CN1233694C - Method for synthesizing super-branched polyester amide - Google Patents
Method for synthesizing super-branched polyester amide Download PDFInfo
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- CN1233694C CN1233694C CN 03156220 CN03156220A CN1233694C CN 1233694 C CN1233694 C CN 1233694C CN 03156220 CN03156220 CN 03156220 CN 03156220 A CN03156220 A CN 03156220A CN 1233694 C CN1233694 C CN 1233694C
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- 238000000034 method Methods 0.000 title claims abstract description 28
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 5
- 229920006149 polyester-amide block copolymer Polymers 0.000 title 1
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- 239000000178 monomer Substances 0.000 claims abstract description 40
- 150000001412 amines Chemical class 0.000 claims abstract description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000009413 insulation Methods 0.000 claims abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 5
- 238000007098 aminolysis reaction Methods 0.000 claims abstract description 5
- 239000012265 solid product Substances 0.000 claims abstract description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 24
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 claims description 14
- 229920000587 hyperbranched polymer Polymers 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 14
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- 238000003786 synthesis reaction Methods 0.000 claims description 10
- 150000008064 anhydrides Chemical class 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000006555 catalytic reaction Methods 0.000 claims description 7
- 239000003921 oil Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000010189 synthetic method Methods 0.000 claims description 6
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 5
- 229960004756 ethanol Drugs 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- 238000002390 rotary evaporation Methods 0.000 claims description 5
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 5
- 239000012043 crude product Substances 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 4
- 125000000350 glycoloyl group Chemical group O=C([*])C([H])([H])O[H] 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000007086 side reaction Methods 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 6
- 229920000728 polyester Polymers 0.000 abstract description 6
- 238000006116 polymerization reaction Methods 0.000 abstract description 6
- 239000000047 product Substances 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000006068 polycondensation reaction Methods 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 3
- 238000007039 two-step reaction Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 230000021736 acetylation Effects 0.000 abstract 1
- 238000006640 acetylation reaction Methods 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 12
- 239000007789 gas Substances 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000007171 acid catalysis Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000006254 rheological additive Substances 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 description 1
- 241000024287 Areas Species 0.000 description 1
- QPRUZWIMJNNVCA-UHFFFAOYSA-N C(CC)(=O)OCCC.OC=1C(=C(C#N)C=C(C1)O)OCC Chemical compound C(CC)(=O)OCCC.OC=1C(=C(C#N)C=C(C1)O)OCC QPRUZWIMJNNVCA-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007707 calorimetry Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- NPSSWQJHYLDCNV-UHFFFAOYSA-N prop-2-enoic acid;hydrochloride Chemical compound Cl.OC(=O)C=C NPSSWQJHYLDCNV-UHFFFAOYSA-N 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyamides (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses a method for synthesizing supper-branched polyester amine, which belongs to the preparation technology of a macromolecular material. First, after a monomer is synthesized by two-step reaction of the aminolysis of acid anhydride and the acetylation of a hydroxy group; second, mature polycondensation reaction is carried out; third, the prepared monomer N-(2-acetoxy propyl)-N-(1', 3'-dicarboxybenzoyl) amine and a catalyst are put into a reaction tube, and reaction systems are heated to react in a heat insulation mode under the protection of nitrogen; fourth, the reaction tube is evacuated; finally, after reaction is finished, the reaction tube is cooled to room temperature, a solid product can be obtained. Compared with the prior art, the method adopts a conventional synthesis method. The present invention is characterized in that the monomer is synthesized by the two-step reaction of commercialization raw materials, and the polymerization reaction is typical polycondensation reaction. The method is mature. A reaction device, operation, and the separation and the purification of products are totally and extremely simple. A yield is high. The present invention is a favorable and applicable method for the industrial mass production and the preparation of supper-branched polymers.
Description
Technical field
The invention belongs to a kind of hyperbranched polymer macromolecular material technology of preparing scope, particularly the method for a kind of synthesis of super branched polyester-acid amides by easy route of synthesis.
