CN110655647A - Thermo-rearrangement poly (benzoxazole-co-amide) copolymer film and preparation and application thereof - Google Patents

Thermo-rearrangement poly (benzoxazole-co-amide) copolymer film and preparation and application thereof Download PDF

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CN110655647A
CN110655647A CN201810713013.1A CN201810713013A CN110655647A CN 110655647 A CN110655647 A CN 110655647A CN 201810713013 A CN201810713013 A CN 201810713013A CN 110655647 A CN110655647 A CN 110655647A
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曹义鸣
叶璐
王丽娜
介兴明
俞聪瑶
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Dalian Institute of Chemical Physics of CAS
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Abstract

The invention relates to a preparation method of a thermal rearrangement poly (benzoxazole-co-amide) copolymer film and gas separation performance thereof. By heat-treating the polyamide copolymer precursor film containing hydroxyl at the ortho-position, the poly (benzoxazole-co-amide) separation film with better mechanical property can be prepared under the conditions of lower temperature and less severe heat treatment. The proportion of diamine monomers and the heat treatment condition are adjusted to obtain the thermally rearranged poly (benzoxazole-co-amide) gas separation membrane with different performances, the permeability and selectivity of most membranes are close to or even exceed the upper limit of Robeson, and the membrane shows excellent thermal stability and anti-plasticizing performance.

Description

Thermo-rearrangement poly (benzoxazole-co-amide) copolymer film and preparation and application thereof
Technical Field
The invention relates to a preparation method of a thermal rearrangement poly (benzoxazole-co-amide) copolymer film and gas separation performance thereof.
Background
Traditional membrane materials such as Polydimethylsiloxane (PDMS), Polysulfone (PSF), Cellulose Acetate (CA), ethyl cellulose (EA), Polycarbonate (PC), Polyimide (PI), etc. have been widely used in the field of gas membrane separation. However, in the field of membrane separation, a gambling relationship exists between permeability and selectivity for most polymeric materials, i.e., high flux polymeric gas separation membranes tend to be less selective and vice versa. Therefore, it is important to study to break through the upper limit relationship between selectivity and permeability. In addition, the traditional membrane material has poor performances in the aspects of chemical erosion resistance, high temperature resistance and plasticization resistance, and limits the application of the gas separation membrane in some special fields such as petroleum refining, so that the research and development of polymer materials with high chemical stability, thermal stability and plasticization resistance are also one of the research hotspots in the field of gas membrane separation.
Microporous organic polymers having a rigid chain structure are used as a separation membrane material, have a high fractional free volume, can improve the solubility of gas in the membrane, and improve effective channels for the diffusion of gas in the membrane, exhibiting relatively high gas permeability and selectivity. In addition, the rigid chain structure in the polymer effectively prevents collapse of membrane pores, and endows the membrane with excellent plasticizing resistance, aging resistance and other properties.
In 2007, HoBumPak et al published a thermally rearranged polybenzoxazole separation membrane with high gas permeability obtained by heat-treating a polyimide membrane having a hydroxyl group at the ortho-position as a precursor at a high temperature on a science. Compared with a precursor thereof, the polymer film after thermal rearrangement has rigid rod-like structure chain segments, more free volume units are formed due to the disordered piling of the rigid chain segments, and the pore distribution presents a bimodal distribution. The thermally rearranged polybenzoxazole membrane shows extremely high gas flux, excellent thermal stability and chemical stability, and is widely concerned by domestic and foreign scholars. However, the heat treatment needs to be carried out at 350-.
Thermally rearranged polybenzoxazole can also be obtained by heat-treating a polyamide containing hydroxyl groups at the ortho-position, the temperature required for thermal rearrangement of the polyamide can be reduced by 100 ℃ compared to the severe heat-treatment conditions when an ortho-hydroxyl polyimide is used as a prepolymer, and there is no requirement for an inert atmosphere due to the higher flexibility of the amide bonds in the polyamide compared to the tertiary amines in the polyimide. Although the mechanical properties of the thermally rearranged polymer membrane are well improved by a reduction in the heat treatment temperature when the ortho-hydroxypolyamide is used as a prepolymer, there is a significant loss in separation performance compared to thermally rearranged membranes derived from ortho-hydroxypolyimide.
The copolymerization method can further regulate and control the mechanical property and the separation property of the polymer, and the acyl chloride with the p-benzene structure has higher reaction activity to diamine than the acyl chloride with the m-benzene structure, thereby being beneficial to obtaining a high-performance membrane material.
Disclosure of Invention
The invention provides a preparation method of a thermo-rearrangement poly (benzoxazole-co-amide) separation membrane, and the prepared separation membrane has excellent gas permeation selectivity and simultaneously has good plasticization resistance and mechanical property.
The technical scheme adopted by the invention is as follows:
polymerizing o-hydroxy diamine and aromatic diamine with p-phthaloyl chloride solution, and polymerizing the obtained polymer
The solution is settled in a non-solvent to form an ortho-hydroxyl polyamide copolymer;
(ii) dissolving the ortho-hydroxypolyamide copolymer of (i) in an organic solvent and casting it into a film;
(iii) heat-treating the film obtained in (ii).
