CN117209751A - Preparation method of all-bio-based polyamide - Google Patents
Preparation method of all-bio-based polyamide Download PDFInfo
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- CN117209751A CN117209751A CN202210626360.7A CN202210626360A CN117209751A CN 117209751 A CN117209751 A CN 117209751A CN 202210626360 A CN202210626360 A CN 202210626360A CN 117209751 A CN117209751 A CN 117209751A
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- 229920006021 bio-based polyamide Polymers 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title abstract description 7
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 claims abstract description 90
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 30
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 7
- 238000006114 decarboxylation reaction Methods 0.000 claims abstract description 6
- 239000012266 salt solution Substances 0.000 claims description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 238000006116 polymerization reaction Methods 0.000 claims description 22
- 230000008569 process Effects 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229920013724 bio-based polymer Polymers 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000011010 flushing procedure Methods 0.000 claims description 2
- 238000005755 formation reaction Methods 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- VSWICNJIUPRZIK-UHFFFAOYSA-N 2-piperideine Chemical compound C1CNC=CC1 VSWICNJIUPRZIK-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000007787 solid Substances 0.000 claims 1
- 239000004952 Polyamide Substances 0.000 abstract description 15
- 229920002647 polyamide Polymers 0.000 abstract description 15
- 238000007069 methylation reaction Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 238000002329 infrared spectrum Methods 0.000 description 7
- 230000008859 change Effects 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- -1 glutarimide furandicarboxylate Chemical compound 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- DNXDYHALMANNEJ-UHFFFAOYSA-N furan-2,3-dicarboxylic acid Chemical compound OC(=O)C=1C=COC=1C(O)=O DNXDYHALMANNEJ-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 230000011987 methylation Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical class [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241001649081 Dina Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 229920006141 Polyamide 5X Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
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- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- FXJUUMGKLWHCNZ-UHFFFAOYSA-N dimethyl furan-2,3-dicarboxylate Chemical compound COC(=O)C=1C=COC=1C(=O)OC FXJUUMGKLWHCNZ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- XTBMQKZEIICCCS-UHFFFAOYSA-N hexane-1,5-diamine Chemical compound CC(N)CCCCN XTBMQKZEIICCCS-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003880 polar aprotic solvent Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920000414 polyfuran Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
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- 150000003384 small molecules Chemical class 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
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- Polyamides (AREA)
Abstract
The invention relates to a preparation method of full bio-based polyamide, which takes bio-based FDCA and bio-based 1, 5-pentanediamine as raw materials and adopts a salification-step polycondensation method to prepare full bio-based polyamide PA5F. Overcomes the defects that the FDCA can generate decarboxylation reaction and thermal shrinkage methylation reaction to generate monofunctional substances or non-reactive micromolecules when the temperature is higher than 190 ℃, and the high-pressure condition inhibits the volatility of 1, 5-pentanediamine in the reaction process, thereby realizing two reactive groups-NH 2 and-COOH equivalent reaction, which is favorable for the generation of polyamide with high molecular weight and narrow molecular weight distribution.
Description
Technical Field
The invention relates to a preparation method of full-biobased polyamide, belonging to the technical field of chemical industry.
Background
The biobased 2, 5-furandicarboxylic acid (FDCA) has fewer carbon atoms than benzene rings and weaker aromaticity than benzene rings, and can be used for producing polyester or polyamide instead of terephthalic acid. The intramolecular hydrogen bond in the FDCA-based polyamide can lead the furan and the amide bond to preferentially adopt a planar all-trans configuration, so that the polyamide chain structure has higher rigidity and fewer free spaces, the glass transition temperature of the material can be improved, and the crystallinity of the material can be reduced. Compared with petroleum-based polyamide, the biological-based polyamide containing furan groups has good solubility, can be completely dissolved in polar aprotic solvents, such as dimethyl sulfoxide, N-dimethylformamide and N, N-dimethylacetamide, and avoids the problem of degradation of the polyamide in different degrees when the polyamide is dissolved in a strong acid-base solvent.