Background technology
At the end of the eighties, the triumphant illiteracy (Kim) of E.I.Du Pont Company etc. are considered the synthetic too difficulty and loaded down with trivial details of branch-shape polymer in carrying out with the research process of branch-shape polymer as rheology modifier and macromole evocating agent, and they have developed by AB
2The method of hyperbranched polymers such as type monomer one-step synthesis polyphenyl.Amazing is that these polymkeric substance have excellent solubility property, and can be used as rheology modifier, and from then on hyperbranched polymer becomes one of focus of polymer science research over past ten years.In following patent: US.5587441, US.5587446, US.5663260, Swe.92005644 report is arranged, hyperbranched polymer is normally by AB
xType (x 〉=2) monomer obtains through the one-step polymerization reaction.Do not need operations such as synthetic, separation, purifying through multistep, be simple and easy to, and have structure similar and character to branch-shape polymer, can be in many Application Areass as the surrogate of branch-shape polymer.Therefore more likely realize large-scale industrial production, have more application potential.Because three-dimensional molecular structure and a large amount of functional end-groups of hyperbranched polymer uniqueness make it have premium propertiess such as low viscosity, high reaction activity and good solubility, thereby have all obtained application in many fields such as coating, tackiness agent, auxiliary rheological agents, medicament slow release, self-assemblies.
The hyperbranched polymer of report comprises hyper-branched polyester, hyperbranched polyether, super branched polyurethane, ultrabranching polyamide, hyperbranched polyether ketone etc. at present.And existing commercial product and industrial application.For example Manas' holders (Malmstr m) were reported with 2 on the 28th phase of nineteen ninety-five " Macromolecules ", the 2-dimethylol propionic acid is that raw material has synthesized the lard type hyper-branched polyester, Johnson (Johansson) has reported that the employing acrylate chloride carries out terminal groups modification to this polymkeric substance, can obtain to be used for the coating of ultraviolet light polymerization on " the Journal of Coating Technology " of the 67th phase of nineteen ninety-five.Chinese patent 00133675.4 has been reported a kind of new method of modifying, promptly directly maleic anhydride is added in the reaction system, initial polymer is carried out terminal groups modification, obtained a kind of new modified ultra-branching polyester, this polymkeric substance is used for ultraviolet-curing paint, high comprehensive performance.Reported a kind of synthetic method of aromatic aliphatic superbranched polyester on Chinese patent 00133673.8, at first with 3, the 5-resorcylic acid is a raw material, under sulphuric acid catalysis, carry out esterification with propyl alcohol, prepare 3,5-resorcylic acid propyl ester, productive rate about 80%; Then, by 3, the solution reaction of 5-resorcylic acid propyl ester and ethylene chlorhydrin synthesizes aromatic aliphatic type AB
2Type monomer 3,5-dihydroxy ethoxy benzonitrile propyl propionate.Chinese patent 02130905.1 has been reported a kind of synthetic method of hyperbranched poly ester-acid amide; be raw material at first with trimellitic acid 1,2-anhydride and Propanolamine; synthon N-(2-hydroxyethyl)-N-(1 '; 3 '-dicarboxyl benzoyl) amine; with this monomer and acetic anhydride, carry out acetylize then, make N-(2-acetoxyl group ethyl)-N-(1 '; 3 '-dicarboxyl benzoyl) amine, polymerization promptly under the certain vacuum degree.U.S. Pat 5225522 has also been reported the different synthesis paths of this aromatic aliphatic superbranched polyester, and its synthetic sepn process complexity needs high-tension apparatus, and cost height, productive rate also only are about 31%.How to synthesize AB simply
xMonomer and then preparation hyperbranched polymer have become the problem of this field specific aim research.The AB of above-mentioned bibliographical information
xThe type monomer mostly needs synthetic in addition, and synthesis step is numerous and diverse, the bottleneck that this has become the research of restriction hyperbranched polymer and has used.
