CN1405205A - Terminal group-adjustable superbranched polyamide and its preparation method - Google Patents
Terminal group-adjustable superbranched polyamide and its preparation method Download PDFInfo
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- CN1405205A CN1405205A CN 02145098 CN02145098A CN1405205A CN 1405205 A CN1405205 A CN 1405205A CN 02145098 CN02145098 CN 02145098 CN 02145098 A CN02145098 A CN 02145098A CN 1405205 A CN1405205 A CN 1405205A
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Abstract
The invention discloses overspending polyamide whose end base is adjustable and the manufacturing method. The manufacturing method is: monomer which contains estolide and multiamido monomer reacts at the proportion of 1/100-100/1 mol under the protection of nitrogen, the agent is non-proton agent, reacting temperature is -50-250 degree C, the time of reaction is from one minute to fifteen days; then the compound is heated to 20-300 degree C and is decompressed under 8000-0.01 vacuum rate to react from 5 minutes to 120 hours, so the end amino or end carboxyl overspending polyamide is produced.
Description
Technical field: the present invention relates to ultrabranching polyamide, particularly adjustable ultrabranching polyamide of end group and preparation method thereof.
Background technology: hyperbranched polymer has highly branched triaxial ellipsoid shape structure, owing to have low viscosity, high resolution, characteristics such as high rheological and a large amount of functional end-groups will obtain important application in fields such as biological medicine, nano material, coating.
Hyperbranched polymer is generally by AB
n(n 〉=2) type monomer polycondensation forms (Kim, Y.H., Webster, O.W.Macromolecules, Vol.25,5561 (1992)).But AB
nThe type monomer generally needs investigator oneself synthetic, and it is expensive to waste time and energy, and makes this method have certain limitation.On the other hand, be certain with the end group of this traditional method synthetic hyperbranched polymer, change its end group, usually need synthetic new monomer, then polymerization and getting.This has brought many constant to its application.
Summary of the invention: the objective of the invention is to the monomer and the polyamino monomer direct reaction that contain acid anhydrides with commercial, synthetic ultrabranching polyamide with wide application prospect.Simultaneously, the end group of polymkeric substance can obtain holding carboxyl or amine-terminated hyperbranced fluidized polymer by changing two kinds of monomeric reinforced adjustings recently.Reduce synthesis step like this, simplified production technique, thereby reduced cost, can satisfy the needs of scale operation.
Content of the present invention is to be raw material with commercial monomer and the polyamino monomer that contains acid anhydrides, has synthesized a series of ultrabranching polyamides.
Preparation method of the present invention is as follows: under nitrogen protection, will contain the monomer of acid anhydrides and polyamino monomer with 1/100～100/1 mol ratio, reaction 1 minute to 15 days in aprotic solvent under-50 ℃～250 ℃; The gained mixture is warming up to 20 ℃～300 ℃ then, vacuum tightness is that decompression was reacted 5 minutes to 120 hours under 8000～0.01Pa, obtains head product, through dissolving, precipitation, filtration, separation, drying, obtains subject polymer.
The monomer that contains acid anhydrides that the present invention adopts comprises the ring malonic anhydride, alkyl substituted cyclopropane dicarboxylic anhydride, ring Succinic anhydried, alkyl substituted ring Succinic anhydried, ring Pyroglutaric acid, alkyl substituted ring Pyroglutaric acid, MALEIC ANHYDRIDE, alkyl replaces MALEIC ANHYDRIDE, alkyl substituted ring adipic anhydride, the cyclohexane diacid acid anhydride, Tetra hydro Phthalic anhydride, alkyl replaces Tetra hydro Phthalic anhydride, naphthalene acid anhydride, alkyl-substituted naphthaline acid anhydrides, and their homologue, derivative and isomer.Wherein these monomeric alkyl refer to C
1～C
20Substituting group.
The polyamino monomer that the present invention adopts comprises Diethylene triamine, three ethylidine tetramines, four ethylidine, five amine, five ethylidine hexamines and other polyamines polyene, triaminobenzene, tetramino benzene and other polyamino aromatic compound, polyamino heterogeneous ring compound, 4-aminomethyl-1,8-octamethylenediamine and other aminoalkyl diamine compound, three-aminoethyl amine, three-aminopropyl amine and other three-aminoalkyl amine, and their homologue, derivative and isomer.
