CN103122063B - Preparation method of poly-p-aminobenzoylamonoundecylamine - Google Patents
Preparation method of poly-p-aminobenzoylamonoundecylamine Download PDFInfo
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- CN103122063B CN103122063B CN201310045200.4A CN201310045200A CN103122063B CN 103122063 B CN103122063 B CN 103122063B CN 201310045200 A CN201310045200 A CN 201310045200A CN 103122063 B CN103122063 B CN 103122063B
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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 synthesis 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 amino undecylamine (PA11T) of poly-p-benzoyl is a kind of novel Long carbon chain semi-aromatic nylon.Usually, by nylon molecules, the nylon of carbon chain lengths more than 10 is called long carbon chain nylon.Except some general characters with general nylon, long carbon chain nylon also has the advantage of many uniquenesses, and as density is little, forming stability is good, and water-intake rate is low etc.Semi-aromatic nylon is the band diamines of aromatic nucleus or dicarboxylic acid and aliphatic dicarboxylic acid or diamines, the nylon resin be prepared from by polycondensation.Owing to having imported aromatic nucleus in nylon molecules main chain, thus improve thermotolerance and mechanical property, reduce water-intake rate, and have more suitable cost performance.And Long carbon chain semi-aromatic nylon by both advantages further combined with, the fields such as automobile, electronic apparatus, precision mechanical part, transition pipeline and travelling belt can be applied to.
In the patents such as CN1390887A, once occurred gathering paraphenylene terephthalamide's undecane diamines about PA11T() report.But the reaction monomers used is 1,11-undecane diamines.Compared with the reaction monomers of other nylon kinds, the synthesis difficulty of 1,11-undecane diamines is large, and preparation cost is high, the serious application constraining PA11T and popularization.
Summary of the invention
The present invention synthesizes the large problem of difficulty to solve existing PA11T, provides a kind of preparation method of the amino undecylamine (PA11T) of poly-p-benzoyl with good heat resistance energy, mechanical property, environmental protection.
The present invention is achieved by the following technical solutions: the preparation method of the amino undecylamine (PA11T) of poly-p-benzoyl, and its preparation process is:
(1) salify: by 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 reacts 3 hours under 120 DEG C of environment; Then 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: by PA11T salt, with distilled water or the organic solvent of PA11T salt identical weight, to be PA11T salt 0.6-1.2%(w/w) end-capping reagent, stir acquisition mixture; Described organic solvent is methyl alcohol, ethanol, N-Methyl pyrrolidone or dimethyl formamide, and described end-capping reagent is monocarboxylic acid or monoamine;
(3) Reactive Synthesis: mixture is warming up to 270-290 DEG C, is forced into 2.5-3MPa under shielding gas atmosphere, insulation (270-290 DEG C) pressurize (2.5-3MPa) 2h; 2h is down to normal pressure subsequently, is warming up to 310-330 DEG C while being down to normal pressure, insulation 2h; Finally be evacuated to-0.095MPa, insulation (310-330 DEG C) pressurize (-0.095MPa) 1h, discharging, obtained PA11T.
In addition, the step of described (3) Reactive Synthesis is: mixture is warming up to 200-220 DEG C, is forced into 1.8-2MPa under shielding gas atmosphere, insulation (200-220 DEG C) pressurize (1.8-2MPa) 4h; 1h is down to normal pressure subsequently, is warming up to 230-250 DEG C while being down to normal pressure; Finally be evacuated to-0.095MPa(negative pressure), insulation (230-250 DEG C) pressurize (-0.095MPa) 20h, discharging, obtained PA11T.Two kinds of Reactive Synthesis steps in the present invention are all feasible, all can obtain PA11T.
When aminoundecanoic acid is 20 weight part, if the weight part of para-amino benzoic acid is not equal to 14, the mol ratio of two kinds of reaction monomers can be caused unequal, thus destroy the polycondensation of nylon, cannot be polymerized.
If the weight part of distilled water is less than 150, reaction monomers solubleness is limited, is difficult to mix, is unfavorable for the carrying out of salt-forming reaction; If be greater than 150, adding of too much distilled water does not have obvious promoter action to salt-forming reaction, easily causes waste.
If the weight part of catalyzer is less than 0.2, catalyzer does not have obvious promoter action to polyreaction; If be 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 is less than the weight of PA11T salt, the mixing of reaction raw materials is not easily even, easily causes heat transfer uneven, occur local run aways phenomenon during polymerization; If be greater than the weight of PA11T salt, the forward that too much solvent (distilled water or organic solvent) hinders polyreaction carries out, and polymerization rate declines, and the molecular weight of product is difficult to improve, and local also there will be solidification phenomenon, 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 polymkeric substance there will be the bad phenomenon such as implode, affects the performance of discharging and polymkeric substance; If be greater than 1.2% of PA11T salt weight, can shift to an earlier date end-blocking, thus affect the speed of polyreaction to the reactive group of polymkeric substance, 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 the performance improving PA11T further.
