CN111925521A - Full-bio-based polyamide and preparation method thereof - Google Patents
Full-bio-based polyamide and preparation method thereof Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
- C08G69/30—Solid state polycondensation
Abstract
The invention discloses 2, 5-furandicarboxylic acid-based polyamide from whole biomass and a preparation method thereof, belonging to the technical field of bio-based polyamide. The structural formula of the 2, 5-furandicarboxylic acid polyamide is shown as (I), wherein R is C4, C5, C6 and C10 alkylene. The method takes 2, 5-furandicarboxylic acid and aliphatic diamine as raw materials, and prepares the 2, 5-furandicarboxylic acid polyamide through salification-prepolycondensation-solid phase polycondensation. The 2, 5-furandicarboxylic acid and the aliphatic diamine monomer adopted by the invention are derived from biomass resources, have wide raw material sources and abundant reserves, are renewable, can be used as supplement and partial replacement of non-renewable fossil raw material monomers, so that the high-performance environment-friendly polyamide is synthesized, is used for the fields of fibers, high-performance engineering plastics and the like, and has important scientific significance and application value.
Description
Technical Field
The invention relates to a bio-based polyamide and a preparation method thereof, in particular to a method for synthesizing 2, 5-furandicarboxylic acid based polyamide by using 2, 5-furandicarboxylic acid and aliphatic diamine as raw materials, belonging to the field of chemical engineering.
Background
Polyamide (PA), also known as nylon, is a polymer containing a nitrogen heterochain containing an amide group (-NHCO-) in the main chain of a polymer, and is known as five general-purpose engineering plastic with Polycarbonate (PC), polybutylene terephthalate (PBT), Polyoxymethylene (POM) and polyphenylene oxide (PPO). Polyamides are mainly classified into aliphatic polyamides, semi-aromatic polyamides and wholly aromatic polyamides according to the composition of the main chain. The main chain of the aliphatic polyamide mainly comprises alkylene and amide, is a typical linear structure, and has better comprehensive performance, but the polyamide has generally lower glass transition temperature, insufficient heat resistance, high water absorption and poor dimensional stability, so that the application of the polyamide in the fields of high temperature resistance and the like is limited. The main chain of the wholly aromatic polyamide mainly comprises aromatic rings and acylamino, the polyamide generally has high heat resistance, high strength and high solvent resistance, but the glass transition temperature and the melting point of the polyamide are too high, and the polyamide cannot be well processed and molded, so that the further application of the polyamide is limited. The main chain of the semi-aromatic polyamide mainly consists of alkylene, aromatic rings and acylamino alternately, the structural characteristics determine that the semi-aromatic polyamide has the advantages of both aliphatic polyamide and wholly aromatic polyamide, and the semi-aromatic polyamide has good heat resistance and dimensional stability, good processing performance and high cost performance, so that the semi-aromatic polyamide has a higher application prospect, the market demand is continuously increased, and the semi-aromatic polyamide is widely applied to industries such as automobiles, electronic appliances and the like.
At present, monomers for producing polyamide are mainly derived from non-renewable fossil resources such as petroleum. With the increase of the number of the world population and the continuous progress of the social economy, the demand of synthetic materials represented by polyamide is increased year by year, so that the consumption of petroleum resources is accelerated, the petroleum resources are gradually decreased, and the sustainable development of the society is not facilitated. Also, the consumption of excessive fossil resources causes the emission of a large amount of greenhouse gases, resulting in the aggravation of the greenhouse effect. In addition, a series of intermediate products and wastes which pollute the environment and are harmful to human health are generated in the production process of the petroleum-based polyamide monomer, and the core concept of green chemical industry is violated. Taking a monomer terephthalic acid (PTA) for synthesizing a semi-aromatic polyamide as an example, the PTA is mainly obtained by oxidizing and refining Paraxylene (PX) extracted from naphtha, and although PX itself is a low-toxicity compound, during the production process, on one hand, many toxic byproducts are generated, such as benzene, acetic acid, ethyl acetate, hydrogen sulfide and the like, and on the other hand, the emission of harmful gases such as sulfur, nitrogen, smoke and the like is increased. For the reasons, although the PX productivity is seriously insufficient in our country at present, the people still object to newly build a PX project. Therefore, the development of the environment-friendly polyamide taking renewable biomass resources and nontoxic and harmless monomers as raw materials has important social significance and ecological value according to multiple requirements on aspects of sustainable development, environmental protection, human health protection and the like.
The biomass resource is a renewable resource and has the advantages of rich stock, wide source, biodegradability and the like. In addition, the biomass resource is considered to realize zero emission of carbon dioxide in the whole utilization period, and the greenhouse effect can be slowed down to a certain extent, so that the production of polyamide by using the biomass-based monomer based on the biomass resource has very important significance.
