CN101230136B - Polyimide microparticle and preparation method thereof - Google Patents
Polyimide microparticle and preparation method thereof Download PDFInfo
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- CN101230136B CN101230136B CN2007100194134A CN200710019413A CN101230136B CN 101230136 B CN101230136 B CN 101230136B CN 2007100194134 A CN2007100194134 A CN 2007100194134A CN 200710019413 A CN200710019413 A CN 200710019413A CN 101230136 B CN101230136 B CN 101230136B
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- polyimide
- diamino
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- tetracarboxylic dianhydride
- polyamic acid
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 66
- 239000004642 Polyimide Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000011859 microparticle Substances 0.000 title claims description 57
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 238000001035 drying Methods 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 150000004985 diamines Chemical class 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000009826 distribution Methods 0.000 claims abstract description 8
- 229920005575 poly(amic acid) Polymers 0.000 claims description 52
- -1 tetracarboxylic anhydride Chemical class 0.000 claims description 43
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 40
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- 239000006185 dispersion Substances 0.000 claims description 28
- 239000003795 chemical substances by application Substances 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 20
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 16
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 16
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 16
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical group C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 claims description 15
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 11
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 238000000354 decomposition reaction Methods 0.000 claims description 7
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 229920002125 Sokalan® Polymers 0.000 claims description 5
- 239000004584 polyacrylic acid Substances 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 159000000000 sodium salts Chemical class 0.000 claims description 3
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical compound C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 claims description 2
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 claims description 2
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 claims description 2
- ICNFHJVPAJKPHW-UHFFFAOYSA-N 4,4'-Thiodianiline Chemical compound C1=CC(N)=CC=C1SC1=CC=C(N)C=C1 ICNFHJVPAJKPHW-UHFFFAOYSA-N 0.000 claims description 2
- FYYYKXFEKMGYLZ-UHFFFAOYSA-N 4-(1,3-dioxo-2-benzofuran-5-yl)-2-benzofuran-1,3-dione Chemical compound C=1C=C2C(=O)OC(=O)C2=CC=1C1=CC=CC2=C1C(=O)OC2=O FYYYKXFEKMGYLZ-UHFFFAOYSA-N 0.000 claims description 2
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 claims description 2
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- OYTKINVCDFNREN-UHFFFAOYSA-N amifampridine Chemical compound NC1=CC=NC=C1N OYTKINVCDFNREN-UHFFFAOYSA-N 0.000 claims description 2
- 229960004012 amifampridine Drugs 0.000 claims description 2
- 150000004984 aromatic diamines Chemical class 0.000 claims description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 235000010980 cellulose Nutrition 0.000 claims description 2
- RBMTXFLUVLIQGN-UHFFFAOYSA-N dodecane-1,10-diamine Chemical compound CCC(N)CCCCCCCCCN RBMTXFLUVLIQGN-UHFFFAOYSA-N 0.000 claims description 2
- 239000003925 fat Substances 0.000 claims description 2
- 229920000591 gum Polymers 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 2
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 2
- 229920000609 methyl cellulose Polymers 0.000 claims description 2
- 239000001923 methylcellulose Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 229920000193 polymethacrylate Polymers 0.000 claims description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims 1
- JHULZOYUZZNNJL-UHFFFAOYSA-N 4,4-diaminobutan-2-one Chemical compound CC(=O)CC(N)N JHULZOYUZZNNJL-UHFFFAOYSA-N 0.000 claims 1
- 239000001913 cellulose Substances 0.000 claims 1
- 238000005406 washing Methods 0.000 abstract description 18
- 239000002270 dispersing agent Substances 0.000 abstract description 14
- 238000000926 separation method Methods 0.000 abstract 2
- 238000004090 dissolution Methods 0.000 abstract 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 abstract 1
- 238000005979 thermal decomposition reaction Methods 0.000 abstract 1
- 238000001914 filtration Methods 0.000 description 19
- 239000004698 Polyethylene Substances 0.000 description 13
