CN102010507A - Method for preparing copolymer with multielement alternating structure - Google Patents
Method for preparing copolymer with multielement alternating structure Download PDFInfo
- Publication number
- CN102010507A CN102010507A CN 201010508918 CN201010508918A CN102010507A CN 102010507 A CN102010507 A CN 102010507A CN 201010508918 CN201010508918 CN 201010508918 CN 201010508918 A CN201010508918 A CN 201010508918A CN 102010507 A CN102010507 A CN 102010507A
- Authority
- CN
- China
- Prior art keywords
- dibromo
- alternating structure
- polynary
- multipolymer
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Nc1ccccc1 Chemical compound Nc1ccccc1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a method for preparing a copolymer with a multielement alternating structure. The method comprises the following steps of: in the presence of a solvent, adding 1mol of nitroso compound, 0.5 to 5mol of dibromo compound, 1 to 10mol of metallic copper or copper salt and 1 to 10mol of polyamine to a reactor and stirring, and reacting for 0.1 to 24 hours at the temperature of 10 to 100 DEG C after deoxidized to obtain the copolymer with the multielement alternating structure. The invention has simple synthetic method and mild reaction condition and can utilize the dibromo compound with different structures to be reacted with the nitroso compound to obtain the copolymer with the multielement alternating structure. The invention overcomes defects of the traditional methods, synthesizes the high molecular weight (Mn>50,000g/mol) copolymer with the multielement alternating structure, and expands the new method for synthetizing high molecules.
Description
Technical field
The present invention relates to the preparation method of polymkeric substance, relate in particular to a kind of preparation method with multipolymer of polynary alternating structure.
Background technology
Synthetic polymkeric substance with polynary alternating structure is the target and the challenge in Polymer Synthesizing field.Though adopt traditional copolymerization can obtain containing the polymkeric substance of multiple monomeric unit, the sequential structure of comonomer but is difficult to accurately control.Have only some special monomers can obtain the multipolymer of strict binary alternatively structure, as vinylbenzene and maleic anhydride by copolymerization.In recent years, during the article of relevant polymer sequence array structure control report is arranged, but existing means can't accomplish also high molecular secondary structure is realized complete controllable polymerization.However, the possibility (PolymerChemistry, 1,55-62,2010) that still has many example let us to see to realize this goal.
(Nature Communication such as Satoh, 1-6,2010) the C-Cl key by designing a kind of C=C of containing key and having reactive behavior, continuous atom transferred free radical addition (ATRA) by metal catalysed reaction, C-Cl key and C=C key are reacted, form C-C key and active lower C-Cl key, obtain main chain and contain vinylbenzene, (ABC) with ternary alternating structure of acrylate and vinylchlorid
nThe type polymkeric substance.But this reaction has certain limitation, has a certain proportion of side reaction, and the polymericular weight that obtains is also lower.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of preparation method with polynary alternating structure multipolymer is provided.
Preparation method with polynary alternating structure multipolymer is under the condition that solvent exists, the polyamine of 1 mole of nitroso compound, 0.5～5 mole of dibromo compound, 1～10 mole metallic copper or mantoquita and 1～10 mole is added in the reactor, stir, after the deoxidation, 10～100 ℃ were reacted 0.1～24 hour, and obtained having polynary alternating structure multipolymer.
Described molecular structural formula with polynary alternating structure multipolymer is:
Wherein, R
1Be sec.-propyl, tertiary butyl, phenyl, 2,3,4,5,6-pentamethyl-phenyl, 4-hydroxy phenyl, 4-aminophenyl or cyano group, R
2Be methyl, ethyl, propyl group, normal-butyl, sec.-propyl or tertiary butyl, n=1,2,3 or 5.
Described dibromo compound is: 2,5-dibromo diethylene adipate, 2,7-dibromo suberic acid dimethyl ester, 2,7-dibromo suberic acid di tert butyl carbonate, 2,13-dibromo tetradecanedioic acid dimethyl ester, 2,13-dibromo tetradecane diacid diethyl ester, 2,13-dibromo tetradecane diacid dipropyl, 2,13-dibromo tetradecane diacid diisopropyl ester, 2,13-dibromo tetradecane diacid di-n-butyl, to (brooethyl) benzene, two (2-bromine isobutyl acyloxy) ethane or two (2-bromine isobutyl acyloxy) hexane.