In the prior art, Chinese patent CN103145979A discloses an aliphatic polyamide and a preparation method thereof, monomers for synthesizing the polyamide are pentanediamine and aliphatic diacid, at least one of the two monomers is prepared by a biological method, and the synthesized polyamide has the advantages of green and reproducibility and has the same mechanical property as the existing polyamide. Although the monomers for synthesizing the polyamide can be completely derived from biomass resources, the aliphatic polyamide has certain gap in the aspects of heat resistance, dimensional stability and the like compared with semi-aromatic polyamide, thereby limiting the application range of the aliphatic polyamide.
Chinese patent CN106191145A discloses a semi-aromatic polyamide based on furandicarboxylic acid and a preparation method thereof, wherein the reactions involved are as follows:
the patent takes furan dicarboxylic acid dimethyl ester and aliphatic diamine as monomers, so as to synthesize polyamide which has similar glass transition temperature with polyphthalamide (PPA) but better processing performance. However, on one hand, the dimethyl furandicarboxylate monomer used in the patent needs to be further esterified with furandicarboxylic acid, which increases the reaction steps and the synthesis cost, and on the other hand, the enzyme-catalyzed polymerization is used in the patent, and the reaction rate and the yield are to be improved.
Among a plurality of bio-based monomers, 2, 5-furandicarboxylic acid can be converted from biomass resources containing hexose, pentose and the like by a "biorefinery" technology, has good reaction activity and thermal stability, meanwhile, diamines such as 1, 4-butanediamine, 1, 5-pentanediamine, 1, 6-hexanediamine and 1, 10-decanediamine can be obtained by converting the biomass resources, and the preparation and purification technologies of the diacid and diamine monomers are mature day by day and the production scale is enlarged day by day, so that the diacid and diamine monomers are expected to be respectively used as substitute materials of petroleum-based monomer PTA and petroleum-based aliphatic diamine, and are used for synthesizing semi-aromatic polyamide.
Disclosure of Invention
The invention aims to synthesize the novel environment-friendly all-bio-based polyamide by salifying-prepolycondensation-solid phase polycondensation reaction by using 2, 5-furandicarboxylic acid and aliphatic diamine which are derived from biomass resources as polymerization monomers, and the monomers have the advantages of high reaction activity, good stability, rich raw material reserves and wide sources.
First, the present invention provides a bio-based polyamide compound, which has a structural formula shown in (i):
wherein R is C4, C5, C6 and C10 alkylene.
The invention also provides a preparation method of the bio-based polyamide compound, which comprises the following steps:
1) salt forming reaction: under the protection of inert gas, adding 2, 5-furandicarboxylic acid, aliphatic diamine, a catalyst and a solvent into a reaction kettle, heating to 40-120 ℃, and reacting for 30-150 min to obtain a polyamide salt solution;
2) pre-polycondensation reaction: under the protection of inert gas, transferring the polyamide salt solution obtained in the step 1) into a polymerization kettle, firstly heating to 180-260 ℃, and reacting for 60-300 min to obtain a prepolymer mixed solution, wherein the absolute pressure of the reaction is 0.100-4.000 MPa;
then gradually reducing the absolute reaction pressure to 0.050MPa-0.100MPa, keeping the temperature unchanged, reacting for 30min-150min, and removing low-boiling-point substances to obtain a low-molecular-weight polyamide prepolymer;
3) solid phase polycondensation: transferring the polyamide prepolymer with low molecular weight obtained in the step 2) into a solid phase polymerization kettle under the protection of inert gas, heating to 220-300 ℃, vacuumizing to ensure that the absolute pressure of the reaction is 0-0.050 MPa, reacting for 180-480 min, and removing micromolecule volatile components to obtain the bio-based polyamide compound.
In the method for producing the bio-based polyamide compound according to the present invention, the type of the aliphatic diamine is not particularly limited, and is preferably one or more selected from the group consisting of 1, 4-butanediamine, 1, 5-pentanediamine, 1, 6-hexanediamine, and 1, 10-decanediamine.
In the method for producing a bio-based polyamide compound according to the present invention, the amount of the aliphatic diamine added is not particularly limited, and the preferable amount of the aliphatic diamine is, based on the molar amount of 2, 5-furandicarboxylic acid: the molar ratio of the aliphatic diamine to the 2, 5-furandicarboxylic acid is 1-1.5: 1. if the molar ratio of the aliphatic diamine to 2, 5-furandicarboxylic acid is less than 1:1, the amount of the aliphatic diamine used is too low, which results in an unbalance of the terminal groups of the polyamide prepolymer and a too low final molecular weight. If the molar ratio of the aliphatic diamine to the 2, 5-furandicarboxylic acid is more than 1.5:1, the amount of the aliphatic diamine used is too high, which also causes an imbalance in the terminal groups of the polyamide prepolymer and a lower final molecular weight.