The ortho-hydroxyamine in (i) has the formula
Q represents a single bond, or O, S, CO, SO2、Si(CH3)2、CH(OH)、(CH2)p(1≤p≤10)、(CF2)q(1≤q≤10)、C(CH3)2、C(CF3)2Substituted or unsubstituted phenylene, wherein the substituted or unsubstituted phenylene is preferably selected from the following structures, but is not limited thereto:
Figure BDA0001716971280000022
wherein A is1，A2，A3，A4，A5，A6，A7，A8,A9，A10，A11,A12Are identical or different and are independently H or C1-C6Alkyl or C1-C6Alkyl or C1-C6Haloalkyl or C1-C6A haloalkoxy group.
The aromatic diamine in (i) has the following formula
H2NArNH2
Ar is an aromatic ring group selected from substituted or unsubstituted divalent C6-C24Arylene and substituted or unsubstituted divalent C4-C24An aromatic group of a heterocyclic group, wherein the aromatic ring group may be any aromatic group independently present, or at least two aromatic groups are fused to form a condensed ring, or at least two aromatic groups are fused by a single bond, O, S, CO, SO2、Si(CH3)2、CH(OH)、(CH2)p(1≤p≤10)、(CF2)q(1≤q≤10)、C(CH3)2、C(CF3)2Ar is preferably selected from one of the following formulae, but is not limited thereto:
Figure BDA0001716971280000031
in the above chemical formula, X1，X2，X3，X4，X5，X6Identical or different and independently of one another are O, S, CO, SO2、Si(CH3)2、CH(OH)、(CH2)p(1≤p≤10)、(CF2)q(1≤q≤10)、C(CH3)2、C(CF3)2One of (1); z1Is O, S, CR1R2Or NR3Wherein R is1、R2、R3Are identical or different and are independently H or C1-C5An alkyl group; z2And Z3Are identical or different and are independently N or CR4Wherein R is4Is H or C1-C5An alkyl group.
The polyamide copolymer in (i) has the following structure,
Figure BDA0001716971280000032
q represents a single bond, or O, S, CO, SO2、Si(CH3)2、CH(OH)、(CH2)p(1≤p≤10)、(CF2)q(1≤q≤10)、C(CH3)2、C(CF3)2Substituted or unsubstituted phenylene, wherein the substituted or unsubstituted phenylene is preferably selected from the following structures, but is not limited thereto:
wherein A is1，A2，A3，A4，A5，A6，A7，A8,A9，A10，A11,A12Are identical or different and are independently H or C1-C6Alkyl or C1-C6Alkyl or C1-C6Haloalkyl or C1-C6A haloalkoxy group;
ar is an aromatic ring group selected from substituted or unsubstituted divalent C6-C24Arylene and substituted or unsubstituted divalent C4-C24An aromatic group of a heterocyclic group, wherein the aromatic ring group may be any aromatic group independently present, or at least two aromatic groups are fused to form a condensed ring, or at least two aromatic groups are fused by a single bond, O, S, CO, SO2、Si(CH3)2、CH(OH)、(CH2)p(1≤p≤10)、(CF2)q(1≤q≤10)、C(CH3)2、C(CF3)2Ar is preferably selected from one of the following formulae, but is not limited thereto:
Figure BDA0001716971280000042
in the above chemical formula, X1，X2，X3，X4，X5，X6Identical or different and independently of one another are O, S, CO, SO2、Si(CH3)2、CH(OH)、(CH2)p(1≤p≤10)、(CF2)q(1≤q≤10)、C(CH3)2、C(CF3)2One of (1); z1Is O, S, CR1R2Or NR3Wherein R is1、R2、R3Are identical or different and are independently H or C1-C5An alkyl group; z2And Z3Are identical or different and are independently N or CR4Wherein R is4Is H or C1-C5An alkyl group;
m and n represent the mole fraction of the corresponding repeating unit, and satisfy 0.1. ltoreq. m.ltoreq.0.9, 0.1. ltoreq. n.ltoreq.0.9, and m + n.ltoreq.1. The resulting polyamide copolymer is a block copolymer or a random copolymer having a weight average molecular weight of 10000 to 2000000.
