CN103122065A - Preparation method of transparent polyamide-polyamide 11 copolymer - Google Patents
Preparation method of transparent polyamide-polyamide 11 copolymer Download PDFInfo
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- CN103122065A CN103122065A CN201310045111XA CN201310045111A CN103122065A CN 103122065 A CN103122065 A CN 103122065A CN 201310045111X A CN201310045111X A CN 201310045111XA CN 201310045111 A CN201310045111 A CN 201310045111A CN 103122065 A CN103122065 A CN 103122065A
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Abstract
The invention relates to the field of copolymers of high polymer materials, particularly a preparation method of a transparent polyamide-polyamide 11 copolymer, which comprises the following steps: (1) feeding: uniformly stirring 50-100 parts by weight of transparent polyamide salt, 10-50 parts by weight of aminoundecanoic acid, 5-40 parts by weight of distilled water or organic solvent, 0.02-2 parts by weight of catalyst, 0.2-5 parts by weight of blocking agent and 0.1-1 part by weight of nucleating agent to obtain a mixture; and (2) reaction synthesis: heating the mixture to 220-250 DEG C in a protective gas atmosphere, pressurizing to 1.6-3.5 MPa, keeping the temperature and pressure for 1-4 hours, reducing to atmospheric pressure within 1-4 hours while heating to 260-300 DEG C, keeping the temperature for 2-4 hours, and discharging, thereby obtaining the transparent polyamide-polyamide 11 copolymer.
Description
Technical field
The present invention relates to the copolymer field of macromolecular material, specifically a kind of preparation method of transparent polyamide-polymeric amide 11 multipolymers.
Background technology
Polyamide resin (PA) has good over-all properties, comprise mechanical property, thermotolerance, wearability, chemical proofing and self lubricity, and frictional coefficient is low, certain flame retardant resistance is arranged, be easy to processing, be suitable for improving performance and broadened application scope with glass fibre and other filler filling enhancing modified, domestic and international application engineering plastics the most widely, first of row five large-engineering plastics.Wherein, polymeric amide 11 (PA11) is a kind of white transparent solid, relative density is 1.04, compares with other nylon, and its feature is that melt temperature is low, processing temperature is high, good stability of the dimension, water-absorbent is low, low-temperature performance good, can keep good flexibilities at-40 ℃～120 ℃.Its odd numbers of carbon atoms makes amide group be positioned at the same side, make polymeric amide 11 no matter parallel or antiparallel all can be completed into intermolecular hydrogen bonding, have the crystalline structure different from other nylon, higher shock strength, good stress cracking resistance.When removing external force, PA11 can return to original shape, and embeds metal parts and not easy to crack, and shock resistance and oil resistant solvent resistance with excellence can satisfy the injection of various melt viscosity scopes and extrude processing.
Summary of the invention
The present invention aims to provide a kind of good mechanical property that has, the preparation method of transparent polyamide-polymeric amide 11 multipolymers transparent, environmental protection.
The present invention is achieved by the following technical solutions: the preparation method of transparent polyamide-polymeric amide 11 multipolymers, and its preparation process is:
(1) reinforced: with the transparent polyamide salt of 50 ~ 100 weight parts, the aminoundecanoic acid of 10 ~ 50 weight parts, the distilled water of 5 ~ 40 weight parts or organic solvent, 0.02 the catalyzer of ~ 2 weight parts, 0.2 the end-capping reagent of ~ 5 weight parts, the nucleator of 0.1 ~ 1 weight part, the acquisition mixture stirs; Described transparent polyamide salt is the wherein mixture of one or more salt arbitrary proportions in T/TMD salt, I/TMD salt, T/DMDC salt, I/DMDC salt; Described organic solvent is methyl alcohol, ethanol, N-Methyl pyrrolidone or dimethyl formamide; Described catalyzer is phosphoric acid, phosphorous acid, Hypophosporous Acid, 50 or their salt compounds; Described end-capping reagent is monocarboxylic acid or monoamine; Described nucleator is saturated carboxylic acid sodium, calcium salt CAV102, NAV101, SURLYN8920, SURLYN 9020;
(2) reaction is synthetic: mixture is warming up to 220 ~ 250 ℃, is forced into 1.6 ~ 3.5MPa under the shielding gas atmosphere, insulation (220 ~ 250 ℃) pressurize (1.6 ~ 3.5MPa) 1 ~ 4h; 1 ~ 4h is down to normal pressure subsequently, is warming up to 260 ~ 300 ℃ when being down to normal pressure, insulation (260 ~ 300 ℃) 2 ~ 4h, and discharging makes transparent polyamide-polymeric amide 11 multipolymers.