Described nitroso compound molecular structural formula is:
Wherein, R
1Be sec.-propyl, tertiary butyl, phenyl, 2,3,4,5,6-pentamethyl-phenyl, 4-hydroxy phenyl, 4-aminophenyl or cyano group.
Described metallic copper is copper powder, copper wire or copper sheet.Described mantoquita is: Red copper oxide, cuprous sulfide, cuprous telluride, selenkupfer, cuprous bromide, cuprous chloride or cuprous iodide.Described polyamine is 2,2 '-dipyridyl, 4,4 '-two (5-nonyls)-2,2 '-dipyridyl, 1,10-phenanthroline, N, N, N ', N '-Tetramethyl Ethylene Diamine, N-propyl group-(2-pyridyl) methylamine, 2,2 ': 6 '; 2 "-terpyridyl, 4,4 ', 4 "-three (5-nonyls)-2; 2 ': 6 '; 2 "-terpyridyl, N, N, N '; N "; N "-pentamethyl-diethyl triamine, N, N-two (2-pyridylmethyl) octylame, 1,1,4,7,10,10-hexamethyl triethyl tetramine, three [2-(dimethylin) ethyl] amine or three [(2-pyridyl) methyl] amine.
The present invention synthesizes a series of dibromo compounds, by generating active diradical,, realize progressively polymerization of free radical addition-coupling with the nitroso compound reaction with metal or metallic salt reaction, it is regular to obtain the sequence monomer distribution, the polynary alternating copolymer that molecular weight is higher.The end group level of response of this method can go for the synthetic of different functional groups polymkeric substance simultaneously near 100%, proposed a kind of polymkeric substance synthetic novel method of synthetic polynary alternating structure, and the monomer scope that is suitable for is wide.The present invention overcomes the deficiency of existing method, synthetic high molecular (M with polynary alternating structure
n＞50000g/mol) polymkeric substance has been expanded the novel method of Polymer Synthesizing.
Embodiment
The present invention illustrates with the following examples, but scope of the present invention is not limited to these embodiment.
All polymeric reaction conditions are to carry out under the reaction conditions of anaerobic.
The nitroso compound molecular formula that is used for embodiment is as follows:
The dibromo compound molecular formula that is used for embodiment is as follows:
Embodiment 12,5-dibromo diethylene adipate (DEDBA) and 2-methyl-2-nitroso-group propane (MNP) reaction
With 70.4mg Cu powder (1.1mmol), 180mg DEDBA (0.5mmol), 43.5mg MNP (0.5mmol) adds in the ampoul tube nitrogen replacement three times.Add the PMDETA 208 μ L (1mmol) that remove peroxide, THF 1mL.Under 25 ℃, reaction 30min, liquid nitrogen quenching termination reaction.Polymkeric substance is dissolved in the acetone, crosses the post copper removal through neutral alumina, concentrates 50 ℃ of vacuum-drying 24 hours.Resulting polymers is tested through gel permeation chromatography (GPC): number-average molecular weight (M
n)=8360g/mol, molecular weight distributing index (PDI)=2.35.
Embodiment 22,7-dibromo suberic acid dimethyl ester (DMDBO) and 2-methyl-2-nitroso-group propane (MNP) reaction
2,7-dibromo suberic acid dimethyl ester (DMDBO) synthetic: with 5.23g (0.03mol) suberic acid, 5.4mL (0.075mol) thionyl chloride adds in the Schlenk bottle of 25mL, is heated to 80 ℃, reacts 1.5 hours.Stop heating, remaining thionyl chloride in the Schlenk bottle is removed.The Schlenk bottle is heated to 85 ℃, with the liquid bromine (Br of 3.9mL (0.076mmol)
2) several times (each 0.5mL) slowly add the Schlenk bottle, added in 6 hours.85 ℃ are continued down to stir 3 hours.The reaction solution of heat is dropwise added in the 50mL ice bath refrigerative absolute methanol solution, rise to room temperature, stirring is spent the night.Methanol solution poured in 0 ℃ the deionized water, obtain yellow troubled liquor.With 5 * 30mL CH
2Cl
2Extraction merges organic layer.Organic layer is used 3 * 25mL 2%Na respectively
2SO
3The aqueous solution, 2%NaHCO
3The aqueous solution, deionized water wash, anhydrous MgSO
4Dry.Filter, concentration of reaction solution, recrystallizing methanol obtains white crystal 10g, yield 93%.The compound characterization result is as follows:
1H NMR (400MHz, CDCl
3): 4.21-4.25 (m, CHCH
2), 3.80 (s, 6H, OCH
3), 1.97-2.14 (m, 4H, CHCH
2), 1.35-1.60 (m, 4H, CH
2(CH
2)
2CH
2).
