JPH0393669A - Production of aluminum nitride and cycloalazane and its polymer to be used therefor - Google Patents
Production of aluminum nitride and cycloalazane and its polymer to be used thereforInfo
- Publication number
- JPH0393669A JPH0393669A JP1227818A JP22781889A JPH0393669A JP H0393669 A JPH0393669 A JP H0393669A JP 1227818 A JP1227818 A JP 1227818A JP 22781889 A JP22781889 A JP 22781889A JP H0393669 A JPH0393669 A JP H0393669A
- Authority
- JP
- Japan
- Prior art keywords
- trimer
- cyclic
- aluminum nitride
- substituents
- cycloalazane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 title claims abstract description 29
- 229920000642 polymer Polymers 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000013638 trimer Substances 0.000 claims abstract description 31
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 21
- -1 amine compound Chemical class 0.000 claims abstract description 12
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 11
- 125000005270 trialkylamine group Chemical group 0.000 claims abstract description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 7
- 239000010936 titanium Substances 0.000 claims abstract description 7
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 7
- 150000001412 amines Chemical class 0.000 claims abstract description 6
- 125000005843 halogen group Chemical group 0.000 claims abstract description 6
- 229910017464 nitrogen compound Inorganic materials 0.000 claims abstract description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000010304 firing Methods 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910052732 germanium Inorganic materials 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 2
- 229910052718 tin Inorganic materials 0.000 claims 2
- 229910052717 sulfur Inorganic materials 0.000 claims 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 abstract description 18
- 239000000835 fiber Substances 0.000 abstract description 14
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 abstract description 11
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 3
- 150000002830 nitrogen compounds Chemical class 0.000 abstract description 3
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000005245 sintering Methods 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 229920001169 thermoplastic Polymers 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000017525 heat dissipation Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- APDDLLVYBXGBRF-UHFFFAOYSA-N [diethyl-(triethylsilylamino)silyl]ethane Chemical compound CC[Si](CC)(CC)N[Si](CC)(CC)CC APDDLLVYBXGBRF-UHFFFAOYSA-N 0.000 description 1
- TWSOFXCPBRATKD-UHFFFAOYSA-N [diphenyl-(triphenylsilylamino)silyl]benzene Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)N[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 TWSOFXCPBRATKD-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- CECABOMBVQNBEC-UHFFFAOYSA-K aluminium iodide Chemical compound I[Al](I)I CECABOMBVQNBEC-UHFFFAOYSA-K 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007033 dehydrochlorination reaction Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- DIAIBWNEUYXDNL-UHFFFAOYSA-N n,n-dihexylhexan-1-amine Chemical compound CCCCCCN(CCCCCC)CCCCCC DIAIBWNEUYXDNL-UHFFFAOYSA-N 0.000 description 1
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- PUGUQINMNYINPK-UHFFFAOYSA-N tert-butyl 4-(2-chloroacetyl)piperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(C(=O)CCl)CC1 PUGUQINMNYINPK-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Inorganic Fibers (AREA)
- Ceramic Products (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は窒化アルミニウム系のセラミックス繊維、フイ
ルム、基板などが製造できる窒化アルミニウムの製造方
法およびその前駆物質であるシクロアラザンとその重合
体に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing aluminum nitride, which can produce aluminum nitride-based ceramic fibers, films, substrates, etc., and its precursor, cycloalazane, and its polymer.
［従来の技術］
従来、放熱基板の素材としてはアルミナが使用されてい
る。しかし基板上の集積度が高まるにしたがってさらに
放熱性の良い素材が求められている。その高放熱性の素
材として窒化アルミニウムが注目されている。そしてそ
の素材用の高純度窒化アルミニウム粉末の製造方法も知
られている。[Prior Art] Conventionally, alumina has been used as a material for a heat dissipation board. However, as the degree of integration on substrates increases, materials with even better heat dissipation are required. Aluminum nitride is attracting attention as a material with high heat dissipation. A method for producing high-purity aluminum nitride powder for use as the material is also known.