- 229920000573 polyethylene Polymers 0.000 description 13
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000012674 dispersion polymerization Methods 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- ODANWMOQWMHGCY-UHFFFAOYSA-N 1,4-diaminobutan-2-one Chemical compound NCCC(=O)CN ODANWMOQWMHGCY-UHFFFAOYSA-N 0.000 description 1
- OLQWMCSSZKNOLQ-UHFFFAOYSA-N 3-(2,5-dioxooxolan-3-yl)oxolane-2,5-dione Chemical compound O=C1OC(=O)CC1C1C(=O)OC(=O)C1 OLQWMCSSZKNOLQ-UHFFFAOYSA-N 0.000 description 1
- ZWUBBMDHSZDNTA-UHFFFAOYSA-N 4-Chloro-meta-phenylenediamine Chemical compound NC1=CC=C(Cl)C(N)=C1 ZWUBBMDHSZDNTA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005700 Putrescine Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001408 amides Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- SSJXIUAHEKJCMH-UHFFFAOYSA-N cyclohexane-1,2-diamine Chemical compound NC1CCCCC1N SSJXIUAHEKJCMH-UHFFFAOYSA-N 0.000 description 1
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- JGGWKXMPICYBKC-UHFFFAOYSA-N phenanthrene-1,8,9,10-tetracarboxylic acid Chemical compound C1=CC=C(C(O)=O)C2=C(C(O)=O)C(C(O)=O)=C3C(C(=O)O)=CC=CC3=C21 JGGWKXMPICYBKC-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses polyimide corpuscule and a preparation method thereof. The specific preparation method adopts the steps that when being stirred, dispersant is added into a solvent, and after dissolution, diamine and tetracarboxylic acid anhydride are added in sequence for reaction; after the reaction is completed, polyimide corpuscule is obtained through separation; imidization is performed to the obtained polyimide corpuscule, and then after separation, washing and drying, polyimide corpuscule is obtained. The polyimide corpuscule prepared through the method is complete spherical corpuscle with the corpuscle diameter of 0.1 to 1 micrometers, the standard deviation coefficient of the corpuscle diameter distribution of 0.01 to 0.2, and the thermal decomposition temperature of higher than 500 DEG C. In addition, the technological line of the invention is simple, and the requirements on the equipment are low, thereby the polyimide corpuscule has very strong practicability.
Description
Technical field
The present invention relates to a kind of field of polymer technology, relate to a kind of polyimide microparticle and preparation method thereof specifically.
Background technology
Polyimide not only has good mechanical property, and has other satisfactory performance, as thermotolerance, and chemical proofing and insulativity; Therefore, it is widely used as electric, electronic material, materials used in auto manufacturing, the surrogate of metal and pottery, and other application.
The synthetic method of polyimide is generally in two steps: the first step system with dianhydride and diamines in N,N-dimethylacetamide, N, dinethylformamide is made the high-molecular weight polyamic acid of solubility earlier in about 70 ℃ in the intensive polar solvents such as dimethyl sulfoxide (DMSO); Second step was heated to this solvable fusile intermediate product more than 150 ℃, obtained polyimide through imidization.A lot of patents have all been reported the preparation method of polyimide microparticle: as patent JP2003252990 the polyamic acid of preparation is dissolved in the polarity good solvent, adding poor solvent again precipitates and obtains the polyamic acid micropartical, the polyamic acid micropartical that obtains is keeping being transformed into polyimide microparticle under the constant situation of size and pattern through adding hot-imide.Patent JP9302089 is dissolved in reacting by heating in a kind of organic solvent with tetracarboxylic dianhydride and diamines, and the polyamic acid of generation is insoluble to this kind organic solvent, is precipitated out to generate the polyamic acid micropartical, obtains polyimide microparticle through imidization again.Above-mentioned preparation method will use strong polar solvent and the polyimide microparticle size distribution that obtains compares broad. and patent JP2000248063 has reported that a kind of preparation method of polyimide microparticle has overcome above-mentioned shortcoming, has obtained the very narrow spherical polyimide microparticle of size distribution.This method comprised for two steps: the first step prepares first kind of solution that contains tetracarboxylic anhydride and the second kind of solution that contains diamine compound respectively; Second step was to make two kinds of solution mixed under the ultrasonic wave effect, along with the polyamic acid micropartical that generates that reacts is precipitated out from solution, again the polyamic acid micropartical that obtains was carried out the imidization processing and obtained polyimide microparticle.