In the preparation method of the bio-based polyamide compound provided by the invention, the catalyst is phosphorous acid and/or sodium phosphite, the adding amount of the catalyst is not particularly limited, and the preferable adding amount of the catalyst is 0.01-1% of the sum of the mass of the 2, 5-furandicarboxylic acid and the mass of the aliphatic diamine. If the added mass is less than 0.01 percent of the sum of the mass of the 2, 5-furandicarboxylic acid and the aliphatic diamine, the dosage of the catalyst is too low, so that the reaction rate is slow and the final molecular weight is low; if the amount of the catalyst added is more than 1% by mass of the sum of the amounts of 2, 5-furandicarboxylic acid and aliphatic diamine, the amount of the catalyst to be used is too high, resulting in difficulty in controlling the polymerization reaction.
In the preparation method of the bio-based polyamide compound provided by the invention, the type of the solvent is not particularly limited, and the solvent is preferably deionized water, ethanol or dimethylformamide.
Preferably, in the preparation method of the bio-based polyamide compound provided by the invention, the solution of the polyamide salt obtained in the 1) salt forming reaction has a pH of 7.0-8.5, and the aliphatic diamine in the solution is in excess to compensate the loss of the aliphatic diamine in the later reaction period, wherein the mass fraction of the polyamide salt is 20% -65%.
Preferably, in the preparation method of the bio-based polyamide compound provided by the invention, in the 1) salt formation reaction, the stirring speed is 100rpm to 500 rpm; in the 2) pre-polycondensation reaction, the stirring speed of the reaction is 50rpm-400rpm, and the stirring speed is 50rpm-300rpm when low-boiling-point substances are removed; and in the 3) solid phase polycondensation reaction, the stirring speed is 20rpm-100 rpm. The higher rotating speed in the salification reaction and the pre-polycondensation reaction can improve the reaction rate and the conversion rate, and the lower rotating speed in the low-boiling-point substance removing reaction and the solid-phase polycondensation reaction can more effectively remove the low-boiling-point substances from the polymer system.
Preferably, in the preparation method of the bio-based polyamide compound provided by the invention, the 2, 5-furandicarboxylic acid and the aliphatic diamine are prepared by biomass resource conversion and purification, and both contain renewable organic carbon meeting the ASTM D6866 standard.
The bio-based polyamide compound provided by the invention has good application in the fields of fibers and high-performance engineering plastics.
The invention can also be described in more detail as follows:
the invention provides a 2, 5-furandicarboxylic acid-based polyamide, which has a structural formula shown in (I):
wherein R is C4, C5, C6 and C10 alkylene.
Secondly, the invention provides a preparation method of the 2, 5-furandicarboxylic acid polyamide, which takes 2, 5-furandicarboxylic acid and aliphatic diamine as polymerization monomers, and adopts a synthesis process of salification-precondensation-solid phase polycondensation in a solvent to prepare the 2, 5-furandicarboxylic acid polyamide.
More specifically, a process for preparing 2, 5-furandicarboxylic acid-based polyamides, comprising the steps of:
the first step is as follows: salt forming reaction: under the protection of inert gas, 2, 5-furandicarboxylic acid, aliphatic diamine, a catalyst and a solvent are added into a reaction kettle, the mixture is heated to 40-120 ℃, the reaction time is controlled to be 30-150 min, and salt forming reaction is carried out on the mixture to obtain the polyamide salt solution.
The second step is that: pre-polycondensation reaction: under the protection of inert gas, transferring the polyamide salt solution obtained in the first step into a polymerization kettle, firstly heating to 180-260 ℃, setting the absolute reaction pressure to 0.100-4.000 MPa, and controlling the reaction time to be 60-300 min, so that the polyamide salt is subjected to polymerization reaction to obtain a prepolymer mixed solution; then exhausting and vacuumizing, gradually reducing the absolute pressure of the reaction to 0.050MPa-0.100MPa, keeping the temperature unchanged, controlling the reaction time to 30min-150min, and removing low-boiling-point substances to obtain the low-molecular-weight polyamide prepolymer.
The third step: solid phase polycondensation: and (3) under the protection of inert gas, transferring the low-molecular-weight polyamide prepolymer obtained in the second step into a solid-phase polymerization kettle, heating to 220-300 ℃, vacuumizing, setting the absolute reaction pressure to 0-0.050 MPa, controlling the reaction time to 180-480 min, performing solid-phase polycondensation, removing micromolecule volatile components, and finally obtaining the all-bio-based polyamide.
The first step is recommended to be in a reaction kettle, and the stirring speed is preferably 100rpm-500rpm, so that the salt forming reaction is carried out to obtain the polyamide salt solution.
In the second step, in the polymerization kettle, the stirring speed in the polymerization kettle is preferably 50rpm-400rpm during the pre-polymerization reaction, so that the polyamide salt is subjected to polymerization reaction to obtain a prepolymer mixed solution; when removing low boiling substances, the stirring speed is preferably 50rpm to 300rpm, and the polyamide prepolymer is obtained.
In the present invention, the aliphatic diamine includes, but is not limited to, one or more of 1, 4-butanediamine, 1, 5-pentanediamine, 1, 6-hexanediamine and 1, 10-decanediamine.
