CN100363397C - Hyperbranched polymer containing crown ether and synthesis process therefor - Google Patents
Hyperbranched polymer containing crown ether and synthesis process therefor Download PDFInfo
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- CN100363397C CN100363397C CNB2005100174324A CN200510017432A CN100363397C CN 100363397 C CN100363397 C CN 100363397C CN B2005100174324 A CNB2005100174324 A CN B2005100174324A CN 200510017432 A CN200510017432 A CN 200510017432A CN 100363397 C CN100363397 C CN 100363397C
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Abstract
The present invention relates to a hyperbranched polymer containing crown ether rings and a synthetic method thereof. Under a temperate reaction condition, single coumaron crown ether containing two active groups or dibenzo crown ether and 1, 3, 5-trisubstituted benzene carry out a condensation reaction to obtain a series of novel hyperbranched polymers containing crown ether rings. Because the crown ether has good coordination characteristics, the present invention has significant application prospect on the aspects of ion selective electrodes, chromatographic separation, functional membrane materials, etc.
Description
Technical field
The invention belongs to hyperbranched polymerization technical field, be particularly related to the hyperbranched polymer that contains crown ether cycle and with the single benzo-crown ether that contains two active groups or dibenzo dilating ether and 1,3,5 trisubstituted benzenes contract under the effect of condensation reagent and react, and form a series of method that contains the hyperbranched polymer of crown ether cycle.
Background technology
With respect to simple linear polymer, hyperbranched polymer has particular structure and performance.Synthetic and the potential applied research of novel hyperbranched polymer obtains people's special concern.Modify the novel high polymer material that can prepare multiple special purpose by the hyperbranched polymer of synthetic different structure and to its end group.Hyperbranched polymer is with a wide range of applications in fields such as medicament slow release, functional film material and tackiness agent, polymer processing aid, photoelectric functional materials.
Distinguish from constitutional features, highly branched polymkeric substance comprises dendritic macromole (Dendrimer) and hyperbranched polymer (Hyperbranched polymer) two big classes.The strict controlled polymerization condition of dendritic macromole palpus, and each step reaction product can obtain the regular dendritic macromole of complete branching at last through careful purifying.If its reaction is not added control then obtains the polymolecularity hyperbranched polymer.The glamour of hyperbranched polymer uniqueness is that it has no winding and high resolution between a large amount of end group of highly branched three-dimensional ball-like structure, the molecule, low-viscosity, higher character such as chemical reactivity, can be used as viscosity modifier, also can be used as solidifying agent, the pharmaceutical carrier of thermosetting material, be widely used in agricultural, medicine, cosmetic industry.In addition, because hyperbranched polymer has numerous end groups, after functionalization, also can be used for coating, adhesive field.At present, though the type of synthetic various hyperbranched polymers has a lot, do not relate to the method for the hyperbranched polymers that contains crown ether cycle.
Summary of the invention
The object of the invention is to provide a kind of synthetic method that contains the hyperbranched polymer of crown ether cycle.
For reaching above-mentioned purpose, the present invention adopts following technical scheme: contain the hyperbranched polymer of crown ether cycle, its structural unit is
N=0,1 or 2, the number-average molecular weight M of polymkeric substance
nBe 11000-31000, weight-average molecular weight M
wBe 16000-63000, molecular weight distribution is 1.10-2.30.
The hyperbranched polymer that contains crown ether cycle, its structural unit is
N=0,1 or 2, the number-average molecular weight M of polymkeric substance
nBe 11000-35000, weight-average molecular weight M
wBe 21000-65000, molecular weight distribution is 1.10-2.30.
The hyperbranched polymer that contains crown ether cycle, its structural unit is
N=0,1 or 2, the number average M of polymkeric substance
nMolecular weight is 16000-45000, weight-average molecular weight M
wBe 27000-135000, molecular weight distribution is 1.30-3.50.