Dispersion copolymerization method is often used preparing the polymeric microsphere from vinyl monomer.Its polymerization system is homogeneous phase solution at first, that is to say monomer, and initiator and stablizer all are dissolved in solvent, but the polymkeric substance after the polymerization must be not dissolved in solvent.Stablizer and solvent, polymkeric substance must all have affinity interaction.After the beginning polymerization, decomposition of initiator and in solvent with monomer reaction, after the polymkeric substance chain length surpasses critical length, just precipitating comes out to form nuclear from solvent, then, a plurality of nuclears are agglomerated into stable growth microballoon mutually, and the absorption stablizer makes polymeric microspheres stabilize in microsphere surface.Then, the growth microballoon absorbs monomer and initiator and polymerization in microballoon from external phase, and promptly the polymerization place moves in the microballoon from external phase.Do not appear in the newspapers as yet about the method for utilizing dispersion copolymerization method to prepare polyimide microparticle.
Summary of the invention
The objective of the invention is in conjunction with dispersion polymerization processes, provides a kind of polyimide microparticle and preparation method thereof on the basis of prior preparation method.
Purpose of the present invention can reach by following measure:
A kind of polyimide microparticle, this micropartical is complete sphere, contains following structural unit in the molecular chain:
Its particle size range is 0.1～1 μ m, and the standard deviation factor of size distribution is 0.01～0.2, and heat decomposition temperature is greater than 500 ℃.Heat decomposition temperature is tested with thermogravimetric analyzer (TAQ600), 10 ℃/min of temperature rise rate, nitrogen atmosphere.
A kind of method for preparing above-mentioned polyimide microparticle is characterized in that under agitation, and dispersion agent is added in the solvent, adds diamines successively after the dissolving and tetracarboxylic anhydride reacts; After finishing, reaction, promptly obtains the polyamic acid micropartical through separating (filtering, centrifugal); The polyamic acid micropartical that obtains is carried out imidization reaction, and through separating (filtering, centrifugal), drying obtains polyimide microparticle again.
Purpose of the present invention specifically can reach by following measure:
Utilize tetracarboxylic anhydride and diamine compound to be raw material, prepare the narrower spherical polyimide microparticle of particle size dispersion through dispersion polymerization.This kind micropartical particle size range is 0.1～1 μ m, the standard deviation factor of size distribution be 0.01～0.2 and heat decomposition temperature greater than 500 ℃.
The add-on of each raw material is by weight in this atomic preparation method:
0.01～10 part of tetracarboxylic anhydride
0.01～10 part of diamines
0.01～10 part of dispersion agent
20～100 parts of solvents.
Described tetracarboxylic anhydride is selected from aromatic series tetracarboxylic acid acid anhydride, as 3, and 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA), 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 2,3,3 ', 4 '-biphenyl tetracarboxylic dianhydride, 1,2,4,5-pyromellitic acid dianhydride, 2,3,3 ', 4 '-benzophenone tetracarboxylic dianhydride, 2,2 ', 3,3 '-benzophenone tetracarboxylic dianhydride, 2,2 ' 6,6 '-biphenyl tetracarboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride etc.; The aliphatics tetracarboxylic anhydride, as butane-1,2,3,4-tetracarboxylic dianhydride etc.; Alicyclic tetracarboxylic anhydride, as tetramethylene-1,2,3,4-tetracarboxylic dianhydride etc.; Heterocycle family tetracarboxylic anhydride, as thiophene-2,3,4,5-tetracarboxylic anhydride, pyridine-2,3,5,6-tetracarboxylic anhydride etc. these compounds can be separately or two or more be used in combination. for the present invention, preferred especially 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride and 1,2,4,5-pyromellitic acid dianhydride.