しかし窒化アルミニウム粉末は、難焼結性であるので酸
化イットリウムなどの焼結助剤を配合しないと焼結でき
ない。そのため得られる窒化アルミニウム焼結体では、
熱伝導率が窒化アルミニウムそれ自体よりも低下する。However, since aluminum nitride powder is difficult to sinter, it cannot be sintered unless it is mixed with a sintering aid such as yttrium oxide. Therefore, in the aluminum nitride sintered body obtained,
Thermal conductivity is lower than aluminum nitride itself.
この焼結助剤の添加による熱伝導率の低下を防ぐ方法と
して、窒化アルミニウムの繊維と樹脂とによる複合材料
を素材に用いた基板の作製が試みられている。そのため
には高純度の窒化アルミニウムＲＭの製造法を確立する
必要がある。As a method for preventing the reduction in thermal conductivity due to the addition of the sintering aid, attempts have been made to fabricate a substrate using a composite material made of aluminum nitride fibers and resin. For this purpose, it is necessary to establish a method for producing high-purity aluminum nitride RM.
窒化アルミニウム繊維の製造法としては、たとえば、ア
ルミナ繊維に加熱分解した後の残炭素量が多い重合体を
含浸させ、次いでこの重合体含浸アルミナ繊維をアンモ
ニアガスの存在下で１６００℃の温度に加熱してアルミ
ナ繊維とする方法が提案ざれている。またアルキルアル
ミニウムとアンモニアとを反応させて、アルミニウムー
窒素結合を骨格とする熱可塑性の重合体を形成し、この
重合体を溶融紡糸し、窒素またはアンモニアの存在下で
焼成する方法も知られている。As a method for producing aluminum nitride fibers, for example, alumina fibers are impregnated with a polymer that has a large amount of residual carbon after thermal decomposition, and then the polymer-impregnated alumina fibers are heated to a temperature of 1600°C in the presence of ammonia gas. A method has been proposed in which alumina fibers are made from alumina fibers. Another known method is to react aluminum alkyl with ammonia to form a thermoplastic polymer with an aluminum-nitrogen bond as a backbone, melt-spun this polymer, and sinter it in the presence of nitrogen or ammonia. There is.
［発明が解決しようとする課題］
前記の窒化アルミニウムｍ維の製造法では高温が必要で
あり、またアルキルアルミニウムによる方法では高活性
の物質を扱う反応のため工程での危険性が高い問題を有
する。[Problems to be Solved by the Invention] The above method for producing aluminum nitride m-fibers requires high temperatures, and the method using alkyl aluminum has the problem of high risk in the process due to the reaction involving highly active substances. .
本発明では安価な物質を利用して容易に形成でき、かつ
容易に成形できその成形体を低い温度で焼成して窒化ア
ルミニウム焼成体を得ること、およびそれを製造する中
間体のシクロアラザンとその重合体を得ることにある。The present invention provides an aluminum nitride sintered body that can be easily formed and molded using inexpensive materials, and the molded body is fired at a low temperature to obtain an aluminum nitride sintered body. The purpose is to obtain polymers.