13C?NMR(100MHz，CDCl
3)：26.32(CH
2(CH
2)
2CH
2)，34.35(2CHCH
2)，45.14-45.18(2CHCH
2)，52.83(2OCH
3)，170.00(2C＝O)。Results of elemental analyses, theoretical value: C, 33.36%; H, 4.48%.Measured value: C, 33.25%; H, 4.46%.APCI-MS result: 361.6[M+1]
+, 201.6[M-2Br+H]
+
With 70.4mg Cu powder (1.1mmol), 180mg DMDBO (0.5mmol), 43.5mg MNP (0.5mmol) adds in the ampoul tube nitrogen replacement three times.Add the PMDETA 208 μ L (1mmol) that remove peroxide, THF 1mL.Under 25 ℃, reacted liquid nitrogen quenching termination reaction 30 minutes.Polymkeric substance is dissolved in the acetone, crosses the post copper removal through neutral alumina, concentrates 50 ℃ of vacuum-drying 24 hours.Resulting polymers is tested through gel permeation chromatography (GPC): number-average molecular weight (M
n)=10200g/mol, molecular weight distributing index (PDI)=3.16.
Embodiment 3-8 2,13-dibromo tetradecanedioic acid dimethyl ester (DMDBT) and 2-methyl-2-nitroso-group propane (MNP) reaction
2,13-dibromo tetradecanedioic acid dimethyl ester (DMDBT) synthetic: with 5.16g (0.02mol) tetradecane diacid, 4.3mL (0.06mol) thionyl chloride adds in the Schlenk bottle of 25mL, is heated to 80 ℃, reacts 1.5 hours.Stop heating, remaining thionyl chloride in the Schlenk bottle is removed.The Schlenk bottle is heated to 85 ℃, with the Br of 2.6mL (0.05mmol)
2(each 0.5mL) slowly adds the Schlenk bottle several times, adds in 4 hours.85 ℃ are continued down to stir 3 hours.The reaction solution of heat is dropwise added in the 40mL ice bath refrigerative absolute methanol solution, rise to room temperature, stirring is spent the night.Methanol solution is poured in the deionized water of 0 ℃ of 80mL, obtained yellow troubled liquor.With 5 * 30mL CH
2Cl
2Extraction merges organic layer.Organic layer is used 3 * 25mL 2%Na respectively
2SO
3The aqueous solution, 2%NaHCO
3The aqueous solution, deionized water wash, anhydrous MgSO
4Dry.Filter, concentration of reaction solution, the crystallization of methylene chloride (v/v=1/2) solution weight obtains light beige solid 5.3g, yield 60%.The compound characterization result is as follows:
1H NMR (400MHz, CDCl
3): 4.20-4.24 (m, 2H, CHCH
2), 3.78 (s, 6H, OCH
3), 1.93-2.11 (m, 4H, CHCH
2), 1.26-1.52 (m, 16H, CH
2(CH
2)
8CH
2).
13C?NMR(100MHz，CDCl
3)：27.10，28.65，29.11，29.22(CH
2(CH
2)
8CH
2)，34.79(2CHCH
2)，45.64(2CHCH
2)，52.74(2OCH
3)，170.26(2C＝O)。Results of elemental analyses: theoretical value: C, 43.26%; H, 6.35%.Measured value: C, 43.20%; H, 6.36%.APCI-MS：445.7[M+1]
+。
With 70.4mg Cu powder (1.1mmol), 222mg DMDBT (0.5mmol), 43.5mg MNP (0.5mmol) adds in the ampoul tube nitrogen replacement three times.Add the PMDETA 208 μ L (1mmol) that remove peroxide, THF 1mL.The different time of reaction under the room temperature.Termination reaction, polymkeric substance are dissolved in the acetone, cross the post copper removal through neutral alumina, concentrate 50 ℃ of vacuum-drying 24 hours.