Described diamine compound is selected from aromatic diamine, as 4, and 4 '-diaminodiphenyl-methane (DDM), 4,4 '-diamino-diphenyl ether (DPE), 4,4 '-diaminodiphenylsulfone(DDS), 3,4-diaminodiphenylsulfone(DDS), 3,3 '-diaminodiphenylsulfone(DDS), 3,4 '-diamino-diphenyl ether, neighbour-phenylenediamine ,-phenylenediamine, right-phenylenediamine, 2,6 '-diaminotoluene, 2,4-diaminochlorobenzene, 3,3 '-dimethyl-4,4 '-benzidine, 4,4 '-diamino diphenyl sulfide etc.; The fats diamines, as 1,2-diamino methane, 1,4-diaminobutane, tetramethylene-diamine, 1,10-diamino dodecane etc.; Alicyclic diamine, as 1,4-diamino-cyclohexane, 1,2-diamino-cyclohexane, 3,4-diamino-pyridine, 1,4-diamino-2-butanone etc.These diamine compounds can use separately, and perhaps two or more materials are used in combination.The present invention is preferred especially 4,4 '-diamino-diphenyl ether (DPE), 4,4 '-diaminodiphenylsulfone(DDS) etc.
Described dispersion agent is selected from polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), methylcellulose gum, carboxymethyl cellulose, hydroxypropylcellulose, derivatived celluloses such as Vltra tears, polyacrylate is (as polyacrylic acid sylvite, polyacrylic acid sodium salt etc.) one or more or in the poly-methyl acrylate (polymethyl acid potassium salt, sodium polymethacrylate salt etc.) etc.
Described solvent is selected from methyl alcohol, ethanol, Virahol, ethyl acetate, tetrahydrofuran (THF), acetone, pentanone, toluene, dimethylbenzene, N, dinethylformamide, N,N-dimethylacetamide, one or more in the N-N-methyl-2-2-pyrrolidone N-etc.
Temperature during described the reaction is 0～130 ℃, preferred 0～80 ℃, and most preferably 0～40 ℃.
The described reaction times is 1min～48h, preferred 0.5h～48h.
Described mixing speed is 50～5000 rev/mins, preferred 100～5000 rev/mins, and most preferably 200～2000 rev/mins.
Described imidization method is characterized in that the polyamic acid micropartical is carried out imidization with traditional imidization method as heating etc. obtains polyimide microparticle.For example: the polyamic acid micropartical that obtains is distributed to is heated to 140 ℃ of backflows in the dimethylbenzene and carries out imidization and obtain polyimide microparticle.Also can realize imidization with known chemical process, as the polyamic acid micropartical being scattered in the organic solvent of being made up of pyridine and diacetyl oxide, under about 60 ℃, the continuously stirring heating was carried out imidization in 24 hours and is obtained polyimide microparticle then.
The present invention adopts diffuse-aggregate method to prepare polyimide microparticle.The polyamide particles minor structure that the present invention makes is complete sphere, particle size range is 0.1～1 μ m, the standard deviation factor of size distribution be 0.01～0.2 and heat decomposition temperature greater than 500 ℃, and operational path of the present invention is simpler, requirement to equipment is lower, and very strong practicality is arranged, and compares with the preparation method of traditional polyimide microparticle, the polyimide microparticle sphere that the present invention obtains is more complete, and the size distribution Z-factor is littler.
The resulting polyimide microparticle of the present invention has thermotolerance, insulativity and other performances of polyimide resin inherent, therefore can be widely used (comprising traditional purposes), coated material in particular as electric insulation part, die material, electric, electronic material, and other matrix materials etc.
Description of drawings
The stereoscan photograph of the polyamide micro-particle that Fig. 1 obtains for the embodiment of the invention 1.
The stereoscan photograph of the polyamide micro-particle that Fig. 2 obtains for Comparative Examples 1.
The stereoscan photograph of the polyamide micro-particle that Fig. 3 obtains for Comparative Examples 2.
The infrared spectrogram of the polyimide microparticle that Fig. 4 obtains for the embodiment of the invention 1.
Among the figure at 1775cm
-1And 1720cm
-1The absorption peak at place is that imido C=O group face inner face vibrates outward, at 1375cm
-1The absorption peak at place is the stretching vibration of C-N between inferior acid amides ring and the adjacent phenyl, this shows that this sample is a polyimide.