［課題を解決するための手段］
本発明の窒化アルミニウムの製造方法は、トリアルキル
アミンとトリハロゲン化アルミニウムとを反応させて付
加物を形成する第１工程と、該付加物とジシラザン系化
合物またはチタン系窒素化合物を反応させて縮合物を形
成する第２工程と、該縮合物を加熱して一般式■の環状
三量体を形成する第３工程と、該環状三量体く一般式■
）をアミン系化合物と反応させてハロゲンをアくンで置
換して一般式工の環状アミノ三量体く一般式工〉を形成
する第４工程と、該環状三量体く一般式■）と該環状ア
ミノ三量体（一般式工）とを混合して加熱するか、該環
状アミノ三量体く一般式工〉を加熱するか、該環状三最
体（一般式■）を加熱してポリシクロアラザン（一般式
■〉を形成する重合工程と、該ポリシクロアラザンを焼
成して窒化アルミニウムとする焼成工程と、からなるこ
とを特徴とする。[Means for Solving the Problems] The method for producing aluminum nitride of the present invention includes a first step of reacting a trialkylamine and an aluminum trihalide to form an adduct, and a step of reacting the adduct with a disilazane-based compound or a second step of reacting a titanium-based nitrogen compound to form a condensate; a third step of heating the condensate to form a cyclic trimer of general formula (2);
) is reacted with an amine compound to replace the halogen with amine to form a cyclic amino trimer of the general formula (General formula); and the cyclic trimer of the general formula Mix and heat the cyclic amino trimer (general formula), heat the cyclic amino trimer (general formula), or heat the cyclic trimer (general formula). The method is characterized by comprising a polymerization step of forming polycycloalazane (general formula (1)), and a firing step of firing the polycycloalazane to form aluminum nitride.
一般式Ｉ、■、■は次の式で表される。（ただし一般式
■、■のＲＩ Ｒ２は水素、または炭素数８以下のアル
キル基をＲ１はＲ１またはＲ２のいずれか一方を表す、
Ｙは３個の置換基を代表して表し、それぞれが炭素数８
以下のアルキル基またはフエニル基であって、置換基は
同一であっても異なっていてもよい、Ｍはｓｉ，Ｔｉ，
ｓｎ，Ｇｅなどの４価の金属元素を表す）。General formulas I, ■, and ■ are represented by the following formulas. (However, in the general formulas ■ and ■, RI R2 is hydrogen or an alkyl group having 8 or less carbon atoms, and R1 represents either R1 or R2.
Y represents three substituents, each having 8 carbon atoms.
The following alkyl groups or phenyl groups, the substituents may be the same or different, M is si, Ti,
(Represents a tetravalent metal element such as sn, Ge, etc.)
ＮＲＩ Ｒ２ 竃 ■ ＭＹ ［Ｉ］ ＭＹ ［ＩＩ］ 重合体は一般式■、 または重合体の幹は一般式 １ｖで表される。NRI R2 stove ■ MY [I] MY [II] The polymer has the general formula ■, or the polymer trunk has the general formula It is expressed in 1v.
ただしｎは重合度である。However, n is the degree of polymerization.
［１１１
ｌ
［ＩＶ］
本発明の一般式■、■で表される環状三量体のシクロア
ラザンは、トリアルキルアミンとトリハロゲン化アルミ
ニウムとを反応させて付加物を形成する第１工程と、該
付加物とジシラザン系化合物またはチタン系窒素化合物
などの活性部保護剤と反応させて縮合物を形成する第２
工程と、該縮合物を加熱して環状三量体を形成する第３
工程、とにより■式の環状三量体が形成される。次いで
この■式の環状三量体をアミン系化合物と反応させてハ
ロゲンをアミンで置換する第４工程で■式の環状アミノ
三量体が形成ざれる。[111 l [IV] The cyclic trimeric cycloalazane represented by the general formulas (1) and (2) of the present invention is produced by a first step of reacting a trialkylamine and an aluminum trihalide to form an adduct; A second step in which the adduct is reacted with an active part protecting agent such as a disilazane compound or a titanium nitrogen compound to form a condensate.
a third step of heating the condensate to form a cyclic trimer;
A cyclic trimer of the formula (1) is formed by the steps. Next, in the fourth step, this cyclic trimer of formula (1) is reacted with an amine compound to replace the halogen with an amine, thereby forming a cyclic amino trimer of formula (2).