Summary of the invention
The purpose of this invention is to provide synthetic AB
2The method of a kind of synthesis of super branched polyester-amine of the monomeric simple and easy approach of type, it is characterized in that: earlier with 1,2,4-benzenetricarboxylic anhydride, Propanolamine and diacetyl oxide are by simple acid anhydrides aminolysis reaction and glycoloyl reaction, synthesized monomer N-(2-acetoxyl group propyl group)-N-(1 ', 3 '-dicarboxyl benzoyl) amine, and adopt the pet reaction method of catalysis and heating that this monomer is prepared into hyper-branched polyester-amine; Its synthetic method comprises following three steps:
1) .N-(2-hydroxypropyl)-N-(1 ', 3 '-dicarboxyl benzoyl) amine is synthetic: with 1 of mol ratio 1: 1～1.2,2,4-benzenetricarboxylic anhydride and Propanolamine are respectively to be dissolved in dehydrated alcohol at 1: 3 by volume, the ethanolic soln of Propanolamine is placed the there-necked flask that has whipping appts, with constant pressure funnel with 1,2, the ethanolic soln of 4-benzenetricarboxylic anhydride slowly drops in the there-necked flask, uses ice-water bath hierarchy of control temperature in the dropping process, to reduce side reaction, dropwise, promptly stirring reaction 1h～4h at room temperature obtains colourless solution, rotary evaporation desolventizes ethanol, obtain concentrated liquid, this liquid is vacuumized 1-5Pa at 80 ℃ of following vacuum drying ovens, dried by the fire 24-48 hour, be dissolved in the 10-20 deionized water doubly continuing spissated liquid, splash into 0.1-1 hydrochloric acid (1mol/L) doubly, placed filtering-depositing 12-24 hour, dry monomer N-(2-hydroxypropyl)-N-(1 ', the 3 '-dicarboxyl benzoyl) amine that gets;
2) .N-(2-acetoxyl group propyl group)-N-(1 ', 3 '-dicarboxyl benzoyl) amine is synthetic: in 60～90 ℃ of water-baths, diacetyl oxide with 1.2～2 times of mol ratios carries out acetylize to the first step monomer, can drip 4 vitriol oils and carry out catalysis, reaction 0.5～1h, get white crude product, with deionized water wash for several times to remove excessive acetic anhydride via and other impurity, obtain preparing the required monomer N-of hyperbranched polymer (2-acetoxyl group propyl group)-N-(1 ', 3 '-dicarboxyl benzoyl) amine;
3) hyper-branched polyester-amine is synthetic: with monomer N-(2-acetoxyl group propyl group)-N-(1 ', 3 '-dicarboxyl benzoyl) amine and catalyzer Zn (OAc)
2Or tosic acid places reaction tubes; the mass ratio that adds is 1: 0.03～0.05; under nitrogen protection; reaction system is heated to 190 ℃～210 ℃; insulation reaction 0.5h～2h vacuumizes 1-5Pa then, continues reaction 1h～8h; after reaction finishes, be cooled to room temperature and can obtain the solid product.
The invention has the beneficial effects as follows with the synthetic technology of the hyperbranched polymer of reporting in the past and compare, characteristics of the present invention are: adopt commercially available commercialized raw materials 1,2,4-benzenetricarboxylic anhydride and Propanolamine react in the middle of monomer, and then obtain the required monomer of polymerization with acetic anhydride, the reaction unit of this two-step reaction process, operation and product separate purify all extremely simple.Measure a kind of method of synthesis of super branched polyester-amine by analysis; it is characterized in that: earlier with 1; 2; 4-benzenetricarboxylic anhydride, Propanolamine and diacetyl oxide are by simple acid anhydrides aminolysis reaction and glycoloyl reaction; synthesized monomer N-(2-acetoxyl group propyl group)-N-(1 '; 3 '-dicarboxyl benzoyl) amine, and adopt the pet reaction method of catalysis and heating that this monomer is prepared into hyper-branched polyester-amine.Institute's synthetic polymkeric substance has thermal characteristics preferably, is expected to be applied aspect polymeric rheology modification, coating and the tackiness agent, and its solution also can be used for the research of molecule self-assembly.The present invention has prepared novel AB by selecting suitable raw material that is easy to get and easy synthesis path
2The type monomer, and obtained a kind of novel hyper-branched polyester-amine by general melt polycondensation method.
Embodiment
The present invention is a kind of method of synthesis of super branched polyester-amine.Earlier with 1; 2; 4-benzenetricarboxylic anhydride, Propanolamine and diacetyl oxide are by simple acid anhydrides aminolysis reaction and glycoloyl reaction; synthesized monomer N-(2-acetoxyl group ethyl)-N-(1 '; 3 '-dicarboxyl benzoyl) amine, and adopt the pet reaction method of catalysis and heating that this monomer is prepared into hyper-branched polyester-amine.Its synthetic method comprises following three steps:
1) .N-(2-hydroxypropyl)-N-(1 '; 3 '-dicarboxyl benzoyl) amine is synthetic: with 1 of mol ratio 1: 1～1.2; 2; 4-benzenetricarboxylic anhydride and Propanolamine are respectively in the dehydrated alcohol that is dissolved at 1: 3 by volume; the ethanolic soln of Propanolamine is placed the there-necked flask that has whipping appts; with constant pressure funnel with 1; 2, the ethanolic soln of 4-benzenetricarboxylic anhydride slowly drops in the there-necked flask, uses ice-water bath hierarchy of control temperature in the dropping process; to reduce side reaction; dropwise, promptly stirring reaction 1h～4h at room temperature obtains colourless solution; rotary evaporation desolventizes ethanol; obtain concentrated liquid, this liquid is vacuumized 1-5Pa at 80 ℃ of following vacuum drying ovens, dried by the fire 24-48 hour; be dissolved in the 10-20 deionized water doubly continuing spissated liquid; splash into 0.1-1 times of hydrochloric acid (1mol/L), placed filtering-depositing 12-24 hour; dry monomer N-(2-hydroxypropyl)-N-(1 ', the 3 '-dicarboxyl benzoyl) amine that gets.
