CN103122065B - Preparation method of transparent polyamide-polyamide 11 copolymer - Google Patents
Preparation method of transparent polyamide-polyamide 11 copolymer Download PDFInfo
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- CN103122065B CN103122065B CN201310045111.XA CN201310045111A CN103122065B CN 103122065 B CN103122065 B CN 103122065B CN 201310045111 A CN201310045111 A CN 201310045111A CN 103122065 B CN103122065 B CN 103122065B
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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 multipolymer.
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, there is certain flame retardant resistance, be easy to processing, be suitable for, by glass fibre and other filler filling enhancing modified, improving performance and broadened application scope, 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 clear solid, relative density is 1.04, and compared with other nylon, its feature is that melt temperature is low, processing temperature is high, good stability of the dimension, water-absorbent are low, low-temperature performance good, can keeps good flexibility at-40 DEG C ~ 120 DEG C.Its odd numbers of carbon atoms makes amide group be positioned at same side, makes the no matter parallel or antiparallel of polymeric amide 11 all can be fully formed intermolecular hydrogen bonding, has 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, has excellent shock resistance and oil resistant solvent resistance, can meet the injection of various melt viscosity ranges and extrude processing.
Summary of the invention
The present invention aims to provide a kind ofly has good mechanical property, the preparation method of transparent polyamide-polymeric amide 11 multipolymer that is transparent, environmental protection.
The present invention is achieved by the following technical solutions: the preparation method of transparent polyamide-polymeric amide 11 multipolymer, and its preparation process is:
(1) reinforced: by 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, the catalyzer of 0.02 ~ 2 weight part, the end-capping reagent of 0.2 ~ 5 weight part, the nucleator of 0.1 ~ 1 weight part, stir acquisition mixture; Described transparent polyamide salt is the mixture of wherein one or more the 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) Reactive Synthesis: mixture is warming up to 220 ~ 250 DEG C, is forced into 1.6 ~ 3.5MPa under shielding gas atmosphere, insulation (220 ~ 250 DEG C) pressurize (1.6 ~ 3.5MPa) 1 ~ 4h; 1 ~ 4h is down to normal pressure subsequently, is warming up to 260 ~ 300 DEG C while being down to normal pressure, insulation (260 ~ 300 DEG C) 2 ~ 4h, discharging, obtained transparent polyamide-polymeric amide 11 multipolymer.
When transparent polyamide salt is 50 ~ 100 weight parts, when aminoundecanoic acid is 10 ~ 50 weight part, if when the weight part of aminoundecanoic acid is less than 10 parts, the mixing of reaction raw materials is not easily even, the loss of diamines is easily caused during polymerization, if when being greater than 50 parts, polymerization rate declines, and polymerization reaction time increases;
If when the weight part of distilled water or organic solvent is less than 5, be unfavorable for the thermally equivalent reacted and the high pressure promoted in reactor, if when being greater than 40, cause bleeding off pressure overlong time and waste solvent;
If when the weight part of catalyzer is less than 0.02 part, the effect that catalyzer plays is not obvious, if when being 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 when the weight part of end-capping reagent is less than 0.2, polymerization velocity is too fast, easily causes copolymerization product to occur the bad phenomenon such as implode, if when being greater than 5, impacts the activity of reactive functionality, and polymerization rate reduces;
If the weight part of nucleator lower than 0.1 time do not have nucleating effect, higher than 1 time its crystallite promoter action do not improve, the performance of goods may be damaged on the contrary, too increase production cost from practical application.
Further, described transparent polyamide salt is the mixture of wherein one or more the salt arbitrary proportions in T/TMD salt, I/TMD salt, T/DMDC salt, I/DMDC salt.The transparency of the multipolymer adopting above-mentioned transparent polyamide salt to obtain and excellent in mechanical performance.
The english abbreviation annotation 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 the performance improving multipolymer further.
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 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 carrying out of copolyreaction.
Described nucleator is saturated carboxylic acid sodium, calcium salt CAV102, NAV101, SURLYN8920, SURLYN 9020.Above-mentioned nucleator is conducive to increasing nucleus quantity, improves Tc, reduces crystal size, thus improves performance of copolymer.Saturated carboxylic acid sodium of the present invention, calcium salt CAV102 and NAV101 are purchased from Clariant chemical industry (China) company limited.Described chemical industry (China) Group Co., Ltd of SURLYN8920 and SURLYN 9020 purchased from American Du Pont.
Further, described preparation process is carried out in autoclave.Described autoclave is purchased from Weihai automatic control reactor company limited.
According to the present inventor to repetition test of the present invention, finally determine preparation method of the present invention, multipolymer of the present invention has following beneficial effect: aminoundecanoic acid 1) used comes from Viscotrol C, the multipolymer of preparation decreases to fossil resources dependency degree, has certain value of environmental protection; 2) tensile strength of the multipolymer prepared, elongation at break and moulding processability are improved; 3) microlitic structure improves shock strength, chemical resistant properties, anti-stress cracking, reduces water-intake rate, improves the dimensional stability problems because crystallization brings; 4) preparation technology's continuous and compact, effectively shortens polymerization cycle.
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. shock 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. 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.
5. water-intake rate (%)
In 23 DEG C of distilled water, test the water-intake rate of copolymer sample, undertaken by standard method of test GB/T 1034-2008.