重合工程では、■式の環状アミノ三量体と■式の環状三
量体を混合して加熱するか、■式の環状アミノ三最体、
■式の環状三屋体をそれぞれ単独で加熱することにより
一般式■に示す熱可塑性の重合体が形成される。また一
般式ＩＶに示す幹をもつ重合体が生或する。この重合体
はそのまま焼成すれば窒化アルミニウムとなる。In the polymerization step, the cyclic amino trimer of the formula ■ and the cyclic trimer of the formula ■ are mixed and heated, or the cyclic amino trimer of the formula ■,
A thermoplastic polymer represented by the general formula (2) is formed by heating each of the cyclic three-dimensional bodies of the formula (2) individually. Polymers having a backbone represented by the general formula IV are also produced. If this polymer is fired as it is, it will become aluminum nitride.
この一般式■の重合体は、重合度がほぼ１０程度で、熱
可塑性を示し２００℃前後の温度で成形可能である。The polymer of general formula (1) has a degree of polymerization of about 10, exhibits thermoplasticity, and can be molded at a temperature of about 200°C.
焼戒工程では、この重合体を比較的低い温度で焼結し、
繊維、フィルム、シートなどの形状をもつ窒化アルミニ
ウムの焼結体とすることができる。In the sintering process, this polymer is sintered at a relatively low temperature,
It can be a sintered body of aluminum nitride in the form of fibers, films, sheets, etc.
この場合、重合体の熱可塑性を利用して戒形した後で焼
成をおこなうことが好ましい。In this case, it is preferable to perform sintering after shaping the polymer by taking advantage of its thermoplasticity.
焼成工程では、この重合体を１０００℃以下のの低い温
度で焼成することが好ましい。In the firing step, this polymer is preferably fired at a low temperature of 1000°C or less.
このシクロアラザンの製造に用いるトリアルキルアミン
は、炭素数が２〜８のアルキル基をもつアルキルアミン
で、トリエチルアミン、トリプロビルアミン、トリブチ
ルアミン、トリヘキシルアミン、トリオクチルアミンな
どが利用できる。またハロゲン化アルミニウムとしては
、塩化アルミニウム、臭化アルミニウム、弗化アルミニ
ウム、ヨウ化アルミニウムなどが利用できる。The trialkylamine used in the production of cycloalazane is an alkylamine having an alkyl group having 2 to 8 carbon atoms, such as triethylamine, triprobylamine, tributylamine, trihexylamine, and trioctylamine. Further, as the aluminum halide, aluminum chloride, aluminum bromide, aluminum fluoride, aluminum iodide, etc. can be used.
第１工程では、トリアルキルアミンとハロゲン化アルミ
ニウムとを付加反応させるとアミンとアルミニウムとが
１：個の割合で付加した生成物が得られる。たとえば、
ハロゲン化炭素水素系の溶媒中でトリエチルアミンと塩
化アルミニウムとの付加反応をおこなうとトリエチルア
ミンと塩化アルミニウム付加生戒物が結晶として析出し
てくる。In the first step, a trialkylamine and an aluminum halide are subjected to an addition reaction to obtain a product in which amine and aluminum are added at a ratio of 1:1. for example,
When an addition reaction between triethylamine and aluminum chloride is carried out in a halogenated hydrocarbon solvent, triethylamine and aluminum chloride adducts precipitate out as crystals.
そのため生戒物は容易に単離でき高純度の付加物（Ｒ”
Ｒ２Ｎ−Ｘ３ＡＩ、式中Ｘはハロゲンを表す〉が得られ
る。Therefore, raw materials can be easily isolated and highly purified adducts (R”
R2N-X3AI, where X represents halogen, is obtained.
第２工程では、付加物にジシラザラン系化合物、たとえ
ばヘキサアルキルジシラザンを反応させるとハロゲンの
１個がジシラザラン系化合物で置換された縮合物が形成
ざれる。この際トリアルキルアミンが副生戒物の塩化水
素の受容体となり塩酸塩として析出して分離でき、縮合
物［Ｘ２ Ａ Ｉ Ｎ（ＳｉＹ）２］は高純度で単離す
ることができる。In the second step, when the adduct is reacted with a disilazalane compound such as hexaalkyldisilazane, a condensate in which one of the halogens is substituted with the disilazalane compound is formed. At this time, the trialkylamine becomes a receptor for the by-product hydrogen chloride and can be precipitated and separated as a hydrochloride, and the condensate [X2 A I N (SiY)2] can be isolated with high purity.
