CN115505120A - High-performance bio-based copolymerized nylon and preparation method thereof - Google Patents

High-performance bio-based copolymerized nylon and preparation method thereof Download PDF

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CN115505120A
CN115505120A CN202211345174.2A CN202211345174A CN115505120A CN 115505120 A CN115505120 A CN 115505120A CN 202211345174 A CN202211345174 A CN 202211345174A CN 115505120 A CN115505120 A CN 115505120A
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monomer
repeating unit
acid
copolymerized nylon
pressure
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张科
谢鸿洲
卢文新
胡四斌
肖敦峰
商宽祥
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China Wuhuan Engineering Co Ltd
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    • 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
    • C08G69/40—Polyamides containing oxygen in the form of ether groups

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  • Health & Medical Sciences (AREA)
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Abstract

The invention discloses high-performance bio-based copolymerized nylon, which comprises a first repeating unit shown in a formula (I), a second repeating unit shown in a formula (II) and a third repeating unit shown in a formula (III), wherein based on the total molar weight of the copolymerized nylon, the content of the first repeating unit is 1-98 mol%, the content of the second repeating unit is 0-97 mol%, and the content of the third repeating unit is 1-98 mol%. The copolymerized nylon is prepared by copolycondensating 2, 5-furandicarboxylic acid, C4-C10 aliphatic diamine, C6-C10 aliphatic dibasic acid, aminoundecanoic acid and/or aminododecanoic acid which are used as raw materials, and has the characteristics of high content of bio-groups and excellent comprehensive properties, such as high strength, good toughness and good gas barrier property. The preparation method is simple and feasible, and is beneficial to industrial application.

Description

High-performance bio-based copolymerized nylon and preparation method thereof
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to high-performance bio-based copolymerized nylon and a preparation method thereof.
Background
At present, the bio-based monomer 2, 5-furandicarboxylic acid (FDCA) derived from biomass resources, cellulose and hemicellulose, is determined by the U.S. department of energy in 2004 to be one of the 12 most competitive biomass monomers due to its structure and properties similar to petroleum-based monomer terephthalic acid (TPA), and has a broad development prospect. FDCA can be used with a series of diamines to form corresponding 2, 5-furandicarboxylic acid semi-aromatic bio-based nylons, which have better strength, higher gas barrier properties, but poorer toughness than petroleum-based nylons terephthalate.
The 11-aminoundecanoic acid is derived from castor oil, which can be polymerized to produce long carbon chain biobased nylon 11. The long carbon chain structural characteristics of the amino undecanoic acid endow the nylon 11 with unique properties, such as good flexibility, good dimensional stability, outstanding low-temperature impact resistance and excellent comprehensive properties, so that the nylon 11 can be widely applied to certain specific fields, in particular to automobile pipes, military equipment, cable light protective sleeves, metal coatings and the like. At present, the popularization of nylon 11 in a larger area depends on the development and optimization of the low-cost industrial production and polymerization process for preparing nylon 11 from aminoundecanoic acid on the one hand, and depends on the development of higher-performance random copolymers and multi-block copolymers based on nylon 11, such as high-temperature-resistant nylon 11 copolymers and thermoplastic elastomers taking nylon 11 as a hard segment.
In summary, the semi-aromatic bio-based nylon of 2, 5-furandicarboxylic acid and the long carbon chain bio-based nylon 11 complement each other in their properties, and in particular nylon 11 can provide toughness to nylon of 2, 5-furandicarboxylic acid, while nylon of 2, 5-furandicarboxylic acid can provide rigidity and gas barrier to nylon 11, and still maintain a high bio-based content. Therefore, how to combine the two effectively is a problem to be solved urgently.
Disclosure of Invention
The invention aims to provide a high-performance bio-based copolymerized nylon and a preparation method thereof, wherein 2, 5-furandicarboxylic acid, C4-C10 aliphatic diamine, C6-C10 aliphatic dibasic acid, aminoundecanoic acid and/or aminododecanoic acid are/is used as raw materials for preparation, and the preparation method is simple and easy to implement, has low cost and is beneficial to industrial application.