The structure and the properties of the bio-based 1, 5-pentanediamine are similar to those of 1, 6-hexanediamine from petrochemical sources, so that the bio-based 1, 5-hexanediamine can also replace the 1, 6-hexanediamine to be used for producing products such as polyamide, polyurethane and the like. The polyamide 5X (PA 54, PA56, etc.) produced by polymerizing the bio-based 1, 5-pentanediamine and the dibasic acid has excellent performance, is a novel bio-based polyamide material developed in recent years, and can be used for preparing fibers (such as clothing, automobile tire cord fabric, carpets, pipelines, etc.) and engineering plastics (such as electronic instrument products, automobile parts, etc.).
The synthesis of furandicarboxylic acid based polyamides has been generally carried out at high temperatures, but furandicarboxylic acid monomers are susceptible to decarboxylation and thermal shrinkage methylation (chemical evolution 2018.30 (12): p.1836-1843.). 1, 5-pentanediamine is volatile and can be lost in large quantities under high temperature conditions. The above properties of the two monomers can lead to the fact that the two reaction groups of amino and carboxyl can not realize equivalent ratio reaction, which brings difficulty to the preparation of the polyfuran diformylpentylene diamine (PA 5F) by a high-temperature polycondensation method. In 2015, yi Jiang, dina Maniar et al used 20wt.% of Norweskinase 435 (N435) in toluene solution at 60℃in one step or in diphenyl ether at 140℃in two steps to prepare PA8F with molecular weight up to 54000g/mol, much higher than PA8F synthesized by high temperature melt polycondensation (RSC Advances,2016.6 (72): p.67941-67953.), however the above method used toxic organic solvents and purification after reaction was complicated. In addition, since the enzyme-catalyzed reaction is selective, huang Weijun et al prepared PA5F, M using 1, 5-pentanediamine and dimethyl furandicarboxylate (DMFDCA) as reaction monomers in the same manner n 5300g/mol, has very low molecular weight (Industrial)&Engineering Chemistry Research,2020.59 (30): p.13588-13594.). And, DMFDCA is much more costly to prepare than FDCA. Whereas the molecular weight distribution (PDI) of PA5F is relatively broad (typically 2 or more) with conventional melt polycondensation processes.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of full bio-based polyamide, which comprises the following steps:
1) The salt formation reaction of biobased 2, 5-furandicarboxylic acid (FDCA) and biobased 1, 5-pentanediamine:
2, 5-furandicarboxylic acid and 1, 5-pentanediamine are mixed in water to carry out salification reaction, the reaction is complete when the pH value of the solution is no longer changed, and the salification reaction equation is as follows:
2) And (3) ammonium salt polycondensation reaction:
adjusting the pH value of the salt solution prepared in the step 1) to 7-9 by using a 1, 5-pentanediamine aqueous solution, measuring the refractive index by an Abbe refractometer, and calibrating the salt solution prepared in the step 1) according to a standard curve of the salt solution with known concentration, wherein the salt solution with the concentration of 30-70 wt% can be subjected to the next polymerization reaction;
placing the salt solution prepared in the step 1) in a high-temperature high-pressure reactor, flushing nitrogen for more than 1 time to remove oxygen existing in the reactor, heating to 180-220 ℃, keeping the pressure to 1.7-2.6 MPa, and carrying out pressure maintaining prepolymerization under the pressure to convert salt from micromolecules to oligomers, so as to prevent decarboxylation of FDCA monomer in the subsequent polycondensation reaction process, wherein the temperature is increased to 200-230 ℃ in the process, the temperature at which ammonium salt starts to degrade is the upper limit of the prepolymerization reaction temperature; then, the polymerization reaction is started before the pressure is reduced to normal pressure, a large amount of water vapor is discharged during the pressure reduction to promote the forward progress of the polycondensation reaction, the temperature is increased to 230-260 ℃ in the process, the temperature at which the PA5F starts to degrade is 260 ℃, and the upper limit of the polymerization reaction temperature is set; and then the mixture enters a post-polymerization reaction stage, and is vacuumized, filled with nitrogen and discharged, so that the full bio-based polymer PA5F can be obtained.
