CN103122063A - Preparation method of poly-p-aminobenzoylamonoundecylamine - Google Patents
Preparation method of poly-p-aminobenzoylamonoundecylamine Download PDFInfo
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- CN103122063A CN103122063A CN2013100452004A CN201310045200A CN103122063A CN 103122063 A CN103122063 A CN 103122063A CN 2013100452004 A CN2013100452004 A CN 2013100452004A CN 201310045200 A CN201310045200 A CN 201310045200A CN 103122063 A CN103122063 A CN 103122063A
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Abstract
The invention relates to the field of synthesis of high polymer materials, particularly a preparation method of poly-p-aminobenzoylamonoundecylamine, which comprises the following steps: (1) salification: uniformly stirring 20 parts by weight of aminoundecanoic acid, 14 parts by weight of p-aminobenzoic acid, 150 parts by weight of distilled water and 0.2 part by weight of catalyst, reacting at 120 DEG C for 3 hours, carrying out vacuum filtration, washing, and carrying out vacuum drying to obtain PA11T salt; (2) feeding: stirring uniformly the PA11T salt, distilled water or organic solvent with the same weight as the PA11T salt, and a blocking agent accounting for 0.6-1.2% (w/w) of the PA11T salt to obtain a mixture; and (3) reaction synthesis: heating the mixture to 270-290 DEG C in a protective gas atmosphere, pressurizing to 2.5-3 MPa, keeping the temperature and pressure for 2 hours, reducing to atmospheric pressure within 2 hours while heating to 310-330 DEG C, keeping the temperature for 2 hours, vacuumizing to -0.095 MPa, keeping the temperature and pressure for 1 hour, and discharging, thereby obtaining the PA11T.
Description
Technical field
The present invention relates to the synthetic field of macromolecular material, specifically the preparation method of the amino undecylamine of a kind of poly-p-benzoyl.
Background technology
Along with the development of science and technology and the continuous expansion of the market requirement, nylon has become very important engineering plastics kind.The poly-amino undecylamine of p-benzoyl (PA11T) is a kind of novel long carbochain semi-aromatic nylon.Usually, in the nylon molecule, carbon chain lengths is called long carbon chain nylon at the nylon more than 10.Except the some general characters with general nylon, long carbon chain nylon also has advantages of many uniquenesses, and is as little in density, and forming stability is good, and water-intake rate is low etc.Semi-aromatic nylon is with the diamines of aromatic nucleus or dicarboxylic acid and aliphatic dicarboxylic acid or diamines, the nylon resin that is prepared from by polycondensation.Owing to having imported aromatic nucleus in the nylon molecular backbone chain, thereby improved thermotolerance and mechanical property, reduced water-intake rate, and more suitable cost performance is arranged.And long carbochain semi-aromatic nylon with both advantage further combined with, can be applied to the fields such as automobile, electronic apparatus, precision mechanical part, transition pipeline and travelling belt.
In the patents such as CN1390887A, poly-paraphenylene terephthalamide's undecane diamines about PA11T(once appearred) report.But the reaction monomers of using is 1,11-undecane diamines.Compare with the reaction monomers of other nylon kinds, the synthetic difficulty of 1,11-undecane diamines is large, and preparation cost is high, serious restriction application and the popularization of PA11T.
Summary of the invention
The present invention provides a kind of preparation method with amino undecylamine of poly-p-benzoyl (PA11T) of good heat resistance energy, mechanical property, environmental protection in order to solve the synthetic large problem of difficulty of existing PA11T.
The present invention is achieved by the following technical solutions: the preparation method of the poly-amino undecylamine of p-benzoyl (PA11T), and its preparation process is:
(1) salify: with the aminoundecanoic acid of 20 weight parts, the para-amino benzoic acid of 14 weight parts, the distilled water of 150 weight parts, the catalyzer of 0.2 weight part stirs, and under 120 ℃ of environment, reaction is 3 hours; Then pass through suction filtration, washing, vacuum-drying obtains PA11T salt; Described catalyzer is phosphoric acid, phosphorous acid, ortho phosphorous acid or their salt compounds;
(2) reinforced: as with PA11T salt, with distilled water or the organic solvent of the identical weight of PA11T salt, to be PA11T salt 0.6-1.2%(w/w) end-capping reagent, the acquisition mixture stirs; Described organic solvent is methyl alcohol, ethanol, N-Methyl pyrrolidone or dimethyl formamide, and described end-capping reagent is monocarboxylic acid or monoamine;
(3) reaction is synthetic: mixture is warming up to 270-290 ℃, is forced into 2.5-3MPa under the shielding gas atmosphere, insulation (270-290 ℃) pressurize (2.5-3MPa) 2h; 2h is down to normal pressure subsequently, is warming up to 310-330 ℃ when being down to normal pressure, insulation 2h; Be evacuated at last-0.095MPa, (0.095MPa) 1h, discharging makes PA11T in insulation (310-330 ℃) pressurize.