The invention provides a high-performance bio-based copolymerized nylon, which has a first repeating unit shown in a formula (I), a second repeating unit shown in a formula (II) and a third repeating unit shown in a formula (III):
(I)；
(II)；
(III)；
R 1 is selected from
R 2 Is selected from;
R 3 is selected from;
wherein x is an integer of 4 to 10, y is an integer of 4 to 8, and z is an integer of 10 to 11.
Based on the total molar weight of the copolymerized nylon, the content of the first repeating unit is 1-98 mol%, the content of the second repeating unit is 0-97 mol%, and the content of the third repeating unit is 1-98 mol%.
In the copolymerized nylon of the present invention, the first repeating unit provides strength and gas barrier property, the third repeating unit provides flexibility and processability, and the second repeating unit can be used to reduce cost. The copolymerized nylon with different performances can be obtained by regulating and controlling the proportion of the three repeating units.
Preferably, the content of the first repeating unit is 39 to 60mol% and the content of the third repeating unit is 39 to 60mol% based on the total molar weight of the copolymerized nylon. If the content of the repeating unit is not within the preferred range, i.e., the content of the first repeating unit providing strength is too low and the content of the third repeating unit providing toughness is too high, the copolymerized nylon has only good toughness but does not have high strength, and the copolymerized nylon has a low furan ring content, which is not favorable for gas barrier properties. The content of the second repeating unit is 0-20 mol%, so that the excellent comprehensive performance of the copolymerized nylon can be maintained as far as possible while the cost of the copolymerized nylon raw material is reduced.
The second aspect of the invention provides a preparation method of high-performance bio-based copolymerized nylon, which comprises the following steps:
(1) In the nitrogen atmosphere, the monomer a and the monomer containing R are mixed uniformly 1 And a monomer b and a monomer containing R 2 The monomer c is added into a reaction kettle together with distilled water, nitrogen is filled into the reaction kettle, the reaction kettle is pressurized to 0.2 to 0.3MPa, and the mass of the added distilled water is equal to the sum of the mass of the monomer a, the mass of the monomer b and the mass of the monomer c;
(2) Starting stirring, heating and carrying out heat preservation and pressure maintaining reaction, wherein redundant water vapor is discharged during the reaction to keep the pressure of the reaction kettle at 2-3 MPa;
(3) Decompressing to reduce the pressure of the reaction kettle to normal pressure to prepare prepolymer X;
(4) And (4) adding a catalyst and a monomer d containing R3 into the prepolymer X prepared in the step (3), rapidly heating and carrying out reduced pressure polycondensation reaction to obtain the copolymerized nylon.
The R is 1 、R 2 、R 3 As claimed in claim 1;
the monomer a is 2, 5-furan dicarboxylic acid, 2, 5-furan dicarboxylic acid diester or a mixture thereof; wherein the 2, 5-furandicarboxylic acid diester is 2, 5-furandicarboxylic acid dimethyl ester or 2, 5-furandicarboxylic acid diethyl ester;
the monomer b is at least one of C4-C10 aliphatic diamine; preferably, the monomer b is butanediamine, pentanediamine, hexanediamine and decanediamine;
the monomer C is at least one of C6-C10 aliphatic dibasic acid; preferably, the monomer c is at least one of adipic acid and sebacic acid;
the monomer d is at least one of aminoundecanoic acid and aminododecanoic acid;
in the step (1), the molar ratio of the sum of the monomer a and the monomer c to the monomer b is 1; the dosage of the monomer c accounts for 0 to 95mol percent of the total molar weight of the monomer a and the monomer c;
in the step (2), the temperature rising rate is 2-5 ℃/min, and the temperature is raised to 240-270 ℃ for heat preservation and pressure maintaining for 1-3 h, wherein the pressure for pressure maintaining is 2-3 MPa;