The structural formula of the finally obtained thermally rearranged poly (benzoxazole-co-amide) copolymer in the technical scheme (iii) is shown in the specification
Figure BDA0001716971280000051
Q represents a single bond, or O, S, CO, SO2、Si(CH3)2、CH(OH)、(CH2)p(1≤p≤10)、(CF2)q(1≤q≤10)、C(CH3)2、C(CF3)2Substituted or unsubstituted phenylene, wherein the substituted or unsubstituted phenylene is preferably selected from the following structures, but is not limited thereto:
Figure BDA0001716971280000052
wherein A is1，A2，A3，A4，A5，A6，A7，A8,A9，A10，A11,A12Are identical or different and are independently H or C1-C6Alkyl or C1-C6Alkyl or C1-C6Haloalkyl or C1-C6A haloalkoxy group;
ar is an aromatic ring group selected from substituted or unsubstituted divalent C6-C24Arylene and substituted or unsubstituted divalent C4-C24An aromatic group of a heterocyclic group, wherein the aromatic ring group may be any aromatic group independently present, or at least two aromatic groups are fused to form a condensed ring, or at least two aromatic groups are fused by a single bond, O, S, CO, SO2、Si(CH3)2、CH(OH)、(CH2)p(1≤p≤10)、(CF2)q(1≤p≤10)、C(CH3)2、C(CF3)2Ar is preferably selected from one of the following formulae, but is not limited thereto:
in the aboveIn the formula, X1，X2，X3，X4，X5，X6Identical or different and independently of one another are O, S, CO, SO2、Si(CH3)2、CH(OH)、(CH2)p(1≤p≤10)、(CF2)q(1≤q≤10)、C(CH3)2、C(CF3)2One of (1); z1Is O, S, CR1R2Or NR3Wherein R is1、R2、R3Are identical or different and are independently H or C1-C5An alkyl group; z2And Z3Are identical or different and are independently N or CR4Wherein R is4Is H or C1-C5An alkyl group;
m and n represent the mole fraction of the corresponding repeating unit, and satisfy 0.1. ltoreq. m.ltoreq.0.9, 0.1. ltoreq. n.ltoreq.0.9, and m + n.ltoreq.1. The resulting thermally rearranged poly (benzoxazole-co-amide) copolymer is a block copolymer or a random copolymer having a weight average molecular weight of 10000 to 2000000.
According to the invention, the poly (benzoxazole-co-amide) separation membrane with better mechanical property can be prepared under the conditions of lower temperature and less severe heat treatment by heat treating the polyamide copolymer precursor membrane containing hydroxyl at the ortho position. The proportion of diamine monomers and the heat treatment condition are adjusted to obtain the thermally rearranged poly (benzoxazole-co-amide) gas separation membrane with different performances, the permeability and selectivity of most membranes are close to or even exceed the upper limit of Robeson, and the membrane shows excellent thermal stability and anti-plasticizing performance.
Drawings
FIG. 1(a) is one of the infrared spectra of each of the films in examples 1 to 8 and comparative examples 1 to 2;
FIG. 1(b) is a second infrared spectrum of each film in examples 1 to 8 and comparative examples 1 to 2;
FIG. 2 shows CO in each of the membranes of examples 1 to 8 and comparative examples 1 to 22/CH4Comparison of separation performance to the upper Robeson limit;
FIG. 3 shows the CO pairs of the membranes in comparative example 1, example 2 and example 32The resistance to plasticization of the rubber composition.
Detailed Description
The method for synthesizing the ortho-hydroxyl polyamide copolymer comprises the following steps: dissolving o-hydroxy diamine and aromatic diamine in N-methyl pyrrolidone in an inert atmosphere, adding a terephthaloyl chloride monomer with the molar weight equal to that of the diamine monomer, reacting in an ice bath at the temperature of-10-5 ℃ for 1-3h, settling the obtained polymer solution in a methanol/deionized water or ethanol/deionized water medium, filtering, and performing vacuum drying at the temperature of 80-120 ℃ to obtain the o-hydroxy polyamide copolymer.
And (ii) dissolving the ortho-hydroxypolyamide copolymer synthesized in the step (i) in an aprotic polar solvent such as N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone, wherein the solid content is 3-12% (mass content), and stirring to obtain a uniform casting solution. And filtering and defoaming the solution, casting the solution on a clean glass plate, and placing the solution on a film casting platform at the temperature of 40-80 ℃. And (3) after the solvent is volatilized for 10-24 hours, putting the membrane in a vacuum oven at 120-200 ℃ for drying to obtain the compact flat membrane.
(iii) heat-treating the film obtained in (ii). The heat treatment may be performed under an inert gas atmosphere or an air atmosphere, and the temperature is raised to 200-400 ℃ at a rate of 1-20 ℃/min and maintained for 1-3 hours to obtain a thermally rearranged poly (benzoxazole-co-amide) polymer film.
The ortho-hydroxyamine in (i) has the formula
Figure BDA0001716971280000071
Q represents a single bond, or O, S, CO, SO2、Si(CH3)2、CH(OH)、(CH2)p(1≤p≤10)、(CF2)q(1≤q≤10)、C(CH3)2、C(CF3)2Substituted or unsubstituted phenylene, wherein the substituted or unsubstituted phenylene is preferably selected from the following structures, but is not limited thereto:
Figure BDA0001716971280000072
wherein A is1，A2，A3，A4，A5，A6，A7，A8,A9，A10，A11,A12Are identical or different and are independently H or C1-C6Alkyl or C1-C6Alkyl or C1-C6Haloalkyl or C1-C6A haloalkoxy group.