The hyperbranched polymer that contains crown ether cycle, its structural unit is
N=0,1 or 2, the number-average molecular weight M of polymkeric substance
nBe 17000-33000, weight-average molecular weight M
wBe 25000-153000, molecular weight distribution is 1.30-3.30.
The synthetic method that contains the hyperbranched polymer of crown ether cycle, with single benzo-crown ether or dibenzo dilating ether and 1,3 of two active groups, 5 trisubstituted benzenes contract and react, and with single benzo-crown ether general formula of two active groups are:
R wherein
1For-NH
2,-Br or-Cl, n=0,1 or 2;
Dibenzo dilating ether general formula with two active groups is
R wherein
2For-NH
2,-Br or-Cl, n=0,1 or 2.
1,3,5 trisubstituted benzene general formulas are
R
3For-OH or-COOH.
R
1, R
2For-Br or-during Cl, R
3For-OH, with single benzo-crown ether of two active groups or with the dibenzo dilating ether and 1 of two active groups, 3,5 trisubstituted benzene mol ratios are 0.5-1.45, contract and the reagent of reaction are alkali metal hydroxide or alkaline carbonate, react on-20-120 ℃, in ethers, halogenated hydrocarbon, hydro carbons, nitrile organic solvent or polar non-proton organic solvent, carry out reaction times 20-48 hour in the inert gas atmosphere.
Organic solvent is selected polar aprotic solvent DMF, DMSO or NMP for use, and temperature of reaction is 0-60 ℃, with single benzo-crown ether of two active groups or with the dibenzo dilating ether and 1,3 of two active groups, 5 trisubstituted benzene mol ratios are 1.1-1.25.
R
1, R
2For-Br, temperature of reaction is 10-30 ℃.
R
1, R
2For-Cl, temperature of reaction is 50 ℃.
R
1, R
2For-NH
2, R
3For-COOH, contract and the reagent of reaction are triphenyl phosphite and pyridine, with single benzo-crown ether of two active groups or with the dibenzo dilating ether and 1 of two active groups, 3,5 trisubstituted benzene mol ratios are 0.9-1.3, react on 50-180 ℃ in ethers, halogenated hydrocarbon, hydro carbons, nitrile organic solvent or polar non-proton organic solvent, in inert gas atmosphere, carry out reaction times 5-10 hour.
With single benzo-crown ether of two active groups or with the dibenzo dilating ether and 1,3 of two active groups, 5 trisubstituted benzene mol ratios are 1.1-1.2, solvent is polar aprotic solvent DMF, DMSO or NMP, and temperature of reaction is 60-100 ℃.
Temperature of reaction is 80 ℃.
Among the present invention, comprise with the dibenzo dilating ether of two active groups:
Single benzo-crown ether with two active groups comprises:
Crown compound has strong coordination, can form the title complex with certain stability constant with some metal ions, can be used for the research of extraction, enrichment and the ligancy of metal ion, can also be used for the fixing of chromatographic separation and equate.Therefore, this serial hyperbranched polymer can effectively carry out molecular recognition, higher ion selectivity is arranged, and has important application prospects at aspects such as ion selective electrode, chromatographic separation, functional film materials.
Description of drawings
Fig. 1 contains crown ether cycle hyperbranched polymer AFM shape appearance figure for embodiment 7 gained;
Fig. 2 is K
+Existing down, embodiment 7 gained contain crown ether cycle hyperbranched polymer AFM shape appearance figure;
Fig. 3 contains crown ether cycle hyperbranched polymer AFM shape appearance figure for embodiment 9 gained;
Fig. 4 is K
+Existing down, embodiment 9 gained contain crown ether cycle hyperbranched polymer AFM shape appearance figure.