6. transmittance (%)
The WGT-S type mist degree determination of light transmittance instrument adopting Guangzhou Biao Ji company limited to produce, is undertaken by standard method of test GB/T 2410-2008.
7. fusing point (DEG C)
Adopt the DSC822e type differential scanning calorimeter of METTLER company, undertaken by standard method of test GB/T 19466-2004.
embodiment 1(every part is 10 grams)
The preparation method of transparent polyamide-polymeric amide 11 multipolymer, its preparation process is:
(1) reinforced: by 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, stir acquisition mixture;
(2) Reactive Synthesis: mixture is warming up to 235 DEG C under nitrogen atmosphere, is forced into 2.0MPa, heat-insulation pressure keeping 3h; 2h is down to normal pressure subsequently, is warming up to 280 DEG C while being down to normal pressure, insulation 4h, discharging, obtained transparent polyamide-polymeric amide 11 multipolymer.
Described preparation process is carried out in autoclave.Described autoclave is purchased from Weihai automatic control reactor company limited.
Performance of copolymer test result is shown in table 2.
embodiment 2(every part is 10 grams)
The preparation method of transparent polyamide-polymeric amide 11 multipolymer, its preparation process is:
(1) reinforced: by 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 grams of NAV101, stir acquisition mixture;
(2) Reactive Synthesis: mixture is warming up to 220 DEG C, is forced into 3.0MPa under argon atmosphere, heat-insulation pressure keeping 4h; 1h is down to normal pressure subsequently, is warming up to 290 DEG C while being down to normal pressure, insulation 3h, discharging, obtained transparent polyamide-polymeric amide 11 multipolymer.
Performance of copolymer test result is shown in table 2.
embodiment 3(every part is 5 grams)
The preparation method of transparent polyamide-polymeric amide 11 multipolymer, its preparation process is:
(1) reinforced: by 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, stir acquisition mixture;
(2) Reactive Synthesis: mixture is warming up to 250 DEG C, is forced into 3.5MPa under helium atmosphere, heat-insulation pressure keeping 2h; 3h is down to normal pressure subsequently, is warming up to 260 DEG C while being down to normal pressure, insulation 2h, discharging, obtained transparent polyamide-polymeric amide 11 multipolymer.
Performance of copolymer test result is shown in table 2.
embodiment 4(every part is 20 grams)
The preparation method of transparent polyamide-polymeric amide 11 multipolymer, its preparation process is:
(1) reinforced: by 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, stir acquisition mixture;
(2) Reactive Synthesis: mixture is warming up to 225 DEG C, is forced into 1.6MPa under neon atmosphere, heat-insulation pressure keeping 1h; 4h is down to normal pressure subsequently, is warming up to 270 DEG C while being down to normal pressure, insulation 1h, discharging, obtained transparent polyamide-polymeric amide 11 multipolymer.
Performance of copolymer test result is shown in table 2.
embodiment 5(every part is 10 grams)
The preparation method of transparent polyamide-polymeric amide 11 multipolymer, its preparation process is:
(1) reinforced: by 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, stir acquisition mixture;
(2) Reactive Synthesis: mixture is warming up to 230 DEG C under nitrogen atmosphere, is forced into 2.5MPa, heat-insulation pressure keeping 4h; 2h is down to normal pressure subsequently, is warming up to 275 DEG C while being down to normal pressure, insulation 2h, discharging, obtained transparent polyamide-polymeric amide 11 multipolymer.
Performance of copolymer test result is shown in table 2.
embodiment 6(every part is 10 grams)
The preparation method of transparent polyamide-polymeric amide 11 multipolymer, its preparation process is:
(1) reinforced: by 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, stir acquisition mixture;
(2) Reactive Synthesis: mixture is warming up to 240 DEG C, is forced into 3.3MPa under argon atmosphere, heat-insulation pressure keeping 2h; 3h is down to normal pressure subsequently, is warming up to 300 DEG C while being down to normal pressure, insulation 4h, discharging, obtained transparent polyamide-polymeric amide 11 multipolymer.
Performance of copolymer test result is shown in table 2.
Performance of copolymer test result obtained by table 2 embodiment 1 ~ 6
Claims (2)
1. the preparation method of transparent polyamide-polymeric amide 11 multipolymer, is characterized in that, its preparation process is:
(1) reinforced: by 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, the catalyzer of 0.02 ~ 2 weight part, the end-capping reagent of 0.2 ~ 5 weight part, the nucleator of 0.1 ~ 1 weight part, stir acquisition mixture; Described transparent polyamide salt is the mixture of wherein one or more the salt arbitrary proportions in 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 calcium salt CAV102, NAV101, SURLYN8920, SURLYN 9020;
(2) Reactive Synthesis: mixture is warming up to 220 ~ 250 DEG C, is forced into 1.6 ~ 3.5MPa under shielding gas atmosphere, heat-insulation pressure keeping 1 ~ 4h; 1 ~ 4h is down to normal pressure subsequently, is warming up to 260 ~ 280 DEG C while being down to normal pressure, insulation 2 ~ 4h, discharging, obtained transparent polyamide-polymeric amide 11 multipolymer.
2. the preparation method of transparent polyamide-polymeric amide 11 multipolymer according to claim 1, it is characterized in that, described preparation process is carried out in autoclave.
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| CN103483581B (en) * | 2013-09-22 | 2016-05-04 | 南京工业大学 | A kind of transparent polyamide and synthetic method thereof |
| 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 |
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 |
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- 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 |
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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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