In the invention, the catalyst can be phosphorous acid, sodium phosphite or a composition of phosphorous acid and sodium phosphite, and the mass content of the catalyst is 0.01-1% of the total weight of the 2, 5-furandicarboxylic acid and the aliphatic diamine.
In the invention, the solvent can be one of deionized water, ethanol and dimethylformamide.
In the invention, the 2, 5-furandicarboxylic acid and the aliphatic diamine monomer are prepared by biomass resource conversion and purification, and both contain renewable organic carbon meeting the ASTM D6866 standard.
In the above production method of the present invention, the molar ratio of 2, 5-furandicarboxylic acid to aliphatic diamine in the first step is preferably from 1:1 to 1: 1.5.
The pH of the solution of polyamide salt obtained in the first step is preferably between 7.0 and 8.5, wherein the mass fraction of polyamide salt is preferably between 20% and 65%.
The invention provides an application of 2, 5-furan diformyl polyamide, the synthesized full bio-based polyamide can be used in the fields of fiber, high-performance engineering plastics and the like,
the invention has the advantages and beneficial effects that:
1. the adopted polymerized monomers, namely the 2, 5-furandicarboxylic acid and the aliphatic diamine, are all derived from renewable biomass resources, namely the synthesized polyamide is a full-bio-based polymer, so that the biomass resources which are originally in a waste state can be effectively utilized, the application range of the biomass resources is widened, waste is turned into wealth, the biomass raw materials are rich in reserves and wide in sources, and the biomass raw materials are inexhaustible, so that the sustainable development of the resources is facilitated.
2. The synthesized 2, 5-furandicarboxylic acid based polyamide can be used as a partial substitute of semi-aromatic polyamide taking PTA as a monomer, thereby reducing the consumption of fossil resources and the emission of toxic wastes, following the concept of 'green chemical industry', reducing the emission intensity of greenhouse gases and being beneficial to alleviating the greenhouse effect.
The 3.2, 5-furan dicarboxylic acid monomer has good reaction activity and thermal stability, can be condensed and polymerized with aliphatic diamine into polyamide with high molecular weight through a salification-precondensation-solid phase polycondensation process, and simultaneously, oxygen atoms on furan rings in a main chain endow the novel bio-based polyamide with different material properties.
Drawings
FIG. 1 is a flow diagram of the preparation of a wholly biobased polyamide based on 2, 5-furandicarboxylic acid.
Detailed Description
The present invention will be described in detail with reference to specific examples for better understanding, but the present invention is not limited to these examples.
The 2, 5-furandicarboxylic acid and aliphatic diamine monomers described in the specific examples were prepared by biomass resource conversion and purification, and all contained renewable organic carbon according to ASTM D6866 standard.
Example 1
Replacing air in a stainless steel salt-forming reaction kettle for three times by adopting a vacuumizing and nitrogen introducing mode, and adding 1mol of 2, 5-furandicarboxylic acid as a bio-based monomer, 1.15mol of 1, 4-butanediamine as a bio-based monomer, 258mg of phosphorous acid catalyst and 400mL of deionized water into the salt-forming reaction kettle under the protection of nitrogen to obtain a mixture; stirring is started to uniformly mix the mixture, the stirring speed is set to be 300rpm, the mixture is heated to 60 ℃ under normal pressure, the reaction is carried out for 60min, the PH of the solution after the reaction is finished is 7.7, and then the polyamide salt solution with the mass fraction of 36% is obtained.
And then, carrying out air tightness inspection on the stainless steel polymerization kettle, replacing air in the stainless steel reaction kettle for three times after the stainless steel polymerization kettle is inspected to be complete, transferring the obtained polyamide salt solution into the polymerization kettle under the protection of nitrogen, heating to 195 ℃, setting the absolute reaction pressure to be 2.200MPa, setting the stirring speed to be 250rpm, and reacting for 120min to enable the polyamide salt to carry out polymerization reaction to obtain a prepolymer mixed solution.
And then, carrying out gas exhaust and vacuum pumping operation, gradually reducing the absolute reaction pressure to 0.070MPa, keeping the temperature unchanged, setting the stirring rotation speed to be 200rpm, reacting for 80min, and removing low-boiling-point substances such as solvent water to obtain the polyamide prepolymer with lower relative molecular mass.
Then, the gas in the solid phase polymerization reactor was replaced three times, the polyamide prepolymer obtained above was transferred to the solid phase polymerization reactor under the protection of an inert gas, and first, the reaction was heated to 270 ℃ and vacuumized, the absolute pressure of the reaction was set to 0.0005MPa, the stirring speed was set to 100rpm, the reaction was carried out for 240min, and small molecule volatiles such as water were removed to promote the reaction in the polycondensation direction, and 187g of all-bio-based polyamide was finally obtained, the viscosity average molecular weight was 2.26 ten thousand.