2) .N-(2-acetoxyl group propyl group)-N-(1 ', 3 '-dicarboxyl benzoyl) amine is synthetic: in 60～90 ℃ of water-baths, with the diacetyl oxide of 1.2～2 times of mol ratios the first step monomer is carried out acetylize, can drip 4 vitriol oils and carry out catalysis.Reaction 0.5～1h gets white crude product, for several times to remove excessive acetic anhydride via and other impurity, obtains preparing the required monomer N-of hyperbranched polymer (2-acetoxyl group propyl group)-N-(1 ', 3 '-dicarboxyl benzoyl) amine with deionized water wash.
3). synthesizing of hyper-branched polyester-amine: with monomer N-(2-acetoxyl group propyl group)-N-(1 ', 3 '-dicarboxyl benzoyl) amine and catalyzer Zn (OAc)
2Or tosic acid places reaction tubes, and the mass ratio of adding is 1: 0.03～0.05, under nitrogen protection, reaction system is heated to 190 ℃～210 ℃.Insulation reaction 0.5h～2h vacuumizes 1-5Pa then, continues reaction 1h～8h.After reaction finishes, be cooled to room temperature and can obtain the solid product.
Give further instruction by the following examples to technology of the present invention again.
Embodiment 1: 13.2ml (440mmol) Propanolamine is dissolved in the 100ml dehydrated alcohol, adds and be equipped with in the there-necked flask of stirring.Place on the ice-water bath, with 78.6g (400mmol) 1,2, the 4-benzenetricarboxylic anhydride is dissolved in the 100ml dehydrated alcohol, places constant pressure funnel, slowly drops in the flask, and about 30min. drips off.Remove ice-water bath, at room temperature continue to stir, react 2h.Obtain colourless solution, rotary evaporation desolventizes ethanol, obtains colourless solution, and rotary evaporation desolventizes ethanol, obtains concentrated liquid.This liquid is vacuumized 1-5Pa at 80 ℃ of following vacuum drying ovens, dried by the fire 24-48 hour.Splash into appropriate hydrochloric acid with continuing in the deionized water that spissated liquid is dissolved in 15 times, placed 12-24 hour, filtering-depositing, drying is won and is gone on foot monomeric products 25.7g, and productive rate is 24.0%.It is 198.2 ℃ that DSC measures fusing point.Proton magnetic spectrum figure (
1H-NMR) result (ppm) is as follows: and 7.9～8.4ppm (3H, ph-H), 3.7ppm (2H ,-CH
2CH
2O-), 3.4ppm (2H ,-CH
2CH
2N-), 1.7ppm (2H, CH
2CH
2O).
With the above-mentioned 25.7g product that obtains, place Erlenmeyer flask.Under 80 ℃ of water-baths, add 183.4ml (192mmol) diacetyl oxide, and drip 4 sulphuric acid catalysis, stir about 30min., reaction promptly finishes, and reaction solution is cooled to room temperature, separates out white precipitate.Crude product with deionized water wash for several times, dry 27.6g monomer F2, productive rate 88.1%.It is 133.4 ℃ that DSC measures its fusing point.Proton magnetic spectrum figure (
1H-NMR) result (ppm) is as follows: and 7.9～8.4ppm (3H, ph-H), 4.0ppm (2H ,-CH
2CH
2O-), 3.7ppm (2H ,-CH
2CH
2N-), 1.8-2.0ppm (2H, CH
2CH
2O; 3H ,-CH
3), turn out to be designed monomer structure.
