CN114349956A - Synthesis of low-density high-molecular-weight bio-based copolyamide transparent high-elasticity material - Google Patents
Synthesis of low-density high-molecular-weight bio-based copolyamide transparent high-elasticity material Download PDFInfo
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Abstract
The invention discloses a synthesis of a low-density high-molecular-weight bio-based copolyamide transparent high-elasticity material, which belongs to the technical field of bio-based material processing, and is prepared by adopting a one-step continuous synthesis reaction process, wherein the one-step continuous synthesis reaction is divided into four reaction stages: the first stage is the salt forming reaction of dibasic acid and diamine monomer; the second stage is the prepolymerization of polyamide; the third stage is the prepolymerization of the copolyamide elastomer; the fourth stage is the polycondensation of the copolyamide elastomer. The elastomer material has the advantages that the problems of poor transparency, low molecular weight and low mechanical strength of the elastomer material are solved, the elastomer material has excellent flexibility, no fracture occurs in the bending process, the Shore hardness is adjustable, the density is lower, the elastomer material is lighter, the elastomer material belongs to a bio-based material, and the development concept of carbon neutralization is met.
Description
Technical Field
The invention belongs to the technical field of processing of bio-based materials, and particularly relates to synthesis of a low-density high-molecular-weight bio-based copolyamide transparent high-elasticity material.
Background
The molecular main chain of the polyamide elastic material contains aliphatic polyvinyl acetate soft segment and polyamide hard segment, and the polyamide elastic material can be used in the technical fields of machinery, electronics, electric appliances, automobile parts, sports goods and the like, but the prior elastomer material has the problems of poor transparency and low molecular weight and mechanical strength.
Disclosure of Invention
The invention aims to solve the existing problems and provide a synthesis method of a low-density high-molecular-weight bio-based copolyamide transparent high-elasticity material.
The invention is realized by the following technical scheme:
the synthesis of the low-density high-molecular-weight bio-based copolyamide transparent high-elasticity material adopts a one-step continuous synthesis reaction process for preparation, and the one-step continuous synthesis reaction is divided into four reaction stages:
the first stage is the salt forming reaction of the monomer of the dibasic acid and the diamine:
accurately weighing bio-based azelaic acid and hexamethylene diamine (or decamethylene diamine or dodecamethylene diamine) in an equal molar ratio, adding the bio-based azelaic acid and hexamethylene diamine (or decamethylene diamine) in an equal molar ratio into a polymerization reaction kettle, adding deionized water in an equal mass into the reaction kettle according to the mass sum of the azelaic acid and the corresponding diamine, and starting stirring at the speed of 200-250 r/min. Setting the reaction temperature to be 50-80 ℃ and reacting for 1-2 h to complete the ammonium salt preparation reaction;
the second stage is a prepolymerization of the polyamide:
continuously heating the prepared ammonium salt to 90-130 ℃ for reaction for 1-3 h, keeping the pressure in the reaction kettle at 0.1-0.4 MPa, stirring at the speed of 150-200 r/min, continuously discharging water vapor generated in the reaction kettle in the reaction process, monitoring the quality of the discharged water vapor in real time through a condensation reflux device, stopping discharging the water vapor until the mass of the discharged water vapor is 60-90% of the mass of the initially added deionized water, and finishing the pre-polymerization reaction;
the third stage is a prepolymerization of the copolyamide elastomer:
after the polyamide prepolymerization reaction is finished, sequentially adding caprolactam, amine-terminated polyether, a catalyst and dicarboxylic acid into a constant-pressure feeding tank on a reaction kettle, continuously raising the temperature to 230-270 ℃ under the protection of inert gas helium, maintaining the reaction pressure at 0.2-1.0 MPa, and continuously stirring at the rotating speed of 100-150 r/min for reaction for 2-4 hours to obtain a copolyamide elastomer prepolymer;
the fourth stage is the polycondensation of the copolyamide elastomer:
and after the prepolymerization reaction of the copolyamide elastomer is finished, immediately controlling the pressure in the reaction kettle to be 0MPa within 0-60 min, keeping the reaction temperature unchanged, adjusting the stirring speed to be 50-100 r/min, continuously reacting for 2-5 h under the protection of inert gas helium to finish the polycondensation reaction, and then removing residual oligomers through belt casting, material cutting and boiling water extraction to obtain the copolyamide elastomer high polymer plastic slice particles.