The thermogravimetric curve figure of the polyimide microparticle that Fig. 5 obtains for the embodiment of the invention 1 in nitrogen.
Among the figure on the curve from 100 ℃ to 300 ℃ about 5% weightlessness be the imidization of the intact polyamic acid of unreacted, near the weightlessness 500 ℃ is the decomposition of polyimide, the carbon of rest parts for generating.
Embodiment
Embodiment 1:
20 ℃, 200rpm stirs down, and 100ml methyl alcohol is joined in the there-necked flask, adds 0.5g polyethylene of dispersing agent pyrrolidone (PVP) again.Treat to add 0.4g 4 successively after the dispersion agent dissolving, 4 '-diamino-diphenyl ether (DPE), 0.65g 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA), reaction 24h, after filtration, washing, drying obtains the polyamic acid micropartical, the polyamic acid micropartical that obtains is distributed to be heated to 140 ℃ of backflows in the dimethylbenzene and to carry out imidization and obtain polyimide microparticle again.
Embodiment 2:
20 ℃, 200rpm stirs down, and 100ml methyl alcohol is joined in the there-necked flask, adds 0.5g polyethylene of dispersing agent pyrrolidone (PVP) again.Treat to add 0.4g 4 successively after the dispersion agent dissolving, 4 '-diamino-diphenyl ether (DPE), 0.65g 1,2,4,5-pyromellitic acid dianhydride, reaction 24h, after filtration, washing, drying obtains the polyamic acid micropartical, the polyamic acid micropartical that obtains is distributed to be heated to 140 ℃ of backflows in the dimethylbenzene and to carry out imidization and obtain polyimide microparticle again.
Embodiment 3:
20 ℃, 200rpm stirs down, and 100ml methyl alcohol is joined in the there-necked flask, adds 0.5g polyethylene of dispersing agent pyrrolidone (PVP) again.Treat to add 0.4g 4 successively after the dispersion agent dissolving, 4 '-diaminodiphenylsulfone(DDS), 0.65g 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA), reaction 24h, after filtration, washing, drying obtains the polyamic acid micropartical, the polyamic acid micropartical that obtains is distributed to be heated to 140 ℃ of backflows in the dimethylbenzene and to carry out imidization and obtain polyimide microparticle again.
Embodiment 4:
20 ℃, 200rpm stirs down, and 50ml methyl alcohol is joined in the there-necked flask, adds 0.5g polyethylene of dispersing agent alcohol (PVA) again.Treat to add 0.4g 4 successively after the dispersion agent dissolving, 4 '-diamino-diphenyl ether (DPE), 0.65g butane-1,2,3, the 4-tetracarboxylic dianhydride, reaction 24h, after filtration, washing, drying obtains the polyamic acid micropartical, the polyamic acid micropartical that obtains is distributed to be heated to 140 ℃ of backflows in the dimethylbenzene and to carry out imidization and obtain polyimide microparticle again.
Embodiment 5:
20 ℃, 200rpm stirs down, and 100ml methyl alcohol is joined in the there-necked flask, add 0.5g dispersion agent carboxymethyl cellulose again. treat to add 0.4g 4 successively, 4 '-diamino-diphenyl ether (DPE), 0.65g tetramethylene-1 after the dispersion agent dissolving, 2,3,4-tetracarboxylic dianhydride, reaction 24h, after filtration, washing, drying obtains the polyamic acid micropartical, the polyamic acid micropartical that obtains is distributed to be heated to 140 ℃ of backflows in the dimethylbenzene and to carry out imidization and obtain polyimide microparticle again.
Embodiment 6:
20 ℃, 200rpm stirs down, and 4000ml ethanol is joined in the there-necked flask, adds 0.5g polyethylene of dispersing agent pyrrolidone (PVP) again.Treat to add 0.4g 4 successively after the dispersion agent dissolving, 4 '-diamino-diphenyl ether (DPE), 0.65g thiophene-2,3,4, the 5-tetracarboxylic anhydride, reaction 24h, after filtration, washing, drying obtains the polyamic acid micropartical, the polyamic acid micropartical that obtains is distributed to be heated to 140 ℃ of backflows in the dimethylbenzene and to carry out imidization and obtain polyimide microparticle again.