Get 1.0g monomer N-(2-acetoxyl group ethyl)-N-(1 ', 3 '-dicarboxyl benzoyl) amine and 0.05g catalyzer Zn (OAc)
2In the reaction tubes that has whipping appts, vacuumize 1-5Pa, fill nitrogen repeatedly after twice, logical N
2Gas shiled, oil bath is heated to 200 ℃ with reaction system, and insulation 1h stops logical N
2Gas vacuumizes 1-5Pa, and after continuing to react 6h, stopped reaction is at N
2Under the gas shiled, naturally cool to room temperature, get brown solid polymkeric substance 0.7g, productive rate 89%.It is 178 ℃ that DSC measures Tg, and it is 240 ℃ that TGA measures its decomposition temperature.Proton magnetic spectrum figure (
1H-NMR) result (ppm) is as follows: 4.0-4.4 (2H ,-CH
2CH
2CH
2-), 3.5-3.9 (2H ,-CH
2CH
2CH
2-) and 1.8-2.2 (2H ,-CH
2CH
2CH
2-), 7.8-8.4 (ph-H, 3H).This polymkeric substance is insoluble to THF (tetrahydrofuran (THF)), acetone, alcohols, is dissolved in DMF (dimethyl formamide), DMSO intensive polar solvents such as (dimethyl sulfoxide (DMSO)).
Embodiment 2:
Except the reaction times that vacuumizes in the polyreaction changes 4h into, other building-up process is identical with embodiment 1, and productive rate is 19.9%, and the Tg that DSC (dynamic scan calorimetry) measures polymkeric substance is 118 ℃.
Embodiment 3:
Except the reaction times that vacuumizes in the polyreaction changes 8h into, other building-up process is identical with embodiment 1, and productive rate is 91.7%.
Embodiment 4:
Except polymeric reaction temperature changes 190 ℃ into, in the polyreaction, vacuumize 1-5Pa, the reaction times changes 2h into, and other building-up process is identical with embodiment 1, and productive rate is 78.0%.
Embodiment 5:
Except polymeric reaction temperature changes 210 ℃ into, vacuumize 1-5Pa in the polyreaction, the reaction times changes 2h into, and other building-up process is identical with embodiment 1, and productive rate is 79.2%.The Tg that DSC measures polymkeric substance is 118.5 ℃.
Embodiment 6:
Except polymeric reaction temperature changes 210 ℃ into, in the polyreaction, vacuumize 1-5Pa, the reaction times changes 2h into, and the catalyzer of polycondensation changes tosic acid into, and other building-up process is identical with embodiment 1, and productive rate is 85.0%.
The first step synthetic N-(2-hydroxyethyl)-N-(1 ', 3 '-dicarboxylic acid benzoyl) amine also is a kind of AB
2The type monomer directly carries out melt phase polycondensation with it, also can obtain hyperbranched polymers in theory.
The comparative example 1:
Synthesizing of monomer N-(2-hydroxyethyl)-N-(1 ', 3 '-dicarboxylic acid benzoyl) amine with embodiment 1.Get 1.0g monomer N-(2-hydroxyethyl)-N-(1 ', 3 '-dicarboxylic acid benzoyl) amine and 0.05g catalyzer Zn (OAc)
2In the reaction tubes that has whipping appts, behind twice of the vacuum nitrogen filling, logical N
2Gas shiled, oil bath are heated to 210 ℃, and insulation 1h stops logical N
2Gas vacuumizes 1-5Pa, and after continuing to react 2h, stopped reaction is at N
2Under the gas shiled, naturally cool to room temperature, get the light yellow solid polymkeric substance.This polymkeric substance only is dissolved among the DMF of hot alkali lye and heat, is insoluble in the organic solvent commonly used.
The comparative example 2:
Get 1.0g monomer N-(2-hydroxypropyl)-N-(1 ', 3 '-dicarboxylic acid benzoyl) amine and 0.05g catalyzer Zn (OAc)
2In the reaction tubes that has whipping appts, vacuumize twice after, logical N
2Gas shiled, oil bath are heated to 210 ℃, and insulation 1h stops logical N
2Gas vacuumizes 1-5Pa, and after continuing to react 0.5h, stopped reaction is at N
2Under the gas shiled, naturally cool to room temperature, get the light yellow solid polymkeric substance.This polymkeric substance also only is dissolved among the DMF of hot alkali lye and heat, is insoluble in the organic solvent commonly used.
The comparative example shows by the direct polymerization of monomer N-(2-hydroxypropyl)-N-(1 ', 3 '-dicarboxylic acid benzoyl) amine, can not obtain soluble polymer.As seen, the first step product is carried out acetylize not only can reduce the product fusing point significantly, and then reduce polymeric reaction temperature, save the energy; And can reduce the generation of crosslinking side reaction in the polyreaction, thereby successfully obtain hyperbranched polymer.