in the step (3), the pressure relief rate is 0.01-0.1 MPa/min;
in the step (4), the using amount of the monomer d accounts for 1-99% of the total mass of the prepolymer X and the monomer d;
in the step (4), the temperature is raised to 280-330 ℃, and the time of the decompression polycondensation reaction is 1-3 h;
in the step (4), the catalyst is one or more of n-butyl titanate, isopropyl titanate, titanium glycol, titanium acetylacetonate, antimony glycol, antimony trioxide, antimony acetate, zinc acetate, manganese acetate, lead acetate, calcium acetate, cobalt acetate, potassium acetate, magnesium acetate, barium acetate, lithium acetate, a silicon dioxide/titanium dioxide compound, a silicon dioxide/titanium dioxide/nitrogen-containing compound and a silicon dioxide/titanium dioxide/phosphorus-containing compound;
in the step (4), an auxiliary agent is added in the reaction, and the dosage of the auxiliary agent is 0.1-20 wt% of the dosage of the monomer d;
the auxiliary agent is one or more of a heat stabilizer, a light stabilizer or an inorganic filler;
further, the heat stabilizer is one or more of 1010, 1076, 425, 330, 1178, 618, 626, 168, TDD, trimethyl phosphite, triethyl phosphite, triisooctyl phosphite, triisodecyl phosphite, trilauryl phosphite, tris (tridecyl) phosphite, trioctadecyl phosphite, triphenyl phosphite, tri-p-tolyl phosphite, ditridecyl phosphite, tris (2, 4-di-tert-butylphenyl) phosphite, pentaerythritol bis (2, 4-tert-butylphenyl) diphosphite, bis (2, 4-di-p-isopropylphenyl) pentaerythritol diphosphite phosphoric acid, pentaerythritol tetrapentaphenyl tridecyl phosphite, pentaerythritol diphosphite, pentaerythritol diisodecyl diphosphite, pentaerythritol dioctadecyl phosphite, phosphoric acid, phosphorous acid, polyphosphoric acid, and triethyl phosphonoacetate;
<xnotran> 791, 700, 783, 119, 770, 622, 944, 2,2,6,6- -4- , (2,2,6,6- -4- ) , (1,2,2,6,6- -4- ) , 2- -4- , (3,5- -2- ) -5- (1- -2,2,6,6- -4- ) ; </xnotran>
The inorganic filler is one or more of nano silicon dioxide, nano titanium dioxide, nano calcium carbonate, nano talcum powder and nano layered silicate.
Compared with the prior art, the invention has the following beneficial effects:
(1) The copolymerized nylon prepared by the invention is prepared by taking 2, 5-furandicarboxylic acid, C4-C10 aliphatic diamine, C6-C10 aliphatic dibasic acid, aminoundecanoic acid and/or aminododecanoic acid as raw materials, and the preparation method is simple and easy to implement, has low cost and is beneficial to industrial application.
(2) The copolymerized nylon prepared by the invention is not only a copolymerized nylon with high bio-based content, but also a high-performance copolymerized nylon with strength, toughness and gas barrier property.
(3) The copolymerized nylon prepared by the invention selectively introduces common low-cost aliphatic dibasic acid, so that the excellent comprehensive performance of the copolymerized nylon is kept as far as possible while the cost of the copolymerized nylon is reduced.
Detailed Description
Comparative example 1
(1) Under the nitrogen atmosphere, adding terephthalic acid and hexamethylene diamine with equal molar ratio and distilled water with equal mass into a reaction kettle, uniformly mixing, filling nitrogen, and pressurizing to 0.2MPa;
(2) Starting stirring, heating to 250 ℃ at the heating rate of 3 ℃/min, discharging redundant water vapor to keep the pressure of the reaction kettle at 2MPa, and carrying out heat preservation and pressure maintaining reaction for 2 hours;
(3) Reducing the pressure of the reaction kettle to normal pressure at the pressure relief rate of 0.05MPa/min to prepare a prepolymer;
(4) And (3) adding catalysts tetrabutyl titanate and aminoundecanoic acid into the prepolymer prepared in the step (3), wherein the addition amounts of tetrabutyl titanate and aminoundecanoic acid are 0.1wt% and 10wt% of the prepolymer respectively, and reacting for 2h at 290 ℃ under the absolute pressure of 5000Pa to obtain the nylon copolymer.
