TWI826744B - 石墨片用之聚醯亞胺膜、其製備方法及由此製得之石墨片 - Google Patents
石墨片用之聚醯亞胺膜、其製備方法及由此製得之石墨片 Download PDFInfo
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- TWI826744B TWI826744B TW109138807A TW109138807A TWI826744B TW I826744 B TWI826744 B TW I826744B TW 109138807 A TW109138807 A TW 109138807A TW 109138807 A TW109138807 A TW 109138807A TW I826744 B TWI826744 B TW I826744B
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- Prior art keywords
- film
- polyimide
- polyimide film
- metal
- metal compound
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 108
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 59
- 239000010439 graphite Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims description 8
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 45
- 239000000178 monomer Substances 0.000 claims abstract description 39
- 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 abstract description 18
- 150000004985 diamines Chemical class 0.000 claims abstract description 18
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 8
- 239000013522 chelant Substances 0.000 claims abstract description 4
- 239000004642 Polyimide Substances 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 19
- 239000004952 Polyamide Substances 0.000 claims description 18
- 229920002647 polyamide Polymers 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 11
- 239000002313 adhesive film Substances 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 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 7
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 239000003292 glue Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- 150000001408 amides Chemical class 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 150000004767 nitrides Chemical class 0.000 claims description 5
- 229910052582 BN Inorganic materials 0.000 claims description 4