When transparent polyamide salt is 50 ~ 100 weight parts, when aminoundecanoic acid is 10 ~ 50 weight part, if the weight part of aminoundecanoic acid is during less than 10 parts, the mixing of reaction raw materials is difficult for evenly, easily cause the loss of diamines during polymerization, if during greater than 50 parts, polymerization rate descends, and polymerization reaction time increases;
If the weight part of distilled water or organic solvent less than 5 o'clock, is unfavorable for the thermally equivalent that reacts and promotes the interior high pressure of reactor, if greater than 40 o'clock, cause bleeding off pressure overlong time and waste solvent;
If the weight part of catalyzer is during less than 0.02 part, the effect that catalyzer plays is not obvious, if during greater than 2 parts, the catalytic effect of catalyzer levels off to a maximum value, and excessive use easily causes the waste of catalyzer;
If the weight part of end-capping reagent was less than 0.2 o'clock, polymerization velocity is too fast, easily causes copolymerization product the bad phenomenon such as implode to occur, if greater than 5 o'clock, the activity of reactive functionality is impacted, and polymerization rate reduces;
If the weight part of nucleator did not have nucleating effect lower than 0.1 o'clock, do not improve higher than 1 o'clock its crystallite promoter action, may damage on the contrary the performance of goods, also increased production cost from practical application.
Further, described transparent polyamide salt is the wherein mixture of one or more salt arbitrary proportions in T/TMD salt, I/TMD salt, T/DMDC salt, I/DMDC salt.Adopt the transparency and the mechanical property of the multipolymer that above-mentioned transparent polyamide salt makes excellent.
The english abbreviation note that table 1 the present invention occurs
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 Properties of the copolymers.
Described catalyzer is phosphoric acid, phosphorous acid, Hypophosporous Acid, 50 or their salt compounds.Above-mentioned catalyzer is conducive to the carrying out of copolyreaction.
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 carrying out of copolyreaction.
Described nucleator is saturated carboxylic acid sodium, calcium salt CAV102, NAV101, SURLYN8920, SURLYN 9020.Above-mentioned nucleator is conducive to increase nucleus quantity, improves Tc, reduces crystal size, thereby improves performance of copolymer.Saturated carboxylic acid sodium of the present invention, calcium salt CAV102 and NAV101 are available from Clariant chemical industry (China) company limited.Described SURLYN8920 and SURLYN 9020 are available from Dupont chemical industry (China) Group Co.,Ltd.
Further, described preparation process is carried out in autoclave.Described autoclave is available from Weihai automatic control reactor company limited.
According to the inventor to repetition test of the present invention, finally determined preparation method of the present invention, multipolymer of the present invention has following beneficial effect: 1) aminoundecanoic acid used comes from Viscotrol C, the multipolymer of preparation decreases to petrochemical industry Resource Dependence degree, has certain value of environmental protection; 2) tensile strength of the multipolymer of preparation, elongation at break and moulding processability are improved; 3) microlitic structure has improved shock strength, chemical resistant properties, anti-stress cracking, has reduced water-intake rate, has improved the dimensional stability problem of bringing due to crystallization; 4) preparation technology's continuous and compact has effectively shortened polymerization cycle.
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. shock 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.
4. 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.
5. water-intake rate (%)
The water-intake rate of test copolymer sample, undertaken by standard method of test GB/T 1034-2008 in 23 ℃ of distilled water.
6. transmittance (%)
The WGT-S type mist degree determination of light transmittance instrument that adopts mark border, Guangzhou company limited to produce is undertaken by standard method of test GB/T 2410-2008.
Fusing point (℃)
Adopt the DSC822e type differential scanning calorimeter of METTLER company, undertaken by standard method of test GB/T 19466-2004.
Every part of embodiment 1(is 10 grams)
The preparation method of transparent polyamide-polymeric amide 11 multipolymers, its preparation process is:
(1) reinforced: with the T/TMD salt of 700 grams, the aminoundecanoic acid of 500 grams, the distilled water of 50 grams, the phosphorous acid of 1 gram, the acetic acid of 2 grams, the calcium salt CAV102 of 10 grams, the acquisition mixture stirs;
(2) reaction is synthetic: mixture is warming up to 235 ℃, is forced into 2.0MPa, heat-insulation pressure keeping 3h under nitrogen atmosphere; 2h is down to normal pressure subsequently, is warming up to 280 ℃ when being down to normal pressure, insulation 4h, and discharging makes transparent polyamide-polymeric amide 11 multipolymers.
Described preparation process is carried out in autoclave.Described autoclave is available from Weihai automatic control reactor company limited.
