CS224832B1 - Methacrylate polymers and copolymers with anchored polyethylene glycols - Google Patents
Methacrylate polymers and copolymers with anchored polyethylene glycols Download PDFInfo
- Publication number
- CS224832B1 CS224832B1 CS267982A CS267982A CS224832B1 CS 224832 B1 CS224832 B1 CS 224832B1 CS 267982 A CS267982 A CS 267982A CS 267982 A CS267982 A CS 267982A CS 224832 B1 CS224832 B1 CS 224832B1
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- CS
- Czechoslovakia
- Prior art keywords
- copolymers
- polyethylene glycols
- anchored
- methacrylate
- polyethylene glycol
- Prior art date
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- 229920001223 polyethylene glycol Polymers 0.000 title claims description 18
- 229920000642 polymer Polymers 0.000 title claims description 16
- 229920001577 copolymer Polymers 0.000 title claims description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 title claims description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 239000012442 inert solvent Substances 0.000 claims description 5
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 4
- 229920001519 homopolymer Polymers 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 claims description 2
- 229920000193 polymethacrylate Polymers 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000001447 alkali salts Chemical class 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000002924 oxiranes Chemical class 0.000 description 2
- 229920002454 poly(glycidyl methacrylate) polymer Polymers 0.000 description 2
- 229940057847 polyethylene glycol 600 Drugs 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000007344 nucleophilic reaction Methods 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229940057838 polyethylene glycol 4000 Drugs 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
Description
Vynález se týká polymerů se zakotvenými polyethylenglykoly.The invention relates to polymers with anchored polyethylene glycols.
Lineární oligomery a polymery oxiranu (ethylenoxidu) polyethylenglykoly a póly(oxirany) se vyznačují schopností tvořit komplexy s kationty kovů, s nízkomolekiilárnimi . polymemími kyselinami a jinými organickými látkami. Póly(oxirany) též urych lují nukleofilní reakce a selektivní transport iontů membránami. (Bailey F.E., Jr., Koleske J.V.: Póly(ethylene oxide), Academie Press 1796; J. Macromol. Sci.- Chem. A13, 321 (1979))··Linear oligomers and polymers of oxirane (ethylene oxide) polyethylene glycols and polyesters (oxiranes) are characterized by the ability to form complexes with low-molecular metal cations. polymeric acids and other organic substances. Poles (oxiranes) also accelerate nucleophilic reactions and selective ion transport across membranes. (Bailey F.E., Jr., Koleske J.V .: Poles (ethylene oxide), Academic Press 1796; J. Macromol. Sci.- Chem. A13, 321 (1979)) ··
Z literatury jsou známy případy imobilisace polyethylenglykolů na polystyrénových skeletech reakcí chlormethylovaného polystyrenu s polyethylenglykoly (j. Am. Chem. Soc. 101, 42^9 (1979)5 Anal. Chem. 52, 869 (1980); J· Chem. Soc., Perkin Trans II 1981, 514)· V produktech obecného vzorce (p)-CH^(OCH^CH^)n°H a <£)-CH2(OCH2CH2)n0CH2- ® ( n>3) je však imobilisací jedna nebo obě hydroxylové skupiny vyřazeny a produktem je polyalkohol nebo polyether. Pro některé účely je však žádoucí zakotvit na polymerním skeletu polyethylenglykol takovým způsobem, aby v strukturní jednotce zůstaly zachovány obě hydroxylové skupiny. Polyglykol tohoto typu nebyl dosud popsán.There are known in the literature cases of immobilization of polyethylene glycols on polystyrene skeletons by the reaction of chloromethylated polystyrene with polyethylene glycols (J. Am. Chem. Soc. 101, 42-9 (1979) 5 Anal. Chem. 52, 869 (1980); J · Chem. Soc. , Perkin Trans II 1981, 514) · In the products of formula (p) -CH 2 (OCH 2 CH 2) n ° H and (R) -CH 2 (OCH 2 CH 2 ) n OCH 2 - ® (n> 3 however, one or both of the hydroxyl groups is eliminated by immobilization and the product is a polyalcohol or a polyether. However, for some purposes it is desirable to anchor the polyethylene glycol on the polymer backbone in such a way that both hydroxyl groups are retained in the structural unit. A polyglycol of this type has not been described.