なおこの分離を容易にするために縮合物を溶解する溶媒
を用いることが好ましい。Note that in order to facilitate this separation, it is preferable to use a solvent that dissolves the condensate.
ここで用いるジシラザン系化合物としては、たとえばへ
キサメチルジシラザン、ヘキサフエニルジシラザラン、
ヘキサエチルジシラザンなどが使用できる。その他活性
部を保護でき４価の金属元素をもつチタン系窒素化合物
などが使用できる。Examples of the disilazane compounds used here include hexamethyldisilazane, hexaphenyldisilazane,
Hexaethyldisilazane and the like can be used. Other materials that can be used include titanium-based nitrogen compounds that can protect the active region and have a tetravalent metal element.
第３工程では、第２工程で得られた縮合物を加熱して、
環状三鰻体［Ｘ３ （Ｎ３Ａ＋３＞（ＳｉＹ）３］とす
る工程である。この反応は、縮合物を加熱するか、縮合
物を溶媒中で加熱してもよい。In the third step, the condensate obtained in the second step is heated,
This is a step to form a cyclic three-eel body [X3 (N3A+3>(SiY)3]).In this reaction, the condensate may be heated or the condensate may be heated in a solvent.
第４工程では環状三母体をアミン系化合物でハロゲンを
置換してアミン化物とする。この反応は、環状三量体を
溶媒に溶解しアミン系化合物を添加することで得られる
。In the fourth step, the halogen of the cyclic trimester is replaced with an amine compound to form an aminated product. This reaction is obtained by dissolving the cyclic trimer in a solvent and adding an amine compound.
ここでいうアミン系化合物は、アンモニア、メチルアミ
ン、ジメチルアミン、エチルアミン、ジエチルアミン、
プロビルアミン、ジプロピルアミン、プチルアミン、ジ
ブチルアミン、などである。The amine compounds mentioned here include ammonia, methylamine, dimethylamine, ethylamine, diethylamine,
These include probylamine, dipropylamine, butylamine, dibutylamine, etc.
また溶媒としては、テトラヒド口フラン、ジメチルホル
ムアミド、ジメチスルホキシド等が使用できる。Further, as the solvent, tetrahydrofuran, dimethylformamide, dimethysulfoxide, etc. can be used.
［実施例］ 以下実施例により具体的に説明する。[Example] This will be explained in detail below using examples.
以下の工程で一般式■で表される重合体を製造した。A polymer represented by the general formula (2) was produced in the following steps.
（第１工程〉１モルの塩化．アルミニウムを３００一の
四塩化炭素に溶解し−７０℃に冷却して１モルのトリエ
チルアミンを攪拌しながら滴下すると塩化アルミニウム
とトリエチルアミンの付加物が沈澱してくる。滴下終了
後充分攪拌し、生或した沈澱を濾別する。この沈澱をエ
タノールで再結晶して融点が１２２℃の付加物（Ｅｔ３
Ｎ−ＡＩＣＩ３＞の結晶が得られた。なお、この結晶は
１２２℃で溶融と同時に分解した。(1st step) Dissolve 1 mol of aluminum chloride in 300 ml of carbon tetrachloride, cool to -70°C, and add 1 mol of triethylamine dropwise with stirring to precipitate an adduct of aluminum chloride and triethylamine. After the addition is complete, stir thoroughly and filter out the precipitate that forms. This precipitate is recrystallized from ethanol to obtain an adduct (Et3) with a melting point of 122°C.
Crystals of N-AICI3> were obtained. Note that this crystal was simultaneously melted and decomposed at 122°C.