The performance of copolymer test result is shown in table 2.
Every part of embodiment 2(is 10 grams)
The preparation method of transparent polyamide-polymeric amide 11 multipolymers, its preparation process is:
(1) reinforced: with the I/TMD salt of 600 grams, the aminoundecanoic acid of 100 grams, the methyl alcohol of 100 grams, the phosphoric acid of 0.2 gram, the lauric acid of 10 grams, 5 gram NAV101, the acquisition mixture stirs;
(2) reaction is synthetic: mixture is warming up to 220 ℃, is forced into 3.0MPa, heat-insulation pressure keeping 4h under argon atmosphere; 1h is down to normal pressure subsequently, is warming up to 290 ℃ when being down to normal pressure, insulation 3h, and discharging makes transparent polyamide-polymeric amide 11 multipolymers.
The performance of copolymer test result is shown in table 2.
Every part of embodiment 3(is 5 grams)
The preparation method of transparent polyamide-polymeric amide 11 multipolymers, its preparation process is:
(1) reinforced: with the T/DMDC salt of 500 grams, the aminoundecanoic acid of 150 grams, the N-Methyl pyrrolidone of 200 grams, the Hypophosporous Acid, 50 of 10 grams, the aniline of 25 grams, the SURLYN8920 of 0.5 gram, the acquisition mixture stirs;
(2) reaction is synthetic: mixture is warming up to 250 ℃, is forced into 3.5MPa, heat-insulation pressure keeping 2h under the helium atmosphere; 3h is down to normal pressure subsequently, is warming up to 260 ℃ when being down to normal pressure, insulation 2h, and discharging makes transparent polyamide-polymeric amide 11 multipolymers.
The performance of copolymer test result is shown in table 2.
Every part of embodiment 4(is 20 grams)
The preparation method of transparent polyamide-polymeric amide 11 multipolymers, its preparation process is:
(1) reinforced: with the I/DMDC salt of 1000 grams, the aminoundecanoic acid of 800 grams, the dimethyl formamide of 600 grams, the sodium hypophosphite of 20 grams, the stearic acid of 60 grams, the SURLYN 9020 of 6 grams, the acquisition mixture stirs;
(2) reaction is synthetic: mixture is warming up to 225 ℃, is forced into 1.6MPa, heat-insulation pressure keeping 1h under the neon atmosphere; 4h is down to normal pressure subsequently, is warming up to 270 ℃ when being down to normal pressure, insulation 1h, and discharging makes transparent polyamide-polymeric amide 11 multipolymers.
The performance of copolymer test result is shown in table 2.
Every part of embodiment 5(is 10 grams)
The preparation method of transparent polyamide-polymeric amide 11 multipolymers, its preparation process is:
(1) reinforced: with the T/TMD of 300 grams, the I/TMD of 500 grams, the aminoundecanoic acid of 200 grams, the ethanol of 200 grams, the sodium phosphate of 0.5 gram, the butylamine of 40 grams, the saturated carboxylic acid sodium of 8 grams, the acquisition mixture stirs;
(2) reaction is synthetic: mixture is warming up to 230 ℃, is forced into 2.5MPa, heat-insulation pressure keeping 4h under nitrogen atmosphere; 2h is down to normal pressure subsequently, is warming up to 275 ℃ when being down to normal pressure, insulation 2h, and discharging makes transparent polyamide-polymeric amide 11 multipolymers.
The performance of copolymer test result is shown in table 2.
Every part of embodiment 6(is 10 grams)
The preparation method of transparent polyamide-polymeric amide 11 multipolymers, its preparation process is:
(1) reinforced: with the T/TMD salt of 450 grams, the T/DMDC salt of 450 grams, the aminoundecanoic acid of 250 grams, the distilled water of 80 grams, the sodium phosphite of 15 grams, the myristic acid of 5 grams, the saturated carboxylic acid sodium of 6 grams, the acquisition mixture stirs;
(2) reaction is synthetic: mixture is warming up to 240 ℃, is forced into 3.3MPa, heat-insulation pressure keeping 2h under argon atmosphere; 3h is down to normal pressure subsequently, is warming up to 300 ℃ when being down to normal pressure, insulation 4h, and discharging makes transparent polyamide-polymeric amide 11 multipolymers.
The performance of copolymer test result is shown in table 2.