Předmětem vynálezu jsou methakrylátové polymery se zakotvenými polyethylenglykoly obecného vzorce:The present invention provides methacrylate polymers with anchored polyethylene glycols of the general formula:
(P)-COOCH_CH CH (θ CH CH )—0H 2 j 2' 2 2 -n(P) -COOCH-CH CH (θ CH CH) - OH 2 j 2 '2 2 -n
OHOH
- ACHgOCO-(p)-COOCHg- ACHgOCO- (p) -COOCHg
CHCELÍOCH CH) OCH^CH J 2 2 n 2jCHCl 3 CH 2 OCH 2 CH 2 2 n 2j
OH OH (li)OH OH (li)
224 832 kde na. 3 a (?) značí lineární nebo trojrozměrný polymerní skelet odvozený od polymethakrylátů a kopolymerů methakrylátů se styrenem. 'Tyto polymery lze připravit tak, že se na lineární nebo trojrozměrný homopolymer nebo kopolymer glycidylmethakrylátu s jinými methakry laty nebo se styrenem působí mono- nebo dialkoxidem polyethylenglykolu s alkalickým kovem, případně za přítomnosti inertního rozpouštědla. Po reakci monoalkoxidu je polyethylenglykol zakotven k polymernímu skeletu na jednom místě, v případě dialkoxidu pak na dvou místech. Způsob vazby polyethylenglykolu lze do značné míry regulovat poměrem obou alkoxidů, zpravidla však resultuje produkt s polyethylenglykolem zakotveným oběma způsoby. Jako výchozí polymer lze užít lineární polymery glycidylmethakrylátu, a to jak homopolymery, tak kopolymery s jinými bifunkčními monomery, jako jsou styren a methylmethakrylát. Reakce probíhá rovněž s trojrozměrnými polymery glycidylmethakrylátu, zesítěnými například ethylendimethakrylátem nebo divinylbenzenem, a to jak gelovými, tak makroporesními.224 832 where na. 3 and (?) Denote a linear or three-dimensional polymer backbone derived from polymethacrylates and styrene-methacrylate copolymers. These polymers can be prepared by treating a linear or three-dimensional homopolymer or copolymer of glycidyl methacrylate with other methacrylates or styrene with an alkali metal mono- or dialkoxide, optionally in the presence of an inert solvent. Following the reaction of the monoalkoxide, the polyethylene glycol is anchored to the polymer backbone at one site, and in the case of the dialkoxide at two sites. The mode of binding of the polyethylene glycol can be largely controlled by the ratio of the two alkoxides, but generally results in a product with polyethylene glycol anchored in both methods. Linear polymers of glycidyl methacrylate, both homopolymers and copolymers with other bifunctional monomers such as styrene and methyl methacrylate, can be used as the starting polymer. The reaction also takes place with three-dimensional polymers of glycidyl methacrylate, cross-linked, for example, with ethylene dimethacrylate or divinylbenzene, both gel and macropores.
Reakce se provádí zahříváním alkalické soli (mono- nebo dvojnásobné) polyethylenglykolu s póly(glycidylmethakrylátem) v inertním rozpouštědle. Je výhodné připravit nejdříve z polyethylenglykolu v inertním rozpouštědle alkalickou sůl a tu potom bez isolace v témže rozpouštědle nechat reagovat s poly(glycidylmethakrylátem).The reaction is carried out by heating the alkali salt (mono- or double) of polyethylene glycol with poly (glycidyl methacrylate) in an inert solvent. It is preferable to first prepare an alkali salt from polyethylene glycol in an inert solvent and then react it with poly (glycidyl methacrylate) without isolation in the same solvent.
K přípravě alkalické soli polyethylenglykolu je možno užít sodíku; u polyethylenglykolů o vyšší molekulové hmotnosti je vhodnější užít hydridu sodného. Jako inertní rozpouštědla se osvědčily cyklické ethery, například dioxan nebo tetrahydrofuran.Sodium may be used to prepare the alkali salt of polyethylene glycol; it is preferable to use sodium hydride for higher molecular weight polyethylene glycols. Cyclic ethers such as dioxane or tetrahydrofuran have proved to be inert solvents.
Uvedená reakce probíhá hladce, za mírných reakčních podmínek a nevznikají při ní žádné vedlejší reakční produkty. Polymery připravené podle vynálezu lze užít k sorpci a dělení iontů kovů, k odstraňování stop kyselin z roztoků, jako katalyzátory fázového přenosu a pod.The reaction proceeds smoothly under mild reaction conditions and does not produce any reaction by-products. The polymers prepared according to the invention can be used for sorption and separation of metal ions, for removing traces of acids from solutions, as phase transfer catalysts and the like.