（第２工程）１モルの上記の付加物をジクロルエタンに
溶解して室温で滑拌しながら１モルのヘキサメチノレジ
シラザラン（［ＭｅａＳｉｌ２Ｎ口）を滴下し、滴下終
了後３時間還流すると付加物とへキサメチルジシラザラ
ンとが置換反応してトリエチルアミンの塩酸塩が析出し
てくる。塩酸塩を濾別しジクロルエタンを溜去すると、
縮合物が得られる。この縮合物はＣＩ２ＡＩＮ（ＳｉＭ
ｅｇ）２の構造を有し、融点は１２２℃であった。しか
しこの縮合物はこの温度で同時に分解した。またこの縮
合物の構造は元素分析、口−ＮＭＲ，１Ｒスペクトルで
確認した。(Second step) 1 mol of the above adduct is dissolved in dichloroethane, 1 mol of hexamethinoresisilazalane ([MeaSil2N port) is added dropwise with stirring at room temperature, and refluxed for 3 hours after the completion of the dropwise addition. The adduct and hexamethyldisilazalane undergo a substitution reaction to precipitate triethylamine hydrochloride. When the hydrochloride is filtered off and dichloroethane is distilled off,
A condensate is obtained. This condensate is CI2AIN (SiM
It had a structure of eg)2 and a melting point of 122°C. However, this condensate simultaneously decomposed at this temperature. The structure of this condensate was confirmed by elemental analysis, NMR, and 1R spectrum.
（第３工程〉得られた上記の縮合物を窒素気流下で１５
０℃に加熱すると下式に示す環状三量体が得られた。こ
の三母体が下式を有することは口−ＮＭＲ，１Ｒスペク
トルで確認した。(Third step) The obtained above condensate was heated under a nitrogen stream for 15
When heated to 0°C, a cyclic trimer shown in the following formula was obtained. It was confirmed by NMR and 1R spectrum that this trimester has the following formula.
以下余白
ＳｉＭｅ３
（第４工程〉上記の環状三量体をテトラヒド口フランに
溶解してアンモニアガスを吹込み反応させると塩素がア
ミンで置換された次式で示す環状アミノ三担体が得られ
た。この環状アミノ三量体は下式の構造を有することを
日一ＮＭＲ，１Ｒスペクトルで確認した。The following margin is SiMe3 (4th step) The above cyclic trimer was dissolved in tetrahydrofuran and ammonia gas was blown into the solution to cause a reaction, thereby obtaining a cyclic amino trimer having the following formula in which chlorine was replaced with amine. It was confirmed by daily NMR and 1R spectra that this cyclic amino trimer had the structure of the following formula.
Ｎ日２
１
（重合工程〉第３工程で得た環状三量体と第４工程で得
た環状アミノ三量体を等モル量混合し、１ＯＯ℃以上に
加熱すると脱塩化水素反応による縮重合反応により下式
に示すポリシクロアラザンの重合体が生或した。N days 2 1 (Polymerization step) When the cyclic trimer obtained in the 3rd step and the cyclic amino trimer obtained in the 4th step are mixed in equimolar amounts and heated to 100°C or higher, condensation polymerization occurs due to dehydrochlorination reaction. The reaction produced a polycycloalazane polymer shown in the following formula.
このポリシクロアラザンは、重合度ｎをＧＰＣ法で確認
した。このポリシクロアラザンは、主として直鎖状に延
びほとんど三次元化していないため、通常の熱可塑性樹
脂と同様に戊形が可能である。また焼結により珪素や炭
化水素が除かれ窒化アルミニウムの焼結体が低温で形成
できる。The degree of polymerization n of this polycycloalazane was confirmed by GPC method. Since this polycycloalazane mainly extends in a linear chain and is hardly three-dimensional, it can be shaped like a normal thermoplastic resin. Moreover, silicon and hydrocarbons are removed by sintering, and a sintered body of aluminum nitride can be formed at a low temperature.