Embodiment
Embodiment 1; by 4; 4 ' (5 ')-dibromo methyldiphenyl also-18-hat-6 (1) and 1; 3; it is as follows that 5-benzene triol obtains the hyperbranched polymer reaction process: with 4,4 ' (5 ')-dibromo methyldiphenyl also-(0.3 gram 0.55mmol) is dissolved in the drying of 7.5mL to 18-hat-6; the heavy N of Zhenging; dinethylformamide (DMF); stirring and dissolving under protection of nitrogen gas adds 1,3; 5-benzene triol (58mg; 0.46mmol), adding lithium hydroxide under stirring (67mg, 2.79mmol); stir in room temperature (RT=20 ℃); point TLC plate reacts completely through 20h, continues reaction 5h again.After reaction finished, reaction solution was evaporated to 2mL, added 30mL water, obtain clarifying transparent brown solution,, have precipitation to occur with the pH=4-5 that is acidified to of 5% dilute hydrochloric acid, the static after-filtration that spends the night, get head product 335mg, head product is dissolved among the 5mLDMF, with the distilled water precipitation of 30mL, through suction filtration, vacuum-drying gets 262mg pale yellow powder shape solid, productive rate 74.89%.Mn=12650, Mw=15900, (gel chromatography detects Mw/Mn=1.26, and chromatographic column is: PLgel 5 μ mMIXED-C, 300 * 7.5mm; Detector: differential detector; DMF+1g/L
-1LiBr is a moving phase; Measure temperature: 25 ℃).The sign of polymkeric substance: IR data: v
MaxCm
-13425,2829,1598,1506,1256,1138;
1H NMR data (DMSO-d
6, TMS): δ ppm, 6.60-5.90,5.15,3.60-4.60.
Embodiment 2, by 4; 4 ' (5 ')-dichloromethyl dibenzo-18-hat-6 (2) and 1; 3; it is as follows that 5-benzene triol obtains the hyperbranched polymer reaction process: with 4, and 4 ' (5 ')-dichloromethyl dibenzo-18-hat-6 (0.25 gram, N that 0.55mmol) be dissolved in the 5.5mL drying, heavily steams; dinethylformamide (DMF); stirring and dissolving under protection of nitrogen gas adds (58mg, 0.46mmol) 1; 3; 5-benzene triol, and adding sodium hydroxide under stirring (111mg, 2.79mmol); in 50 ℃ of stirring reactions; point TLC plate reacts completely through 40h, continues reaction 8h again.After reaction finished, reaction solution was evaporated to 2mL, added 30mL water, obtain clarifying transparent brown solution,, have precipitation to occur with the pH=4-5 that is acidified to of 5% dilute hydrochloric acid, the static after-filtration that spends the night, get head product 326mg, head product is dissolved among the 5mLDMF, with the distilled water precipitation of 30mL, through suction filtration, vacuum-drying gets 203mg pale yellow powder shape solid, productive rate 58.03%.Mn=11220, Mw=16330, Mw/Mn=1.45 (the gel chromatography condition is with embodiment 1).The sign of polymkeric substance: IR data: v
MaxCm
-13426,2827,1598,1506,1256,12125;
1H NMR data (DMSO-d
6, TMS): δ ppm, 6.60-5.90,4.83,3.60-4.60.
Embodiment 3; in the present embodiment by 4; 4 ' (5 ')-two amido dibenzo-18-hat-6 (5) and 1; 3; it is as follows that the reaction of 5-benzenetricarboxylic acid obtains the hyperbranched polymer reaction process: with 4; 4 '-two amidos dibenzo-18-hat-6 (1.0 grams; 2.56 mmol); 1; 3, and the 5-benzenetricarboxylic acid (488mg, 2.23mmol); 1.90mL pyridine and 40mL N-Methyl pyrrolidone (NMP) are gone into 100mL and are executed in the Ranque tube; after stirring makes its dissolving under nitrogen protection; add then triphenyl phosphite (2mL, 7.68mmol), reaction solution stirs and to be warming up to 80 ℃ of reaction 3h; then reaction solution is poured in the methyl alcohol that 120mL contains the 2.5mL concentrated hydrochloric acid; product precipitates in methyl alcohol, filters, and gets thick product 1.87 grams; thick product is dissolved in 40mL N-Methyl pyrrolidone (NMP); with the methanol extraction of 150mL, through suction filtration, product washs with hot methanol; vacuum-drying gets 1.52 gram brown powder shape solids.Productive rate=76.61%, Mn=18320, Mw=28580, Mw/Mn=1.56 (the gel chromatography condition is with embodiment 1).The sign of polymkeric substance: IR data: v
MaxCm
-13505-3100 (wide), 2827,1730,1650,1600,1510,1263,1133;
1H NMR data (DMSO-d
6, TMS): δ ppm, 6.80-9.90,3.60-4.50.