According to an embodiment of the present invention, in step 1), the purity of 2, 5-furandicarboxylic acid is 95% or more, preferably 98% or more, and still preferably 99% or more.
According to an embodiment of the present invention, in step 1), the purity of 1, 5-pentanediamine is 95% or more, preferably 98% or more, and still preferably 99% or more.
According to an embodiment of the invention, in step 1), the molar ratio of 2, 5-furandicarboxylic acid to 1, 5-pentanediamine is 1 (1-1.2), preferably 1:1.
According to the present inventionIn an embodiment of the invention, in step 1), the reaction is carried out under oxygen-free conditions, for example by passing N 2 Oxygen is removed.
According to an embodiment of the invention, in step 1), the reaction temperature is 40℃to 90 ℃.
According to an embodiment of the invention, in step 1), the reaction time is from 10 to 120 minutes, preferably from 40 to 60 minutes.
According to an embodiment of the invention, in step 2) the concentration of the aqueous 1, 5-pentanediamine solution used to adjust the pH is 30-70 wt.%, e.g., 40-60 wt.%, such as 50wt.%.
According to an embodiment of the invention, in step 2), the nitrogen is flushed 2-5 times, for example 3 times, to remove the oxygen present in the reactor.
According to the embodiment of the invention, in the step 2), the pH of the salt solution depends on the relative content of 1, 5-pentanediamine and FDCA in the system, and the salt solution is generally prepared by feeding according to the molar ratio of FDCA to 1, 5-pentanediamine of 1 (1-1.2), and the 1, 5-pentanediamine is inevitably carried out by water vapor in the prepolymerization process, so that the subsequent equivalent polymerization reaction of amino groups and carboxyl groups cannot be realized to obtain a polymer with higher molecular weight, and therefore, a proper amount of 1, 5-pentanediamine needs to be added. The newly prepared salt solution can smoothly react by adjusting the pH value to 7-9 by using 30-70 wt.% of newly rectified 1, 5-pentanediamine aqueous solution; the pH of the salt solution is adjusted to 8-10 by adding 1, 5-pentanediamine for reaction, and the polymer with higher amino content can be obtained by higher pH.
According to an embodiment of the invention, in step 2), the heating to 180-220℃and the pressure to 1.7-2.6 MPa are controlled to be carried out within 0.5-4 hours, for example within 1.5-2.5 hours.
According to an embodiment of the invention, in step 2), the dwell time is from 0.5 to 4 hours, for example from 1.5 to 2.5 hours.
According to an embodiment of the present invention, in step 2), the pre-polymerization is depressurized to normal pressure within 10 to 60 minutes.
According to an embodiment of the invention, in step 2), the time required for the evacuation of the post-polymerization stage is from 5 to 240 minutes, for example from 10 to 120 minutes.
According to an embodiment of the invention, in step 2), the pressure during the reaction must not be lower than 1.7MPa in order to prevent volatilization of 1, 5-pentanediamine, and the loss of 1, 5-pentanediamine during the pressure maintaining and evacuating stages is relatively large, for example, the pressure is controlled to be 1.7-2 MPa.
The invention also provides an all-bio-based polymer PA5F obtained by the method.
According to an embodiment of the invention, M of the all-bio-based polymer PA5F w In the range of 11000 to 21000g/mol, a higher molecular weight can be obtained by adjusting the temperature and polymerization time of the post-polymerization reaction.
According to an embodiment of the invention, the all bio-based polymer PA5F has a PDI of 1 to 1.8, preferably 1.2 to 1.4.