Further, based on the total mass of the azelaic acid, the diamine, the caprolactam and the amine-terminated polyether, the amount of the amine-terminated polyether is 10 wt% to 50 wt%, the amount of the caprolactam is 10 wt% to 60 wt%, and the amount of the monomer of the azelaic acid and the diamine thereof is 5 wt% to 40 wt%.
Furthermore, the catalyst is used in an amount of 0.05 wt% to 0.5 wt% based on the total mass of azelaic acid, diamine, caprolactam and amine terminated polyether.
Furthermore, the catalyst is used in an amount of 0.1-0.3 wt% based on the total mass of azelaic acid, diamine, caprolactam and amine terminated polyether.
Further, the dicarboxylic acid is present in an equimolar ratio to the polyetheramine, in an amount based on the mass of the polyetheramine/the relative molecular weight of the dicarboxylic acid.
Compared with the prior art, the invention has the following advantages:
the elastomer material has the advantages that the problems of poor transparency, low molecular weight and low mechanical strength of the elastomer material are solved, the elastomer material has excellent flexibility, no fracture occurs in the bending process, the Shore hardness is adjustable, the density is lower, the elastomer material is lighter, the elastomer material belongs to a bio-based material, and the development concept of carbon neutralization is met.
Detailed Description
For further explanation of the present invention, reference will now be made to the following specific examples.
The synthesis of the low-density high-molecular-weight bio-based copolyamide transparent high-elasticity material adopts a one-step continuous synthesis reaction process for preparation, and the one-step continuous synthesis reaction is divided into four reaction stages:
the first stage reaction:
adding 470g of azelaic acid, 430g of decamethylene diamine and 900g of deionized water into a 10L polymerization kettle, starting stirring at a rotating speed of 200r/min, setting the reaction temperature at 70 ℃ and reacting for 1h to obtain ammonium salt of azelaic acid acyl decamethylene diamine, wherein the ammonium salt preparation reaction is finished;
and (3) second-stage reaction:
immediately heating the reaction system to 110 ℃ for h, keeping the pressure in the reaction kettle at 0.1MPa, stirring at the speed of 150r/min, continuously discharging water vapor generated in the reaction kettle in the reaction process, and stopping discharging until the mass of the discharged water vapor is 80% of the mass of the initially added deionized water, so as to obtain a polyamide 109(PA109) prepolymer;
and (3) a third-stage reaction:
adding 1500g of caprolactam, 600g of terminal amino polypropylene glycol with the number average molecular weight of 2000, 3g of phosphotungstic acid and 61g of sebacic acid into a polyamide prepolymer reaction system in sequence through a constant-pressure feeding tank, continuously heating to 250 ℃ under the protection of inert gas helium, maintaining the reaction pressure at 0.6MPa, and continuously stirring at the rotating speed of 100r/min for reaction for 3 hours to obtain a copolyamide PA109-PA6 elastomer prepolymer;
and a fourth stage reaction: and then, the pressure in the reaction kettle is 0MPa within 30min, the reaction temperature is kept unchanged, the stirring speed is adjusted to 50r/min, the reaction is continued for 4h under the protection of inert gas helium, the stirring is stopped, the reaction is stopped after the reaction is stopped for 10min, the polycondensation reaction of the copolyamide elastomer is completed, and the finished product is obtained after discharging, belt casting, cutting, extraction and drying.
The performance of the prepared low-density high-molecular-weight bio-based copolyamide transparent high-elasticity material is tested, and the specific test data are shown in the following table 1.
TABLE 1
As can be seen from the above table 1, the low-density high-molecular-weight bio-based copolyamide transparent high-elasticity material prepared by the method disclosed by the application has the problems of high molecular weight and high mechanical strength, and has the advantages of excellent flexibility, no fracture in the bending process, adjustable Shore hardness, lower density and lighter weight.