Embodiment 4, by 4,4 ' (5 ')-dibromo methyldiphenyl also-24-hat-8 (3) and 1,3, it is as follows that 5-benzene triol obtains the hyperbranched polymer reaction process: identical with embodiment 1 step, just with 4,4 ' (5 ')-dibromo methyldiphenyl also-18-hat-6 (3) replace 4,4 ' (5 ')-dibromo methyldiphenyls also-18-is preced with-6 (1), other conditions are identical, productive rate 82.31%.Mn=15350, Mw=20130, Mw/Mn=1.31 (the gel chromatography condition is with embodiment 1), the sign of polymkeric substance: IR data: v
MaxCm
-13430,2828,1602,1503,1251,1133;
1H NMR data (DMSO-d
6, TMS): δ ppm, 6.60-5.90,5.22,3.70-4.80.
Embodiment 6, by 4,4 ' (5 ')-two amido dibenzo-24-hat-8 (6) and 1,3, it is as follows that the 5-benzenetricarboxylic acid obtains the hyperbranched polymer reaction process: identical with embodiment 3 steps, just with 4,4 ' (5 ')-two amido dibenzo-24-hat-8 (6) replaces 4,4 ' (5 ')-two amido dibenzo-18-hat-6 (5), other conditions are identical, productive rate 63.25%.Mn=19330, Mw=27690, Mw/Mn=1.43 (the gel chromatography condition is with embodiment 1), the sign of polymkeric substance: IR data: v
MaxCm
-13510-3000 (wide), 2825,1733,1645,1600,1495,1265,1130;
1H NMR data (DMSO-d
6, TMS): δ ppm, 6.80-9.90,3.60-4.50.
In embodiment 7, the present embodiment by 4; the 5-xylylene bromide also-15-hat-5 (7) and 1; 3; it is as follows that 5-benzene triol obtains the hyperbranched polymer reaction process: with 4, the 5-xylylene bromide also-15-hat-5 (0.5 gram, the N that 1.10mmol) be dissolved in the 11.5mL drying, heavily steam; dinethylformamide (DMF); stirring and dissolving under protection of nitrogen gas adds 1,3; 5-benzene triol (126mg; 1.00mmol), adding lithium hydroxide under stirring (144mg, 6.00mmol); in stirring at room; point TLC plate reacts completely through 35h, is continuing reaction 5h.After reaction finished, reaction solution was evaporated to 2mL, added 20mL water and was clarifying well-illuminated solution, the pH=4-5 that is acidified to 5% dilute hydrochloric acid, have precipitation to occur, the static after-filtration that spends the night gets head product 468mg, head product is dissolved in the 5mL chloroform, with the methanol extraction of 30mL, through suction filtration, vacuum-drying, get 372mg pale yellow powder shape solid, productive rate 74.63%.Mn=13770, Mw=16080, Mw/Mn=1.17 (the gel chromatography condition is with embodiment 1), the sign of polymkeric substance: IR data: v
MaxCm
-13420,2825,1606,1511,1269,1138;
1H NMR data (CDCl
3, TMS): δ ppm, 6.60-5.90,4.78,3.70-4.50.