Advantageous effects
The preparation method of the invention avoids the problem that the molecular weight is difficult to be increased in the polycondensation process caused by FDCA decarboxylation reaction and 1, 5-pentanediamine volatilization by indirectly regulating and controlling the material proportion by means of pH, regulating and controlling the temperature, the pressure and the like in the prepolymerization and the polymerization processes, and obtains M by the reaction of two simple monomers of FDCA and 1, 5-pentanediamine w PA5 f=11000 to 21000 g/mol. The process conditions of the invention have the characteristic of green reaction process, and compared with enzyme catalytic reaction, the invention has great advantages in the aspect of reaction efficiency (short reaction time and no need of purification of the obtained product).
The invention takes biobased FDCA and biobased 1, 5-pentanediamine as raw materials, and adopts a salification-step polycondensation method to prepare the full biobased polyamide PA5F. First, the polymerization process overcomes the decarboxylation and thermal condensation methylation of FDCA to monofunctional species or non-reactive small molecules at temperatures above 190 ℃. Secondly, the bio-based FDCA and the bio-based 1, 5-pentanediamine are used for high-pressure prepolymerization in aqueous solution, thereby inhibiting the volatilization of the 1, 5-pentanediamine in the reaction process and realizing two reactive groups-NH 2 and-COOH equivalent reaction, which is favorable for the generation of polyamide with high molecular weight and narrow molecular weight distribution.
In addition, the molecular weight of the all-bio-based polyamide PA5F product obtained by the method of the invention is high (M n 10000 or more), and the molecular weight distribution of the product is obviously improved (narrow molecular weight distribution (PDI is 1.2-1.4)]. Secondly, the obtained polymer product has higher structural rigidity and less free space, improves the glass transition temperature, reduces the crystallinity and even does not crystallize. In addition, the organic solvent can be dissolved in various organic solvents, so that the organic solvent has high potential commercial application value.
Drawings
FIG. 1 is a standard curve of salt solution concentration as measured by Abbe refractometer.
FIG. 2 is an infrared spectrum of glutarimide furandicarboxylate and polymer PA5F.
FIG. 3 is a nuclear magnetic hydrogen spectrum of PA5F.
FIG. 4 shows the dissolution of the product PA5F into DMF, DMAc, DMSO and formic acid at a concentration of 100mg/mL.
FIG. 5 shows DSC curves of PA5F with heating and cooling rates of 10℃per minute.
Detailed Description
The technical scheme of the invention will be further described in detail below with reference to specific embodiments. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods.
The number average molecular weight and the weight average molecular weight of the product in the following examples were determined by Gel Permeation Chromatography (GPC), N-dimethylformamide DMF as a solvent, and lithium bromide LiBr (99%, 0.1M) was added to the solvent to avoid aggregation of the polyamide. PMMA standard was calibrated.
The salt concentrations in the following examples were each determined by means of a standard curve by means of an Abbe refractometer.
The standard curve making method comprises the following steps: 5.24g of FDCA and 3.44g of 1, 5-pentanediamine are mixed, 16.12 g, 13.02 g, 5.79 g and 3.72g of deionized water are respectively added for reaction, and 30, 40, 60 and 70wt.% of salt solution are obtained, and the refractive indexes of the salt solution are respectively 1.41, 1.42, 1.47 and 1.50 as measured by an Abbe refractometer. The mass percent and refractive index of the salt solution are plotted as shown in FIG. 1. Linear fitting was performed to obtain the linear equation y=0.23477x+1.32928, r 2 ＝0.9978。
Example 1
52.24g of FDCA (99.7% purity) and 86.54g of deionized water were placed in a 250mL three-necked flask, and a magnet was placed therein and stirred at a rotation speed of 150r/min to form a white homogenate. Introducing N 2 The gas removes oxygen from the solution. After 30min, the mixture was heated to 60℃and 36.70g of 1, 5-pentanediamine (purity 98%) was added dropwise using a constant pressure dropping funnel. The pH change in the solution was monitored throughout. After 40min of reaction, the pH remained unchanged at 7.6, indicating the end of the reaction. Then adding 90g of active carbon and a proper amount of distilled water, uniformly stirring and decoloring, standing for 1h, and carrying out suction filtration for 3 times to obtain a colorless transparent aqueous solution, and carrying out rotary evaporation and concentration. The refractive index of the solution was measured by Abbe refractometer, and the salt content was 50wt.% compared with the standard curve (FIG. 1) and used for the next polymerization reaction.