Embodiment 7:
40 ℃, 200rpm stirs down, and 100ml methyl alcohol is joined in the there-necked flask, adds 0.5g polyethylene of dispersing agent pyrrolidone (PVP) again.Treat to add 0.4g 1 successively after the dispersion agent dissolving, 2-diamino methane, 0.65g 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA), reaction 24h, after filtration, washing, drying obtains the polyamic acid micropartical, the polyamic acid micropartical that obtains is distributed to be heated to 140 ℃ of backflows in the dimethylbenzene and to carry out imidization and obtain polyimide microparticle again.
Embodiment 8:
0 ℃, 200rpm stirs down, and 100ml methyl alcohol is joined in the there-necked flask, adds 0.5g polyethylene of dispersing agent pyrrolidone (PVP) again.Treat to add 0.4g 1 successively after the dispersion agent dissolving, the 4-diamino-cyclohexane, 0.65g 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA), reaction 24h, after filtration, washing, drying obtains the polyamic acid micropartical, the polyamic acid micropartical that obtains is distributed to be heated to 140 ℃ of backflows in the dimethylbenzene and to carry out imidization and obtain polyimide microparticle again.
Embodiment 9:
20 ℃, 200rpm stirs down, and 1000ml methyl alcohol is joined in the there-necked flask, adds 0.5g polyethylene of dispersing agent pyrrolidone (PVP) again.Treat to add 0.4g 4 successively after the dispersion agent dissolving, 4 '-diamino-diphenyl ether (DPE), 0.65g 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA), reaction 24h, after filtration, washing, drying obtains the polyamic acid micropartical, the polyamic acid micropartical that obtains is distributed to be heated to 140 ℃ of backflows in the dimethylbenzene and to carry out imidization and obtain polyimide microparticle again.
Embodiment 10:
20 ℃, 100rpm stirs down, and 100ml methyl alcohol is joined in the there-necked flask, adds 5g polyethylene of dispersing agent pyrrolidone (PVP) again.Treat to add 0.4g 4 successively after the dispersion agent dissolving, 4 '-diamino-diphenyl ether (DPE), 0.65g 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA), reaction 48h, after filtration, washing, drying obtains the polyamic acid micropartical, the polyamic acid micropartical that obtains is distributed to be heated to 140 ℃ of backflows in the dimethylbenzene and to carry out imidization and obtain polyimide microparticle again.
Embodiment 11:
20 ℃, 200rpm stirs down, and 100ml methyl alcohol is joined in the there-necked flask, adds 0.5g dispersion agent polyacrylic acid sodium salt again.Treat to add 4g 4 successively after the dispersion agent dissolving, 4 '-diamino-diphenyl ether (DPE), 0.65g 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA), reaction 24h, after filtration, washing, drying obtains the polyamic acid micropartical, the polyamic acid micropartical that obtains is distributed to be heated to 140 ℃ of backflows in the dimethylbenzene and to carry out imidization and obtain polyimide microparticle again.
Embodiment 12:
20 ℃, 200rpm stirs down, and the 100ml ethyl acetate is joined in the there-necked flask, adds 0.5g polyethylene of dispersing agent pyrrolidone (PVP) again.Treat to add 0.4g 4 successively after the dispersion agent dissolving, 4 '-diamino-diphenyl ether (DPE), 6.5g 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA), reaction 24h, after filtration, washing, drying obtains the polyamic acid micropartical, the polyamic acid micropartical that obtains is distributed to be heated to 140 ℃ of backflows in the dimethylbenzene and to carry out imidization and obtain polyimide microparticle again.
Embodiment 13:
20 ℃, 1000rpm stirs down, and 100ml acetone is joined in the there-necked flask, adds 0.5g polyethylene of dispersing agent pyrrolidone (PVP) again.Treat to add 0.4g 4 successively after the dispersion agent dissolving, 4 '-diamino-diphenyl ether (DPE), 0.65g 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA), reaction 24h, after filtration, washing, drying obtains the polyamic acid micropartical, the polyamic acid micropartical is scattered in the organic solvent of being made up of pyridine and diacetyl oxide again, under about 60 ℃, the continuously stirring heating was carried out imidization in 24 hours and is obtained polyimide microparticle then.