The molecular formula of compound or structural formula are in the specification sheets of the present invention
NH
3CH
2CH
2CH
2OH?
Propanolamine 1,2,4-benzenetricarboxylic anhydride N-(2-acetoxyl group propyl group)-N-(1 ', 3 '-dicarboxyl benzoyl)
Amine
Diacetyl oxide N-(2-acetoxyl group propyl group)-N-(1 ', 3 '-dicarboxyl benzoyl) amine hyperbranched poly ester-acid amide
Claims (1)
1. the method for a novel synthesis of super branched polyester-amine, it is characterized in that: earlier with 1,2,4-benzenetricarboxylic anhydride, Propanolamine and diacetyl oxide are by simple acid anhydrides aminolysis reaction and glycoloyl reaction, synthesized monomer N-(2-acetoxyl group propyl group)-N-(1 ', 3 '-dicarboxyl benzoyl) amine, and adopt the pet reaction method of catalysis and heating that this monomer is prepared into hyper-branched polyester-amine; Its synthetic method comprises following three steps:
1) .N-(2-hydroxypropyl)-N-(1 ', 3 '-dicarboxyl benzoyl) amine is synthetic: with 1 of mol ratio 1: 1～1.2,2,4-benzenetricarboxylic anhydride and Propanolamine are respectively in the dehydrated alcohol that is dissolved at 1: 3 by volume, the ethanolic soln of Propanolamine is placed the there-necked flask that has whipping appts, with constant pressure funnel with 1,2, the ethanolic soln of 4-benzenetricarboxylic anhydride slowly drops in the there-necked flask, uses ice-water bath hierarchy of control temperature in the dropping process, to reduce side reaction, dropwise, promptly stirring reaction 1～4 hour at room temperature obtains colourless solution, rotary evaporation desolventizes ethanol, obtain concentrated liquid, this liquid is vacuumized 1-5Pa at 80 ℃ of following vacuum drying ovens, dried by the fire 24-48 hour, be dissolved in the 10-20 times of deionized water of liquid volume continuing spissated liquid, splash into the hydrochloric acid of 0.1-1 times of 1mol/L of liquid volume, placed filtering-depositing 12-24 hour, dry monomer N-(2-hydroxypropyl)-N-(1 ', the 3 '-dicarboxyl benzoyl) amine that gets;
2) .N-(2-acetoxyl group propyl group)-N-(1 ', 3 '-dicarboxyl benzoyl) amine is synthetic: in 60～90 ℃ of water-baths, with the diacetyl oxide of 1.2～2 times of mol ratios the first step monomer is carried out acetylize, drip 4 vitriol oils and carry out catalysis; Reacted 0.5～1 hour, and got white crude product, for several times to remove excessive acetic anhydride via and other impurity, obtain preparing the required monomer N-of hyperbranched polymer (2-acetoxyl group propyl group)-N-(1 ', 3 '-dicarboxyl benzoyl) amine with deionized water wash;
3). synthesizing of hyper-branched polyester-amine: with monomer N-(2-acetoxyl group propyl group)-N-(1 ', 3 '-dicarboxyl benzoyl) amine and catalyzer Zn (OAc)
2Or tosic acid places reaction tubes; the mass ratio that adds is 1: (0.03～0.05); under nitrogen protection; reaction system is heated to 190 ℃～210 ℃; insulation reaction 0.5～2 hour vacuumizes 1-5Pa then, continues reaction 1～8 hour; after reaction finishes, be cooled to room temperature and can obtain the solid product.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03156220 CN1233694C (en) | 2003-09-05 | 2003-09-05 | Method for synthesizing super-branched polyester amide |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 03156220 CN1233694C (en) | 2003-09-05 | 2003-09-05 | Method for synthesizing super-branched polyester amide |
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| CN1488661A CN1488661A (en) | 2004-04-14 |
| CN1233694C true CN1233694C (en) | 2005-12-28 |
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| CN 03156220 Expired - Fee Related CN1233694C (en) | 2003-09-05 | 2003-09-05 | Method for synthesizing super-branched polyester amide |
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| CN106366310B (en) * | 2016-08-26 | 2020-09-08 | 威海晨源分子新材料有限公司 | Carboxyl-containing high-refractive-index hyperbranched polyesteramide, preparation method thereof and application thereof in plastic modification |
| CN115073735B (en) * | 2021-03-10 | 2023-05-26 | 上海交通大学 | Hyperbranched semiaromatic polyester imide polymer and preparation method thereof |
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