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 arbitrary monocarboxylic acid or monoamine as end-capping reagent in theory, 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 purchased from Chaoyang, Weihai chemical machinery company limited.
According to the present inventor to repetition test of the present invention, finally determine 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 polymerization cost; 2) aminoundecanoic acid used comes from Viscotrol C, belongs to biological species renewable resources, has certain value of environmental protection; 3) preparation technology's continuous and compact, for further large-scale industrial production creates condition.
Embodiment
All characteristics, measure all 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 Izod notched impact trier of Chengde trier company limited, undertaken by standard method of test GB1843-2008.
4. heat-drawn wire (DEG C)
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.
5. fusing point (DEG C)
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): the limiting viscosity measuring copolymer sample in the vitriol oil of 25 DEG C, is undertaken by standard method of test GB/T 12006-2009.
embodiment 1(every part is 10 grams)
The preparation method of the amino undecylamine of poly-p-benzoyl, its preparation process is:
(1) salify: by 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 reacts 3 hours under 120 DEG C of environment; Then through suction filtration, washing, vacuum-drying, obtains PA11T salt;
(2) reinforced: by PA11T salt, with the distilled water of PA11T salt identical weight, to be PA11T salt 0.6%(w/w) acetic acid, stir acquisition mixture;
(3) Reactive Synthesis: mixture is warming up to 270 DEG C, is forced into 3MPa under helium atmosphere, heat-insulation pressure keeping 2h; 2h is down to normal pressure subsequently, is warming up to 320 DEG C while being down to normal pressure, insulation 2h; Finally be evacuated to-0.095MPa, heat-insulation pressure keeping 1h, discharging, obtained PA11T.
Described preparation process is carried out in autoclave.Described autoclave is purchased from Chaoyang, Weihai chemical machinery company limited
PA11T the performance test results is shown in table 1.
embodiment 2(every part is 20 grams)
The preparation method of the amino undecylamine of poly-p-benzoyl, its preparation process is:
(1) salify: by 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 reacts 3 hours under 120 DEG C of environment; Then through suction filtration, washing, vacuum-drying, obtains PA11T salt;
(2) reinforced: by PA11T salt, with the methyl alcohol of PA11T salt identical weight, to be PA11T salt 1.2%(w/w) butylamine, stir acquisition mixture;
(3) Reactive Synthesis: mixture is warming up to 280 DEG C, is forced into 2.5MPa under argon atmosphere, heat-insulation pressure keeping 2h; 2h is down to normal pressure subsequently, is warming up to 310 DEG C while being down to normal pressure, insulation 2h; Finally be evacuated to-0.095MPa, heat-insulation pressure keeping 1h, discharging, obtained PA11T.
PA11T the performance test results is shown in table 1.
embodiment 3(every part is 15 grams)
The preparation method of the amino undecylamine of poly-p-benzoyl, its preparation process is:
(1) salify: by 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 reacts 3 hours under 120 DEG C of environment; Then through suction filtration, washing, vacuum-drying, obtains PA11T salt;
(2) reinforced: by PA11T salt, with the ethanol of PA11T salt identical weight, to be PA11T salt 1.0%(w/w) lauric acid, stir acquisition mixture;
(3) Reactive Synthesis: mixture is warming up to 290 DEG C under nitrogen atmosphere, is forced into 2.7MPa, heat-insulation pressure keeping 2h; 2h is down to normal pressure subsequently, is warming up to 330 DEG C while being down to normal pressure, insulation 2h; Finally be evacuated to-0.095MPa, heat-insulation pressure keeping 1h, discharging, obtained PA11T.
PA11T the performance test results is shown in table 1.
embodiment 4(every part is 5 grams)
The preparation method of the amino undecylamine of poly-p-benzoyl, its preparation process is:
(1) salify: by 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 reacts 3 hours under 120 DEG C of environment; Then through suction filtration, washing, vacuum-drying, obtains PA11T salt;
(2) reinforced: by PA11T salt, with the N-Methyl pyrrolidone of PA11T salt identical weight, to be PA11T salt 0.8%(w/w) myristic acid, stir acquisition mixture;
(3) Reactive Synthesis: mixture is warming up to 210 DEG C, is forced into 1.8MPa under helium atmosphere, heat-insulation pressure keeping 4h; 1h is down to normal pressure subsequently, is warming up to 250 DEG C while being down to normal pressure; Finally be evacuated to-0.095MPa, heat-insulation pressure keeping 20h, discharging, obtained PA11T.