The molecular weight of the polymkeric substance of the prepared acquisition of embodiment 3-8 and distribution thereof are as shown in Table 1.
Table one
2 of embodiment 9-15 different mol ratio, 13-dibromo tetradecanedioic acid dimethyl ester (DMDBT) and 2-methyl-2-nitroso-group propane (MNP) reaction
With 70.4mg Cu powder (1.1mmol), the DMDBT (as shown in Table 2) of 43.5mg MNP (0.5mmol) and corresponding mol ratio amount adds in the ampoul tube, nitrogen replacement three times.Add the PMDETA 208 μ L (1mmol) that remove peroxide, THF 1mL.Termination reaction, reaction is 30 minutes under the room temperature.Polymkeric substance is dissolved in the acetone, crosses the post copper removal through neutral alumina, concentrates 50 ℃ of vacuum-drying 24 hours.
The molecular weight of the polymkeric substance of the prepared acquisition of embodiment 9-12 and distribution thereof are as shown in Table 2.
Table two
Embodiment 162,13-dibromo tetradecane diacid diethyl ester (DEDBT) and 2-methyl-2-nitroso-group propane (MNP) reaction
2,13-dibromo tetradecane diacid diethyl ester (DEDBT) synthetic: with 5.16g (0.02mol) tetradecane diacid, 3.6mL (0.05mol) thionyl chloride (SOCl
2) add in the Schlenk bottle of 25mL, be heated to 80 ℃, begin to reflux, reacted 1.5 hours.Stop heating, with remaining SOCl in the Schlenk bottle
2Remove.Be heated to 85 ℃, with the Br of 2.6mL (0.05mmol)
2Slowly add the Schlenk bottle several times, added in 4 hours.85 ℃ are continued down to stir 3 hours.The reaction solution of heat is dropwise added in the 40mL ice bath refrigerative ethanol solution, rise to room temperature, stirring is spent the night.Ethanolic soln is poured in the deionized water of 0 ℃ of 80mL, obtained yellow troubled liquor.With 5 * 30mL CH
2Cl
2Extraction merges organic layer.Organic layer is used 3 * 25mL 2%Na respectively
2SO
3The aqueous solution, 2%NaHCO
3The aqueous solution, deionized water wash, anhydrous MgSO
4Dry.Filter, concentration of reaction solution with the crystallization of methylene chloride (v/v=1/5) solution weight, obtains faint yellow solid.The compound characterization result is as follows:
1H NMR (400MHz, CDCl
3): 4.17-4.26 (m, 6H ,-CHCH
2With-OCH
2CH
3), 1.92-2.10 (m, 4H ,-CHCH
2), 1.26-1.56 (m, 22H ,-CH
2(CH
2)
8CH
2-and-OCH
2CH
3).Results of elemental analyses theoretical value: C, 43.26%; H, 6.35%.Measured value: C, 43.20%; H, 6.36%.APCI-MS：445.7[M+1]
+。
With 70.4mg Cu powder (1.1mmol), 43.5mg MNP (0.5mmol) and 236mg DEDBT (0.5mmol) add in the ampoul tube, nitrogen replacement three times.Add the PMDETA 208 μ L (1mmol) that remove peroxide, THF 1mL.Reaction is 30 minutes under the room temperature.Termination reaction, polymkeric substance are dissolved in the acetone, cross the post copper removal through neutral alumina, concentrate 50 ℃ of vacuum-drying 24 hours.Resulting polymers is tested through gel permeation chromatography (GPC): number-average molecular weight (M
n)=57200g/mol, molecular weight distributing index (PDI)=3.01.
Embodiment 17 2,13-dibromo tetradecanedioic acid dimethyl ester (DMDBT) and nitrosobenzene (NB) reaction
With 320mg Cu powder (5mmol), 54mgNB (0.5mmol) and 222mg DMDBT (0.5mmol) add in the ampoul tube, nitrogen replacement three times.Add the PMDETA 208 μ L (1mmol) that remove peroxide, THF 1mL.Reaction is 30 minutes under the room temperature.Termination reaction, polymkeric substance are dissolved in the acetone, cross the post copper removal through neutral alumina, concentrate 50 ℃ of vacuum-drying 24 hours.Resulting polymers is tested through gel permeation chromatography (GPC): number-average molecular weight (M
n)=19800g/mol, molecular weight distributing index (PDI)=3.22.