Comparative example 2
(1) Under the nitrogen atmosphere, adding terephthalic acid, adipic acid and hexamethylene diamine and distilled water with equal mass into a reaction kettle, uniformly mixing, and filling nitrogen to pressurize to 0.2MPa. Wherein the molar ratio of terephthalic acid and adipic acid to hexamethylenediamine is 1, and the molar ratio of terephthalic acid to adipic acid is 5;
(2) Starting stirring, heating to 250 ℃ at the heating rate of 3 ℃/min, discharging redundant water vapor to keep the pressure of the reaction kettle at 2MPa, and carrying out heat preservation and pressure maintaining reaction for 2h;
(3) Reducing the pressure of the reaction kettle to normal pressure at the pressure relief rate of 0.05MPa/min to prepare a prepolymer;
(4) And (3) adding catalysts tetrabutyl titanate and aminoundecanoic acid into the prepolymer prepared in the step (3), wherein the addition amounts of tetrabutyl titanate and aminoundecanoic acid are 0.1wt% and 10wt% of the prepolymer respectively, and reacting for 2h at 290 ℃ under the absolute pressure of 5000Pa to obtain the nylon copolymer.
Comparative example 3
(1) Adding furandicarboxylic acid and hexamethylenediamine in equal molar ratio and distilled water in equal mass into a reaction kettle under the nitrogen atmosphere, uniformly mixing, and filling nitrogen to pressurize to 0.2MPa;
(2) Starting stirring, heating to 250 ℃ at the heating rate of 3 ℃/min, discharging redundant water vapor to keep the pressure of the reaction kettle at 2MPa, and carrying out heat preservation and pressure maintaining reaction for 2h to obtain a prepolymer;
(3) And (3) adding a catalyst tetrabutyl titanate into the prepolymer prepared in the step (2), wherein the addition amount of the tetrabutyl titanate is 0.1wt% of the prepolymer, and reacting for 2h at 290 ℃ under the absolute pressure of 5000Pa to prepare the nylon.
Example 1
(1) Adding furandicarboxylic acid and hexamethylenediamine in equal molar ratio and distilled water in equal mass into a reaction kettle under the nitrogen atmosphere, uniformly mixing, and filling nitrogen to pressurize to 0.2MPa;
(2) Starting stirring, heating to 250 ℃ at the heating rate of 3 ℃/min, discharging redundant water vapor to keep the pressure of the reaction kettle at 2MPa, and carrying out heat preservation and pressure maintaining reaction for 2h;
(3) Reducing the pressure of the reaction kettle to normal pressure at the pressure relief rate of 0.05MPa/min to prepare a prepolymer;
(4) And (3) adding catalysts tetrabutyl titanate and aminoundecanoic acid into the prepolymer prepared in the step (3), wherein the addition amounts of tetrabutyl titanate and aminoundecanoic acid are 0.1wt% and 10wt% of the prepolymer respectively, and reacting for 2h at 290 ℃ under the absolute pressure of 5000Pa to obtain the nylon copolymer.
Example 2
(1) Adding furandicarboxylic acid, adipic acid, hexamethylene diamine and distilled water with equal mass into a reaction kettle under the nitrogen atmosphere, uniformly mixing, and filling nitrogen to pressurize to 0.2MPa. Wherein the molar ratio of furandicarboxylic acid and adipic acid to hexamethylenediamine is 1, and the molar ratio of furandicarboxylic acid to adipic acid is 5;
(2) Starting stirring, heating to 250 ℃ at the heating rate of 3 ℃/min, discharging redundant water vapor to keep the pressure of the reaction kettle at 2MPa, and carrying out heat preservation and pressure maintaining reaction for 2 hours;
(3) Reducing the pressure of the reaction kettle to normal pressure at the pressure relief rate of 0.05MPa/min to prepare a prepolymer;
(4) And (4) adding catalysts of tetrabutyl titanate and aminoundecanoic acid into the prepolymer prepared in the step (3), wherein the addition amounts of tetrabutyl titanate and aminoundecanoic acid are 0.1wt% and 10wt% of the prepolymer respectively, and reacting for 2h at 290 ℃ under the absolute pressure of 5000Pa to prepare the nylon copolymer.