Embodiment 14:
80 ℃, 5000rpm stirs down, and 80ml dimethylbenzene is joined in the there-necked flask, adds 0.5g polyethylene of dispersing agent pyrrolidone (PVP) again.Treat to add 4g 4 successively after the dispersion agent dissolving, 4 '-diamino-diphenyl ether (DPE), 6.5g 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA), reaction 0.5h, after filtration, washing, drying obtains the polyamic acid micropartical, the polyamic acid micropartical that obtains is distributed to be heated to 140 ℃ of backflows in the dimethylbenzene and to carry out imidization and obtain polyimide microparticle again.
Embodiment 15:
20 ℃, 200rpm stirs down, and with 90ml N, dinethylformamide joins in the there-necked flask, adds 0.5g polyethylene of dispersing agent pyrrolidone (PVP) again.Treat to add 0.4g 4 successively after the dispersion agent dissolving, 4 '-diamino-diphenyl ether (DPE), 0.65g 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA), reaction 1h, after filtration, washing, drying obtains the polyamic acid micropartical, the polyamic acid micropartical that obtains is distributed to be heated to 140 ℃ of backflows in the dimethylbenzene and to carry out imidization and obtain polyimide microparticle again.
Comparative Examples 1:
With 0.4g 4,4 '-diamino-diphenyl ether (DPE) and 0.65g 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA) joins respectively in the 50ml ethanol, under 20 ℃ that two kinds of solution are mixed, react 10min in the ultrasonic wave, after filtration, washing, drying obtains the polyamic acid micropartical, the polyamic acid micropartical that obtains is distributed to be heated to 140 ℃ of backflows in the dimethylbenzene and to carry out imidization and obtain polyimide microparticle again.
Comparative Examples 2:
20 ℃, 200rpm stirs down, and 100ml methyl alcohol is joined in the there-necked flask, adds 0.4g more successively
4,4 '-diamino-diphenyl ether (DPE), 0.65g 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA), reaction 24h, after filtration, washing, drying obtains the polyamic acid micropartical, the polyamic acid micropartical that obtains is distributed to be heated to 140 ℃ of backflows in the dimethylbenzene and to carry out imidization and obtain polyimide microparticle again.
Claims (9)
1. polyimide microparticle, this micropartical is complete sphere, contains following structural unit in the molecular chain:
Its particle size range is 0.1～1 μ m, and the standard deviation factor of size distribution is 0.01～0.2, and heat decomposition temperature is greater than 500 ℃;
The method of this polyimide microparticle is: under 50～5000 rev/mins stirring, dispersion agent is added in the solvent, add diamines successively after the dissolving and tetracarboxylic anhydride reacts, the temperature during reaction is 0～130 ℃, and the reaction times is 1min～48h; After finishing, reaction promptly obtains the polyamic acid micropartical through separating; The polyamic acid micropartical that obtains is carried out imidization reaction, through separating, wash, drying obtains polyimide microparticle;
Wherein the add-on of each raw material is by weight:
0.01～10 part of tetracarboxylic anhydride
0.01～10 part of diamines
0.01～10 part of dispersion agent
20～100 parts of solvents.
2. method for preparing the described polyimide microparticle of claim 1, it is characterized in that under 50～5000 rev/mins stirring, dispersion agent is added in the solvent, add diamines successively after the dissolving and tetracarboxylic anhydride reacts, temperature during reaction is 0～130 ℃, and the reaction times is 1min～48h; After finishing, reaction promptly obtains the polyamic acid micropartical through separating; The polyamic acid micropartical that obtains is carried out imidization reaction, through separating, wash, drying obtains polyimide microparticle.
3. the preparation method of polyimide microparticle according to claim 2 is characterized in that described tetracarboxylic anhydride is selected from one or more in aromatic series tetracarboxylic acid acid anhydride, aliphatics tetracarboxylic anhydride, alicyclic tetracarboxylic anhydride or the heterocycle family tetracarboxylic anhydride.