Embodiment 8, with embodiment 7,4,5-dichloromethyl benzo-18-hat-6 (8) replaces 4, the 5-xylylene bromide also-15-hat-5 (7), sodium hydroxide replaces lithium hydroxide, other condition is identical, productive rate 59.31%.Mn=16120, Mw=23890, Mw/Mn=1.48 (the gel chromatography condition is with embodiment 1), the sign of polymkeric substance: IR data: v
MaxCm
-13392,2825,1605,1510,1270,1135;
1H NMR data (CDCl
3, TMS): δ ppm, 6.60-5.90,4.76,3.70-4.40.
Embodiment 9,4, the 5-xylylene bromide also-18-hat-6 (9) replaces 4, the 5-xylylene bromide also-15-hat-5 (7), other condition is with embodiment 7, productive rate 71.57%.Mn=15170, Mw=21578, Mw/Mn=1.42 (the gel chromatography condition is with embodiment 1), the sign of polymkeric substance: IR data: v
MaxCm
-13420,2823,1606,1515,1280,1133;
1H NMR data (CDCl
3, TMS): δ ppm, 6.60-5.90,4.86,3.70-4.40.
Embodiment 10,4, and 5-dichloromethyl benzo-18-hat-6 (10) replaces 4,5-dichloromethyl benzo-15-hat-5 (8), and other condition is with embodiment 8, productive rate 56.35%.Mn=19230, Mw=32490, Mw/Mn=1.69 (the gel chromatography condition is with embodiment 1), the sign of polymkeric substance: IR data: v
MaxCm
-13400,2825,1606,1515,1280,1136;
1H NMR data (CDCl
3, TMS): δ ppm, 6.60-5.90,4.86,3.70-4.40.
Embodiment 11,4, and 5-two amido phendioxin 5-hat-5 (11) replaces 4,4 ' (5 ')-two amido dibenzo-18-hat-6 (5), and other condition is with embodiment 3.Productive rate=80.18%, Mn=20350, Mw=30730, Mw/Mn=1.51 (the gel chromatography condition is with embodiment 1), the sign of polymkeric substance: IR data: v
MaxCm
-13600～3000 (wide), 2830,1740,1635,1610,1495,1265,1130;
1H NMR data (DMSO-d
6, TMS): δ ppm, 6.80-9.90,3.60-4.50.
Embodiment 12,4, and 5-two amido phendioxin 8-hat-6 (12) replaces 4,4 ' (5 ')-two amido dibenzo-18-hat-6 (5), and other condition is with embodiment 3.Productive rate=75.31%, Mn=16920, Mw=22330, Mw/Mn=1.32 (the gel chromatography condition is with embodiment 1), the sign of polymkeric substance: IR data: v
MaxCm
-13580-3000 (wide), 2832,1733,1645,1598,1508,1260,1128;
1H NMR data (DMSO-d
6, TMS): δ ppm, 6.80-9.90,3.60-4.50.
The cooperation percentage extraction test that embodiment 7,9,10 gained is contained the crown ether cycle hyperbranched polymer is as follows:
Accurately draw organic phase ([crown ether unit]=1 * 10
-3CHCl
3Solution) and water ([MC1]=0.50mol/L, [picrate]=5 * 10
-3Mol/L, M
+=Li
+, Na
+, K
+, Cs
+) each 5.0 milliliters, place colorimetric cylinder, vibration 60 minutes (trial test show reach extraction equilibrium) under 25 ℃ of constant temperature.Behind the standing demix, water intaking is at the content of 355nm mensuration aqueous phase picrate, and the content in the organic phase is obtained by minusing, according to formula:
Obtain polymkeric substance to each alkalimetal ion percentage extraction (seeing Table 1).
Table 1 contains the cooperation percentage extraction (%) of crown ether cycle hyperbranched polymer to picrate
Embodiment 1,7,9 gained are contained the crown ether cycle hyperbranched polymer, and to carry out phase-transfer catalysis test as follows:
10mmol n-bromooctane is dissolved in the 10mL toluene solution, 25mmol potassiumiodide (or 25mmol sodium iodide) is dissolved in the 4mL distilled water, they are put into reaction flask, add 0.05mmol and contain crown ether cycle hyperbranched polymer (embodiment 7,9,10) catalyzer (pressing the crown ether unit calculates), in 90 ℃ of following stirring and refluxing reactions, measure every the certain hour sampling.