得られたポリシクロアラザンは１５０〜２００℃の温度
で溶融紡糸すると繊維状に形成できた。The obtained polycycloalazane could be formed into a fiber by melt spinning at a temperature of 150 to 200°C.
〈焼成工程〉この繊維は４００〜８００℃の温度で窒素
ガスまたはアンモニアガス中で焼結すると窒化アルミニ
ウム繊維か生成できた。また同様にしてフイルム状また
はシート状に成形することができ、その戊形体を焼成す
ることにより窒化アルミニウムのセラミックスシ一ト状
物が容易に得られた。<Sintering process> When this fiber was sintered in nitrogen gas or ammonia gas at a temperature of 400 to 800°C, aluminum nitride fibers could be produced. In addition, it could be formed into a film or sheet in the same manner, and a ceramic sheet of aluminum nitride could be easily obtained by firing the hollow body.
［効果］
本発明においては、トリアルキルアミンとトリハロゲン
化アルミニウムを原料とし容易に得られるシクロアラザ
ンは、熱可塑性で低い温度で或形可能なポリシクロアラ
ザンの重合体を形成する。[Effect] In the present invention, cycloalazane, which is easily obtained using trialkylamine and aluminum trihalide as raw materials, forms a polycycloalazane polymer that is thermoplastic and can be shaped at low temperatures.
この重合体は焼成によりセラミックスの窒化アルミニウ
ムの焼成体を形成できる。This polymer can be fired to form a ceramic aluminum nitride fired body.
したがってこのシクロアラザン類は窒化アルミニウム焼
結体の前駆物質として容易に作製でき、有用である。ま
たこの重合体は、熱可塑性重合体′として或形が容易で
繊維、フイルム、シート状に成形可能な重合度を有しそ
の形状を保持して焼成体を形戊できる。また重合体の一
部が三次元化したとしても重合体の幹がアルミニウムと
窒素との結合で形成ざれているので、低い温度での焼成
により高純度の窒化アルミニウムが生或できる。Therefore, these cycloalazane compounds can be easily produced and are useful as precursors for aluminum nitride sintered bodies. In addition, this polymer has a degree of polymerization that allows it to be easily shaped into a fiber, film, or sheet as a thermoplastic polymer, and can be formed into a fired product while maintaining its shape. Further, even if a part of the polymer becomes three-dimensional, since the polymer backbone is formed by a combination of aluminum and nitrogen, highly pure aluminum nitride can be produced by firing at a low temperature.
この重合体の成形物は、１０００℃以下の低い温度の焼
成により高純度の窒化アルミニウムの焼成体が生戒でき
る。A molded product of this polymer can be fired at a low temperature of 1000° C. or lower to produce a fired product of high purity aluminum nitride.
ざらにこの窒化アルミニウムの製造方法は、安価な材料
で簡単な反応工程で容易に製造することができる。This method for producing aluminum nitride can be easily produced using inexpensive materials and simple reaction steps.
Claims (4)
ムとを反応させて付加物を形成する第１工程と、該付加
物とジシラザン系化合物またはチタン系窒素化合物を反
応させて縮合物を形成する第２工程と、該縮合物を加熱
して環状三量体を形成する第３工程と、該環状三量体を
アミン系化合物と反応させてハロゲンをアミンで置換し
て環状アミノ三量体を形成する第４工程と、該環状三量
体と該環状アミノ三量体とを混合して加熱するか、該環
状アミノ三量体を加熱するか、該環状三量体を加熱して
ポリシクロアラザンを形成する重合工程と、該ポリシク
ロアラザンを焼成して窒化アルミニウムとする焼成工程
と、からなることを特徴とする窒化アルミニウムの製造
方法。(1) A first step of reacting a trialkylamine and aluminum trihalide to form an adduct, and a second step of reacting the adduct with a disilazane compound or a titanium nitrogen compound to form a condensate. a third step of heating the condensate to form a cyclic trimer; and a third step of reacting the cyclic trimer with an amine compound to replace the halogen with an amine to form a cyclic amino trimer. 4 steps, mixing and heating the cyclic trimer and the cyclic amino trimer, heating the cyclic amino trimer, or heating the cyclic trimer to form polycycloalazane. 1. A method for producing aluminum nitride, comprising: a polymerization step, and a firing step, in which the polycycloalazane is fired to form aluminum nitride.