4. the preparation method of polyimide microparticle according to claim 3 is characterized in that described tetracarboxylic anhydride is selected from 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 2,3,3 ', 4 '-biphenyl tetracarboxylic dianhydride, 1,2,4,5-pyromellitic acid dianhydride, 2,3,3 ', 4 '-benzophenone tetracarboxylic dianhydride, 2,2 ', 3,3 '-benzophenone tetracarboxylic dianhydride, 2,2 ' 6,6 '-biphenyl tetracarboxylic dianhydride, luxuriant and rich with fragrance-1,8,9, the 10-tetracarboxylic dianhydride, butane-1,2,3, the 4-tetracarboxylic dianhydride, tetramethylene-1,2,3, the 4-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic anhydride or pyridine-2,3,5, one or more in the 6-tetracarboxylic anhydride.
5. the preparation method of polyimide microparticle according to claim 2 is characterized in that described diamines is selected from one or more in aromatic diamine, fats diamines or the alicyclic diamine.
6. the preparation method of polyimide microparticle according to claim 5, it is characterized in that described diamines is selected from 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl ether, 4,4 '-diaminodiphenylsulfone(DDS), 3, the 4-diaminodiphenylsulfone(DDS), 3,3 '-diaminodiphenylsulfone(DDS), 3,4 '-diamino-diphenyl ether, neighbour-phenylenediamine, between-phenylenediamine, right-phenylenediamine, 2,6 '-diaminotoluene, 2, the 4-diaminochlorobenzene, 3,3 '-dimethyl-4,4 '-benzidine, 4,4 '-diamino diphenyl sulfide, 1,2-diamino methane, 1, the 4-diaminobutane, tetramethylene-diamine, 1,10-diamino dodecane, 1, the 4-diamino-cyclohexane, 1, the 2-diamino-cyclohexane, 3,4-diamino-pyridine or 1, one or more in 4-diamino-2-butanone.
7. the preparation method of polyimide microparticle according to claim 2 is characterized in that described dispersion agent is selected from one or more in polyvinylpyrrolidone, polyvinyl alcohol, derivatived cellulose, polyacrylate or the poly-methyl acrylate.
8. the preparation method of polyimide microparticle according to claim 7 is characterized in that described dispersion agent is selected from one or more in polyvinylpyrrolidone, polyvinyl alcohol, methylcellulose gum, carboxymethyl cellulose, hydroxypropylcellulose, Vltra tears, polyacrylic acid sylvite, polyacrylic acid sodium salt, polymethyl acid potassium salt or the sodium polymethacrylate salt.
9. the preparation method of polyimide microparticle according to claim 2, it is characterized in that described solvent is selected from methyl alcohol, ethanol, Virahol, ethyl acetate, tetrahydrofuran (THF), acetone, pentanone, toluene, dimethylbenzene, N, in dinethylformamide, N,N-dimethylacetamide, the N-N-methyl-2-2-pyrrolidone N-one or more.
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| US20130178597A1 (en) * | 2010-07-22 | 2013-07-11 | Ube Industries, Ltd. | Polyimide precursor, polyimide, and materials to be used in producing same |
| CN102585253B (en) * | 2011-12-23 | 2014-07-09 | 云南云天化股份有限公司 | Preparation method of thermoplastic polyimide (TPI) particles for modifying surfaces of polyimide (PI) films |
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| CN106997947A (en) * | 2017-05-22 | 2017-08-01 | 大连理工大学 | A kind of self assembly polyimide porous material, preparation method and its application in lithium-sulfur cell |
| CN108929438A (en) * | 2017-05-23 | 2018-12-04 | 万华化学集团股份有限公司 | A kind of preparation method of polyamic acid and the method that polyimides is prepared by the polyamic acid |
| CN109749100B (en) * | 2018-12-21 | 2022-11-18 | 航天科工(长沙)新材料研究院有限公司 | Preparation method and application of small-particle-size polyimide powder |
| CN115318212B (en) * | 2022-07-19 | 2023-06-20 | 曲阜师范大学 | Polyimide carbon microspheres (PCMs), preparation method, electrode and capacitive deionization |
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