In addition, the synthetic step of described (3) reaction is: mixture is warming up to 200-220 ℃, is forced into 1.8-2MPa under the shielding gas atmosphere, insulation (200-220 ℃) pressurize (1.8-2MPa) 4h; 1h is down to normal pressure subsequently, is warming up to 230-250 ℃ when being down to normal pressure; Be evacuated at last-the 0.095MPa(negative pressure), (0.095MPa) 20h, discharging makes PA11T in insulation (230-250 ℃) pressurize.Two kinds of reaction synthesis steps in the present invention are all feasible, all can make PA11T.
When aminoundecanoic acid is 20 weight part, if the weight part of para-amino benzoic acid is not equal to 14, can cause mole proportioning of two kinds of reaction monomers unequal, thereby destroy the polycondensation of nylon, can't carry out polymerization.
If the weight part of distilled water is less than 150, reaction monomers solubleness is limited, is difficult to mix, and is unfavorable for the carrying out of salt-forming reaction; If greater than 150, too much adding of distilled water salt-forming reaction is not had obvious promoter action, easily cause waste.
If the weight part of catalyzer is less than 0.2, catalyzer does not have obvious promoter action to polyreaction; If greater than 0.2, the catalytic effect of catalyzer levels off to a maximum value, and excessive use can cause the waste of catalyzer.
In addition step, if the weight of distilled water or organic solvent less than the weight of PA11T salt, the mixing of reaction raw materials is difficult for evenly, easily causes during polymerization to conduct heat inhomogeneously, local temperature runaway phenomenon occurs; If greater than the weight of PA11T salt, the forward that too much solvent (distilled water or organic solvent) has hindered polyreaction carries out, and polymerization rate descends, and the molecular weight of product is difficult to improve, and phenomenon also can appear solidifying in the part, affects the performance of polymkeric substance.
If the weight of end-capping reagent is less than 0.6% of PA11T salt weight, polymerization velocity is not easy to control, and the bad phenomenon such as implode can appear in polymkeric substance, affect the performance of discharging and polymkeric substance; If greater than 1.2% of PA11T salt weight, can shift to an earlier date end-blocking to the reactive group of polymkeric substance, thereby affect the speed of polyreaction, molecular weight is difficult to improve.
Organic solvent of the present invention is methyl alcohol, ethanol, N-Methyl pyrrolidone or dimethyl formamide.Above-mentioned organic solvent is conducive to further improve the performance of PA11T.
Described catalyzer is phosphoric acid, phosphorous acid, ortho phosphorous acid or their salt compounds.Above-mentioned catalyzer is conducive to the carrying out of polyreaction.
End-capping reagent described in the present invention is monocarboxylic acid or monoamine.Adopt in theory arbitrarily monocarboxylic acid or monoamine as end-capping reagent all can, but the common monocarboxylic acid in laboratory has acetic acid, lauric acid, stearic acid and myristic acid, common monoamine has aniline and butylamine.Above-mentioned common monocarboxylic acid and monoamine as end-capping reagent cost of the present invention rationally, draw materials easily, and be conducive to the control of polyreaction.
Further, described preparation process is carried out in autoclave.Described autoclave is available from Chaoyang, Weihai chemical machinery company limited.
According to the inventor to repetition test of the present invention, finally determined preparation method of the present invention, polymkeric substance of the present invention has following beneficial effect: 1) use para-amino benzoic acid and aminoundecanoic acid as reaction monomers, replace 1,11-undecane diamines effectively reduces the polymerization cost; 2) aminoundecanoic acid used comes from Viscotrol C, belongs to the biological species renewable resources, has certain value of environmental protection; 3) preparation technology's continuous and compact is for further large-scale industrial production has been created condition.
Embodiment
All characteristics, all measure by the following method in an embodiment.