Example 2
Replacing air in a stainless steel salt-forming reaction kettle for three times by adopting a vacuumizing and nitrogen introducing mode, and adding 1mol of bio-based monomer 2, 5-furandicarboxylic acid, 1.10mol of bio-based monomer 1, 5-pentanediamine, 536mg of phosphorous acid catalyst and 500mL of ethanol into the salt-forming reaction kettle under the protection of nitrogen to obtain a mixture; and starting stirring to uniformly mix the mixture, setting the stirring speed at 350rpm, heating the mixture to 72 ℃ under normal pressure, reacting for 75min, and obtaining a polyamide salt solution with the mass fraction of 38%, wherein the pH of the solution after the reaction is 7.4.
And then, carrying out air tightness inspection on the stainless steel polymerization kettle, replacing air in the stainless steel reaction kettle for three times after the stainless steel polymerization kettle is inspected to be complete, transferring the obtained polyamide salt solution into the polymerization kettle under the protection of nitrogen, heating to 220 ℃, setting the absolute reaction pressure to be 2.200MPa, setting the stirring speed to be 250rpm, and reacting for 180min to enable the polyamide salt to have polymerization reaction, thereby obtaining a prepolymer mixed solution.
And then, carrying out gas exhaust and vacuum pumping operation, gradually reducing the absolute reaction pressure to 0.060MPa, keeping the temperature unchanged, setting the stirring speed to be 150rpm, reacting for 90min, and removing low-boiling-point substances such as solvent water and the like to obtain the polyamide prepolymer with lower relative molecular mass.
And then, replacing the gas in the solid-phase polymerization kettle for three times, transferring the obtained polyamide prepolymer into the solid-phase polymerization kettle under the protection of inert gas, heating to 250 ℃, vacuumizing, setting the absolute pressure of the reaction to be 0.00006MPa, setting the stirring speed to be 80rpm, reacting for 280min, removing micromolecule volatile components such as water and the like, and promoting the reaction to be carried out in the polycondensation direction to finally obtain 191g of all-bio-based polyamide with the viscosity-average molecular weight of 2.48 ten thousand.
Example 3
Replacing air in a stainless steel salt-forming reaction kettle for three times by adopting a vacuumizing and nitrogen introducing mode, and adding 1mol of 2, 5-furandicarboxylic acid as a bio-based monomer, 1.08mol of 1, 6-hexamethylenediamine as a bio-based monomer, 145mg of a sodium phosphite catalyst and 350mL of deionized water into the salt-forming reaction kettle under the protection of nitrogen to obtain a mixture; stirring is started to uniformly mix the mixture, the stirring speed is set to be 200rpm, the mixture is heated to 90 ℃ under normal pressure, the reaction is carried out for 120min, the PH of the solution after the reaction is finished is 7.2, and then the polyamide salt solution with the mass fraction of 42% is obtained.
And then, carrying out air tightness inspection on the stainless steel polymerization kettle, replacing air in the stainless steel reaction kettle for three times after the stainless steel polymerization kettle is inspected to be complete, transferring the obtained polyamide salt solution into the polymerization kettle under the protection of nitrogen, firstly heating to 225 ℃, setting the absolute reaction pressure to be 2.500MPa, setting the stirring speed to be 200rpm, and reacting for 180min to enable the polyamide salt to have polymerization reaction, thereby obtaining a prepolymer mixed solution.
And then, exhausting and vacuumizing, gradually reducing the absolute pressure of the reaction to 0.055MPa, keeping the temperature unchanged, setting the stirring speed to 180rpm, reacting for 100min, and removing low-boiling-point substances such as solvent water to obtain the polyamide prepolymer with lower relative molecular mass.
And then, replacing the gas in the solid-phase polymerization kettle for three times, transferring the obtained polyamide prepolymer into the solid-phase polymerization kettle under the protection of inert gas, heating to 250 ℃, vacuumizing, setting the absolute pressure of the reaction to be 0.001MPa, setting the stirring speed to be 60rpm, reacting for 300min, removing micromolecule volatile components such as water and the like, and promoting the reaction to be carried out in the polycondensation direction to finally obtain 182g of all-bio-based polyamide with the viscosity-average molecular weight of 1.93 ten thousand.
Example 4
Replacing air in a stainless steel salt-forming reaction kettle for three times by adopting a vacuumizing and nitrogen introducing mode, and adding 1mol of 2, 5-furandicarboxylic acid as a bio-based monomer, 0.58mol of 1, 4-butanediamine as a bio-based monomer, 0.52mol of 1, 6-hexanediamine as a bio-based monomer, 802mg of a sodium phosphite catalyst and 500mL of deionized water into the salt-forming reaction kettle under the protection of nitrogen to obtain a mixture; stirring is started to uniformly mix the mixture, the stirring speed is set to be 400rpm, the mixture is heated to 80 ℃ under normal pressure, the reaction is carried out for 90min, the PH of the solution after the reaction is finished is 7.4, and then the polyamide salt solution with the mass fraction of 32% is obtained.