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 238000005266 casting Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- 150000002500 ions Chemical group 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 229910052799 carbon Inorganic materials 0.000 description 12
- 238000005087 graphitization Methods 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 11
- -1 γ-butylene ester Chemical class 0.000 description 10
- 239000012024 dehydrating agents Substances 0.000 description 8
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000003763 carbonization Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910003481 amorphous carbon Inorganic materials 0.000 description 3
- 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 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 108010025899 gelatin film Proteins 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000003495 polar organic solvent Substances 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 238000006798 ring closing metathesis reaction Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- UIVOFKCQIFEAFX-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl.OC1=CC=CC=C1Cl UIVOFKCQIFEAFX-UHFFFAOYSA-N 0.000 description 1
- AURKDQJEOYBJSQ-UHFFFAOYSA-N 2-hydroxypropanoyl 2-hydroxypropanoate Chemical compound CC(O)C(=O)OC(=O)C(C)O AURKDQJEOYBJSQ-UHFFFAOYSA-N 0.000 description 1
- XUGNTQWDISZRDW-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1.OC1=CC=C(Cl)C=C1 XUGNTQWDISZRDW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
- C04B35/524—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite obtained from polymer precursors, e.g. glass-like carbon material
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- C01B32/00—Carbon; Compounds thereof
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
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- C08G73/1003—Preparatory processes
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- C08G73/1003—Preparatory processes