The infrared spectrum of the obtained glutarimide furandicarboxylate salt is shown in figure 2, which is 1637cm -1 At the carboxyl group (-COO) - ) And 2500-3700 cm -1 Ammonium salt-NH at 3 + The binding peak demonstrated that glutarimide furandicarboxylate was obtained.
Example 2
52.24g of FDCA (99.7% purity) and 86.54g of deionized water were placed in a 250mL three-necked flask, and a magnet was placed therein and stirred at a rotation speed of 150r/min to form a white homogenate. Introducing N 2 The gas removes oxygen from the solution. After 30min, the mixture was heated to 40℃and 36.70g of 1, 5-pentanediamine (purity 98%) was added dropwise using a constant pressure dropping funnel. The pH value in the solution is monitored to change in the whole process, and after the reaction is carried out for 60min, the pH value is kept at 8.5 and does not change any more, which indicates that the reaction is finished. Then 90g of activated carbon and are addedAnd (3) uniformly stirring and decoloring a proper amount of distilled water, standing for 1h, and carrying out suction filtration for 3 times to obtain a colorless transparent aqueous solution, and concentrating by rotary evaporation. The refractive index of the solution was measured by Abbe refractometer, and the salt content was 50wt.% compared with the standard curve (FIG. 1) and used for the next polymerization reaction. The infrared spectrum of the salt was the same as in example 1.
Example 3
52.24g of FDCA (99.7% purity) and 86.54g of deionized water were placed in a 250mL three-necked flask, and a magnet was placed therein and stirred at a rotation speed of 150r/min to form a white homogenate. Introducing N 2 The gas removes oxygen from the solution. After 30min, the mixture was heated to 90℃and 36.70g of 1, 5-pentanediamine (purity 98%) was added dropwise using a constant pressure dropping funnel. The pH value in the solution is monitored to change in the whole process, and after the reaction is carried out for 40min, the pH value is kept at 7.0 and does not change any more, which indicates that the reaction is finished. Then adding 90g of active carbon and a proper amount of distilled water, uniformly stirring and decoloring, standing for 1h, and carrying out suction filtration for 3 times to obtain a colorless transparent aqueous solution, and carrying out rotary evaporation and concentration. The refractive index of the solution was measured by Abbe refractometer, and the salt content was 50wt.% compared with the standard curve (FIG. 1) and used for the next polymerization reaction. The infrared spectrum of the salt was the same as in example 1.
Example 4
The salt solution freshly prepared in example 1 was placed in a high temperature and high pressure reactor, the pH was adjusted to about 8.0 with freshly distilled 50wt.% aqueous 1, 5-pentanediamine at 60 ℃, vacuum pumped, nitrogen filled three times, warmed up to 210℃over 2 hours, the pressure reached 2.0MPa, and the prepolymer was maintained at this pressure for 2 hours. During which the temperature was increased to 230 c. Then decompression is started, the pressure is reduced to normal pressure for 50min, the reaction temperature reaches 260 ℃, then vacuum is pumped for 60min, and nitrogen is filled for discharging. M of the product PA5F obtained by GPC testing n 15000g/mol, M w 21000g/mol and PDI of 1.4.
3316cm in the IR spectrum of PA5F in FIG. 2 -1 Amide N-H stretching vibration 1655cm -1 C=o stretching vibration 1529cm -1 N-H bending vibrations and C-N stretching vibrations are combined. 1575-1596 cm -1 C=c stretching vibration on furan ring.