And then, carrying out air tightness inspection on the stainless steel polymerization kettle, replacing air in the stainless steel reaction kettle for three times after the stainless steel polymerization kettle is inspected to be complete, transferring the obtained polyamide salt solution into the polymerization kettle under the protection of nitrogen, heating to 210 ℃, setting the absolute reaction pressure to 2.350MPa, setting the stirring speed to 350rpm, and reacting for 140min to enable the polyamide salt to carry out polymerization reaction to obtain a prepolymer mixed solution.
And then, carrying out gas exhaust and vacuum pumping operation, gradually reducing the absolute pressure of the reaction to 0.070MPa, keeping the temperature unchanged, setting the stirring speed to be 250rpm, reacting for 120min, and removing low-boiling-point substances such as solvent water to obtain the polyamide prepolymer with lower relative molecular mass.
And then, replacing the gas in the solid-phase polymerization kettle for three times, transferring the obtained polyamide prepolymer into the solid-phase polymerization kettle under the protection of inert gas, heating to 255 ℃, vacuumizing, setting the absolute pressure of the reaction to be 0.00001MPa, setting the stirring speed to be 40rpm, reacting for 260min, removing micromolecule volatile components such as water and the like, and promoting the reaction to be carried out in the polycondensation direction to finally obtain 188g of all-bio-based polyamide with the viscosity-average molecular weight of 2.69 ten thousand.
Example 5
Replacing air in a stainless steel salt-forming reaction kettle for three times by adopting a vacuumizing and nitrogen introducing mode, and adding 1mol of bio-based monomer 2, 5-furandicarboxylic acid, 1.02mol of bio-based monomer 1, 10-decamethylene diamine, 1657mg of sodium phosphite catalyst and 400mL of dimethylformamide into the salt-forming reaction kettle under the protection of nitrogen to obtain a mixture; and starting stirring to uniformly mix the mixture, setting the stirring speed to be 450rpm, heating the mixture to 105 ℃ under normal pressure, reacting for 120min, cooling and precipitating after the reaction is finished, carrying out centrifugal separation, and washing the obtained precipitate with dimethylformamide and deionized water for several times to obtain the decamethylenediamine furandicarboxylate.
And then, carrying out air tightness inspection on the stainless steel polymerization kettle, replacing air in the stainless steel reaction kettle for three times after the stainless steel polymerization kettle is inspected to be complete, transferring the obtained decamethylenediamine furandicarboxylate and 500mL of deionized water into the polymerization kettle under the protection of nitrogen, firstly heating to 230 ℃, setting the absolute reaction pressure to be 3.000MPa, setting the stirring speed to be 300rpm, and reacting for 240min to enable the polyamide salt to carry out polymerization reaction to obtain a prepolymer mixed solution.
And then, exhausting and vacuumizing, gradually reducing the absolute reaction pressure to 0.050MPa, keeping the temperature unchanged, setting the stirring speed to be 200rpm, reacting for 120min, and removing low-boiling-point substances such as solvent water to obtain the polyamide prepolymer with lower relative molecular mass.
And then, replacing the gas in the solid-phase polymerization kettle for three times, transferring the obtained polyamide prepolymer into the solid-phase polymerization kettle under the protection of inert gas, heating to 260 ℃, vacuumizing, setting the absolute pressure of the reaction to be 0.001MPa, setting the stirring speed to be 20rpm, reacting for 360min, removing micromolecule volatile components such as water and the like, and promoting the reaction to be carried out in the polycondensation direction to finally obtain 239g of all-bio-based polyamide with the viscosity-average molecular weight of 1.63 ten thousand.
Example 6
Replacing air in a stainless steel salt-forming reaction kettle for three times by adopting a vacuumizing and nitrogen introducing mode, and adding 1mol of 2, 5-furandicarboxylic acid as a bio-based monomer, 1.5mol of 1, 4-butanediamine as a bio-based monomer, 1440mg of a phosphorous acid catalyst, 1440mg of a sodium phosphite catalyst and 300mL of ethanol into the salt-forming reaction kettle under the protection of nitrogen to obtain a mixture; and starting stirring to uniformly mix the mixture, setting the stirring speed at 100rpm, heating the mixture to 115 ℃ under normal pressure, reacting for 150min, and obtaining a polyamide salt solution with the mass fraction of 52%, wherein the pH of the solution is 8.1 after the reaction is finished.
And then, carrying out air tightness inspection on the stainless steel polymerization kettle, replacing air in the stainless steel reaction kettle for three times after the stainless steel polymerization kettle is inspected to be complete, transferring the obtained polyamide salt solution into the polymerization kettle under the protection of nitrogen, heating to 250 ℃, setting the absolute reaction pressure to be 4.000MPa, setting the stirring speed to be 150rpm, and reacting for 300min to enable the polyamide salt to carry out polymerization reaction to obtain a prepolymer mixed solution.