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- C08G73/1021—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the catalyst used
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- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
- C08G73/1032—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous characterised by the solvent(s) used
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- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
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- C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
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- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
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- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
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- C08K3/38—Boron-containing compounds
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- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
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Abstract
本文揭露一種石墨片用之聚醯亞胺膜、其製備方法及由此製得之石墨片。透過醯亞胺化由二酐單體和二胺單體之間反應形成的聚醯胺酸來製備聚醯亞胺膜,其中所述反應是在金屬化合物存在的情況下進行且聚醯胺酸與金屬離子形成螯合物。
Description
本發明係關於一種石墨片用之聚醯亞胺膜、其製備方法及由此製得之石墨片,且特別是有關於一種可提供良好的熱導率並同時降低製造成本的石墨片用之聚醯亞胺膜、其製備方法及由此製得之石墨片。
近來,隨著重量、尺寸和厚度的下降及整合度(integration degree)的提升,電子裝置受到發熱量增加的困擾。電子裝置中產生的熱量可導致電子裝置的失效、故障和壽命縮短。因此,電子裝置的熱管理成為了重要的課題。
比起像是銅或鋁的金屬片,石墨片具有更高的熱導率並且作為電子裝置的散熱元件而引起關注。可透過各種方法來製備這種石墨片,例如,聚合物膜的碳化和石墨化。特別地,聚醯亞胺膜因其良好的機械和熱尺寸穩定性及化學穩定性,故適合作為石墨片用之聚合物膜。
已知由聚醯亞胺膜製得的石墨片其特性取決於聚醯亞胺膜的特性。儘管已經開發出各種石墨片用之聚醯亞胺膜,但是仍然需要適於製備具有更高熱導率的石墨片之聚醯亞胺膜。
透過聚醯亞胺膜的石墨化來製備石墨片一般需要2,800°C或更高的高溫,這導致大量的能量消耗並因此增加了製造成本。因此,需要可以在較低溫度下被石墨化的聚醯亞胺膜。
本發明的一個目的是提供一種石墨片用之聚醯亞胺膜,其可提供良好的熱導率同時降低製造成本。
本發明的另一個目的是提供一種上述聚醯亞胺膜的製備方法。
本發明的又一個目的是提供一種使用上述聚醯亞胺膜所製得的石墨片。
1. 根據本發明的一方面,提供一種石墨片用之聚醯亞胺膜。所述聚醯亞胺膜是透過醯亞胺化由二酐單體和二胺單體之間反應形成的聚醯胺酸而製得,其中所述反應是在金屬化合物存在的情況下進行且聚醯胺酸與金屬離子形成螯合物。
2. 在實施例1中,組成所述金屬化合物的金屬可包括鎳、鉑、硼、鋁、或前述之組合。
3. 在實施例1或2中,所述金屬化合物可包括金屬氧化物、金屬碳化物、金屬氮化物、或前述之組合。
4. 在實施例1至3的任一者中,所述金屬化合物可包括氮化硼。