The aromatic diamine in (i) has the following formula
H2NArNH2
Ar is an aromatic ring group selected from substituted or unsubstituted divalent C6-C24Arylene and substituted or unsubstituted divalent C4-C24An aromatic group of a heterocyclic group, wherein the aromatic ring group may be any aromatic group independently present, or at least two aromatic groups are fused to form a condensed ring, or at least two aromatic groups are fused by a single bond, O, S, CO, SO2、Si(CH3)2、CH(OH)、(CH2)p(1≤p≤10)、(CF2)q(1≤q≤10)、C(CH3)2、C(CF3)2Ar is preferably selected from one of the following formulae, but is not limited thereto:
Figure BDA0001716971280000081
in the above chemical formula, X1，X2，X3，X4，X5，X6Identical or different and independently of one another are O, S, CO, SO2、Si(CH3)2、CH(OH)、(CH2)p(1≤p≤10)、(CF2)q(1≤q≤10)、C(CH3)2、C(CF3)2One of (1); z1Is O, S, CR1R2Or NR3Wherein R is1、R2、R3The same or differentAnd is independently H or C1-C5An alkyl group; z2And Z3Are identical or different and are independently N or CR4Wherein R is4Is H or C1-C5An alkyl group.
The polyamide in (i) has the following structure,
Figure BDA0001716971280000091
q represents a single bond, or O, S, CO, SO2、Si(CH3)2、CH(OH)、(CH2)p(1≤p≤10)、(CF2)q(1≤q≤10)、C(CH3)2、C(CF3)2Substituted or unsubstituted phenylene, wherein the substituted or unsubstituted phenylene is preferably selected from the following structures, but is not limited thereto:
Figure BDA0001716971280000092
wherein A is1，A2，A3，A4，A5，A6，A7，A8,A9，A10，A11,A12Are identical or different and are independently H or C1-C6Alkyl or C1-C6Alkyl or C1-C6Haloalkyl or C1-C6A haloalkoxy group;
ar is an aromatic ring group selected from substituted or unsubstituted divalent C6-C24Arylene and substituted or unsubstituted divalent C4-C24An aromatic group of a heterocyclic group, wherein the aromatic ring group may be any aromatic group independently present, or at least two aromatic groups are fused to form a condensed ring, or at least two aromatic groups are fused by a single bond, O, S, CO, SO2、Si(CH3)2、CH(OH)、(CH2)p(1≤p≤10)、(CF2)q(1≤q≤10)、C(CH3)2、C(CF3)2Ar is preferably selected from one of the following formulae, but is not limited thereto:
Figure BDA0001716971280000093
Figure BDA0001716971280000101
in the above chemical formula, X1，X2，X3，X4，X5，X6Identical or different and independently of one another are O, S, CO, SO2、Si(CH3)2、CH(OH)、(CH2)p(1≤q≤10)、(CF2)q(1≤q≤10)、C(CH3)2、C(CF3)2One of (1); z1Is O, S, CR1R2Or NR3Wherein R is1、R2、R3Are identical or different and are independently H or C1-C5An alkyl group; z2And Z3Are identical or different and are independently N or CR4Wherein R is4Is H or C1-C5An alkyl group;
m and n represent the mole fraction of the corresponding repeating unit, and satisfy 0.1. ltoreq. m.ltoreq.0.9, 0.1. ltoreq. n.ltoreq.0.9, and m + n.ltoreq.1.
The final thermally rearranged poly (benzoxazole-co-amide) copolymer obtained in (iii) has the formula
Q represents a single bond, or O, S, CO, SO2、Si(CH3)2、CH(OH)、(CH2)p(1≤q≤10)、(CF2)q(1≤q≤10)、C(CH3)2、C(CF3)2Substituted or unsubstituted phenylene, wherein the substituted or unsubstituted phenylene is preferably selected from the following structures, but is not limited thereto:
Figure BDA0001716971280000103
wherein A is1，A2，A3，A4，A5，A6，A7，A8,A9，A10，A11,A12Are identical or different and are independently H or C1-C6Alkyl or C1-C6Alkyl or C1-C6Haloalkyl or C1-C6A haloalkoxy group;
ar is an aromatic ring group selected from substituted or unsubstituted divalent C6-C24Arylene and substituted or unsubstituted divalent C4-C24An aromatic group of a heterocyclic group, wherein the aromatic ring group may be any aromatic group independently present, or at least two aromatic groups are fused to form a condensed ring, or at least two aromatic groups are fused by a single bond, O, S, CO, SO2、Si(CH3)2、CH(OH)、(CH2)p(1≤p≤10)、(CF2)q(1≤q≤10)、C(CH3)2、C(CF3)2Ar is preferably selected from one of the following formulae, but is not limited thereto:
Figure BDA0001716971280000111
in the above chemical formula, X1，X2，X3，X4，X5，X6Identical or different and independently of one another are O, S, CO, SO2、Si(CH3)2、CH(OH)、(CH2)p(1≤p≤10)、(CF2)q(1≤q≤10)、C(CH3)2、C(CF3)2One of (1); z1Is O, S, CR1R2Or NR3Wherein R is1、R2、R3Are identical or different and independently of one another areH or C1-C5An alkyl group; z2And Z3Are identical or different and are independently N or CR4Wherein R is4Is H or C1-C5An alkyl group;
m and n represent the mole fraction of the corresponding repeating unit, and satisfy 0.1. ltoreq. m.ltoreq.0.9, 0.1. ltoreq. n.ltoreq.0.9, and m + n.ltoreq.1.