And then, carrying out exhausting and vacuumizing operation, gradually reducing the absolute reaction pressure to 0.080MPa, keeping the temperature unchanged, setting the stirring speed to 80rpm, reacting for 150min, and removing low-boiling-point substances such as solvent water and the like to obtain the polyamide prepolymer with lower relative molecular mass.
Then, the gas in the solid phase polymerization kettle is replaced three times, the obtained polyamide prepolymer is transferred into the solid phase polymerization kettle under the protection of inert gas, the temperature is firstly heated to 290 ℃, the vacuumizing operation is carried out, the absolute pressure of the reaction is 0.0002MPa, the stirring speed is 40rpm, the reaction is 480min, and small molecular volatile components such as water and the like are removed, so that the reaction is promoted to be carried out in the polycondensation direction, and 185g of total bio-based polyamide is finally obtained, wherein the viscosity-average molecular weight is 2.31 ten thousand.
Example 7
Replacing air in a stainless steel salt-forming reaction kettle for three times by adopting a vacuumizing and nitrogen introducing mode, and adding 1mol of bio-based monomer 2, 5-furandicarboxylic acid, 1.0mol of bio-based monomer 1, 10-pentanediamine, 32.8mg of phosphorous acid catalyst and 400mL of dimethylformamide into the salt-forming reaction kettle under the protection of nitrogen to obtain a mixture; and starting stirring to uniformly mix the mixture, setting the stirring speed at 500rpm, heating the mixture to 120 ℃ under normal pressure, reacting for 140min, cooling and precipitating after the reaction is finished, carrying out centrifugal separation, and washing the obtained precipitate with dimethylformamide and deionized water for several times to obtain the decamethylenediamine furandicarboxylate.
And then, carrying out air tightness inspection on the stainless steel polymerization kettle, replacing air in the stainless steel reaction kettle for three times after the stainless steel polymerization kettle is inspected to be complete, transferring the obtained decamethylenediamine furandicarboxylate and 500mL of deionized water into the polymerization kettle under the protection of nitrogen, firstly heating to 260 ℃, setting the absolute reaction pressure to 0.500MPa, setting the stirring speed to 400rpm, and reacting for 280min to enable the polyamide salt to carry out polymerization reaction, thereby obtaining a prepolymer mixed solution.
And then, carrying out exhausting and vacuumizing operation, gradually reducing the absolute reaction pressure to 0.050MPa, keeping the temperature unchanged, setting the stirring speed to be 300rpm, reacting for 140min, and removing low-boiling-point substances such as solvent water and the like to obtain the polyamide prepolymer with lower relative molecular mass.
And then, replacing the gas in the solid-phase polymerization kettle for three times, transferring the obtained polyamide prepolymer into the solid-phase polymerization kettle under the protection of inert gas, heating to 280 ℃, vacuumizing, setting the absolute pressure of the reaction to be 0.002MPa, setting the stirring speed to be 30rpm, reacting for 420min, removing micromolecule volatile components such as water and the like, and promoting the reaction to be carried out in the polycondensation direction to finally obtain 214g of all-bio-based polyamide with the viscosity-average molecular weight of 1.55 ten thousand.
Claims (10)
1. A bio-based polyamide compound, characterized in that it has the structural formula (I):
wherein R is C4, C5, C6 and C10 alkylene.
2. A method for producing a bio-based polyamide compound, which is the method for producing a bio-based polyamide compound according to claim 1, comprising the steps of:
1) salt forming reaction: under the protection of inert gas, adding 2, 5-furandicarboxylic acid, aliphatic diamine, a catalyst and a solvent into a reaction kettle, heating to 40-120 ℃, and reacting for 30-150 min to obtain a polyamide salt solution;
2) pre-polycondensation reaction: under the protection of inert gas, transferring the polyamide salt solution obtained in the step 1) into a polymerization kettle, firstly heating to 180-260 ℃, and reacting for 60-300 min to obtain a prepolymer mixed solution, wherein the absolute pressure of the reaction is 0.100-4.000 MPa;
then gradually reducing the absolute reaction pressure to 0.050MPa-0.100MPa, keeping the temperature unchanged, reacting for 30min-150min, and removing low-boiling-point substances to obtain a low-molecular-weight polyamide prepolymer;
3) solid phase polycondensation: transferring the polyamide prepolymer with low molecular weight obtained in the step 2) into a solid phase polymerization kettle under the protection of inert gas, heating to 220-300 ℃, vacuumizing to ensure that the absolute pressure of the reaction is 0-0.050 MPa, reacting for 180-480 min, and removing micromolecule volatile components to obtain the bio-based polyamide compound.
3. The method of claim 2, wherein the aliphatic diamine is one or more selected from the group consisting of 1, 4-butanediamine, 1, 5-pentanediamine, 1, 6-hexanediamine, and 1, 10-decanediamine.
4. The method for producing a bio-based polyamide compound according to claim 2, wherein the aliphatic diamine is used in an amount, based on the molar amount of 2, 5-furandicarboxylic acid: the molar ratio of the aliphatic diamine to the 2, 5-furandicarboxylic acid is 1-1.5: 1.