5. 在實施例1至4的任一者中,以聚醯亞胺膜的總重量為基準,金屬化合物於所述聚醯亞胺膜中存在的量可為約0.05 wt%至約1 wt%。
6. 在實施例1至5的任一者中,所述二酐單體可包括均苯四甲酸二酐(pyromellitic dianhydride)、3,3',4,4'-聯苯四羧酸二酐(3,3',4,4'-biphenyltetracarboxylic dianhydride)、或前述之組合。
7. 在實施例1至6的任一者中,所述二胺單體可包括4,4'-二氨基二苯醚(4,4'-diaminodiphenylether)、4,4'-二氨基二苯甲烷(4,4'-diaminodiphenylmethane)、或前述之組合。
8. 根據本發明的另一方面,提供一種聚醯亞胺膜之製備方法。所述聚醯亞胺膜之製備方法包括:透過將有機溶劑與二酐單體、二胺單體、和金屬化合物混合並進行反應來製備與金屬離子螯合的聚醯胺酸溶液;透過將所述聚醯胺酸溶液與脫水劑和醯亞胺化劑(imidizing agent)混合來製備聚醯亞胺前驅物組合物;透過將所述聚醯亞胺前驅物組合物澆鑄(casting)到支撐物上並乾燥來形成膠膜(gel film);以及透過對所述膠膜的熱處理來形成聚醯亞胺膜。
9. 在實施例8中,所述膠膜的熱處理可在約100°C至約700°C的溫度下進行。
10. 根據本發明的又一方面,提供一種石墨片。使用實施例1至7中任一者的聚醯亞胺膜或使用實施例8或9的聚醯亞胺膜製備方法所製得的聚醯亞胺膜來製備所述石墨片。
11. 在實施例10中,所述石墨片可透過在低於2800℃的溫度下石墨化所述聚醯亞胺膜而製得。
12. 在實施例10或11中,所述石墨片的熱導率可為使用不含有金屬化合物的聚醯亞胺膜所製得之石墨片的熱導率之約1.1至1.6倍。
13. 在實施例10至12的任一者中,所述石墨片的熱導率可為約1300 W/m·K以上。
本發明提供了一種石墨片用之聚醯亞胺膜、其製備方法以及由此製得之石墨片,所述聚醯亞胺膜可提供良好的熱導率同時降低製造成本。
將省略可能不必要地模糊本發明標的之已知功能和構造的描述。
應進一步理解的是,用詞“包括(comprises)”、“包括(comprising)”、“包含(includes)”及/或“包含(including)”在本說明書中使用時指出所述之部件(features)、整數、步驟、操作、元件、構件、及/或前述之群組(group)的存在,但不排除一或多個其他部件、整數、步驟、操作、元件、構件、及/或前述之群組的存在或增加。如本文所使用的,除非上下文另外明確指出,單數形式的“一(a/an)”和“該”也包括複數形式。
此外,除非另外明確說明,否則在解釋構件時,與特定構件相關的數值應解釋為包括公差範圍(tolerance range)。
本文中用來表示特定數值範圍之表述“a至b”表示“≥a且≤b”。
[石墨片用之聚醯亞胺膜]
根據本發明的一方面,提供了一種石墨片用之聚醯亞胺膜。透過醯亞胺化由二酐單體和二胺單體之間的反應形成的聚醯胺酸來製備石墨片用之聚醯亞胺膜,其中所述反應是在金屬化合物存在的情況下進行且聚醯胺酸與金屬離子形成螯合物。不含有金屬化合物的聚醯亞胺膜具有緻密的線性聚合物層結構,而在金屬化合物存在下所製得的聚醯亞胺膜具有含有增加的纏結(entanglement)之龐大的聚合物結構,因此可以在較低的溫度下進行石墨化。另外,使用在金屬化合物存在下製得的聚醯亞胺膜所製造的石墨片由於金屬成分的協同熱傳導效應而具有增加的熱導率。
金屬化合物可包括可與聚醯胺酸形成螯合物的任何金屬化合物。
在一實施例中,構成金屬化合物的金屬可包括鎳、鉑、硼、鋁、或前述之組合。例如,金屬可包括硼,其對於提高熱導率和降低聚醯亞胺膜的石墨化溫度是有效的,但不限於此。
在一個實施例中,金屬化合物可包括金屬氧化物、金屬碳化物、金屬氮化物、或前述之組合。例如,金屬化合物可包括金屬氮化物,其對於提高熱導率和降低聚醯亞胺膜的石墨化溫度是有效的,但不限於此。
在一個實施例中,金屬化合物可包括氮化硼,其可提供高的面內熱導率(in-plane thermal conductivity)以及良好的機械穩定性和耐熱性,並且對於聚醯亞胺膜的石墨化是有效的,但不限於此。