Example 1
In a 100ml three-necked flask with mechanical stirring, 5 mmol of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (bisAPAF) and 5 mmol of 4, 4' -dihydroxydiphenyl ether (ODA) were dissolved in 12ml of anhydrous NMP under a high purity nitrogen atmosphere. After cooling to O ℃, 10 mmol of terephthaloyl chloride and 8ml of anhydrous NMP were added thereto. The reaction mixture was stirred at O ℃ for 3 h. After the reaction is finished, cooling the light yellow polymer solution to room temperature, slowly settling the light yellow polymer solution to 800ml of ethanol/water mixed solution with the volume ratio of 1:1, standing and displacing for 24 hours, washing and filtering with deionized water for three times, drying in a vacuum oven at 80 ℃ for 24 hours to obtain an ortho hydroxyl-containing polyamide copolymer, dissolving the copolymer in NMP to form a casting solution with the mass content of 8 percent, filtering and defoaming, pouring the casting solution on a clean glass plate, placing the glass plate on a platform at 60 ℃ for 24 hours, and then placing the glass plate in the vacuum oven at 180 ℃ for drying for at least 24 hours. The resulting random copolymer of o-hydroxypolyamide was named APAF-ODA (5:5) PHA and its structural formula was as follows:
Figure BDA0001716971280000121
m and n are the molar fractions of the corresponding repeating units, with m ═ 0.5 and n ═ 0.5.
The resulting defect-free APAF-ODA (5:5) PHA precursor film was placed in a muffle furnace, heated to 250 ℃ at a rate of 5 ℃ per minute under nitrogen, and maintained at that temperature for 1 hour. After heat treatment, the muffle furnace is slowly cooled to room temperature at a rate of less than 10 ℃/min to produce a thermally rearranged poly (benzoxazole-co-amide) film, with too fast a cooling rate causing the film to become more brittle and the mechanical properties to deteriorate. The resulting thermally rearranged poly (benzoxazole-co-amide) film was named APAF-ODA (5:5) -250, having the structure shown in chemical potential 1:
[ chemical formula 1]
Figure BDA0001716971280000122
m and n are the mole fractions of the corresponding repeating units, satisfying m 0.5 and n 0.5. Since the thermally rearranged polymer film is insoluble in general organic solvents, its weight average molecular weight is difficult to directly measure, but is very small in difference from that of its precursor.
Examples 2 to 8
The molar ratio of diamine monomers was adjusted as in table 1, and the prepolymer was obtained by the same synthesis method as in example 1 under the other conditions and procedures, and the prepolymer was placed in a nitrogen-protected muffle furnace, heated to various temperatures at a rate of 5 ℃/min, and maintained at the same temperature for 1 hour. After the heat treatment, the muffle furnace was slowly cooled to room temperature at a rate of less than 10 ℃/min.
Table 1
Figure BDA0001716971280000123
Figure BDA0001716971280000131
Comparative examples 1 to 2
The precursor film prepared in example 1 and example 5 were not subjected to any heat treatment to compare the effect of the heat treatment on the film properties, as shown in table 2.
Table 2
Figure BDA0001716971280000132
The weight average molecular weight of the membrane in comparative example 1 is between 80000 and 100000, the weight average molecular weight of the membrane in comparative example 2 is between 50000 and 80000, and the weight average molecular weight of each of the rearranged polymer membranes in examples 1 to 8 is difficult to directly measure due to poor solubility in general organic solvents, but is slightly different from that of the prepolymer if degradation does not occur.
The infrared spectra of the films of examples 1-8 and comparative examples 1-2 are shown in FIGS. 1(a) (b), and the characteristic peak of amide bond (1644 cm) before heat treatment-1(-C＝O)and 1500cm-1(-C-N)) is evident, the characteristic peak of the amide bond gradually decreases with increasing heat treatment temperature after heat treatment, and the characteristic absorption peak of the benzoxazole ring is 1558cm-1(-C＝N),1477cm-1(-C＝N),1058cm-1(-C-O)and 921cm-1And gradually enhanced.
The densities and free volume fractions (FFVs) of the respective films in examples 1 to 8 and comparative examples 1 to 2 are shown in Table 3:
table 3
Figure BDA0001716971280000133
H of membranes in examples 1-8 and comparative examples 1-22、O2、N2、CO2And CH4The permeability of five pure gases was tested and is shown in table 4. The gas permeability of the thermally rearranged poly (benzoxazole-co-amide) separation membrane is significantly increased compared to the polyamide copolymer prepolymer.
Table 4 pure gas permeability and selectivity of the membranes in examples 1-8 and comparative examples 1-2, test conditions: 0.2MPa, 35 ℃.