1. tensile strength (MPa) and elongation at break (%)
Adopt the CMT6104 type microcomputer controlled electronic universal tester of Shenzhen Sans Material Detection Co., Ltd, undertaken by standard method of test GB/T 1040-2006.
2. flexural strength (MPa) and modulus in flexure (MPa)
Adopt the CMT6104 type microcomputer controlled electronic universal tester of Shenzhen Sans Material Detection Co., Ltd, undertaken by standard method of test GB/T 9341-2000.
3. notched Izod impact strength (KJ/m
2) and unnotched impact strength (KJ/m
2)
Adopt the XJU-22 type socle girder test with notched test piece machine of Chengde trier company limited, undertaken by standard method of test GB1843-2008.
Heat-drawn wire (℃)
Adopt the XRW-300M type thermal distortion vicat softening point temperature determinator of Chengde Jinjian Testing Instrument Co., Ltd., undertaken by standard method of test GB/T 1634-2004.
Fusing point (℃)
Adopt the DSC822e type differential scanning calorimeter of METTLER company, undertaken by standard method of test GB/T 19466-2004.
6. limiting viscosity (dl/g): measure the limiting viscosity of copolymer sample in the vitriol oil of 25 ℃, undertaken by standard method of test GB/T 12006-2009.
Every part of embodiment 1(is 10 grams)
The preparation method of the amino undecylamine of poly-p-benzoyl, its preparation process is:
(1) salify: with the aminoundecanoic acid of 200 grams, the para-amino benzoic acid of 140 grams, the distilled water of 1500 grams, the phosphoric acid of 2 grams stirs, and under 120 ℃ of environment, reaction is 3 hours; Then pass through suction filtration, washing, vacuum-drying obtains PA11T salt;
(2) reinforced: as with PA11T salt, with the distilled water of the identical weight of PA11T salt, to be PA11T salt 0.6%(w/w) acetic acid, the acquisition mixture stirs;
(3) reaction is synthetic: mixture is warming up to 270 ℃, is forced into 3MPa, heat-insulation pressure keeping 2h under the helium atmosphere; 2h is down to normal pressure subsequently, is warming up to 320 ℃ when being down to normal pressure, insulation 2h; Be evacuated at last-0.095MPa, heat-insulation pressure keeping 1h, discharging makes PA11T.
Described preparation process is carried out in autoclave.Described autoclave is available from Chaoyang, Weihai chemical machinery company limited
The PA11T the performance test results is shown in table 1.
Every part of embodiment 2(is 20 grams)
The preparation method of the amino undecylamine of poly-p-benzoyl, its preparation process is:
(1) salify: with the aminoundecanoic acid of 400 grams, the para-amino benzoic acid of 280 grams, the distilled water of 3000 grams, the sodium phosphate of 4 grams stirs, and under 120 ℃ of environment, reaction is 3 hours; Then pass through suction filtration, washing, vacuum-drying obtains PA11T salt;
(2) reinforced: as with PA11T salt, with the methyl alcohol of the identical weight of PA11T salt, to be PA11T salt 1.2%(w/w) butylamine, the acquisition mixture stirs;
(3) reaction is synthetic: mixture is warming up to 280 ℃, is forced into 2.5MPa, heat-insulation pressure keeping 2h under argon atmosphere; 2h is down to normal pressure subsequently, is warming up to 310 ℃ when being down to normal pressure, insulation 2h; Be evacuated at last-0.095MPa, heat-insulation pressure keeping 1h, discharging makes PA11T.
The PA11T the performance test results is shown in table 1.
Every part of embodiment 3(is 15 grams)
The preparation method of the amino undecylamine of poly-p-benzoyl, its preparation process is:
(1) salify: with the aminoundecanoic acid of 300 grams, the para-amino benzoic acid of 210 grams, the distilled water of 2250 grams, the phosphorous acid of 3 grams stirs, and under 120 ℃ of environment, reaction is 3 hours; Then pass through suction filtration, washing, vacuum-drying obtains PA11T salt;
(2) reinforced: as with PA11T salt, with the ethanol of the identical weight of PA11T salt, to be PA11T salt 1.0%(w/w) lauric acid, the acquisition mixture stirs;
(3) reaction is synthetic: mixture is warming up to 290 ℃, is forced into 2.7MPa, heat-insulation pressure keeping 2h under nitrogen atmosphere; 2h is down to normal pressure subsequently, is warming up to 330 ℃ when being down to normal pressure, insulation 2h; Be evacuated at last-0.095MPa, heat-insulation pressure keeping 1h, discharging makes PA11T.