儘管金屬化合物的量沒有特別限制,以聚醯亞胺膜的總重量為基準,金屬化合物於聚醯亞胺膜中存在的量可例如為約0.05 wt%至約1 wt%(例如0.05 wt%、0.1 wt%、0.15 wt%、0.2 wt%、0.25 wt%、0.3 wt%、0.35 wt%、0.4 wt%、0.45 wt%、0.5 wt%、0.55 wt%、0.6 wt%、0.65 wt%、0.7 wt%、0.75 wt%、0.8 wt%、0.85 wt%、0.9 wt%、0.95 wt%、或1 wt%)。在此範圍內,金屬化合物可提供增加的熱導率,同時降低聚醯亞胺膜的石墨化溫度。在一實施例中,以聚醯亞胺膜的總重量為基準,金屬化合物於聚醯亞胺膜中存在的量可例如為約0.05 wt%至約0.9 wt%,並且在另一實施例中,以聚醯亞胺膜的總重量為基準,金屬化合物於聚醯亞胺膜中存在的量可例如為約0.05 wt%至約0.8 wt%,但不限於此。
二酐單體可包括本技術領域常用的任何二酐單體。例如,二酐單體可包括均苯四甲酸二酐、3,3',4,4'-聯苯四羧酸二酐、或前述之組合,其對於增加熱導率和降低聚醯亞胺膜的石墨化溫度是有效的,但不限於此。
二胺單體可包括本技術領域常用的任何二胺單體而沒有限制。例如,二胺單體可包括4,4'-二氨基二苯醚、4,4'-二氨基二苯甲烷、或前述之組合,其對於增加熱導率和降低聚醯亞胺膜的石墨化溫度是有效的,但不限於此。
聚醯亞胺膜的厚度沒有特別限制。聚醯亞胺膜的厚度可例如為約30 μm至約120 μm,作為另一示例,約30 μm至約80 μm,作為又一示例,約50 μm至約80 μm,但不限於此。
可透過製備聚醯亞胺膜領域中常用的任何合適的方法來製備上述石墨片用之聚醯亞胺膜。在一個實施例中,可透過包括以下步驟的方法來製備聚醯亞胺膜:透過將有機溶劑與二酐單體、二胺單體、和金屬化合物混合並進行反應來製備與金屬離子螯合的聚醯胺酸溶液;透過將聚醯胺酸溶液與脫水劑和醯亞胺化劑混合來製備聚醯亞胺前驅物組合物;透過將聚醯亞胺前驅物組合物澆鑄到支撐物上並乾燥來形成膠膜;以及透過對膠膜的熱處理來形成聚醯亞胺膜。
首先,將有機溶劑與二酐單體、二胺單體、和金屬化合物混合並進行反應,藉以製備與金屬離子螯合的聚醯胺酸溶液。由於二酐單體、二胺單體、和金屬化合物與上述相同,因此將省略其詳細描述。
可透過將實質上(substantially)等莫耳量的二酐單體和二胺單體與金屬化合物一起溶解在有機溶劑中並進行反應來得到聚醯胺酸溶液。取決於用作二酐單體和二胺單體的單體的類型以及聚醯亞胺膜的所需特性,可以將所有單體一次或依序添加到反應器中。單體之間可能產生部分聚合。
有機溶劑可包括能夠溶解聚醯胺酸的任何有機溶劑,例如非質子極性有機溶劑。非質子極性有機溶劑的例子可包括醯胺溶劑,例如N,N′-二甲基甲醯胺(N,N'-dimethylformamide, DMF)和N,N′-二甲基乙醯胺(N,N'-dimethylacetamide, DMAC);酚類溶劑,例如對氯苯酚(p-chlorophenol)和鄰氯苯酚(o-chlorophenol)、N-甲基吡咯烷酮(N-methyl-pyrrolidone, NMP)、γ-丁內酯(γ-butyrolactone, GBL)、和二甘二甲醚(diglyme)。這些可單獨使用或組合使用。根據需要,可進一步使用輔助溶劑,例如甲苯、四氫呋喃(tetrahydrofuran)、丙酮、甲乙酮、甲醇、乙醇、或水,以調節聚醯胺酸的溶解度。在一個實施例中,有機溶劑可為醯胺溶劑,例如N,N′-二甲基甲醯胺或N,N′-二甲基乙醯胺,但不限於此。
之後,可透過將聚醯胺酸溶液與脫水劑和醯亞胺化劑混合來製備聚醯亞胺前驅物組合物。
在此,脫水劑是指透過脫水而促使聚醯胺酸閉環的物質,可包括例如脂肪族酸酐、芳香族酸酐、N,N'-二烷基碳二亞胺(N,N'-dialkylcarbodiimide)、低碳數脂肪族鹵化物(lower aliphatic halides)、鹵代低碳數脂肪酸酐(halogenated lower fatty acid anhydrides)、芳基膦酸二鹵化物(aryl phosphonic dihalides)、和亞硫醯鹵化物(thionyl halides)。這些可單獨使用或混合使用。其中,考慮到可用性(availability)和成本,優選脂肪族酸酐,像是乙酸酐、丙酸酐、和乳酸酐。這些可單獨使用或混合使用。
醯亞胺化劑是指促使聚醯胺酸閉環的物質,並且可包括例如脂肪族三級胺(aliphatic tertiary amines)、芳香族三級胺(aromatic tertiary amines)、和雜環三級胺(heterocyclic tertiary amines)。其中,考慮到催化反應性,優選雜環三級胺。雜環三級胺的例子可包括喹啉、異喹啉、β-甲基吡啶(β-picoline)、和吡啶。這些可單獨使用或混合使用。