FIG. 3 is a nuclear magnetic hydrogen spectrum, delta, of PA5F=1.0 to 1.4, 1.4 to 1.79, 3.0 to 3.6ppm ascribed to diamine segment-NHCH 2 CH 2 CH 2 CH 2 CH 2 Hydrogen on methylene in NH-, δ=7.11 ppm is attributed to hydrogen in furan ring, δ=8.47 to 8.48ppm is attributed to hydrogen in amide bond-CONH-.
Solubility test: 100mg of the product PA5F was taken and placed in 1mL of N, N-Dimethylacetamide (DMF), N-dimethylformamide (DMAc), dimethyl sulfoxide (DMSO) and formic acid, respectively, and the results showed that PA5F was completely dissolved in the above solvent for 30 min. The dissolution results are shown in FIG. 4.
Thermal performance test: DSC test is carried out by taking 6mg of PA5F, heating to 300 ℃ at a heating rate of 10 ℃/min, eliminating heat history isothermally for 5min, then cooling to 40 ℃ at a cooling rate of 10 ℃/min, and heating to 300 ℃ again at a heating rate of 10 ℃/min, thus obtaining a DSC curve shown in figure 5. The results indicate T of the polymer g The melting peak and crystallization peak of the polymer are not detected at 97.8 ℃, which indicates that intramolecular hydrogen bonds in the FDCA-based polyamide can lead furan and amide bonds to preferentially adopt a planar all-trans configuration, and the performance of the material can be really influenced, so that the rigidity of the polyamide chain structure is higher, the free space is less, the glass transition temperature is improved, the crystallinity is reduced, and even the polyamide chain is not crystallized.
Example 5
The freshly prepared salt solution of example 2 was placed in a high temperature and high pressure reactor, the pH was adjusted to about 7.6 with freshly distilled 50wt.% aqueous 1, 5-pentanediamine at 60 ℃, vacuum pumped, nitrogen filled three times, warmed up to 200℃over 2 hours, the pressure reached 1.8MPa, and the prepolymer was maintained at this pressure for 2 hours. During which the temperature was increased to 220 c. Then decompression is started, the pressure is reduced for 50min to normal pressure, the reaction temperature reaches 250 ℃, then vacuum is pumped for 20min, and nitrogen is filled for discharging. M of the product PA5F obtained by GPC testing n 11000g/mol, M w 13000g/mol and PDI 1.2. The results of the structural characterization, solubility and thermal properties of the infrared spectrum and the nuclear magnetic hydrogen spectrum are the same as those of example 4.
Example 6
The freshly prepared salt solution of example 3 was placed in a high temperature and high pressure reactor at 60 ℃The pH is regulated to about 9.0 by using a newly distilled 50wt.% 1, 5-pentanediamine aqueous solution, vacuumizing and filling nitrogen three times, heating is carried out, the temperature is increased to 220 ℃ in 2 hours, the pressure reaches 1.9MPa, and the pressure is maintained for prepolymerization for 2 hours. During which the temperature was increased to 230 c. Then decompression is started, the pressure is reduced to normal pressure for 10min, the reaction temperature reaches 240 ℃, then vacuum is pumped for 120min, and nitrogen is filled for discharging. M of the product PA5F obtained by GPC testing n 14000g/mol, M w 18000g/mol and PDI of 1.3. The results of the structural characterization, solubility and thermal properties of the infrared spectrum and the nuclear magnetic hydrogen spectrum are the same as those of example 4.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for preparing an all-bio-based polyamide, comprising the steps of:
1) The salt formation reaction of biobased 2, 5-furandicarboxylic acid (FDCA) and biobased 1, 5-pentanediamine:
2, 5-furandicarboxylic acid and 1, 5-pentanediamine are mixed in water to carry out salification reaction, the reaction is complete when the pH value of the solution is no longer changed, and the salification reaction equation is as follows:
2) And (3) ammonium salt polycondensation reaction:
adjusting the pH value of the salt solution prepared in the step 1) to 7-9 by using a 1, 5-pentanediamine aqueous solution, measuring the refractive index by an Abbe refractometer, and calibrating the salt solution prepared in the step 1) according to a standard curve of the salt solution with known concentration, wherein the salt solution with the concentration of 30-70 wt% can be subjected to the next polymerization reaction;