5. the method for producing a bio-based polyamide compound according to claim 2, wherein the catalyst is phosphorous acid and/or sodium phosphite, and the amount of the added catalyst is 0.01 to 1% by mass of the sum of 2, 5-furandicarboxylic acid and aliphatic diamine.
6. The method for preparing a bio-based polyamide compound according to claim 2, wherein the solvent is deionized water, ethanol or dimethylformamide.
7. The method of claim 2, wherein the solution of the polyamide salt obtained in the 1) salt-forming reaction has a pH of 7.0 to 8.5, and the mass fraction of the polyamide salt is 20 to 65%.
8. The method for producing a bio-based polyamide compound according to claim 2, wherein 1) in the salt-forming reaction, the stirring speed is 100rpm to 500 rpm; in the 2) pre-polycondensation reaction, the stirring speed of the reaction is 50rpm-400rpm, and the stirring speed is 50rpm-300rpm when low-boiling-point substances are removed; and in the 3) solid phase polycondensation reaction, the stirring speed is 20rpm-100 rpm.
9. The method of claim 2, wherein the 2, 5-furandicarboxylic acid and the aliphatic diamine are obtained by biomass resource conversion and purification, and each of the compounds contains organic carbon of renewable origin according to ASTM D6866 standard.
10. The use of the bio-based polyamide compound according to claim 1, wherein the bio-based polyamide compound is used in the fields of fiber and high performance engineering plastics.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113999391A (en) * | 2021-11-24 | 2022-02-01 | 合肥利夫生物科技有限公司 | Bio-based polyamide and preparation method thereof |
| CN114437005A (en) * | 2022-03-14 | 2022-05-06 | 郑州大学 | Butanediamine furan diformate and crystal thereof |
| CN115477751A (en) * | 2022-10-26 | 2022-12-16 | 南京先进生物材料与过程装备研究院有限公司 | Biomass furyl soluble aromatic polyamide and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140228523A1 (en) * | 2013-02-12 | 2014-08-14 | Korea Institute Of Science And Technology | Method for preparing furanic copolyamide derived from biomass using solid-state polymerization |
| CN104098765A (en) * | 2014-06-27 | 2014-10-15 | 广东威林工程塑料有限公司 | Synthesis method for biologically based transparent semi-aromatic poly-amide material |
| CN106191145A (en) * | 2016-07-22 | 2016-12-07 | 南京工业大学 | A kind of semi-aromatic polyamide based on furandicarboxylic acid and preparation method thereof |
-
2019
- 2019-05-13 CN CN201910397072.7A patent/CN111925521A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140228523A1 (en) * | 2013-02-12 | 2014-08-14 | Korea Institute Of Science And Technology | Method for preparing furanic copolyamide derived from biomass using solid-state polymerization |
| CN104098765A (en) * | 2014-06-27 | 2014-10-15 | 广东威林工程塑料有限公司 | Synthesis method for biologically based transparent semi-aromatic poly-amide material |
| CN106191145A (en) * | 2016-07-22 | 2016-12-07 | 南京工业大学 | A kind of semi-aromatic polyamide based on furandicarboxylic acid and preparation method thereof |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023000871A1 (en) * | 2021-07-23 | 2023-01-26 | 四川大学 | Method for preparing high molecular weight furan polyamide |
| US11643502B1 (en) | 2021-07-23 | 2023-05-09 | Sichuan University | Method for preparing high molecular weight furan polyamide |
| WO2023045820A1 (en) * | 2021-09-24 | 2023-03-30 | 珠海万通特种工程塑料有限公司 | Furan diacid-based polyamide, preparation method therefor, and furan diacid-based polyamide composition |
| CN113999391A (en) * | 2021-11-24 | 2022-02-01 | 合肥利夫生物科技有限公司 | Bio-based polyamide and preparation method thereof |
| CN114437005A (en) * | 2022-03-14 | 2022-05-06 | 郑州大学 | Butanediamine furan diformate and crystal thereof |
| CN114437005B (en) * | 2022-03-14 | 2023-11-14 | 郑州大学 | Butanediamine furan diformate and crystal thereof |
| CN115477751A (en) * | 2022-10-26 | 2022-12-16 | 南京先进生物材料与过程装备研究院有限公司 | Biomass furyl soluble aromatic polyamide and preparation method thereof |
| CN115505120A (en) * | 2022-10-31 | 2022-12-23 | 中国五环工程有限公司 | High-performance bio-based copolymerized nylon and preparation method thereof |
| CN116355205A (en) * | 2023-03-29 | 2023-06-30 | 四川轻化工大学 | Bio-based polyamide and preparation method thereof |
| CN116355205B (en) * | 2023-03-29 | 2024-03-26 | 四川轻化工大学 | Bio-based polyamide and preparation method thereof |
| CN116874451A (en) * | 2023-07-17 | 2023-10-13 | 南京工业大学 | Aliphatic diamine furan diformate and crystal thereof |
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