儘管脫水劑和醯亞胺化劑的量沒有特別限制,但是相對於每莫耳聚醯胺酸中的醯胺酸基團,脫水劑存在的量可為約0.5 mol至約5 mol(例如0.5 mol、1 mol、1.5 mol、2 mol、2.5 mol、3 mol、3.5 mol、4 mol、4.5 mol、或5 mol),例如約1.0 mol至約4 mol,且相對於每莫耳聚醯胺酸中的醯胺酸基團,醯亞胺化劑存在的量可為約0.05 mol至約3 mol(例如0.05 mol、0.1 mol、0.5 mol、1 mol、1.5 mol、2 mol、2.5 mol、或3 mol),例如約0.2 mol至約2 mol。在這些範圍內,可以實現足夠的醯亞胺化,並且可容易地將聚醯亞胺前驅物組合物澆鑄為膜的形式。
在一個實施例中,以聚醯亞胺前驅物組合物的總重量為基準,聚醯胺酸存在的量可為約5 wt%至約35 wt%(例如5 wt%、10 wt%、15 wt%、20 wt%、25 wt%、30 wt%、或35 wt%)。在此範圍內,前驅物組合物可具有合適的分子量和溶液黏度以形成膜。以前驅物組合物的總重量為基準,聚醯胺酸存在的量可為約10 wt%至約30 wt%,作為另一個示例,約15 wt%至約20 wt%,但不限於此。
在一個實施例中,聚醯亞胺前驅物組合物在25°C溫度下的黏度可為約100,000 cP至約500,000 cP(例如100,000 cP、150,000 cP、200,000 cP、250,000 cP、300,000 cP、350,000 cP、400,000 cP、450,000 cP、或500,000 cP)。在此範圍內,在使聚醯胺酸具有預定的重量平均分子量的同時,前驅物組合物在聚醯亞胺膜的形成期間可展現良好的可加工性。在此,可使用布氏黏度計(Brookfield viscometer)來測量“黏度”。聚醯亞胺前驅物組合物在25°C溫度下的黏度可例如為約150,000 cP至約450,000 cP,作為另一示例,約200,000 cP至約400,000 cP,作為又一示例,約250,000 cP至約350,000 cP,但不限於此。
在一個實施例中,聚醯胺酸的重量平均分子量(Mw)可為約100,000 g/mol以上,例如約100,000 g/mol至約500,000 g/mol(例如100,000 g/mol、150,000 g/mol、200,000 g/mol、250,000 g/mol、300,000 g/mol、350,000 g/mol、400,000 g/mol、450,000 g/mol、或500,000 g/mol),但不限於此。在此範圍內,使用聚醯亞胺膜製得的石墨片可具有進一步改善的熱導率。在此,可透過膠滲透層析法(gel permeation chromatography)測量“重量平均分子量”。
之後,可透過將聚醯亞胺前驅物組合物澆鑄到支撐物上並乾燥來形成膠膜。
支撐物可包括本技術領域常用的任何支撐物。支撐物的例子可包括玻璃板、鋁箔、環形不銹鋼帶、和不銹鋼圓筒(stainless drum)。
可在例如約40°C至約300°C的溫度下對聚醯亞胺前驅物組合物進行乾燥,作為另一示例,約80°C至約200°C,作為又一示例,約100°C至約180°C,作為再一示例,約100°C至約130°C。在此範圍內,可活化脫水劑和醯亞胺化劑,從而使澆鑄的前驅物組合物發生部分固化及/或乾燥,藉以形成膠膜。在此,“膠膜”是指在聚醯胺酸轉化為聚醯亞胺的中間階段所形成的自支撐膜中間體(self-supported film intermediate)。
視需要,根據本發明的方法可進一步包括拉伸膠膜以調節最終獲得的聚醯亞胺膜之厚度和尺寸,以改善聚醯亞胺膜的配向(orientation)。在此,可在縱向(machine direction, MD)和橫向(TD)中的至少一者上進行膠膜的拉伸。
膠膜可具有約5 wt%至約500 wt%的揮發物含量,例如約5 wt%至約200 wt%,作為另一示例,約5 wt%至約150 wt%,但不限於此。在此範圍內,可避免在隨後用以獲得聚醯亞胺膜的熱處理期間發生膜破裂、色調不均勻、及特性變異等缺陷。在此,可根據方程式1來計算膠膜的揮發物含量。在方程式1中,A表示膠膜的初始重量,並且B表示將膠膜加熱至450°C20分鐘後的膠膜的重量。
<方程式1>
(A-B)×100/B
之後,可透過對膠膜進行熱處理來形成聚醯亞胺膜。
膠膜的熱處理可在可變溫度下進行,例如約100°C至約700°C,作為另一示例,約200°C至約600°C,作為又一示例,約250°C至約550°C,持續一段時間,例如約0.05至0.4小時,作為另一示例,約0.08至0.3小時,作為又一示例,約0.1至0.2小時。在這些條件下,可從膠膜去除剩餘的溶劑,且幾乎所有剩餘的醯胺酸基團都可被醯亞胺化,藉以獲得聚醯亞胺膜。