Example 3
(1) Under the nitrogen atmosphere, adding furandicarboxylic acid and decamethylene diamine with equal molar ratio and distilled water with equal mass into a reaction kettle, uniformly mixing, filling nitrogen and pressurizing to 0.3MPa;
(2) Starting stirring, heating to 250 ℃ at the heating rate of 5 ℃/min, discharging redundant water vapor to keep the pressure of the reaction kettle at 3MPa, and carrying out heat preservation and pressure maintaining reaction for 1h;
(3) Reducing the pressure of the reaction kettle to normal pressure at the pressure relief rate of 0.05MPa/min to prepare a prepolymer;
(4) Adding a catalyst of a silicon dioxide/titanium dioxide compound and aminoundecanoic acid into the prepolymer prepared in the step (3), wherein the addition amounts of the silicon dioxide/titanium dioxide and the aminododecanoic acid are 0.2wt% and 50wt% of the prepolymer respectively, and reacting for 3h at 300 ℃ and 2000Pa absolute pressure to prepare the nylon copolymer.
Example 4
(1) Adding furandicarboxylic acid, sebacic acid, decamethylene diamine and distilled water with equal mass into a reaction kettle under the nitrogen atmosphere, uniformly mixing, filling nitrogen and pressurizing to 0.2MPa. Wherein, the molar ratio of furan dicarboxylic acid and sebacic acid to decamethylene diamine is 1.8, and the molar ratio of furan dicarboxylic acid to sebacic acid is 4;
(2) Starting stirring, heating to 260 ℃ at the heating rate of 5 ℃/min, discharging redundant water vapor to keep the pressure of the reaction kettle at 2MPa, and carrying out heat preservation and pressure maintaining reaction for 2h;
(3) Reducing the pressure of the reaction kettle to normal pressure at the pressure relief rate of 0.08MPa/min to prepare a prepolymer;
(4) And (4) adding tetrabutyl titanate and aminoundecanoic acid serving as catalysts into the prepolymer prepared in the step (3), wherein the addition amounts of zinc acetate and aminoundecanoic acid are 0.2wt% and 5wt% of the prepolymer respectively, and reacting for 1.5h at 320 ℃ under the absolute pressure of 1000Pa to obtain the nylon copolymer.
Example 5
(1) Under the nitrogen atmosphere, adding furandicarboxylic acid, sebacic acid, butanediamine and distilled water with equal mass into a reaction kettle, uniformly mixing, filling nitrogen and pressurizing to 0.2MPa. Wherein, the molar ratio of furan dicarboxylic acid and sebacic acid to decamethylene diamine is 1.2, and the molar ratio of furan dicarboxylic acid to sebacic acid is 6;
(2) Starting stirring, heating to 270 ℃ at the heating rate of 5 ℃/min, discharging redundant water vapor to keep the pressure of the reaction kettle at 2MPa, and carrying out heat preservation and pressure maintaining reaction for 2h;
(3) Reducing the pressure of the reaction kettle to normal pressure at the pressure relief rate of 0.01MPa/min to prepare a prepolymer;
(4) Adding ethylene glycol antimony and aminoundecanoic acid serving as catalysts into the prepolymer prepared in the step (3), wherein the addition amounts of the ethylene glycol antimony and the aminoundecanoic acid are 0.2wt% and 20wt% of the prepolymer respectively, and reacting for 3h at 300 ℃ and 8000Pa absolute pressure to obtain the nylon copolymer.
TABLE 1 Table of sample Property parameters
Figure BDA0003916953060000081

Claims (10)

1. A high-performance bio-based copolymerized nylon, comprising a first repeating unit represented by formula (I), a second repeating unit represented by formula (II), and a third repeating unit represented by formula (III):
Figure FDA0003916953050000011
Figure FDA0003916953050000012
Figure FDA0003916953050000013
R 1 is selected from
Figure FDA0003916953050000014
R 2 Is selected from
Figure FDA0003916953050000015
R 3 Is selected from
Figure FDA0003916953050000016
Wherein x is an integer of 4 to 10, y is an integer of 4 to 8, and z is an integer of 10 to 11;
based on the total molar weight of the copolymerized nylon, the content of the first repeating unit is 1-98 mol%, the content of the second repeating unit is 0-97 mol%, and the content of the third repeating unit is 1-98 mol%.