Claims (5)
1. The synthesis of the low-density high-molecular-weight bio-based copolyamide transparent high-elasticity material is characterized by adopting a one-step continuous synthesis reaction process for preparation, wherein the one-step continuous synthesis reaction is divided into four reaction stages:
the first stage is the salt forming reaction of the monomer of the dibasic acid and the diamine:
accurately weighing bio-based azelaic acid and hexamethylene diamine (or decamethylene diamine or dodecamethylene diamine) in an equal molar ratio, adding the bio-based azelaic acid and hexamethylene diamine (or decamethylene diamine) in an equal molar ratio into a polymerization reaction kettle, adding deionized water in an equal mass into the reaction kettle according to the mass sum of the azelaic acid and the corresponding diamine, and starting stirring at the speed of 200-250 r/min. Setting the reaction temperature to be 50-80 ℃ and reacting for 1-2 h to complete the ammonium salt preparation reaction;
the second stage is a prepolymerization of the polyamide:
continuously heating the prepared ammonium salt to 90-130 ℃ for reaction for 1-3 h, keeping the pressure in the reaction kettle at 0.1-0.4 MPa, stirring at the speed of 150-200 r/min, continuously discharging water vapor generated in the reaction kettle in the reaction process, monitoring the quality of the discharged water vapor in real time through a condensation reflux device, stopping discharging the water vapor until the mass of the discharged water vapor is 60-90% of the mass of the initially added deionized water, and finishing the pre-polymerization reaction;
the third stage is a prepolymerization of the copolyamide elastomer:
after the polyamide prepolymerization reaction is finished, sequentially adding caprolactam, amine-terminated polyether, a catalyst and dicarboxylic acid into a constant-pressure feeding tank on a reaction kettle, continuously raising the temperature to 230-270 ℃ under the protection of inert gas helium, maintaining the reaction pressure at 0.2-1.0 MPa, and continuously stirring at the rotating speed of 100-150 r/min for reaction for 2-4 hours to obtain a copolyamide elastomer prepolymer;
the fourth stage is the polycondensation of the copolyamide elastomer:
and after the prepolymerization reaction of the copolyamide elastomer is finished, immediately controlling the pressure in the reaction kettle to be 0MPa within 0-60 min, keeping the reaction temperature unchanged, adjusting the stirring speed to be 50-100 r/min, continuously reacting for 2-5 h under the protection of inert gas helium to finish the polycondensation reaction, and then removing residual oligomers through belt casting, material cutting and boiling water extraction to obtain the copolyamide elastomer high polymer plastic slice particles.
2. The synthesis of the low-density high-molecular-weight bio-based copolyamide transparent high-elasticity material according to claim 1, wherein the amount of the amine-terminated polyether is 10-50 wt%, the amount of the caprolactam is 10-60 wt%, and the amount of the monomer of the azelaic acid and the diamine thereof is 5-40 wt%, based on the total mass of the azelaic acid, the diamine, the caprolactam and the amine-terminated polyether.
3. The synthesis of the low-density high-molecular-weight bio-based copolyamide transparent high-elasticity material according to claim 1, wherein the catalyst is used in an amount of 0.05-0.5 wt% based on the total mass of azelaic acid, diamine, caprolactam and amine-terminated polyether.
4. The synthesis of the low-density high-molecular-weight bio-based copolyamide transparent high-elasticity material according to claim 1, wherein the catalyst is used in an amount of 0.1-0.3 wt% based on the total mass of azelaic acid, diamine, caprolactam and amine-terminated polyether.
5. The synthesis of the low-density high-molecular-weight bio-based copolyamide transparent high-elasticity material according to claim 1, wherein the dicarboxylic acid and the polyether amine are in an equimolar ratio, and the amount of the dicarboxylic acid to the polyether amine is the mass of the polyether amine/the relative molecular weight of the polyether amine.
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| WO2005098128A1 (en) * | 2004-04-08 | 2005-10-20 | Ems Chemie Ag | Press felt for paper machine and method and device for producing said felt |
| US20100203275A1 (en) * | 2007-07-25 | 2010-08-12 | Botho Hoffmann | Transparent polyamide elastomers |
| CN104629044A (en) * | 2015-02-16 | 2015-05-20 | 北京旭阳化工技术研究院有限公司 | Preparation method of polyamide 6 thermoplastic elastomer and thermoplastic elastomer prepared by method |
| CN106893096A (en) * | 2017-02-21 | 2017-06-27 | 东华大学 | A kind of biological poly acid amides and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005098128A1 (en) * | 2004-04-08 | 2005-10-20 | Ems Chemie Ag | Press felt for paper machine and method and device for producing said felt |
| US20100203275A1 (en) * | 2007-07-25 | 2010-08-12 | Botho Hoffmann | Transparent polyamide elastomers |
| CN104629044A (en) * | 2015-02-16 | 2015-05-20 | 北京旭阳化工技术研究院有限公司 | Preparation method of polyamide 6 thermoplastic elastomer and thermoplastic elastomer prepared by method |
| CN106893096A (en) * | 2017-02-21 | 2017-06-27 | 东华大学 | A kind of biological poly acid amides and preparation method thereof |
Non-Patent Citations (2)
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| AHN, TO，等: "THERMAL AND MECHANICAL-PROPERTIES OF POLY(ETHER URETHANE) MODIFIED BY COPOLYAMIDE SEGMENTS" * |
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