Embodiment 18 2 (2-bromine isobutyl acyloxy) ethane (BBiBE) and 2-methyl-2-nitroso-group propane (MNP) reaction
Synthesizing of two (2-bromine isobutyl acyloxy) ethane (BBiBE): with 1.1mL ethylene glycol (0.02mol), 8.7mL triethylamine (0.06mL) is dissolved in the 50mL methylene dichloride, place the 250mL there-necked flask, the ice bath cooling, slowly Dropwise 5 0mL contains the dichloromethane solution of 7.4mL 2-bromo isobutyl acylbromide (0.06mol), dripped off in 2 hours, and stirred under the room temperature and spend the night.Filter, filtrate is used 5%NaHCO
3Solution washing 3 times, deionized water water washing 3 times, anhydrous magnesium sulfate drying concentrates, and uses recrystallizing methanol, obtains colourless acicular crystal, yield 78%.Test result is as follows:
1H NMR (400MHz, CDCl
3): 1.93 (CH
3), 3.70 (OCH
2);
13C NMR:56.63 (OCH
2), 75.72 (C-Br), 171.12 (C=O).
With 70.4mg Cu powder (1.1mmol), 43.5mg MNP (0.5mmol) and 180mg BBiBE (0.5mmol) add in the ampoul tube, nitrogen replacement three times.Add the PMDETA 208 μ L (1mmol) that remove peroxide, THF 1mL.Reaction is 30 minutes under the room temperature.Termination reaction, polymkeric substance are dissolved in the acetone, cross the post copper removal through neutral alumina, concentrate 50 ℃ of vacuum-drying 24 hours.Resulting polymers is tested through gel permeation chromatography (GPC): number-average molecular weight (M
n)=31200g/mol, molecular weight distributing index (PDI)=2.23.
Embodiment 19 2 (2-bromine isobutyl acyloxy) ethane (BBiBE) and nitrosobenzene (NB) reaction
With 32mg Cu powder (0.5mmol), 54mg NB (0.5mmol), 78mg 2, and 2-dipyridyl (0.5mmol) 180mg BBiBE (0.5mmol) adds in the ampoul tube, nitrogen replacement three times.Add the THF 1mL that removes peroxide.100 ℃ were reacted 2 hours down.Termination reaction, polymkeric substance are dissolved in the acetone, cross the post copper removal through neutral alumina, concentrate 50 ℃ of vacuum-drying 24 hours.Resulting polymers is tested through gel permeation chromatography (GPC): number-average molecular weight (M
n)=21800g/mol, molecular weight distributing index (PDI)=3.12.
Embodiment 20 is to (brooethyl) benzene and 2-methyl-2-nitroso-group propane (MNP) reaction
With 70.4mg Cu powder (1.1mmol), 43.5mg MNP (0.5mmol), 132mg adds in the ampoul tube nitrogen replacement three times to (brooethyl) benzene (0.5mmol) and 290mg three [(2-pyridyl) methyl] amine (1mmol).Add the toluene 1mL that removes peroxide.10 ℃ were reacted 24 hours down.Termination reaction, polymkeric substance are dissolved in the acetone, cross the post copper removal through neutral alumina, concentrate, and 50 ℃ of vacuum-drying 24 hours obtains white powder.Resulting polymers is tested through gel permeation chromatography (GPC): number-average molecular weight (M
n)=30100g/mol, molecular weight distributing index (PDI)=2.98.
Claims (7)
1. preparation method with polynary alternating structure multipolymer, it is characterized in that under the condition that solvent exists, the polyamine of 1 mole of nitroso compound, 0.5～5 mole of dibromo compound, 1～10 mole metallic copper or mantoquita and 1～10 mole is added in the reactor, stir, after the deoxidation, 10～100 ℃ were reacted 0.1～24 hour, and obtained having polynary alternating structure multipolymer.
2. a kind of preparation method with polynary alternating structure multipolymer according to claim 1 is characterized in that described molecular structural formula with polynary alternating structure multipolymer is:
Wherein, R
1Be sec.-propyl, tertiary butyl, phenyl, 2,3,4,5,6-pentamethyl-phenyl, 4-hydroxy phenyl, 4-aminophenyl or cyano group, R
2Be methyl, ethyl, propyl group, normal-butyl, sec.-propyl or tertiary butyl, n=1,2,3 or 5.