Catalyzed reaction is measured the concentration of n-bromooctane in the mixture with interior scalar quantity method, and contrasts with blank test (not adding hyperbranched polymer).Determining instrument adopts Agilent 6890 type gas chromatographs, HP-5 fused-silica capillary column.The results are shown in Table 2.
Table 2 contains the phase-transfer-catalyzed reactions of crown ether cycle hyperbranched polymer to n-bromooctane/iodide
*
| Catalyzer | Potassiumiodide | Sodium iodide | ||
| Reaction times (h) | The transformation efficiency of n-bromooctane (%) | Reaction times (h) | The transformation efficiency of n-bromooctane (%) | |
| The polymkeric substance of embodiment 1 | 1.5 4.5 | 37.8 92.7 | 8 20 | 29.7 68.9 |
| The polymkeric substance of embodiment 7 | 2 6 | 39.6 90.3 | 7.5 18 | 35.6 82.3 |
| The polymkeric substance of embodiment 9 | 2 5 | 45.8 91.6 | 8 20 | 22.9 65.2 |
* annotate: test shows that react through 20h when not adding hyperbranched polymer, the transformation efficiency of n-bromooctane is less than 4%.
It is as follows that embodiment 7,9 gained are contained crown ether cycle hyperbranched polymer self-assembly test:
Embodiment 7,9 gained are contained the crown ether cycle hyperbranched polymer be dissolved in chloroform, concentration is 0.02mg/mL, films with above chloroformic solution, utilizes atomic force microscope (AFM) to scan its pattern, sees Fig. 1,3.As we know from the figure, the pattern of polymkeric substance is the ellipse globe of nanometer, and the diameter dimension size is 70-100nm, because solutions employed is very rare in the experiment, the film of formation should be unimolecular layer membrane, and such shape appearance figure should be the true reflection of its polymkeric substance unit molecule form.
Chloroformic solution to polymkeric substance adds an amount of K
+Solution does not have precipitation to take place, and can the long period keep solution state.This solution analysis revealed of filming there is K
+Have (acetonitrile solution of KSCN) down, it is elongated that the shape appearance figure of polymkeric substance can broaden, and is self-assembled into the nanometer column form object gradually.At mixing solutions ([crown ether unit]/[K
+]=1: 9) after room temperature left standstill 48h, it was 700-850nm that nano-pillar length increases, and width is 300-450nm, sees Fig. 2,4.The variation of this polymkeric substance pattern in solution should be owing to crown ether cycle and K in the polymkeric substance
+Intermolecular complexing power makes the result of polymkeric substance generation self-assembly.
Claims (12)
1. contain the hyperbranched polymer of crown ether cycle, it is characterized in that, its structural unit is
N=0,1 or 2, the number-average molecular weight M of polymkeric substance
nBe 11000-31000, weight-average molecular weight M
wBe 16000-63000, molecular weight distribution is 1.10-2.30.
2. contain the hyperbranched polymer of crown ether cycle, it is characterized in that, its structural unit is
N=0,1 or 2, the number-average molecular weight M of polymkeric substance
nBe 11000-35000, weight-average molecular weight M
wBe 21000-65000, molecular weight distribution is 1.10-2.30.
3. contain the hyperbranched polymer of crown ether cycle, it is characterized in that, its structural unit is
N=0,1 or 2, the number average M of polymkeric substance
nMolecular weight is 16000-45000, weight-average molecular weight M
wBe 27000-135000, molecular weight distribution is 1.30-3.50.
4. contain the hyperbranched polymer of crown ether cycle, it is characterized in that, its structural unit is
N=0,1 or 2, the number-average molecular weight M of polymkeric substance
nBe 17000-33000, weight-average molecular weight M
wBe 25000-153000, molecular weight distribution is 1.30-3.30.