PA11T the performance test results is shown in table 1.
embodiment 5(every part is 40 grams)
The preparation method of the amino undecylamine of poly-p-benzoyl, its preparation process is:
(1) salify: by 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 reacts 3 hours under 120 DEG C of environment; Then through suction filtration, washing, vacuum-drying, obtains PA11T salt;
(2) reinforced: by PA11T salt, with the dimethyl formamide of PA11T salt identical weight, to be PA11T salt 0.7%(w/w) stearic acid, stir acquisition mixture;
(3) Reactive Synthesis: mixture is warming up to 200 DEG C, is forced into 2MPa under argon atmosphere, heat-insulation pressure keeping 4h; 1h is down to normal pressure subsequently, is warming up to 240 DEG C while being down to normal pressure; Finally be evacuated to-0.095MPa, heat-insulation pressure keeping 20h, discharging, obtained PA11T.
PA11T the performance test results is shown in table 1.
embodiment 6(every part is 20 grams)
The preparation method of the amino undecylamine of poly-p-benzoyl, its preparation process is:
(1) salify: by 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 reacts 3 hours under 120 DEG C of environment; Then through suction filtration, washing, vacuum-drying, obtains PA11T salt;
(2) reinforced: by PA11T salt, with the distilled water of PA11T salt identical weight, to be PA11T salt 1.1%(w/w) aniline, stir acquisition mixture;
(3) Reactive Synthesis: mixture is warming up to 220 DEG C under nitrogen atmosphere, is forced into 1.9MPa, heat-insulation pressure keeping 4h; 1h is down to normal pressure subsequently, is warming up to 230 DEG C while being down to normal pressure; Finally be evacuated to-0.095MPa, heat-insulation pressure keeping 20h, discharging, obtained PA11T.
PA11T the performance test results is shown in table 1.
Performance of copolymer test result obtained by table 1 embodiment 1 ~ 6
Claims (2)
1. the preparation method of the amino undecylamine of poly-p-benzoyl, it is characterized in that, its preparation process is:
(1) salify: by 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 reacts 3 hours under 120 DEG C of environment; Then 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: by PA11T salt, with distilled water or the organic solvent of PA11T salt identical weight, to be PA11T salt 0.6-1.2%(w/w) end-capping reagent, stir acquisition mixture; Described organic solvent is methyl alcohol, ethanol, N-Methyl pyrrolidone or dimethyl formamide, and described end-capping reagent is monocarboxylic acid or monoamine;
(3) Reactive Synthesis: mixture is warming up to 280-290 DEG C, is forced into 2.5-3MPa under shielding gas atmosphere, heat-insulation pressure keeping 2h; 2h is down to normal pressure subsequently, is warming up to 310-330 DEG C while being down to normal pressure, insulation 2h; Finally be evacuated to-0.095MPa, heat-insulation pressure keeping 1h, discharging, obtained PA11T.
2. the preparation method of the amino undecylamine of poly-p-benzoyl according to claim 1, it is characterized in that, described preparation process is carried out in autoclave.
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| CN106633042A (en) * | 2016-09-14 | 2017-05-10 | 金发科技股份有限公司 | Semi-aromatic copolyamide resin and polyamide molding composition with same |
| 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 |
| 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 |
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4438240A (en) * | 1982-05-27 | 1984-03-20 | Toray Industries, Incorporated | Polyamide elastomer |
| CN102775601A (en) * | 2012-08-03 | 2012-11-14 | 中北大学 | Preparation method of semi-aromatic polyamide-polyamide 11 copolymer |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP2035481A1 (en) * | 2006-07-05 | 2009-03-18 | E.I. Du Pont De Nemours And Company | Manufacture of polyamides |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4438240A (en) * | 1982-05-27 | 1984-03-20 | Toray Industries, Incorporated | Polyamide elastomer |
| CN102775601A (en) * | 2012-08-03 | 2012-11-14 | 中北大学 | Preparation method of semi-aromatic polyamide-polyamide 11 copolymer |
Non-Patent Citations (1)
| Title |
|---|
| 王忠强.耐高温尼龙11T可行性报告.《百度文库,http://wenku.baidu.com/link?url=oj7fo4a3rT9JiAvMPdHKNIiZtZi6rYRR48QhFwWdF8xEGXx0kLnQza8sYdQfw4Uq0cd8BIpMzKyoLdhBvVBFJ4azjs4vLlo_Z4UndlDCrBG》.2011,正文第3.1-3.2节. * |
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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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Free format text: CORRECT: INVENTOR; FROM: HU GUOSHENG LI JIE LIU YUCHEN QU ZHEN WANG JIANXIA LI YINGCHUN YANG YUNFENG ZHANG JINGTING SONG JIANGFENG WANG ZHIQIANG TO: HU GUOSHENG LIU YUCHEN QU ZHEN WANG ZHONGQIANG WANG JIANXIA LI YINGCHUN YANG YUNFENG ZHANG JINGTING |
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