Příklad 1 224 832Example 1 224 832
V roztoku 124 g bezvodého polyethylenglykolu 600 v 70 ml suchého 1,4-dioxanu se rozpustí 2,3 g sodíku a přidá se 19,7 g poly(glycidylmethakrylát-co-ethylendimethakrylátu) a reakční směs se zahřívá v dusíkové atmosféře na teplotu 100° po dobu 24 hodin. Potom se polymer odfiltruje, promyje methanolem a suší do konstant ní hmotnosti. Výtěžek produktu 26 g. Polymer obsahuje 0,4 mmol váz aného polyethy 1englykolu/g.In a solution of 124 g of anhydrous polyethylene glycol 600 in 70 ml of dry 1,4-dioxane, 2.3 g of sodium are dissolved and 19.7 g of poly (glycidyl methacrylate-co-ethylenedimethacrylate) are added and the reaction mixture is heated to 100 ° under nitrogen. for 24 hours. Then the polymer is filtered off, washed with methanol and dried to constant weight. Yield of product 26 g. The polymer contains 0.4 mmol bound polyethylene glycol / g.
Příklad 2Example 2
V roztoku 4θ g polyethylenglykolu 4000 v 50 ml sujhého 1,4dioxanu se rozpustí 0,48 g 50$ hydridu sodného a přidá se 2 g póly(glýcidylmethakrylát-co-ethylendimethakrylátu). Dále se postupuje stejným způsobem jako v příkladu 1. Výtěžek produktu 2,8 g. Polymer obsahuje' 0,07 mmol zakotveného polyethylenglykolu/g.Dissolve 0.48 g of 50% sodium hydride in 4 ml of polyethylene glycol 4000 in 50 ml of dry 1,4-dioxane and add 2 g of poly (glycidyl methacrylate-co-ethylenedimethacrylate). The procedure was as in Example 1. Yield of product 2.8 g. The polymer contains 0.07 mmol of anchored polyethylene glycol / g.
Příklad 3Example 3
V roztoku 6 g bezvodého polyethylenglykolu 600 v 5 ml bezvodého tetrahydrofuranu se rozpustí 0,2 g sodíku a přidá se 4,2 g póly(styren-co-glycidylmjethakrylát-co-ethylendimethakrylátu) a dále se postupuje stejným způsobem jako v přikladu 1. Produkt obsahuje 0,2 mmol zakotveného polyethylenglykolu/g.Dissolve 0.2 g of sodium in a solution of 6 g of anhydrous polyethylene glycol 600 in 5 ml of anhydrous tetrahydrofuran and add 4.2 g of poly (styrene-co-glycidyl methacrylate-co-ethylenedimethacrylate) and proceed as in Example 1. contains 0.2 mmol anchored polyethylene glycol / g.
Příklad 4Example 4
0,1 g sorbentu připraveného podle příkladu 1 bylo přidáno 35 k 4 ml 0,0012M kyseliny solné obsahující stroncia. Po ekvilibraci za normální teploty byl radiometricky nalezen rozdělovači koefi cient pro stróncium D = 39θΟΟ ml.g 1.0.1 g of the sorbent prepared according to example 1 was added to 35 ml of strontium-containing 0.0012M hydrochloric acid. After equilibration at normal temperature, a strontium distribution coefficient D = 39θΟΟ ml.g 1 was found radiometrically.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS267982A CS224832B1 (en) | 1982-04-15 | 1982-04-15 | Methacrylate polymers and copolymers with anchored polyethylene glycols |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS267982A CS224832B1 (en) | 1982-04-15 | 1982-04-15 | Methacrylate polymers and copolymers with anchored polyethylene glycols |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CS224832B1 true CS224832B1 (en) | 1984-01-16 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS267982A CS224832B1 (en) | 1982-04-15 | 1982-04-15 | Methacrylate polymers and copolymers with anchored polyethylene glycols |
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| Country | Link |
|---|---|
| CS (1) | CS224832B1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116655848A (en) * | 2023-05-24 | 2023-08-29 | 安徽大学 | Preparation method and application of degradable polyepoxy chain extender |
-
1982
- 1982-04-15 CS CS267982A patent/CS224832B1/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116655848A (en) * | 2023-05-24 | 2023-08-29 | 安徽大学 | Preparation method and application of degradable polyepoxy chain extender |
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