The prepared performance of copolymer test result of table 2 embodiment 1 ~ 6
Claims (2)
1. the preparation method of transparent polyamide-polymeric amide 11 multipolymers, is characterized in that, its preparation process is:
(1) reinforced: with the transparent polyamide salt of 50 ~ 100 weight parts, the aminoundecanoic acid of 10 ~ 50 weight parts, the distilled water of 5 ~ 40 weight parts or organic solvent, 0.02 the catalyzer of ~ 2 weight parts, 0.2 the end-capping reagent of ~ 5 weight parts, the nucleator of 0.1 ~ 1 weight part, the acquisition mixture stirs; Described transparent polyamide salt is the wherein mixture of one or more salt arbitrary proportions in T/TMD salt, I/TMD salt, T/DMDC salt, I/DMDC salt; Described organic solvent is methyl alcohol, ethanol, N-Methyl pyrrolidone or dimethyl formamide; Described catalyzer is phosphoric acid, phosphorous acid, Hypophosporous Acid, 50 or their salt compounds; Described end-capping reagent is monocarboxylic acid or monoamine; Described nucleator is saturated carboxylic acid sodium, calcium salt CAV102, NAV101, SURLYN8920, SURLYN 9020;
(2) reaction is synthetic: mixture is warming up to 220 ~ 250 ℃, is forced into 1.6 ~ 3.5MPa, heat-insulation pressure keeping 1 ~ 4h under the shielding gas atmosphere; 1 ~ 4h is down to normal pressure subsequently, is warming up to 260 ~ 300 ℃ when being down to normal pressure, insulation 2 ~ 4h, and discharging makes transparent polyamide-polymeric amide 11 multipolymers.
2. the preparation method of transparent polyamide-polymeric amide 11 multipolymers according to claim 1, is characterized in that, described preparation process is carried out in autoclave.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103483581A (en) * | 2013-09-22 | 2014-01-01 | 南京工业大学 | Transparent polyamide and synthetic method thereof |
| CN115536853A (en) * | 2022-10-28 | 2022-12-30 | 中国五环工程有限公司 | Method for preparing PA11 elastomer from 11-aminoundecanoic acid |
Citations (4)
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| EP0982342A1 (en) * | 1998-08-27 | 2000-03-01 | Ube Industries, Ltd. | Polyamide having excellent stretching properties |
| CN101058670A (en) * | 2006-04-21 | 2007-10-24 | Ems-化学公开股份有限公司 | Transparent polyamide molding compositions |
| CN102382453A (en) * | 2011-09-28 | 2012-03-21 | 深圳市科聚新材料有限公司 | Antistatic nylon material and preparation method thereof |
| 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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2013
- 2013-02-05 CN CN201310045111.XA patent/CN103122065B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0982342A1 (en) * | 1998-08-27 | 2000-03-01 | Ube Industries, Ltd. | Polyamide having excellent stretching properties |
| CN101058670A (en) * | 2006-04-21 | 2007-10-24 | Ems-化学公开股份有限公司 | Transparent polyamide molding compositions |
| CN102382453A (en) * | 2011-09-28 | 2012-03-21 | 深圳市科聚新材料有限公司 | Antistatic nylon material and preparation method thereof |
| CN102775601A (en) * | 2012-08-03 | 2012-11-14 | 中北大学 | Preparation method of semi-aromatic polyamide-polyamide 11 copolymer |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103483581A (en) * | 2013-09-22 | 2014-01-01 | 南京工业大学 | Transparent polyamide and synthetic method thereof |
| CN103483581B (en) * | 2013-09-22 | 2016-05-04 | 南京工业大学 | A kind of transparent polyamide and synthetic method thereof |
| CN115536853A (en) * | 2022-10-28 | 2022-12-30 | 中国五环工程有限公司 | Method for preparing PA11 elastomer from 11-aminoundecanoic acid |
| CN115536853B (en) * | 2022-10-28 | 2023-06-27 | 中国五环工程有限公司 | Method for preparing PA11 elastomer from 11-aminoundecanoic acid |
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Inventor after: Hu Guosheng Inventor after: Sun Bingzhen Inventor after: Jiao Guining Inventor after: Wang Zhongqiang Inventor after: Zhang Jingting Inventor before: Hu Guosheng Inventor before: Yang Yunfeng Inventor before: Sun Bingzhen Inventor before: Li Yingchun Inventor before: Jiao Guining Inventor before: Zhang Jingting Inventor before: Song Jiangfeng Inventor before: Wang Zhiqiang Inventor before: Li Jie |
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Free format text: CORRECT: INVENTOR; FROM: HU GUOSHENG YANG YUNFENG SUN BINGZHEN LI YINGCHUN JIAO GUINING ZHANG JINGTING SONG JIANGFENG WANG ZHIQIANG LI JIE TO: HU GUOSHENG SUN BINGZHEN JIAO GUINING WANG ZHONGQIANG ZHANG JINGTING |
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