placing the salt solution prepared in the step 1) in a high-temperature high-pressure reactor, flushing nitrogen for more than 1 time to remove oxygen existing in the reactor, heating to 180-220 ℃, keeping the pressure to 1.7-2.6 MPa, and carrying out pressure maintaining prepolymerization under the pressure to convert salt from micromolecules to oligomers, so as to prevent decarboxylation of FDCA monomer in the subsequent polycondensation reaction process, wherein the temperature is increased to 200-230 ℃ in the process, the temperature at which ammonium salt starts to degrade is the upper limit of the prepolymerization reaction temperature; then, the polymerization reaction is started before the pressure is reduced to normal pressure, a large amount of water vapor is discharged during the pressure reduction to promote the forward progress of the polycondensation reaction, the temperature is increased to 230-260 ℃ in the process, the temperature at which the PA5F starts to degrade is 260 ℃, and the upper limit of the polymerization reaction temperature is set; and then the mixture enters a post-polymerization reaction stage, and is vacuumized, filled with nitrogen and discharged, so that the full bio-based polymer PA5F can be obtained.
2. The process according to claim 1, wherein in step 1), the purity of 2, 5-furandicarboxylic acid is 95% or more;
preferably, the purity of 1, 5-pentanediamine is 95% or more.
Preferably, the molar ratio of 2, 5-furandicarboxylic acid to 1, 5-pentanediamine is 1 (1-1.2).
3. The process according to claim 1 or 2, wherein in step 1) the reaction is carried out under oxygen-free conditions.
4. A process according to any one of claims 1 to 3, wherein in step 1) the reaction temperature is from 40 ℃ to 90 ℃;
preferably, the reaction time is from 10 to 120 minutes.
5. The process according to any one of claims 1 to 4, wherein in step 2), the concentration of the aqueous solution of 1, 5-pentanediamine used for adjusting the pH is 30 to 70wt.%.
6. The process according to any one of claims 1 to 5, wherein in step 2), the pH of the salt solution depends on the relative contents of 1, 5-pentanediamine and FDCA in the system, and the salt solution is generally prepared by feeding the salt solution according to the molar ratio of FDCA to 1, 5-pentanediamine of 1 (1-1.2), wherein the 1, 5-pentanediamine is inevitably carried out by steam in the prepolymerization process, so that the equivalent polymerization of amino and carboxyl in the subsequent reaction cannot be realized to obtain a polymer with higher molecular weight, and therefore, a proper amount of 1, 5-pentanediamine is required to be added;
preferably, the newly prepared salt solution can be smoothly reacted by adjusting the pH to 7-9 with 30-70 wt.% aqueous solution of freshly rectified 1, 5-pentanediamine; the 1, 5-pentanediamine in the salt solution stored for a period of time can be degenerated into tetrahydropyridine, so that the pH of the salt solution is increased, but the salt solution is volatilized at about 110-130 ℃, and yellow foam-like solid is brought out of the evacuated tube by water vapor after the pressure is maintained for about 0.5-3 hours, so that the polymerization is not affected, but the pH of the salt solution is adjusted to 8-10 by adding the 1, 5-pentanediamine for reaction.
7. The process according to any one of claims 1 to 6, wherein in step 2), the temperature is raised to 180 to 220 ℃ and the pressure is controlled to 1.7 to 2.6MPa within 0.5 to 4 hours.
8. The process according to any one of claims 1 to 7, wherein in step 2), the dwell time is from 0.5 to 4 hours.
Preferably, the pre-polymerization is depressurized to normal pressure within 10 to 60 minutes.
Preferably, the time required for evacuation in the post-polymerization stage is 10 to 120 minutes.
9. An all-bio-based polymer PA5F obtained by the production process according to any one of claims 1-8.
10. The all-bio-based polymer PA5F of claim 9, wherein M of the all-bio-based polymer PA5F w 11000-21000 g/mol;
preferably, the PDI is 1 to 1.8.