視需要,可將獲得的聚醯亞胺膜在約400°C和約650°C的溫度下進行約5至400秒的熱加工處理(heat-finishing treatment)以進一步固化。 在此,可在預定張力下進行熱加工處理以減輕所獲得的聚醯亞胺膜的任何殘餘應力。
[石墨片]
根據本發明的另一方面,提供了一種使用上述石墨片用之聚醯亞胺膜製備的石墨片。
可在較低的溫度下石墨化聚醯亞胺膜,例如低於2,800°C(例如2,700°C以下、2,600°C以下、2,500°C以下、2,400°C以下、2,300°C以下、2,200°C以下、2,100°C以下、2,000°C以下、或1,900°C以下),作為另一示例,約1,900°C至約2,300°C,作為又一示例,約1,950°C至約2,250°C,作為再一示例,約2,000°C至約2,200°C,作為再一示例,約2,050°C至約2,150°C,從而降低了石墨片的製造成本,同時由於其金屬成分而提高了石墨片的熱導率。
在一個實施例中,比起在相同條件下(除了不存在金屬化合物之外)使用聚醯亞胺膜所製備的石墨片,石墨片(亦即,使用在金屬化合物存在下製得的聚醯亞胺膜所製備的石墨片)可具有更高的熱導率。例如,比起使用不含有金屬化合物的聚醯亞胺膜製得的石墨片,所述石墨片可具有約1.1至1.6倍(例如1.1倍、1.2倍、1.3倍、1.4倍、1.5倍、或1.6倍)的熱導率,例如約1.1至1.5倍,作為另一示例,約1.2至1.5倍,但不限於此。
在一個實施例中,石墨片可具有約1,300 W/m·K以上的熱導率(例如1,350 W/m·K以上、1,400 W/m·K以上、或1,450 W/m·K以上、1,500 W/m·K以上、1,550 W/m·K以上、1,600 W/m·K以上、或1,650 W/m·K以上)。例如,石墨片可具有約1,300 W/m·K至約2,000 W/m·K的熱導率,作為另一示例,約1,300 W/m·K至約1,800 W/m·K,作為又一示例,約1,400 W/m·K至約1,800 W/m·K,但不限於此。
石墨片的厚度沒有特別限制。石墨片的厚度可例如為約15 μm至約70 μm,作為另一示例,約15 μm至約50 μm,作為又一示例,約20 μm至約40 μm,但不限於此。
可透過製備石墨片領域中常用的任何合適的方法來製備石墨片。例如,可透過聚醯亞胺膜的碳化和石墨化來製備石墨片。
在此,碳化製程可在例如約1,000°C至約1,500°C的溫度下進行約1至5小時,但不限於此。透過碳化製程,聚醯亞胺膜的聚合物鏈被熱分解,藉以形成包括非結晶(non-crystalline)碳體及/或非晶質(amorphous)碳體的初期石墨片。
在此,石墨化製程可在例如低於約2,800°C的溫度下進行(例如2,700°C以下、2,600°C以下、2,500°C以下、2,400°C以下、2,300°C以下、2,200°C以下、2,100°C以下、2,000°C以下、或1,900°C以下),作為另一示例,約1,900°C至約2,300°C,作為又一示例,約1,950°C至約2,250°C,作為再一示例,約2,000°C至約2,200°C,作為再一示例,約2,050°C至約2,150°C,持續約1至10小時,但不限於此。透過石墨化過程,非結晶碳體及/或非晶質碳體的碳原子被重新排列,從而形成石墨片。
接下來,將參照實施例更詳細地描述本發明。然而,應注意的是,提供這些實施例僅用於舉例說明,而不應以任何方式解釋為限制本發明。
[實施例]
[實施例1]
首先,將50 g作為二酐單體的均苯四甲酸酐、50 g作為二胺單體的4,4'-二氨基二苯醚、1 g作為金屬化合物的氮化硼(3M公司)、及300 g作為有機溶劑的二甲基甲醯胺混合在一起,然後進行聚合,藉以製備聚醯胺酸溶液。
之後,將100 g製得的聚醯胺酸溶液與20 g作為脫水劑的乙酸酐、3 g作為醯亞胺化劑的β-甲基吡啶、及15 g的二甲基甲醯胺混合,藉以製備具有最終黏度為300,000 cP的聚醯亞胺前驅物組合物。
之後,使用刮刀在SUS板(100SA, Sandvik Co., Ltd)上將製得的聚醯亞胺前驅物組合物澆鑄至80 μm的厚度,然後在100°C下乾燥5分鐘,藉以形成膠膜。接著,將膠膜與SUS板分離,然後在300°C下進行熱處理5分鐘,並在500°C下進行熱處理5分鐘,藉以製備出厚度為50 μm的聚醯亞胺膜。在此,以聚醯亞胺膜的總重量為基準,金屬化合物的存在量為0.05 wt%。