The PA11T the performance test results is shown in table 1.
Every part of embodiment 4(is 5 grams)
The preparation method of the amino undecylamine of poly-p-benzoyl, its preparation process is:
(1) salify: with the aminoundecanoic acid of 100 grams, the para-amino benzoic acid of 70 grams, the distilled water of 750 grams, the ortho phosphorous acid of 1 gram stirs, and under 120 ℃ of environment, reaction is 3 hours; Then pass through suction filtration, washing, vacuum-drying obtains PA11T salt;
(2) reinforced: as with PA11T salt, with the N-Methyl pyrrolidone of the identical weight of PA11T salt, to be PA11T salt 0.8%(w/w) myristic acid, the acquisition mixture stirs;
(3) reaction is synthetic: mixture is warming up to 210 ℃, is forced into 1.8MPa, heat-insulation pressure keeping 4h under the helium atmosphere; 1h is down to normal pressure subsequently, is warming up to 250 ℃ when being down to normal pressure; Be evacuated at last-0.095MPa, heat-insulation pressure keeping 20h, discharging makes PA11T.
The PA11T the performance test results is shown in table 1.
Every part of embodiment 5(is 40 grams)
The preparation method of the amino undecylamine of poly-p-benzoyl, its preparation process is:
(1) salify: with the aminoundecanoic acid of 800 grams, the para-amino benzoic acid of 560 grams, the distilled water of 6000 grams, the inferior sodium phosphate of 8 grams stirs, and under 120 ℃ of environment, reaction is 3 hours; Then pass through suction filtration, washing, vacuum-drying obtains PA11T salt;
(2) reinforced: as with PA11T salt, with the dimethyl formamide of the identical weight of PA11T salt, to be PA11T salt 0.7%(w/w) stearic acid, the acquisition mixture stirs;
(3) reaction is synthetic: mixture is warming up to 200 ℃, is forced into 2MPa, heat-insulation pressure keeping 4h under argon atmosphere; 1h is down to normal pressure subsequently, is warming up to 240 ℃ when being down to normal pressure; Be evacuated at last-0.095MPa, heat-insulation pressure keeping 20h, discharging makes PA11T.
The PA11T the performance test results is shown in table 1.
Every part of embodiment 6(is 20 grams)
The preparation method of the amino undecylamine of poly-p-benzoyl, its preparation process is:
(1) salify: with the aminoundecanoic acid of 400 grams, the para-amino benzoic acid of 280 grams, the distilled water of 3000 grams, the sodium hypophosphite of 4 grams stirs, and under 120 ℃ of environment, reaction is 3 hours; Then pass through suction filtration, washing, vacuum-drying obtains PA11T salt;
(2) reinforced: as with PA11T salt, with the distilled water of the identical weight of PA11T salt, to be PA11T salt 1.1%(w/w) aniline, the acquisition mixture stirs;
(3) reaction is synthetic: mixture is warming up to 220 ℃, is forced into 1.9MPa, heat-insulation pressure keeping 4h under nitrogen atmosphere; 1h is down to normal pressure subsequently, is warming up to 230 ℃ when being down to normal pressure; Be evacuated at last-0.095MPa, heat-insulation pressure keeping 20h, discharging makes PA11T.
The PA11T the performance test results is shown in table 1.
The prepared performance of copolymer test result of table 1 embodiment 1 ~ 6
Claims (3)
1. the preparation method of the amino undecylamine of poly-p-benzoyl, is characterized in that, its preparation process is:
(1) salify: with the aminoundecanoic acid of 20 weight parts, the para-amino benzoic acid of 14 weight parts, the distilled water of 150 weight parts, the catalyzer of 0.2 weight part stirs, and under 120 ℃ of environment, reaction is 3 hours; Then pass through suction filtration, washing, vacuum-drying obtains PA11T salt; Described catalyzer is phosphoric acid, phosphorous acid, ortho phosphorous acid or their salt compounds;
(2) reinforced: as with PA11T salt, with distilled water or the organic solvent of the identical weight of PA11T salt, to be PA11T salt 0.6-1.2%(w/w) end-capping reagent, the acquisition mixture stirs; Described organic solvent is methyl alcohol, ethanol, N-Methyl pyrrolidone or dimethyl formamide, and described end-capping reagent is monocarboxylic acid or monoamine;
(3) reaction is synthetic: mixture is warming up to 270-290 ℃, is forced into 2.5-3MPa, heat-insulation pressure keeping 2h under the shielding gas atmosphere; 2h is down to normal pressure subsequently, is warming up to 310-330 ℃ when being down to normal pressure, insulation 2h; Be evacuated at last-0.095MPa, heat-insulation pressure keeping 1h, discharging makes PA11T.