3. a kind of preparation method according to claim 1 with multipolymer of polynary alternating structure, it is characterized in that described dibromo compound is: 2,5-dibromo diethylene adipate, 2,7-dibromo suberic acid dimethyl ester, 2,7-dibromo suberic acid di tert butyl carbonate, 2,13-dibromo tetradecanedioic acid dimethyl ester, 2,13-dibromo tetradecane diacid diethyl ester, 2,13-dibromo tetradecane diacid dipropyl, 2,13-dibromo tetradecane diacid diisopropyl ester, 2,13-dibromo tetradecane diacid di-n-butyl, to (brooethyl) benzene, two (2-bromine isobutyl acyloxy) ethane or two (2-bromine isobutyl acyloxy) hexane.
4. a kind of preparation method with multipolymer of polynary alternating structure according to claim 1 is characterized in that described nitroso compound molecular structural formula is:
Wherein, R
1Be sec.-propyl, tertiary butyl, phenyl, 2,3,4,5,6-pentamethyl-phenyl, 4-hydroxy phenyl, 4-aminophenyl or cyano group.
5. a kind of preparation method with multipolymer of polynary alternating structure according to claim 1 is characterized in that described metallic copper is copper powder, copper wire or copper sheet.
6. a kind of polynary alternately preparation method of the multipolymer of alternating structure that has according to claim 1 is characterized in that described mantoquita is: Red copper oxide, cuprous sulfide, cuprous telluride, selenkupfer, cuprous bromide, cuprous chloride or cuprous iodide.
7. a kind of preparation method with multipolymer of polynary alternating structure according to claim 1 is characterized in that described polyamine is 2,2 '-dipyridyl, 4,4 '-two (5-nonyls)-2,2 '-dipyridyl, 1, the 10-phenanthroline, N, N, N ', N '-Tetramethyl Ethylene Diamine, N-propyl group-(2-pyridyl) methylamine, 2,2 ': 6 ', 2 "-and terpyridyl; 4; 4 '; 4 "-three (5-nonyl)-2,2 ': 6 ', 2 "-terpyridyl; N; N; N ', N ", N "-the pentamethyl-diethyl triamine; N; N-two (2-pyridylmethyl) octylame, 1,1,4,7,10,10-hexamethyl triethyl tetramine, three [2-(dimethylin) ethyl] amine or three [(2-pyridyl) methyl] amine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105089189A CN102010507B (en) | 2010-10-15 | 2010-10-15 | Method for preparing copolymer with multielement alternating structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105089189A CN102010507B (en) | 2010-10-15 | 2010-10-15 | Method for preparing copolymer with multielement alternating structure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102010507A true CN102010507A (en) | 2011-04-13 |
| CN102010507B CN102010507B (en) | 2012-03-28 |
Family
ID=43840851
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010105089189A Expired - Fee Related CN102010507B (en) | 2010-10-15 | 2010-10-15 | Method for preparing copolymer with multielement alternating structure |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102010507B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391507A (en) * | 2011-07-12 | 2012-03-28 | 浙江大学 | Preparation method of periodic polymer containing alkyl group, amide and ester functional group |
| CN105461904A (en) * | 2015-11-27 | 2016-04-06 | 浙江大学 | Novel method for preparing polymer on basis of carbon free radical coupling reaction |
| CN105504232A (en) * | 2016-01-15 | 2016-04-20 | 浙江大学 | Novel method for preparing copolymer based on co-coupling reaction of two different kinds of carbon free radicals |
| CN108658762A (en) * | 2018-06-12 | 2018-10-16 | 浙江凯普化工有限公司 | A kind of synthetic method of alicyclic ring neighbour diester |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050096438A1 (en) * | 2003-11-03 | 2005-05-05 | Symyx Therapeutics, Inc. | Polyamine polymers |
| CN101198581A (en) * | 2005-05-10 | 2008-06-11 | 科勒研究有限公司 | Method for decarboxylating C-C cross-linking of carboxylic acids with carbon electrophiles |
-
2010
- 2010-10-15 CN CN2010105089189A patent/CN102010507B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050096438A1 (en) * | 2003-11-03 | 2005-05-05 | Symyx Therapeutics, Inc. | Polyamine polymers |