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4806623A (en) * | 1986-08-20 | 1989-02-21 | Stamicarbon B.V. | Poly(p-phenylene-2,5-furandicarbonamide), anisotropic solution, filament, film thereof |
| US5504182A (en) * | 1990-12-01 | 1996-04-02 | Hoechst Aktiengesellschaft | Thermoplastically processable aromatic polyether amide |
| CN106011192A (en) * | 2016-07-22 | 2016-10-12 | 南京工业大学 | Bio-based aramid fiber based on furandicarboxylic acid and preparation method thereof |
| CN106191145A (en) * | 2016-07-22 | 2016-12-07 | 南京工业大学 | Semi-aromatic polyamide based on furandicarboxylic acid and preparation method thereof |
| CN110669216A (en) * | 2019-10-21 | 2020-01-10 | 四川斯派恩新材料有限公司 | Bio-based semi-aromatic polyamide and preparation method thereof |
| CN110684190A (en) * | 2019-08-19 | 2020-01-14 | 浙江新力新材料股份有限公司 | Preparation method of bio-based high-temperature nylon |
| CN111234207A (en) * | 2020-03-04 | 2020-06-05 | 东华大学 | Transparent bio-based polyamide and preparation method thereof |
| CN111471297A (en) * | 2020-05-11 | 2020-07-31 | 浙江新力新材料股份有限公司 | Preparation method and application of bio-based transparent polyamide |
| CN111925521A (en) * | 2019-05-13 | 2020-11-13 | 中国石油天然气股份有限公司 | Full-bio-based polyamide and preparation method thereof |
| CN112111058A (en) * | 2020-10-16 | 2020-12-22 | 天津工业大学 | Preparation method of furan dicarboxylic acid diamine high polymer |
| CN113429569A (en) * | 2021-07-23 | 2021-09-24 | 四川大学 | Preparation method of high molecular weight furan polyamide |
-
2022
- 2022-06-02 CN CN202210626360.7A patent/CN117209751A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4806623A (en) * | 1986-08-20 | 1989-02-21 | Stamicarbon B.V. | Poly(p-phenylene-2,5-furandicarbonamide), anisotropic solution, filament, film thereof |
| US5504182A (en) * | 1990-12-01 | 1996-04-02 | Hoechst Aktiengesellschaft | Thermoplastically processable aromatic polyether amide |
| CN106011192A (en) * | 2016-07-22 | 2016-10-12 | 南京工业大学 | Bio-based aramid fiber based on furandicarboxylic acid and preparation method thereof |
| CN106191145A (en) * | 2016-07-22 | 2016-12-07 | 南京工业大学 | Semi-aromatic polyamide based on furandicarboxylic acid and preparation method thereof |
| CN111925521A (en) * | 2019-05-13 | 2020-11-13 | 中国石油天然气股份有限公司 | Full-bio-based polyamide and preparation method thereof |
| CN110684190A (en) * | 2019-08-19 | 2020-01-14 | 浙江新力新材料股份有限公司 | Preparation method of bio-based high-temperature nylon |
| CN110669216A (en) * | 2019-10-21 | 2020-01-10 | 四川斯派恩新材料有限公司 | Bio-based semi-aromatic polyamide and preparation method thereof |
| CN111234207A (en) * | 2020-03-04 | 2020-06-05 | 东华大学 | Transparent bio-based polyamide and preparation method thereof |
| CN111471297A (en) * | 2020-05-11 | 2020-07-31 | 浙江新力新材料股份有限公司 | Preparation method and application of bio-based transparent polyamide |
| CN112111058A (en) * | 2020-10-16 | 2020-12-22 | 天津工业大学 | Preparation method of furan dicarboxylic acid diamine high polymer |
| CN113429569A (en) * | 2021-07-23 | 2021-09-24 | 四川大学 | Preparation method of high molecular weight furan polyamide |
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