2. the preparation method of the amino undecylamine of poly-p-benzoyl according to claim 1, it is characterized in that, the synthetic step of described (3) reaction is: mixture is warming up to 200-220 ℃, is forced into 1.8-2MPa, heat-insulation pressure keeping 4h under the shielding gas atmosphere; 1h is down to normal pressure subsequently, is warming up to 230-250 ℃ when being down to normal pressure; Be evacuated at last-0.095MPa, heat-insulation pressure keeping 20h, discharging makes PA11T.
3. the preparation method of the amino undecylamine of poly-p-benzoyl according to claim 1 and 2, is characterized in that, described preparation process is carried out in autoclave.
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| CN106336508A (en) * | 2016-09-14 | 2017-01-18 | 金发科技股份有限公司 | Semi-aromatic copolyamide resin and polyamide model composition comprising same |
| WO2018049808A1 (en) * | 2016-09-14 | 2018-03-22 | 金发科技股份有限公司 | Semi-aromatic copolyamide resin and polyamide molding composition consisting of semi-aromatic copolyamide resin |
| CN114749210A (en) * | 2022-04-22 | 2022-07-15 | 济宁学院 | Preparation method and application of catalyst of room-temperature-terminated 107 glue |
| CN114917856A (en) * | 2022-05-31 | 2022-08-19 | 中国五环工程有限公司 | Process system and method for preparing nylon 11 by polymerizing 11-aminoundecanoic acid |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106336508A (en) * | 2016-09-14 | 2017-01-18 | 金发科技股份有限公司 | Semi-aromatic copolyamide resin and polyamide model composition comprising same |
| WO2018049807A1 (en) | 2016-09-14 | 2018-03-22 | 金发科技股份有限公司 | Semi-aromatic copolyamide resin and polyamide molding composition consisting of semi-aromatic copolyamide resin |
| WO2018049808A1 (en) * | 2016-09-14 | 2018-03-22 | 金发科技股份有限公司 | Semi-aromatic copolyamide resin and polyamide molding composition consisting of semi-aromatic copolyamide resin |
| CN106336508B (en) * | 2016-09-14 | 2018-05-18 | 金发科技股份有限公司 | A kind of semi-aromatic copolyamide resin and the polyamide moulding composition being made from it |
| JP2018530626A (en) * | 2016-09-14 | 2018-10-18 | 金発科技股▲ふん▼有限公司 | Semi-aromatic copolyamide resin and polyamide molding composition produced therewith |
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| CN114749210A (en) * | 2022-04-22 | 2022-07-15 | 济宁学院 | Preparation method and application of catalyst of room-temperature-terminated 107 glue |
| CN114749210B (en) * | 2022-04-22 | 2023-05-30 | 济宁学院 | Preparation method and application of catalyst of room temperature end-capped 107 glue |
| CN114917856A (en) * | 2022-05-31 | 2022-08-19 | 中国五环工程有限公司 | Process system and method for preparing nylon 11 by polymerizing 11-aminoundecanoic acid |
| CN114917856B (en) * | 2022-05-31 | 2023-12-19 | 中国五环工程有限公司 | Process system and method for preparing nylon 11 by polymerizing 11-aminoundecanoic acid |
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Inventor after: Hu Guosheng Inventor after: Liu Yuchen Inventor after: Qu Zhen Inventor after: Wang Zhongqiang Inventor after: Wang Jianxia Inventor after: Li Yingchun Inventor after: Yang Yunfeng Inventor after: Zhang Jingting Inventor before: Hu Guosheng Inventor before: Wang Zhiqiang Inventor before: Li Jie Inventor before: Liu Yuchen Inventor before: Qu Zhen Inventor before: Wang Jianxia Inventor before: Li Yingchun Inventor before: Yang Yunfeng Inventor before: Zhang Jingting Inventor before: Song Jiangfeng |
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