Figure BDA0001716971280000142
1barrer＝10-10cm3(STP)cm/(s·cm2·cmHg)
CO of membranes in examples 1-8 and comparative examples 1-22/CH4Comparison of separation Performance with the Robeson Upper Limit, see FIG. 2, the thermally rearranged poly (benzoxazole-co-amide) membranes of the examples exhibit better permeability and selectivity with separation Performance substantially close to, or even nearly soExceeding the Robeson upper limit.
The plasticization resistance of comparative example 1, example 2, and example 3 was measured by gradually increasing the pressure at 35 ℃ and measuring the CO of the film at each pressure point2The results are shown in fig. 3, and it can be seen from fig. 3 that the plasticizing pressure of the polyamide film without thermal rearrangement is about 1.8MPa, the plasticizing pressure is increased to 2.2MPa after the heat treatment at 300 ℃, the plasticizing pressure is further increased to 2.7MPa when the heat treatment temperature is 350 ℃, and the difference between the gas permeability at several points after the plasticization and before the plasticization is very small, thus showing excellent anti-plasticization capability.
In addition, there are many other structures of thermally rearranged polymers, see the following examples:
example 9:
using 3,3 ' -dihydroxy-4, 4 ' -biphenyldiamine (HAB) and 4,4 ' -dihydroxydiphenyl ether (ODA) as diamine monomers for polymerization, the other conditions and procedures were the same as in example 1 to prepare a thermally rearranged poly (benzoxazole-co-amide) copolymer having a structure shown in chemical formula 2:
[ chemical formula 2]
Figure BDA0001716971280000151
m and n are the molar fractions of the corresponding repeating units, with m ═ 0.5 and n ═ 0.5
Example 10:
using 3,3 '-dihydroxy-4, 4' -biphenyldiamine (HAB) and 2,4, 6-trimethyl-m-phenylenediamine (DAM) as diamine monomers for polymerization, the same conditions and procedures as in example 1 were repeated to prepare a thermally rearranged poly (benzoxazole-co-amide) copolymer having a structure shown in chemical formula 3:
[ chemical formula 3]
Figure BDA0001716971280000152
m and n are the molar fractions of the corresponding repeating units, with m ═ 0.5 and n ═ 0.5
Example 11:
using 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (bisAPF) and 2,4, 6-trimethyl-m-phenylenediamine (DAM) as diamine monomers for polymerization, the other conditions and procedures were the same as in example 1 to prepare a thermally rearranged poly (benzoxazole-co-amide) copolymer having a structure shown in chemical formula 4:
[ chemical formula 4]
Figure BDA0001716971280000161
m and n are the molar fractions of the corresponding repeating units, with m ═ 0.5 and n ═ 0.5
Example 12:
using 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (bisAPF) and 3, 5-diaminobenzoic acid (DABA) as diamine monomers for polymerization, the other conditions and procedures were the same as in example 1 to prepare a thermally rearranged poly (benzoxazole-co-amide) copolymer having a structure shown in chemical formula 5:
[ chemical formula 5]
m and n are the molar fractions of the corresponding repeating units, with m ═ 0.5 and n ═ 0.5
Example 13:
the same procedure as in example 1 was carried out using 3,3 '-dihydroxy-4, 4' -biphenyldiamine (HAB) and 3, 5-diaminobenzoic acid (DABA) as diamine monomers for polymerization to prepare a thermally rearranged poly (benzoxazole-co-amide) copolymer having a structure represented by chemical formula 6:
[ chemical formula 6]
Figure BDA0001716971280000163
m and n are the molar fractions of the corresponding repeating units, with m ═ 0.5 and n ═ 0.5
Example 14:
the same procedure as in example 1 was repeated except for using 3,3 '-dihydroxy-4, 4' -biphenyldiamine (HAB) and 2, 3-diaminonaphthalene as the diamine monomers for polymerization to prepare a thermally rearranged poly (benzoxazole-co-amide) copolymer having a structure represented by chemical formula 7:
[ chemical formula 7]
Figure BDA0001716971280000171
m and n are the molar fractions of the corresponding repeating units, with m ═ 0.5 and n ═ 0.5
Example 15:
using 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (bisAPAF) and 2, 7-diaminofluorene as the polymerized diamine monomers, the other conditions and procedures were the same as in example 1, to prepare a thermally rearranged poly (benzoxazole-co-amide) copolymer having a structure shown in chemical formula 8:
[ chemical formula 8]
Figure BDA0001716971280000172
m and n are the mole fractions of the corresponding repeating units, satisfying m 0.5 and n 0.5.
Example 16:
using 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (bisAPAF) and 3, 6-diaminocarbazole as the polymerized diamine monomers, the other conditions and procedures were the same as in example 1 to prepare a thermally rearranged poly (benzoxazole-co-amide) copolymer having a structure shown in chemical formula 9:
[ chemical formula 9]
Figure BDA0001716971280000173
m and n are the mole fractions of the corresponding repeating units, satisfying m 0.5 and n 0.5.
