained by this method is 85%.
11
HNMR (rozpuszczalnik DMSO-d6, wzorzec TMS): ~1,45 ppm, CH3 przy łańcuchu głównym polimeru; -1,7-2,0 ppm, CH2 w łańcuchu głównym polimeru; ~2,3 ppm, CH3 przy pierścieniu 4-metylopirymidyn-2-ylowym ~3,1 ppm, CH3N- ; ~3,6 ppm, -CH2N-; ~4,3 ppm -CH2O-; -6,5-7,0 ppm protony w pierścieniu 4-metylopirymidyn-2-ylowym; ~7,6-8,0 ppm protony w pierścieniu fenylowym w pozycji orto i meta do grupy N=N; ~8,1-8,4 ppm protony w pierścieniu fenylowym w pozycji orto i meta do grupy SO2.HNMR (DMSO-d 6 solvent, TMS pattern): ~ 1.45 ppm, CH 3 on the polymer backbone; -1.7-2.0 ppm, CH 2 in the polymer backbone; ~ 2.3 ppm, CH 3 on the 4-methylpyrimidin-2-yl ring ~ 3.1 ppm, CH 3 N-; ~ 3.6 ppm, -CH 2 N-; ~ 4.3 ppm -CH 2 O-; -6.5-7.0 ppm protons in the 4-methylpyrimidin-2-yl ring; ~ 7.6-8.0 ppm protons in the phenyl ring in ortho position and meta to the group N = N; ~ 8.1-8.4 ppm protons in the phenyl ring in the ortho position and meta to the SO2 group.
UV-Vis: Xmax (DMSO) = 445 nm.UV-Vis: X ma x (DMSO) = 445 nm.
P r z y k ł a d 2P r z k ł a d 2
Sposób wytwarzania poli(2-metyloprop-2-enianu 2-[4-[(E)-[4-[(4-metylopirymidyn-2-ilo)sulfamoilo]fenylo]azo]-N-etylo-anilino]etylu) o wzorze 1, w którym R oznacza podstawnik etylowy -CH2CH3 3 Preparation of 2- [4 - [(E) - [4 - [(4-methylpyrimidin-2-yl) sulfamoyl] phenyl] azo] -N-ethylanilino] ethyl poly (2-methylprop-2-enate) with Formula 1, wherein R is ethyl -CH 2 CH 3 3
W kolbie okrągłodennej o pojemności 50 cm3 umieszcza się 0,51 g (1,0 mmol) 2-metyloprop-2-enianu 2-[4-[(E)-[4-[(4-metylopirymidyn-2-ilo)sulfamoilo]fenylo]azo]-N-etylo-anilino]etylu i rozpuszcza 3 się w 10 cm3 tetrahydrofuranu. Kolbę łączy się z chłodnicą zwrotną i przedmuchuje azotem. Następnie dodaje się 0,061 g inicjatora nadtlenku benzoilu (12% wagowych w stosunku do masy monomeru) i ponownie przedmuchuje się azotem. Mieszaninę ogrzewa się w temperaturze 120°C przez 48 godzin przy ciągłym mieszaniu. Po tym czasie zawartość kolby ochładza się do temperatury pokojowej, wyle3 wa do mieszaniny wodno-lodowej (70 cm3 wody destylowanej i 70 g lodu). Zawiesinę wytrąconego homopolimeru pozostawia się w chłodziarce na 24 godziny w celu koagulacji osadu. Efektywność koagulacji osadu można zwiększyć poprzez dodatek chlorku amonu. Osad homopolimeru odsącza się na lejku ze spiekiem, pod zmniejszonym ciśnieniem, przemywa kilkukrotnie wodą destylowaną i suszy w temperaturze 45°C. Wydajność produktu otrzymanego tą metodą wynosi 86%.In round bottom flask is placed 50 cm 3 0.51 g (1.0 mmol) of 2-methylprop-2-enoate 2- [4 - [(E) - [4 - [(4-methyl-pyrimidin-2-yl) sulfamoyl] phenyl] azo] -N-ethyl-anilino] acetate are dissolved in 3 10 cm 3 of tetrahydrofuran. The flask is connected to a reflux condenser and purged with nitrogen. Then 0.061 g of benzoyl peroxide initiator (12% by weight based on the weight of the monomer) was added and purged with nitrogen again. The mixture is heated at 120 ° C for 48 hours with constant stirring. After this time, the flask content is cooled to room temperature and sends the shaft 3 to a mixture of ice water (70 cm 3 of distilled water and 70 g of ice). The homopolymer suspension is left in the refrigerator for 24 hours to coagulate the precipitate. The effectiveness of sludge coagulation can be increased by adding ammonium chloride. The homopolymer precipitate is filtered off on a fritted funnel under reduced pressure, washed several times with distilled water and dried at 45 ° C. The yield of the product obtained by this method is 86%.
1 1HNMR (rozpuszczalnik DMSO, wzorzec TMS): ~1,13 ppm, CH3 przy łańcuchu głównym polimeru; ~1,9-2,0 ppm, CH2 w łańcuchu głównym polimeru; ~2,3 ppm CH3 przy pierścieniu 4-metylopirymidyn-2-ylowym ~3,4 ppm, CH3N- ; ~4,2 ppm, -CH2N-; ~4,3 ppm, -CH2O-; ~6,7-7,0 ppm, protony w pierścieniu 4-metylopirymidyn-2-ylowym; ~7,6-7,9 ppm, protony w pierścieniu fenylowym w pozycji orto i meta do grupy N=N; ~8,0-8,2 ppm, protony w pierścieniu fenylowym w pozycji orto do grupy SO2; ~8,3 ppm, protony w pierścieniu fenylowym w pozycji meta do grupy SO2. 1 1 H NMR (solvent DMSO, TMS standard): ~ 1.13 ppm, CH 3 on the backbone of the polymer; ~ 1.9-2.0 ppm, CH2 in the polymer backbone; ~ 2.3 ppm CH3 on the 4-methylpyrimidin-2-yl ring ~ 3.4 ppm, CH3N-; ~ 4.2 ppm, -CH2N-; ~ 4.3 ppm, -CH2O-; ~ 6.7-7.0 ppm, protons in the 4-methylpyrimidin-2-yl ring; ~ 7.6-7.9 ppm, ortho protons in the phenyl ring and meta to N = N; ~ 8.0-8.2 ppm, protons in the phenyl ring ortho to the SO2 group; ~ 8.3 ppm, protons in the phenyl ring meta to the SO2 group.
UV-Vis: Xmax (DMSO) = 452 nm.UV-Vis: X ma x (DMSO) = 452 nm.
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