The aprotic solvent that the present invention adopts comprises N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), N-N-methyl-2-2-pyrrolidone N-, tetramethylene sulfone, chloroform, tetrahydrofuran (THF), ethyl acetate, tetracol phenixin perhaps contain the mixed solvent of these aprotic solvent.
The structure of polymkeric substance is confirmed through infrared spectra and nuclear magnetic resonance spectroscopy.Molecular weight is measured with GPC, is solvent with DMF.
Novel ultrabranching polyamide produced according to the present invention, raw material sources are extensive, low price, simple synthetic method, controllability is good, and end group can be regulated, and preparation cost is low.
Embodiment: the following examples are to further specify of the present invention, rather than limit the scope of the invention.
Embodiment 1: 0.1mol is encircled butyryl oxide be dissolved in 20mL N, in the dinethylformamide, stir adding 0.1mol three-aminoethyl amine down, at N
2Under the gas shiled, normal-temperature reaction 50h, vacuum tightness is under the 300Pa decompression, is warming up to 150 ℃ of reaction 4h.Stopped reaction, product add 30mL N, and the 800mL ether sedimentation is used in the dinethylformamide dissolving, through suction filtration, washing, vacuum-drying, get the amino hyperbranched polymer of solid end.Molecular weight of product is 28,400.
Embodiment 2: 0.2mol is encircled butyryl oxide be dissolved in 30mL N, in the dinethylformamide, stir adding 0.1mol three-aminoethyl amine down, at N
2Under the gas shiled, normal-temperature reaction 50h; Vacuum tightness is under the 300Pa decompression, is warming up to 150 ℃ of reaction 5h.Stopped reaction, product add 35mL N, and the 1000mL ether sedimentation is used in the dinethylformamide dissolving, through suction filtration, washing, vacuum-drying, get the solid end carboxyl super branched polymer.Molecular weight of product is 17,300.
Embodiment 3: the 0.1mol Tetra hydro Phthalic anhydride is dissolved in 30mL N, in the dinethylformamide, stirs adding 0.1mol three ethylidine tetramines down, at N
2Under the gas shiled, normal-temperature reaction 50h; Vacuum tightness is under the 200Pa decompression, is warming up to 150 ℃ of reaction 5h.Stopped reaction, product add 30mL N, and the 800mL ether sedimentation is used in the dinethylformamide dissolving, through suction filtration, washing, vacuum-drying, must glue the amino hyperbranched polymer of shape solid end.Molecular weight of product is 13,500.
Embodiment 4: the 0.3mol Tetra hydro Phthalic anhydride is dissolved in 40mL N, in the dinethylformamide, stirs adding 0.1mol three ethylidine tetramines down, at N
2Under the gas shiled, normal-temperature reaction 80h; Vacuum tightness is under the 100Pa decompression, is warming up to 150 ℃ of reaction 5h.Stopped reaction, product add 50mL N, and the 1000mL ether sedimentation is used in the dinethylformamide dissolving, through suction filtration, washing, vacuum-drying, get end carboxyl super branched polymer.Molecular weight of product is 20,700.
Claims (5)
1, adjustable ultrabranching polyamide of end group and preparation method thereof, it is characterized in that the preparation method is as follows: under nitrogen protection, to contain the monomer of acid anhydrides and polyamino monomer with 1/100～100/1 mol ratio, reaction 1 minute to 15 days in aprotic solvent under-50 ℃～250 ℃; The gained mixture is warming up to 20 ℃～300 ℃ then, vacuum tightness is that decompression was reacted 5 minutes to 120 hours under 8000～0.01Pa, obtains head product, through dissolving, precipitation, filtration, separation, drying, obtains subject polymer.
2, the preparation method of the adjustable ultrabranching polyamide of end group according to claim 1 is characterized in that the monomer that contains acid anhydrides comprises the ring malonic anhydride, alkyl substituted cyclopropane dicarboxylic anhydride, the ring Succinic anhydried, alkyl substituted ring Succinic anhydried, ring Pyroglutaric acid, alkyl substituted ring Pyroglutaric acid, MALEIC ANHYDRIDE, alkyl replaces MALEIC ANHYDRIDE, alkyl substituted ring adipic anhydride, the cyclohexane diacid acid anhydride, Tetra hydro Phthalic anhydride, alkyl replaces Tetra hydro Phthalic anhydride, naphthalene acid anhydride, the alkyl-substituted naphthaline acid anhydrides.Wherein these monomeric alkyl refer to C
1～C
20Substituting group.