| CN101198581A (en) * | 2005-05-10 | 2008-06-11 | 科勒研究有限公司 | Method for decarboxylating C-C cross-linking of carboxylic acids with carbon electrophiles |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391507A (en) * | 2011-07-12 | 2012-03-28 | 浙江大学 | Preparation method of periodic polymer containing alkyl group, amide and ester functional group |
| CN102391507B (en) * | 2011-07-12 | 2012-12-26 | 浙江大学 | Preparation method of periodic polymer containing alkyl group, amide and ester functional group |
| CN105461904A (en) * | 2015-11-27 | 2016-04-06 | 浙江大学 | Novel method for preparing polymer on basis of carbon free radical coupling reaction |
| CN105504232A (en) * | 2016-01-15 | 2016-04-20 | 浙江大学 | Novel method for preparing copolymer based on co-coupling reaction of two different kinds of carbon free radicals |
| CN105504232B (en) * | 2016-01-15 | 2017-07-18 | 浙江大学 | The new method of copolymer is prepared based on two kinds of different carbon radicals co-coupling reactions |
| CN108658762A (en) * | 2018-06-12 | 2018-10-16 | 浙江凯普化工有限公司 | A kind of synthetic method of alicyclic ring neighbour diester |
| CN108658762B (en) * | 2018-06-12 | 2021-03-02 | 浙江凯普化工有限公司 | Synthesis method of alicyclic o-diester |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102010507B (en) | 2012-03-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102010507B (en) | Method for preparing copolymer with multielement alternating structure | |
| CN101983976A (en) | Preparation method of fluorine-silicon segmented copolymer | |
| CN100465197C (en) | Preparation method of acrylic nitrile homopolymer (copolymer) | |
| Erdogan et al. | Facile synthesis of AB2‐type miktoarm star polymers through the combination of atom transfer radical polymerization and ring‐opening polymerization | |
| Liu et al. | Dihydroxyl-terminated telechelic polymers prepared by RAFT polymerization using functional trithiocarbonate as chain transfer agent | |
| JP2006249130A5 (en) | ||
| CN110606902B (en) | Novel macromolecular photoinitiator and synthesis method thereof | |
| CN101792503B (en) | Fluorinated acrylate atom transfer radical polymerization (ATRP) macromolecule initiator as well as preparation method and application thereof | |
| Ali et al. | Polymerization of functionalized diallyl quaternary ammonium salt to poly (ampholyte–electrolyte) | |
| CN105461904B (en) | A kind of new method that polymer is prepared based on carbon radicals coupling reaction | |
| JP5083556B2 (en) | Living radical polymerization initiator and method for producing polymer | |
| Guan et al. | Synthesis and characterization of graft copolymers based on poly (p-phenylene terephthalamide) backbone and well-defined polystyrene side chains | |
| CN102503844B (en) | Atom transfer free radical polymerization initiator with gemini surface activity and synthetic method thereof | |
| Feng et al. | Synthesis and self-assembly study of two-armed polymers containing crown ether core | |
| CN103923247B (en) | A kind of production technology of styrene maleic anhydride copolymer | |
| CN105601772B (en) | The method that one step prepares crosslinked polystyrene or cross-linked copolymer | |
| JP2007131683A (en) | Acrylic acid ester-based polymer having excellent thermal characteristic and optical characteristic and monomer for the same | |
| Kobatake et al. | Sterically hindered elementary reactions in radical polymerization of α-ethylacrylic esters as studied by ESR spectroscopy | |
| JP2009091376A (en) | N-acryloyl azetidine-based polymer and method for producing the same | |
| CN102746515B (en) | Method for preparing block copolymers | |
| US8796386B2 (en) | Thiocarbonyl compound and process for producing polymer using same and that polymer | |
| CN104530126B (en) | A kind of quaternary alkylphosphonium salt and application thereof | |
| JP6618812B2 (en) | 2-Methylene glutarate ester polymer | |
| Sun et al. | Thermal self-initiation in stable free-radical polymerization of styrene | |
| Liao et al. | Preparation and properties of azobenzene-containing amphiphilic miktoarm star polymers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120328 Termination date: 20181015 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |