CN117924689A - Preparation method of high-strength high-crystallinity low-thermal expansion coefficient poly (arylene ether nitrile) film - Google Patents
Preparation method of high-strength high-crystallinity low-thermal expansion coefficient poly (arylene ether nitrile) film Download PDFInfo
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- -1 poly (arylene ether nitrile Chemical class 0.000 title claims abstract description 71
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 31
- 150000002825 nitriles Chemical class 0.000 claims abstract description 18
- 229920000090 poly(aryl ether) Polymers 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 238000005266 casting Methods 0.000 claims abstract description 10
- 239000013078 crystal Substances 0.000 claims abstract description 9
- 238000001556 precipitation Methods 0.000 claims abstract description 7
- 239000000376 reactant Substances 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- YOYAIZYFCNQIRF-UHFFFAOYSA-N 2,6-dichlorobenzonitrile Chemical compound ClC1=CC=CC(Cl)=C1C#N YOYAIZYFCNQIRF-UHFFFAOYSA-N 0.000 claims description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000010907 mechanical stirring Methods 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 abstract description 8
- 238000002425 crystallisation Methods 0.000 abstract description 6
- 230000008025 crystallization Effects 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000010534 nucleophilic substitution reaction Methods 0.000 abstract description 5
- 238000006068 polycondensation reaction Methods 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 239000002861 polymer material Substances 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- 238000002844 melting Methods 0.000 description 13
- 230000008018 melting Effects 0.000 description 13
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 239000010977 jade Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000004088 simulation Methods 0.000 description 4
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- 239000004697 Polyetherimide Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 229920001601 polyetherimide Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
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- Polyethers (AREA)
Abstract
A preparation method of a polyarylether nitrile film with high strength, high crystallinity and low thermal expansion coefficient belongs to the technical field of special polymer material synthesis and processing technology. The invention synthesizes high molecular weight crystallization type poly (arylene ether nitrile) by nucleophilic substitution polycondensation reaction, and then the poly (arylene ether nitrile) powder is subjected to solution casting method program heating to prepare the poly (arylene ether nitrile) film with high strength, high crystallinity and low thermal expansion coefficient. According to the invention, the effective collision between reactants is ensured by strictly controlling the amount of the N-methylpyrrolidone added in the reaction process, and finally the polyarylether nitrile with high molecular weight and high crystallization degree is prepared; when precipitation occurs along with the rise of the temperature of the reaction liquid, the precipitated crystal is dissolved in the reaction liquid by adding N-methyl pyrrolidone into the reaction liquid and adjusting the position of a stirring rod, and the molecular weight is improved while the reaction is continuously carried out.
Description
Technical Field
The invention belongs to the technical field of special polymer material synthesis and processing technology, and particularly relates to a preparation method of a high-strength high-crystallinity polyarylether nitrile film with low thermal expansion coefficient.
Background
At present, the requirements for high-temperature resistant polymer materials are increasing in both military aviation field and electronic and electric field. The high-temperature polymer films widely applied to the market mainly comprise Polycarbonate (PC), polyimide (PI), polyphenylene sulfide (PPS), fluorene Polyester (FPE), polyether imide (PEI), divinyl siloxane-dibenzocyclobutene (BCB), polyether ether ketone (PEEK), polytetrafluoroethylene (PTFE), aromatic polyurea (ArPU) and the like. The poly (arylene ether nitrile) (PEN) is a poly (arylene ether) polymer with cyano side groups on the molecular chain, and is a novel high-performance polymer material. The crystal type poly (arylene ether nitrile) is used as a special polymer engineering material with important application value in PEN, and the strength, the modulus and the use temperature of the poly (arylene ether nitrile) are greatly improved due to the action of a crystal region. Compared with amorphous poly (arylene ether nitrile), the crystalline poly (arylene ether nitrile) has more excellent mechanical property, thermal property, creep resistance and chemical corrosion resistance. However, the high-crystallinity crystalline poly (arylene ether nitrile) is easy to separate out in the synthesis process, so that effective collision between molecules is difficult to occur, the polymerization reaction is difficult to continue, and the molecular weight cannot be increased. Therefore, the development of the polyarylether nitrile with high mechanical strength, high temperature resistance, high crystallinity and low thermal expansion coefficient has important significance.
At present, the poly (arylene ether nitrile) film is improved in terms of mechanical strength and thermal expansion coefficient: the poly (arylene ether nitrile) reported in literature He L,Tong L,Bai Z,et al.Investigation of the controllable thermal curing reaction for ultrahigh Tpolyarylene ether nitrile compositions[J].Polymer,2022,254. cures at 360 ℃ and incorporates 4,4' - (bis 3, 4-dicyanophenoxy) biphenyl and ZnCl 2 with a coefficient of thermal expansion of 98.2ppm/°c, a mechanical strength of only 106MPa, and an elongation at break of only 6.7%; the bisphenol AF type poly (arylene ether nitrile) film reported in literature Lei X-T,Tong L-F,Xu M-Z,et al.PEN/BADCy Interlayer Dielectric Films with Tunable Microstructures via an Assist of Temperature for Enhanced Frequency Stability[J].Chinese Journal of Polymer Science,2020,38(11):1258-1266. has a mechanical strength of only 92MPa, an elongation at break of only 6% and a thermal expansion coefficient of 65ppm/K; patent CN112625233a discloses a high molecular weight crystalline poly (arylene ether nitrile) and a preparation method thereof, and poly (arylene ether nitrile) film with higher strength and crystallinity is prepared by adjusting the proportion of hydroquinone and bisphenol a, but bisphenol a is amorphous poly (arylene ether nitrile), and the addition of bisphenol a can greatly reduce the crystallization capacity, thus causing uneven crystal size, wider melting peak, reducing the use temperature and thermal stability and limiting the practical application thereof; the maximum tensile strength of the prepared poly (arylene ether nitrile) film is 134MPa, but the elongation at break is only 9.54 percent, and the thermal expansion coefficient is not measured. In conclusion, the poly (arylene ether nitrile) film prepared by the prior method has higher tensile strength, but has lower elongation at break and higher thermal expansion coefficient, and has great influence on the reprocessing of the poly (arylene ether nitrile) film.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a preparation method of a polyarylether nitrile film with high strength, high crystallinity and low thermal expansion coefficient. The invention adopts a simple nucleophilic substitution polycondensation reaction and solution casting mode to obtain the polyarylether nitrile film with high strength, high crystallinity and low thermal expansion coefficient, and the mechanical strength and the crystallinity of the polyarylether nitrile film are randomly copolymerized and synthesized by regulating and controlling the molar ratio of diphenol and hydroquinone in the crystalline polyarylether nitrile, and meanwhile, the problem of precipitation in the synthesis process is solved, the high molecular weight polyarylether nitrile is obtained, and an effective way is provided for mass production of the polyarylether nitrile film with excellent performance.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
A high strength high crystallinity low thermal expansion coefficient poly (arylene ether nitrile) film, the structural formula of the poly (arylene ether nitrile) film being:
wherein m=200 to 475, n=20 to 25, n: m=1: (8-24).
A preparation method of a high-strength high-crystallinity low-thermal expansion coefficient poly (arylene ether nitrile) film comprises the following steps:
Step 1, adding hydroquinone, biphenol and 2, 6-dichlorobenzonitrile as reactants, adding potassium carbonate as a catalyst, adding N-methylpyrrolidone and toluene as solvents into a three-necked flask with a thermometer, a water knockout drum, a condensation reflux device and a mechanical stirring device, injecting toluene into the water knockout drum, and then heating and refluxing for 2-3 hours at 145-155 ℃; wherein, the mol ratio of hydroquinone, biphenol, 2, 6-dichlorobenzonitrile, potassium carbonate and N-methyl pyrrolidone is (0.16 mol to 0.19 mol): (0.01 mol to 0.04 mol): 0.202mol:0.28mol: (0.92-0.96 mol), the volume ratio of N-methyl pyrrolidone and toluene solvent is 3:1, a step of;
Step 2, after heating reflux is finished, 1 mL-5 mL of toluene is separated from the water separator every 10 min-30 min until the temperature reaches 190 ℃ -198 ℃, then heating and stirring are carried out for 2-3 h at the temperature of 190 ℃ -198 ℃, then N-methylpyrrolidone is added to enable the solution to have good fluidity, heating and stirring are continued for 30-60 min, and after completion, the solution is poured into deionized water to obtain off-white strip solids; wherein, the mol ratio of the added N-methyl pyrrolidone to the N-methyl pyrrolidone in the step 1 is 1 (1.47-3.10);
Step 3, after crushing the off-white strip solid obtained in the step 2, dispersing the crushed off-white strip solid in deionized water, adding hydrochloric acid until the pH value of the solution is=1-2, standing for more than 30min, and filtering; treating the filtered powder in boiling water for 1-2 h, filtering, repeating the process of treating in boiling water for 1-2 h and filtering for 3-5 times until the solution is neutral, filtering, separating and drying to obtain crystalline polyarylether nitrile;
step 4, dissolving the crystalline poly (arylene ether nitrile) obtained in the step3 into N-methylpyrrolidone, and preparing a crystalline poly (arylene ether nitrile) film by solution casting; wherein, the temperature rising process of the solution casting method is as follows: the temperature is kept at 80 ℃, 100 ℃, 120 ℃ and 160 ℃ for 1 hour, then at 200 ℃ for 2 hours, and finally at 230 ℃ for 3 hours.
In step 2, when precipitation occurs, N-methylpyrrolidone is added to the reaction solution and the position of the stirring rod is adjusted, so that the precipitated crystals are dissolved in the reaction solution, and the molecular weight is improved while the reaction is continued.
The invention provides a preparation method of a high-strength high-crystallinity low-thermal expansion coefficient poly (arylene ether nitrile) film, which adopts nucleophilic substitution polycondensation reaction to synthesize high-molecular-weight crystalline poly (arylene ether nitrile), and then the poly (arylene ether nitrile) powder is subjected to solution casting method program heating to prepare the high-strength high-crystallinity low-thermal expansion coefficient poly (arylene ether nitrile) film. The poly (arylene ether nitrile) copolymer is developed by utilizing hydroquinone poly (arylene ether nitrile) and biphenyl diphenol poly (arylene ether nitrile) in the crystallization poly (arylene ether nitrile) to solve the precipitation problem in the synthesis process, and the poly (arylene ether nitrile) with high molecular weight is synthesized, and the poly (arylene ether nitrile) film with high strength, high crystallinity and low thermal expansion coefficient is obtained.
Compared with the prior art, the invention has the beneficial effects that:
1. According to the preparation method of the high-strength high-crystallinity low-thermal expansion coefficient poly (arylene ether nitrile) film, provided by the invention, the effective collision between reactants is ensured by strictly controlling the amount of the N-methylpyrrolidone added in the reaction process, and the poly (arylene ether nitrile) with high molecular weight and high crystallinity is finally prepared. When precipitation occurs along with the rise of the temperature of the reaction liquid, the precipitated crystal is dissolved in the reaction liquid by adding N-methyl pyrrolidone into the reaction liquid and adjusting the position of a stirring rod, and the molecular weight is improved while the reaction is continuously carried out.
2. According to the preparation method of the high-strength high-crystallinity low-thermal expansion coefficient poly (arylene ether nitrile) film, provided by the invention, nucleophilic substitution polycondensation reaction is adopted to synthesize crystalline poly (arylene ether nitrile), and the regularity of hydroquinone is broken by using a small amount of biphenol by utilizing the easy crystallization characteristic of hydroquinone poly (arylene ether nitrile) and the rigidity of biphenol poly (arylene ether nitrile), so that good fluidity in the polymerization process is ensured, and the molecular weight is effectively improved while higher crystallization capability is maintained. And the flexibility of the p-benzene/biphenyl type polyarylether nitrile is greatly improved by utilizing the toughening effect of the crystal structure. In summary, the invention provides a film prepared by a simple nucleophilic substitution polycondensation reaction and solution casting method, wherein the tensile strength is more than or equal to 130MPa, the elongation at break is more than or equal to 50%, the linear thermal expansion coefficient is less than or equal to 35ppm/K, the elongation at break of the prepared polyarylether nitrile film is obviously improved, the linear thermal expansion coefficient is obviously reduced, and the film has good application prospect.
Drawings
FIG. 1 is a structural formula of a high strength, high crystallinity, low coefficient of thermal expansion poly (arylene ether nitrile) of the present invention;
FIG. 2 is a DSC of the poly (arylene ether nitrile) film prepared in examples 1-4;
FIG. 3 is a TGA graph of the poly (arylene ether nitrile) films prepared in examples 1-4;
FIG. 4 is an XRD pattern of the poly (arylene ether nitrile) films prepared in examples 1-4;
FIG. 5 shows the results of the Jade simulation calculation of the crystallinity of the poly (arylene ether nitrile) films prepared in examples 1 to 4;
FIG. 6 is a graph showing the mechanical properties of the poly (arylene ether nitrile) films prepared in examples 1-3;
FIG. 7 is a graph showing the water absorption of the poly (arylene ether nitrile) films prepared in examples 1 to 4;
FIG. 8 is a graph showing the contact angle of the poly (arylene ether nitrile) films prepared in examples 1 to 4;
FIG. 9 is a SEM solvent etching cross-sectional view of the poly (arylene ether nitrile) films prepared in examples 1-4;
FIG. 10 is a TMA chart of the poly (arylene ether nitrile) films prepared in examples 2 to 4.
Detailed Description
The technical scheme of the invention is described in detail below with reference to the accompanying drawings and examples. However, this is not a limitation of the present invention, and various modifications or changes may be made by those skilled in the art based on the basic idea of the present invention without departing from the scope thereof.
Example 1
The preparation method of the polyarylether nitrile film with high strength, high crystallinity and low thermal expansion coefficient specifically comprises the following steps:
Step 1, adding hydroquinone, biphenol and 2, 6-dichlorobenzonitrile as reactants, adding potassium carbonate as a catalyst, adding N-methylpyrrolidone and toluene as solvents into a three-necked flask with a thermometer, a water knockout drum, a condensation reflux device and a mechanical stirring device, injecting toluene into the water knockout drum, and then heating and refluxing for 2-3 hours at 145-155 ℃; wherein, the mol ratio of hydroquinone, biphenol, 2, 6-dichlorobenzonitrile, potassium carbonate and N-methyl pyrrolidone is 0.19mol:0.01mol:0.202mol:0.28mol:0.92mol, the volume ratio of N-methylpyrrolidone to toluene solvent is 3:1, a step of;
Step 2, after heating reflux is finished, 1 mL-5 mL of toluene is separated from the water separator every 10 min-30 min until the temperature reaches 190 ℃ -198 ℃, then heating and stirring are carried out for 2-3 h at the temperature of 190 ℃ -198 ℃, then N-methylpyrrolidone is added to enable the solution to have good fluidity, heating and stirring are continued for 30-60 min, and after completion, the solution is poured into deionized water to obtain off-white strip solids; wherein, the mol ratio of the added N-methyl pyrrolidone to the N-methyl pyrrolidone in the step 1 is 1 (1.47-3.10);
step 3, after crushing the off-white strip solid obtained in the step 2, dispersing the crushed off-white strip solid in deionized water, adding hydrochloric acid until the pH value of the solution is 1-2, standing for 30min, and filtering; treating the filtered powder in boiling water for 1-2h, filtering, repeating the process of treating in boiling water for 1-2h and filtering for 3-5 times until the solution is neutral, filtering, separating and drying to obtain crystalline polyarylether nitrile;
step 4, dissolving the crystalline poly (arylene ether nitrile) obtained in the step3 into N-methylpyrrolidone, and preparing a crystalline poly (arylene ether nitrile) film by solution casting; wherein, the temperature rising process of the solution casting method is as follows: the temperature is kept at 80 ℃, 100 ℃, 120 ℃ and 160 ℃ for 1 hour, then at 200 ℃ for 2 hours, and finally at 230 ℃ for 3 hours.
In the step 2, when precipitation occurs, N-methyl pyrrolidone is added into the reaction liquid in batches and the positions of the stirring rod (the upper, middle and lower positions of the reactant) are adjusted for a plurality of times, so that the precipitated crystals are dissolved in the reaction liquid, and the molecular weight is improved while the reaction is continuously carried out.
The crystalline poly (arylene ether nitrile) film obtained in example 1 had a glass transition temperature of 204.3 ℃, a melting enthalpy of 32.99J/g, a melting peak melting point of 341.9 ℃, and a temperature of 528.2 ℃ at a loss of 5% by mass at high temperature; the crystallinity of XRD results was 49.29% calculated using the Jade 6 simulation; the contact angle at normal temperature was 102.2 °.
Example 2
This embodiment differs from embodiment 1 in that: in step 1, the molar ratio of hydroquinone, biphenol, 2, 6-dichlorobenzonitrile, potassium carbonate and N-methylpyrrolidone was adjusted to 0.18mol:0.02mol:0.202mol:0.28mol:0.932mol. The remaining steps were the same as in example 1.
The crystalline poly (arylene ether nitrile) film obtained in example 2 had a glass transition temperature of 189.2℃and a melting enthalpy of 26.93J/g, a melting peak melting point of 329.6 ℃and a temperature at which 5% by mass was lost at high temperature of 519.8 ℃; the tensile strength is 121.1MPa, the tensile modulus is 2365.71MPa, and the elongation at break is 10.71%. The crystallinity of XRD results was 41.07% calculated by analogue calculation using Jade 6; the contact angle at normal temperature is 97.9 degrees; the linear expansion coefficient at 50-150 ℃ is 33.25ppm/K.
Example 3
This embodiment differs from embodiment 1 in that: in step 1, the molar ratio of hydroquinone, biphenol, 2, 6-dichlorobenzonitrile, potassium carbonate and N-methylpyrrolidone was adjusted to 0.17mol:0.03mol:0.202mol:0.28mol:0.944mol. The remaining steps were the same as in example 1.
The crystalline poly (arylene ether nitrile) film obtained in example 3 had a glass transition temperature of 188.1 ℃, a melting enthalpy of 16.9J/g, a melting peak melting point of 303.2 ℃ and a temperature of 518.7 ℃ when 5% by mass was lost at high temperature; the tensile strength is 131.21MPa, the tensile modulus is 2341.6MPa, and the elongation at break is 55.69%. The crystallinity of XRD results was 30.28% calculated using the Jade 6 simulation; the contact angle at normal temperature is 88.2 degrees; the linear expansion coefficient at 50-150 ℃ is 37.57ppm/K.
Example 4
This embodiment differs from embodiment 1 in that: in step 1, the molar ratio of hydroquinone, biphenol, 2, 6-dichlorobenzonitrile, potassium carbonate and N-methylpyrrolidone was adjusted to 0.16mol:0.04mol:0.202mol:0.28mol:0.956mol. The remaining steps were the same as in example 1.
The crystalline poly (arylene ether nitrile) film obtained in example 4 had a glass transition temperature of 204.3 ℃, a melting enthalpy of 32.99J/g, a melting peak melting point of 341.9 ℃, and a temperature of 427.2 ℃ at a loss of 5% by mass at high temperature; the tensile strength is 112.9MPa, the tensile modulus is 2200.32MPa, and the elongation at break is 19.87%. The crystallinity of XRD results was 10.89% calculated using the Jade 6 simulation; the contact angle at normal temperature is 59.7 degrees; the linear expansion coefficient is 46.15ppm/K at 50-150 ℃.
Claims (3)
1. The polyarylether nitrile film with high strength, high crystallinity and low thermal expansion coefficient is characterized by comprising the following structural formula:
wherein m=200 to 475, n=20 to 25, n: m=1: (8-24).
2. The preparation method of the polyarylether nitrile film with high strength, high crystallinity and low thermal expansion coefficient is characterized by comprising the following steps:
Step 1, adding hydroquinone, biphenol and 2, 6-dichlorobenzonitrile as reactants, adding potassium carbonate as a catalyst, adding N-methylpyrrolidone and toluene as solvents into a three-necked flask with a thermometer, a water knockout drum, a condensation reflux device and a mechanical stirring device, injecting toluene into the water knockout drum, and then heating and refluxing for 2-3 hours at 145-155 ℃; wherein, the mol ratio of hydroquinone, biphenol, 2, 6-dichlorobenzonitrile, potassium carbonate and N-methyl pyrrolidone is (0.16 mol to 0.19 mol): (0.01 mol to 0.04 mol): 0.202mol:0.28mol: (0.92-0.96 mol), the volume ratio of N-methyl pyrrolidone and toluene solvent is 3:1, a step of;
Step2, after heating reflux is finished, 1 mL-5 mL of toluene is separated from the water separator every 10 min-30 min until the temperature reaches 190 ℃ to 198 ℃, then heating and stirring are carried out for 2-3 h at the temperature of 190 ℃ to 198 ℃, then N-methylpyrrolidone is added, heating and stirring are continued for 30-60 min, and after completion, the mixture is poured into deionized water to obtain off-white strip solids; wherein, the mol ratio of the added N-methyl pyrrolidone to the N-methyl pyrrolidone in the step 1 is 1 (1.47-3.10);
Step 3, after crushing the off-white strip solid obtained in the step 2, dispersing the crushed off-white strip solid in deionized water, adding hydrochloric acid until the pH value of the solution is=1-2, standing for more than 30min, and filtering; treating the filtered powder in boiling water for 1-2 h, filtering, repeating the process of treating in boiling water for 1-2 h and filtering for 3-5 times until the solution is neutral, filtering, separating and drying to obtain crystalline polyarylether nitrile;
step 4, dissolving the crystalline poly (arylene ether nitrile) obtained in the step3 into N-methylpyrrolidone, and preparing a crystalline poly (arylene ether nitrile) film by solution casting; wherein, the temperature rising process of the solution casting method is as follows: the temperature is kept at 80 ℃, 100 ℃, 120 ℃ and 160 ℃ for 1 hour, then at 200 ℃ for 2 hours, and finally at 230 ℃ for 3 hours.
3. The method for producing a poly (arylene ether nitrile) film having high strength, high crystallinity and low thermal expansion coefficient according to claim 2, wherein in step 2, when precipitation occurs, the precipitated crystals are dissolved in the reaction solution by adding N-methylpyrrolidone to the reaction solution and adjusting the position of the stirring rod.
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