CN1232567C - End-amino water-soluble ultrabranching polyamide and preparation process thereof - Google Patents
End-amino water-soluble ultrabranching polyamide and preparation process thereof Download PDFInfo
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- CN1232567C CN1232567C CN 02111578 CN02111578A CN1232567C CN 1232567 C CN1232567 C CN 1232567C CN 02111578 CN02111578 CN 02111578 CN 02111578 A CN02111578 A CN 02111578A CN 1232567 C CN1232567 C CN 1232567C
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Abstract
The present invention discloses terminal-amino group water-soluble super-branched polyamide and a preparation method thereof. The preparation method of the terminal-amino group water-soluble super-branched polyamide is as follows: step (a): a monomer AB containing double bonds (which is named groups A in the present invention), carboxyl groups or ester groups (which are named groups B in the present invention), and a monomer (which is named a multiamido monomer in the present invention, and is shorted for a C type monomer, wherein n is greater then or equal to 2) containing two or more than two amino groups directly react, a used solvent is an aprotic solvent; reaction temperature is from-50 DEG C to 100 DEG C, and reaction time is from one minute to 15 days; step (b): mixtures obtained from step (a) are heated to 50 DEG C to 280 DEG C, and continuously react for 5 minutes to 10 days under the condition of pressure reduction, and the super-branched polyamide is prepared. An obtained polymer contains a lot of terminal amino groups or terminal carboxyl groups, can be dissolved in water and an organic solvent, and can be degraded. The super-branched polyamide is suitable for being used as a high efficient paint, a crosslinking agent, a biological medicine carrier, basal bodies of an immobilized enzyme and protein, an antioxidant, a disinfectant, a surfactant, a rheologic processing additive, a precursor of a functional material, etc. The super-branched polyamide has wide application prospects.
Description
Technical field:
The present invention relates to ultrabranching polyamide, particularly end-amino water-soluble ultrabranching polyamide and preparation method thereof.
Background technology:
Hyperbranched polymer is the new polymers of the highly branched 3 D stereo structure of a class, has low viscosity, high resolution, and 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, photoelectric materials.
Hyperbranched polymer is generally by AB
n(n 〉=2) type monomer polycondensation forms (Yang, G.; Jikei, M.; Kakimoto, M.Macromolecules, Vol.31,5964 (1998)).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.
Summary of the invention:
The objective of the invention is to by molecular designing, utilize the differential responses activity between different functional groups, with commercial monomer and the polyamino monomer direct reaction that contains two keys and carboxyl or ester group, synthetic hyperbranched polymer with wide application prospect.So just can reduce synthesis step, simplify production technique, thereby reduce cost greatly, satisfy the needs of scale operation.
Content of the present invention is to be raw material with the commercial monomer that contains two keys and carboxyl or ester group with containing two or more amino monomers, has synthesized a series of end-amino water-soluble ultrabranching polyamides.
Concrete synthetic method of the present invention is: the first step, and the monomer that will contain two keys and carboxyl or ester group and polyamino monomer reacted 1 hour to 10 days under-50～100 ℃ temperature with 1/100～100/1 mol ratio; Second step was warming up to 50～280 ℃ with the first step gained mixture, and decompression continues down reaction 30 minutes to 5 days, precipitated in precipitation agent, after filtration, separation, drying, obtained subject polymer.
The monomer that contains two keys and carboxyl or ester group that the present invention adopts is to contain two keys and the compound of carboxyl or ester group or their mixture, methyl acrylate (MA) particularly, ethyl propenoate (EA), methyl methacrylate (MMA), Jia Jibingxisuanyizhi (MEA), vinylformic acid (AA), methacrylic acid (MAA), and their homologue, derivative and isomer.
The polyamino monomer that the present invention adopts is to contain two or more amino compounds or their mixture, quadrol particularly, diethylenetriamine, Triethylenetetramine (TETA), tetren, penten and other polyamines polyene, Ursol D, triaminobenzene and other polyamino aromatic compound, diamino heterogeneous ring compound, triamino heterogeneous ring compound and other polyamino heterogeneous ring compound, and their homologue, derivative and isomer.
The present invention's dimethyl sulfoxide (DMSO), N, dinethylformamide, N, aprotic solvent such as N-N,N-DIMETHYLACETAMIDE, N-N-methyl-2-2-pyrrolidone N-, tetramethylene sulfone, chloroform, tetrahydrofuran (THF), ethyl acetate, methyl alcohol, ethanol, tetracol phenixin or the mixed solvent that contains these aprotic solvent are reaction medium, perhaps need not any solvent.
The present invention is a catalyzer with hydrochloric acid, toluene sulfonic acide, sulfuric acid, butyl (tetra) titanate, lauric acid butyl tin, sodium alkoxide, potassium alcoholate, sodium amide, potassium amide, butyllithium, zinc acetate perhaps without catalyzer.
The present invention's acetone, ether, perhaps their mixture is as precipitation agent.
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 end-amino water-soluble ultrabranching polyamide produced according to the present invention, raw material sources are extensive, and cost of material is cheap, simple synthetic method, technology is simple, and controllability is good, and the product solvability is good, and preparation cost is low.Resulting polymers contains a large amount of end amino, water soluble and organic solvent, degradable, suit to do efficient coating, linking agent, biological medicine carrier, immobilized enzyme and proteinic matrix, antioxidant, sterilant, tensio-active agent, rheology processing additives, functional materials precursor etc., have a wide range of applications.