5. contain the synthetic method of the hyperbranched polymer of crown ether cycle, it is characterized in that, with single benzo-crown ether or dibenzo dilating ether and 1,3 of two active groups, 5 trisubstituted benzenes contract and react, and with single benzo-crown ether general formula of two active groups are:
R wherein
1For-NH
2,-Br or-Cl, n=0,1 or 2;
Dibenzo dilating ether general formula with two active groups is
R wherein
2For-NH
2,-Br or-Cl, n=0,1 or 2;
1,3,5 trisubstituted benzene general formulas are
R
3For-OH or-COOH.
6. method as claimed in claim 5 is characterized in that R
1, R
2For-Br or-during Cl, R
3For-OH, with single benzo-crown ether of two active groups or with the dibenzo dilating ether and 1 of two active groups, 3,5 trisubstituted benzene mol ratios are 0.5-1.45, contract and the reagent of reaction are alkali metal hydroxide or alkaline carbonate, react on-20-120 ℃, in ethers, halogenated hydrocarbon, hydro carbons, nitrile organic solvent or polar non-proton organic solvent, carry out reaction times 20-48 hour in the inert gas atmosphere.
7. method as claimed in claim 6, it is characterized in that, organic solvent is selected polar aprotic solvent N for use, dinethylformamide, dimethyl sulfoxide (DMSO) or N-Methyl pyrrolidone, temperature of reaction is 0-60 ℃, with single benzo-crown ether of two active groups or with the dibenzo dilating ether and 1,3 of two active groups, 5 trisubstituted benzene mol ratios are 1.1-1.25.
8. method as claimed in claim 7 is characterized in that R
1, R
2For-Br, temperature of reaction is 10-30 ℃.
9. method as claimed in claim 7 is characterized in that R
1, R
2For-Cl, temperature of reaction is 50 ℃.
10. method as claimed in claim 5 is characterized in that R
1, R
2For-NH
2, R
3For-COOH, contract and the reagent of reaction are triphenyl phosphite and pyridine, with single benzo-crown ether of two active groups or with the dibenzo dilating ether and 1 of two active groups, 3,5 trisubstituted benzene mol ratios are 0.9-1.3, react on 50-180 ℃ in ethers, halogenated hydrocarbon, hydro carbons, nitrile organic solvent or polar non-proton organic solvent, in inert gas atmosphere, carry out reaction times 5-10 hour.
11. method as claimed in claim 10, it is characterized in that, with single benzo-crown ether of two active groups or with the dibenzo dilating ether and 1 of two active groups, 3,5 trisubstituted benzene mol ratios are 1.1-1.2, solvent is polar aprotic solvent N, dinethylformamide, dimethyl sulfoxide (DMSO) or N-Methyl pyrrolidone, and temperature of reaction is 60-100 ℃.
12. method as claimed in claim 11 is characterized in that, temperature of reaction is 80 ℃.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1296985A (en) * | 2000-12-01 | 2001-05-30 | 清华大学 | Process for synthesizing aromatic aliphatic superbranched polyester |
| JP2003342273A (en) * | 2002-05-30 | 2003-12-03 | National Institute Of Advanced Industrial & Technology | Crowned polybenzyl ether-type dendrimer |
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2005
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1296985A (en) * | 2000-12-01 | 2001-05-30 | 清华大学 | Process for synthesizing aromatic aliphatic superbranched polyester |
| JP2003342273A (en) * | 2002-05-30 | 2003-12-03 | National Institute Of Advanced Industrial & Technology | Crowned polybenzyl ether-type dendrimer |
Non-Patent Citations (2)
| Title |
|---|
| 树枝状大分子的新进展. 陈永明.化学通报，第10期. 1995 * |
| 超支化聚合物. 韩巧荣.化学通报，第4期. 2004 * |
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