Example 16:
using 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (bisAPF) and 2, 2-bis [4- (4-aminophenoxy) phenyl ] -1,1,1,3,3, 3-hexafluoropropane as the diamine monomers for polymerization, the other conditions and procedures were the same as in example 1, a thermally rearranged poly (benzoxazole-co-amide) copolymer having a structure represented by chemical formula 10 was prepared:
[ chemical formula 10]
Figure BDA0001716971280000181
m and n are the mole fractions of the corresponding repeating units, satisfying m 0.5 and n 0.5.

Claims (11)

1. A thermally rearranged poly (benzoxazole-co-amide) copolymer film, characterized in that the copolymer has the following structural formula of repeating units:
Figure FDA0001716971270000011
wherein Q represents a single bond, or O, S, CO, SO2、Si(CH3)2、CH(OH)、(CH2)p(1≤p≤10)、(CF2)q(1≤q≤10)、C(CH3)2、C(CF3)2Substituted or unsubstituted phenylene;
ar is an aromatic ring group selected from substituted or unsubstituted divalent C6-C24Arylene and substituted or unsubstituted divalent C4-C24An aromatic group of a heterocyclic group, wherein the aromatic ring group may be any aromatic group independently present, or at least two aromatic groups are fused to form a condensed ring, or at least two aromatic groups are fused by a single bond, O, S, CO, SO2、Si(CH3)2、CH(OH)、(CH2)p(1≤p≤10)、(CF2)q(1≤q≤10)、C(CH3)2、C(CF3)2A group in which an isofunctional group is bonded;
m and n represent the mole fraction of the corresponding repeating unit, and satisfy 0.1. ltoreq. m.ltoreq.0.9, 0.1. ltoreq. n.ltoreq.0.9, and m + n.ltoreq.1.
2. The copolymer film of claim 1 wherein Q represents a single bond, or is O, S, CO, SO2、Si(CH3)2、CH(OH)、(CH2)p(1≤p≤10)、(CF2)q(1≤q≤10)、C(CH3)2、C(CF3)2Substituted or unsubstituted phenylene, wherein the substituted or unsubstituted phenylene can be selected from the following structures:
Figure FDA0001716971270000012
A1，A2，A3，A4，A5，A6，A7，A8,A9，A10，A11,A12are identical or different and are independently H or C1-C6Alkyl or C1-C6Alkyl or C1-C6Haloalkyl or C1-C6A haloalkoxy group.
3. The copolymer film of claim 1 wherein Ar is selected from one of the following formulas:
Figure FDA0001716971270000021
in the above chemical formula, X1，X2，X3，X4，X5，X6Identical or different and independently of one another are O, S, CO, SO2、Si(CH3)2、CH(OH)、(CH2)p(1≤p≤10)、(CF2)q(1≤q≤10)、C(CH3)2、C(CF3)2One of (1); z1Is O, S, CR1R2Or NR3Wherein R is1、R2、R3Are identical or different and are independently H or C1-C5An alkyl group; z2And Z3Are identical or different and are independently N or CR4Wherein R is4Is H or C1-C5An alkyl group.
4. The copolymer film according to any one of claims 1 to 3, which may have a weight average molecular weight of 10000 to 200000.
5. The copolymer film according to any one of claims 1 to 4, wherein the copolymer is a block copolymer or a random copolymer.
6. A method of preparing a thermally rearranged poly (benzoxazole-co-amide) copolymer film according to any one of claims 1-5, comprising:
polymerizing an ortho-hydroxy diamine and an aromatic diamine with a solution of terephthaloyl chloride and settling the resulting polymer solution in a non-solvent to form an ortho-hydroxy polyamide copolymer;
(ii) dissolving the ortho-hydroxypolyamide copolymer of (i) in an organic solvent and casting it into a film;
(iii) heat-treating the film obtained in (ii).
7. The method of claim 6, wherein the ortho-hydroxy diamine of (i) has the following structure:
Figure FDA0001716971270000031
q represents a single bond, or O, S, CO, SO2、Si(CH3)2、CH(OH)、(CH2)p(1≤p≤10)、(CF2)q(1≤q≤10)、C(CH3)2、C(CF3)2Substituted or unsubstituted phenylene, wherein the substituted or unsubstituted phenylene is preferably selected from the following structures:
Figure FDA0001716971270000032
wherein A is1，A2，A3，A4，A5，A6，A7，A8,A9，A10，A11,A12Are identical or different and are independently H or C1-C6Alkyl or C1-C6Alkyl or C1-C6Haloalkyl or C1-C6A haloalkoxy group;
wherein the aromatic diamine of (i) has the general formula:
H2N-Ar-NH2
ar is an aromatic ring group selected from substituted or unsubstituted divalent C6-C24Arylene and substituted or unsubstituted divalent C4-C24An aromatic group of a heterocyclic group, wherein the aromatic ring group may be any aromatic group independently present, or at least two aromatic groups are fused to form a condensed ring, or at least two aromatic groups are fused by a single bond, O, S, CO, SO2、Si(CH3)2、CH(OH)、(CH2)p(1≤p≤10)、(CF2)q(1≤q≤10)、C(CH3)2、C(CF3)2A group in which an isofunctional group is bonded; ar is preferably selected from one of the following formulae:
Figure FDA0001716971270000033
Figure FDA0001716971270000041
in the above chemical formula, X1，X2，X3，X4，X5，X6Identical or different and independently of one another are O, S, CO, SO2、Si(CH3)2、CH(OH)、(CH2)p(1≤p≤10)、(CF2)q(1≤q≤10)、C(CH3)2、C(CF3)2One of (1); z1Is O, S, CR1R2Or NR3Wherein R is1、R2、R3Are identical or different and are independently H or C1-C5An alkyl group; z2And Z3Are identical or different and are independently N or CR4Wherein R is4Is H or C1-C5An alkyl group.