Embodiment:
The following examples are to further specify of the present invention, rather than limit the scope of the invention.Embodiment 1: the 0.1mol methyl acrylate is dissolved in the 20mL methyl alcohol, stirs adding 0.1mol Diethylene triamine down, with the sealing of turned welt soft rubber ball, fill N
25-10min.React 80h at normal temperatures, decompression is warming up to 150 ℃ of reaction 5h down.Stopped reaction is used the 500mL ether sedimentation, through suction filtration, washing, vacuum-drying, gets faint yellow sticking shape solid.Molecular weight of product is 15,300.
Embodiment 2: the 0.1mol methyl acrylate is dissolved in the 20mL methyl alcohol, adds 0.1mol four ethylidine five amine under stirring, with the sealing of turned welt soft rubber ball, react 100h down in normal temperature, be warming up to 145 ℃ of reaction 5h under the decompression.Use the 500mL ether sedimentation,, get faint yellow sticking shape solid through suction filtration, washing, vacuum-drying.Molecular weight of product is 21,500.
Claims (7)
1. the preparation method of end-amino water-soluble ultrabranching polyamide, it is characterized in that reacting by following two steps and undertaken: the first step, the monomer that will contain two keys and carboxyl or ester group and polyamino monomer reacted 1 hour to 10 days under-50～100 ℃ temperature with 1/100～100/1 mol ratio; Second step was warming up to 50～280 ℃ with the first step gained mixture, and decompression continues down reaction 30 minutes to 5 days, precipitated in precipitation agent, after filtration, separation, drying, obtained subject polymer.
2. the preparation method of end-amino water-soluble ultrabranching polyamide according to claim 1, it is characterized in that the used monomer that contains two keys and carboxyl or ester group is to contain two keys and the compound of carboxyl or ester group or their mixture, comprising methyl acrylate, ethyl propenoate, methyl methacrylate, Jia Jibingxisuanyizhi, acrylic or methacrylic acid.
3. the preparation method of end-amino water-soluble ultrabranching polyamide according to claim 1, it is characterized in that used polyamino monomer is to contain two or more amino compounds or their mixture, comprising quadrol, diethylenetriamine, Triethylenetetramine (TETA), tetren, penten and other polyamines polyene, Ursol D, triaminobenzene and other polyamino aromatic compound, diamino heterogeneous ring compound, triamino heterogeneous ring compound or polyamino heterogeneous ring compound.
4. the preparation method of end-amino water-soluble ultrabranching polyamide according to claim 1, it is characterized in that with dimethyl sulfoxide (DMSO), N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, N-N-methyl-2-2-pyrrolidone N-, tetramethylene sulfone, chloroform, tetrahydrofuran (THF), ethyl acetate, methyl alcohol, ethanol or tetracol phenixin aprotic solvent or the mixed solvent that contains these aprotic solvent are reaction medium, perhaps need not any solvent.
5. the preparation method of end-amino water-soluble ultrabranching polyamide according to claim 1, it is characterized in that without catalyzer, is catalyzer with hydrochloric acid, toluene sulfonic acide, sulfuric acid, butyl (tetra) titanate, lauric acid butyl tin, sodium alkoxide, potassium alcoholate, sodium amide, potassium amide, butyllithium or zinc acetate perhaps.
6. the preparation method of end-amino water-soluble ultrabranching polyamide according to claim 1 is characterized in that perhaps their mixture is as precipitation agent with acetone or ether.
7. end-amino water-soluble ultrabranching polyamide, it is characterized in that the end-amino water-soluble ultrabranching polyamide that adopts the described preparation method of claim 1～6 to be obtained, polymkeric substance contains amido bond and a large amount of amino, has branching unit, linear unit and terminal units that typical hyperbranched polymer has.
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| CN 02111578 CN1232567C (en) | 2002-04-30 | 2002-04-30 | End-amino water-soluble ultrabranching polyamide and preparation process thereof |
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| CN 02111578 CN1232567C (en) | 2002-04-30 | 2002-04-30 | End-amino water-soluble ultrabranching polyamide and preparation process thereof |
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| CN1232567C true CN1232567C (en) | 2005-12-21 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102712761A (en) * | 2009-12-21 | 2012-10-03 | 帝斯曼知识产权资产管理有限公司 | Polymer, process and composition |
| CN114395078A (en) * | 2021-12-27 | 2022-04-26 | 宁波捷傲创益新材料有限公司 | Humidity control material and preparation method thereof |
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2002
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102712761A (en) * | 2009-12-21 | 2012-10-03 | 帝斯曼知识产权资产管理有限公司 | Polymer, process and composition |
| CN102712761B (en) * | 2009-12-21 | 2014-09-24 | 帝斯曼知识产权资产管理有限公司 | Polymer, process and composition |
| CN114395078A (en) * | 2021-12-27 | 2022-04-26 | 宁波捷傲创益新材料有限公司 | Humidity control material and preparation method thereof |
| CN114395078B (en) * | 2021-12-27 | 2024-01-23 | 宁波捷傲创益新材料有限公司 | Humidity control material and preparation method thereof |
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