3, the preparation method of the adjustable ultrabranching polyamide of end group according to claim 1, it is characterized in that polyamino comprises Diethylene triamine, three ethylidine tetramines, four ethylidine, five amine, five ethylidine hexamines and other polyamines polyene, triaminobenzene, tetramino benzene and other polyamino aromatic compound, polyamino heterogeneous ring compound, 4-aminomethyl-1,8-octamethylenediamine and other aminoalkyl diamine compound, three-aminoethyl amine, three-aminopropyl amine and other three-aminoalkyl amine.
4, the preparation method of the adjustable ultrabranching polyamide of end group according to claim 1, it is characterized in that aprotic solvent comprises N, dinethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), N-N-methyl-2-2-pyrrolidone N-, tetramethylene sulfone, chloroform, tetrahydrofuran (THF), ethyl acetate, tetracol phenixin.
5, ultrabranching polyamide is characterized in that the hyperbranched polymer that adopts the described preparation method of claim 1～4 to obtain.
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| CN 02145098 CN1232565C (en) | 2002-11-07 | 2002-11-07 | Terminal group-adjustable superbranched polyamide and its preparation method |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102585215A (en) * | 2012-02-02 | 2012-07-18 | 南京工业大学 | Amino-terminated aliphatic hyperbranched polymer and preparation method and application thereof |
| CN102863822A (en) * | 2012-09-24 | 2013-01-09 | 陕西科技大学 | Hyperbranched macromolecule dispersing agent for dispersing dyes and preparation method thereof |
| CN105622928A (en) * | 2014-10-28 | 2016-06-01 | 株洲时代新材料科技股份有限公司 | Branched polyamide and preparation method thereof |
| CN106146829A (en) * | 2016-07-11 | 2016-11-23 | 烟台大学 | A kind of polymer containing two or more pyrenyl groups and its production and use |
| CN108383997A (en) * | 2018-05-07 | 2018-08-10 | 扬州工业职业技术学院 | A kind of high molecular weight flame retardant, preparation method and applications |
| CN108727962A (en) * | 2018-06-27 | 2018-11-02 | 南京林业大学 | A kind of aqueous polyurethane coating and graphene oxide composite coating interface ultrabranching polyamide adhering method |
| CN108976388A (en) * | 2018-06-27 | 2018-12-11 | 南京林业大学 | A kind of carbon fiber epoxy prepreg interface ultrabranching polyamide coupling method |
-
2002
- 2002-11-07 CN CN 02145098 patent/CN1232565C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102585215A (en) * | 2012-02-02 | 2012-07-18 | 南京工业大学 | Amino-terminated aliphatic hyperbranched polymer and preparation method and application thereof |
| CN102863822A (en) * | 2012-09-24 | 2013-01-09 | 陕西科技大学 | Hyperbranched macromolecule dispersing agent for dispersing dyes and preparation method thereof |
| CN105622928A (en) * | 2014-10-28 | 2016-06-01 | 株洲时代新材料科技股份有限公司 | Branched polyamide and preparation method thereof |
| CN105622928B (en) * | 2014-10-28 | 2017-12-15 | 株洲时代新材料科技股份有限公司 | Branched polyamides and preparation method thereof |
| CN106146829A (en) * | 2016-07-11 | 2016-11-23 | 烟台大学 | A kind of polymer containing two or more pyrenyl groups and its production and use |
| CN106146829B (en) * | 2016-07-11 | 2018-01-30 | 烟台大学 | A kind of polymer containing two or more pyrenyl groups and its production and use |
| CN108383997A (en) * | 2018-05-07 | 2018-08-10 | 扬州工业职业技术学院 | A kind of high molecular weight flame retardant, preparation method and applications |
| CN108727962A (en) * | 2018-06-27 | 2018-11-02 | 南京林业大学 | A kind of aqueous polyurethane coating and graphene oxide composite coating interface ultrabranching polyamide adhering method |
| CN108976388A (en) * | 2018-06-27 | 2018-12-11 | 南京林业大学 | A kind of carbon fiber epoxy prepreg interface ultrabranching polyamide coupling method |
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| CN1232565C (en) | 2005-12-21 |
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