[實施例2至5及比較例1]
除了金屬化合物的量如表1所列改變之外,以與實施例1相同的方式製備聚醯亞胺膜。
[評價例:石墨片的熱導率測量(單位:W/m·K)]
將實施例和比較例中製備的各聚醯亞胺膜在氮氣下使用電爐以1°C/分鐘的加熱速度加熱至1,000°C,然後維持該溫度3小時使聚醯亞胺膜碳化。接著,將碳化的聚醯亞胺膜在氬氣下以20°C/分鐘的加熱速率加熱至表1中所示的溫度,然後維持該溫度3小時使聚醯亞胺膜石墨化,藉以製備石墨片。
接著,使用熱擴散率測試儀(LFA 467, Netzsch Co.)透過雷射閃光法測量製得的石墨片之面內熱擴散率,然後,將得出的面內熱擴散率測量值乘以密度(重量/體積)和比熱(透過DSC測量)來計算石墨片的熱導率。結果顯示於表1。
表1
金屬化合物的量 (wt%) | 石墨化溫度 (°C) | 石墨片的熱導率 (W/m·K) | |
實施例1 | 0.05 | 2,300 | 1,550 |
實施例2 | 0.1 | 2,300 | 1,600 |
實施例3 | 0.15 | 2,300 | 1,650 |
實施例4 | 0.2 | 2,300 | 1,630 |
實施例5 | 0.25 | 2,300 | 1,580 |
比較例1 | - | 2,800 | 1,200 |
從表1所示的結果可看出,比起不含有金屬化合物的比較例1的聚醯亞胺膜,儘管在金屬化合物的存在下所製得之實施例1至5的聚醯亞胺膜在較低的溫度下被石墨化,但其可被製備為具有較佳熱導率的石墨片。
應理解的是,本技術領域具有通常知識者在不脫離本發明的精神和範圍內,可作出各種修改、更動、潤飾及等效之實施例。
無。
無。
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Claims (4)
- 一種石墨片用之聚醯亞胺膜,該聚醯亞胺膜是透過對醯亞胺化由二酐單體和二胺單體之間反應形成的一聚醯胺酸形成的一膠膜進行熱處理而製得,其中該反應是在一金屬化合物存在的情況下進行且該聚醯胺酸與金屬離子形成一螯合物,其中該二酐單體由均苯四甲酸二酐(pyromellitic dianhydride)所組成,其中該二胺單體由4,4'-二氨基二苯醚(4,4'-diaminodiphenylether)所組成,其中該金屬化合物包括一金屬氧化物、一金屬碳化物、一金屬氮化物、或前述之組合,其中組成該金屬化合物的金屬包括鎳、鉑、硼、鋁、或前述之組合,其中以該聚醯亞胺膜的總重量為基準,該金屬化合物於該聚醯亞胺膜中存在的量為0.05wt%至1wt%,其中該聚醯胺酸的重量平均分子量(Mw)為100,000g/mol至500,000g/mol,且該膠膜具有根據方程式1來計算,5wt%至500wt%的一揮發物含量<方程式1>膠膜的揮發物含量=(A-B)×100/B在方程式1中,A表示該膠膜的初始重量,並且B表示將該膠膜加熱至450℃20分鐘後的該膠膜的重量。
- 如請求項1之聚醯亞胺膜,其中該金屬化合物包括氮化硼。
- 一種聚醯亞胺膜的製備方法,包括: 透過將一有機溶劑與二酐單體、二胺單體、和一金屬化合物混合並進行反應來製備與金屬離子螯合的一聚醯胺酸溶液;透過將該聚醯胺酸溶液與一脫水劑和一醯亞胺化劑(imidizing agent)混合來製備一聚醯亞胺前驅物組合物;透過將該聚醯亞胺前驅物組合物澆鑄到一支撐物上並乾燥來形成一膠膜;以及透過對該膠膜的熱處理來形成一聚醯亞胺膜,其中該二酐單體由均苯四甲酸二酐(pyromellitic dianhydride)所組成,其中該二胺單體由4,4'-二氨基二苯醚(4,4'-diaminodiphenylether)所組成,其中該金屬化合物包括一金屬氧化物、一金屬碳化物、一金屬氮化物、或前述之組合,其中組成該金屬化合物的金屬包括鎳、鉑、硼、鋁、或前述之組合,其中以該聚醯亞胺膜的總重量為基準,該金屬化合物於該聚醯亞胺膜中存在的量為0.05wt%至1wt%,其中該聚醯胺酸的重量平均分子量(Mw)為100,000g/mol至500,000g/mol,且該膠膜具有根據方程式1來計算,5wt%至500wt%的一揮發物含量,<方程式1>膠膜的揮發物含量=(A-B)×100/B在方程式1中,A表示該膠膜的初始重量,並且B表示將該膠膜加熱至450℃20分鐘後的該膠膜的重量。
- 如請求項3之聚醯亞胺膜的製備方法,其中該膠膜的熱處理是在100℃至700℃的溫度下進行。
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