8. The method of claim 6, wherein the solution polymerization in (i) is carried out in an ice bath at-10 to 5 ℃ (preferably-4 to 4 ℃) for 1 to 5 hours; the solvent can be one or more of N-methyl pyrrolidone, N, N '-dimethylformamide and N, N' -dimethylacetamide; wherein the non-solvent used in the sedimentation process in (i) is ethanol/deionized water or a mixed solution of methanol/deionized water, and the volume ratio of the alcohol to the water is 1:4-4: 1.
9. The method of claim 6, wherein the synthetic polyamide prepolymer of (i) has a general structural formula comprising repeating units of:
Figure FDA0001716971270000042
wherein Q represents a single bond, or O, S, CO, SO2、Si(CH3)2、CH(OH)、(CH2)p(1≤p≤10)、(CF2)q(1≤q≤10)、C(CH3)2、C(CF3)2Substituted or unsubstituted phenylene;
ar is an aromatic ring group selected from substituted or unsubstituted divalent C6-C24Arylene and substituted or unsubstituted divalent C4-C24An aromatic group of a heterocyclic group, wherein the aromatic ring group may be any aromatic group independently present, or at least two aromatic groups are fused to form a condensed ring, or at least two aromatic groups are fused by a single bond, O, S, CO, SO2、Si(CH3)2、CH(OH)、(CH2)p(1≤p≤10)、(CF2)q(1≤q≤10)、C(CH3)2、C(CF3)2A group in which an isofunctional group is bonded;
m and n represent the mole fraction of the corresponding repeating unit, and satisfy 0.1. ltoreq. m.ltoreq.0.9, 0.1. ltoreq. n.ltoreq.0.9, and m + n 1;
wherein Q represents a single bond, or O, S, CO, SO2、Si(CH3)2、CH(OH)、(CH2)p(1≤p≤10)、(CF2)q(1≤q≤10)、C(CH3)2、C(CF3)2Substituted or unsubstituted phenylene, wherein the substituted or unsubstituted phenylene is preferably selected from the following structures:
Figure FDA0001716971270000051
wherein A is1，A2，A3，A4，A5，A6，A7，A8,A9，A10，A11,A12Are identical or different and are independently H or C1-C6Alkyl or C1-C6Alkyl or C1-C6Haloalkyl or C1-C6A haloalkoxy group;
wherein Ar is an aromatic ring group selected from substituted or unsubstituted divalent C6-C24Arylene and substituted or unsubstituted divalent C4-C24An aromatic group of a heterocyclic group, wherein the aromatic ring group may be any aromatic group independently present, or at least two aromatic groups are fused to form a condensed ring, or at least two aromatic groups are fused by a single bond, O, S, CO, SO2、Si(CH3)2、CH(OH)、(CH2)p(1≤p≤10)、(CF2)q(1≤q≤10)、C(CH3)2、C(CF3)2An isofunctional group, Ar preferably selected from one of the following formulae:
Figure FDA0001716971270000052
Figure FDA0001716971270000061
in the above chemical formula, X1，X2，X3，X4，X5，X6Identical or different and independently of one another are O, S, CO, SO2、Si(CH3)2、CH(OH)、(CH2)p(1≤p≤10)、(CF2)q(1≤q≤10)、C(CH3)2、C(CF3)2One of (1); z1Is O, S, CR1R2Or NR3Wherein R is1、R2、R3Are identical or different and are independently H or C1-C5An alkyl group; z2And Z3Are identical or different and are independently N or CR4Wherein R is4Is H or C1-C5An alkyl group.
10. The method according to claim 6, wherein the organic solvent in (ii) is one or more of aprotic polar solvent selected from the group consisting of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone;
wherein the heat treatment described in (iii) may be performed under an inert atmosphere (one or two or more of nitrogen or an inert gas), or may be performed under an air atmosphere, and the temperature is increased from room temperature to 200-400 ℃ at a rate of 1-20 ℃/min and maintained for 1-3 hours.
11. Use of the thermally rearranged poly (benzoxazole-co-amide) copolymer membrane according to any one of claims 1-5 as a gas separation membrane in gas membrane separation processes, such as nitrogen separation in air separation, carbon dioxide separation in biogas, or carbon dioxide separation in natural gas.
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