2. The high performance bio-based copolymerized nylon of claim 1, wherein the content of the first repeating unit is 39 to 60mol%, the content of the third repeating unit is 39 to 60mol%, and the content of the second repeating unit is 0 to 20mol%, based on the total molar weight of the copolymerized nylon.
3. A method for preparing the high-performance bio-based copolymerized nylon of claim 1, comprising:
(1) Under the nitrogen atmosphere, the monomer a and the monomer containing R which are uniformly mixed are added 1 And a monomer b and a monomer containing R 2 The monomer c and distilled water are added into a reaction kettle together, nitrogen is filled into the reaction kettle, the pressure is increased to 0.2 to 0.3MPa, and the mass of the added distilled water is equal to the sum of the mass of the monomer a, the mass of the monomer b and the mass of the monomer c;
(2) Starting stirring, heating, keeping the temperature and pressure for reaction, and discharging redundant water vapor to keep the pressure of the reaction kettle at 2-3 MPa;
(3) Decompressing to reduce the pressure of the reaction kettle to normal pressure to prepare prepolymer X;
(4) Adding a catalyst and a catalyst containing R to the prepolymer X obtained in the step (3) 3 Heating the monomer d, and carrying out reduced pressure polycondensation reaction to obtain copolymerized nylon;
said R is 1 、R 2 、R 3 As claimed in claim 1;
the monomer a is 2, 5-furan dicarboxylic acid, 2, 5-furan dicarboxylic diester or a mixture thereof; wherein the 2, 5-furandicarboxylic acid diester is dimethyl 2, 5-furandicarboxylic acid or diethyl 2, 5-furandicarboxylic acid;
the monomer b is at least one of pentanediamine, hexanediamine and decanediamine;
the monomer c is at least one of adipic acid and sebacic acid;
the monomer d is at least one of aminoundecanoic acid and aminododecanoic acid.
4. The method for preparing high-performance bio-based copolymerized nylon according to claim 3, wherein in the step (1), the molar ratio of the sum of the monomer a and the monomer c to the monomer b is 1; the amount of the monomer c is 0 to 95mol percent of the total molar amount of the monomer a and the monomer c.
5. The method for preparing high performance bio-based copolymerized nylon of claim 3, wherein in the step (2), the temperature raising rate is 2-5 ℃/min, and the temperature is raised to 240-270 ℃ for heat preservation and pressure maintenance for 1-3 h, and the pressure for pressure maintenance is 2-3 MPa.
6. The method for preparing high-performance bio-based copolymerized nylon according to claim 3, wherein in the step (3), the rate of pressure release is 0.04-0.1 MPa/min.
7. The method for preparing high-performance bio-based copolymerized nylon according to claim 3, wherein in the step (4), the amount of the monomer d is 1 to 99% of the total mass of the prepolymer X and the monomer d.
8. The method for preparing high-performance bio-based copolymerized nylon according to claim 3, wherein in the step (4), the temperature is raised to 280-330 ℃ and the time of the polycondensation reaction under reduced pressure is 1-3 h.
9. The method for preparing high performance bio-based nylon copolymer according to claim 3, wherein in the step (4), the catalyst is one or more of n-butyl titanate, isopropyl titanate, titanium glycol, titanium acetylacetonate, antimony glycol, antimony trioxide, antimony acetate, zinc acetate, manganese acetate, lead acetate, calcium acetate, cobalt acetate, potassium acetate, magnesium acetate, barium acetate, lithium acetate, a silica/titania composite, a silica/titania/nitrogen-containing compound composite, and a silica/titania/phosphorus-containing compound composite.
10. The method for preparing high-performance bio-based copolymerized nylon according to claim 3, wherein in the step (4), an auxiliary agent is added in the reduced pressure polycondensation reaction, and the amount of the auxiliary agent is 0.1-20% of the amount of the monomer d;
the auxiliary agent is one or more of a heat stabilizer, a light stabilizer or an inorganic filler.
CN202211345174.2A 2022-10-31 2022-10-31 High-performance bio-based copolymerized nylon and preparation method thereof Pending CN115505120A (en)

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