＾１Ｒ＾２は水素、または炭素数８以下のアルキル基を
表す、Ｙは３個の置換基を代表して表し、それぞれが炭
素数８以下のアルキル基またはフェニル基であって、置
換基は同一であっても異なつていてもよい、ＭはＳｉ、
Ｔｉ、Ｓｎ、Ｇｅなどの４価の金属元素を表す）。 ▲数式、化学式、表等があります▼(2) Cycloalazane (where R
^1R^2 represents hydrogen or an alkyl group having 8 or less carbon atoms, Y represents 3 substituents, each of which is an alkyl group or phenyl group having 8 or less carbon atoms, and the substituents are May be the same or different, M is Si,
(Represents a tetravalent metal element such as Ti, Sn, Ge, etc.) ▲Contains mathematical formulas, chemical formulas, tables, etc.▼
は３個の置換基を代表して表し、それぞれが炭素数８以
下のアルキル基またはフェニル基であって、置換基は同
一であっても異なつていてもよい、ＭはＳｉ、Ｔｉ、Ｓ
ｎ、Ｇｅなどの４価の金属元素を表す）。 ▲数式、化学式、表等があります▼(3) Cycloalazane (where Y
represents three substituents, each of which is an alkyl group or phenyl group having 8 or less carbon atoms, and the substituents may be the same or different; M is Si, Ti, S
represents a tetravalent metal element such as n, Ge, etc.). ▲Contains mathematical formulas, chemical formulas, tables, etc.▼
ただしｎは重合度を表す。Ｒ＾１Ｒ＾２は水素、または
炭素数８以下のアルキル基をＲ＾３はＲ＾１またはＲ＾
２のいずれか一方を表す、Ｙは３個の置換基を代表して
表し、それぞれが炭素数８以下のアルキル基またはフエ
ニル基であって、置換基は同一であつても異なつていて
もよい。ＭはＳｉ、Ｔｉ、Ｓｎ、Ｇｅなどの４価の金属
元 ▲数式、化学式、表等があります▼ 素を表す）。 （４）重合体の幹が次の一般式で表される重合体。(4) Polycycloalazane is represented by the following general formula (
However, n represents the degree of polymerization. R^1R^2 is hydrogen or an alkyl group having 8 or less carbon atoms R^3 is R^1 or R^
2, Y represents three substituents, each of which is an alkyl group or phenyl group having 8 or less carbon atoms, and the substituents may be the same or different. good. M is a tetravalent metal element such as Si, Ti, Sn, Ge, etc. ▲ Numerical formula, chemical formula, table, etc. ▼ Represents element). (4) A polymer whose polymer backbone is represented by the following general formula.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1227818A JPH0393669A (en) | 1989-09-02 | 1989-09-02 | Production of aluminum nitride and cycloalazane and its polymer to be used therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1227818A JPH0393669A (en) | 1989-09-02 | 1989-09-02 | Production of aluminum nitride and cycloalazane and its polymer to be used therefor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0393669A true JPH0393669A (en) | 1991-04-18 |
Family
ID=16866857
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1227818A Pending JPH0393669A (en) | 1989-09-02 | 1989-09-02 | Production of aluminum nitride and cycloalazane and its polymer to be used therefor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0393669A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0601407A1 (en) * | 1992-12-08 | 1994-06-15 | Bayer Ag | Silicon-aluminium nitride ceramics, their precursors, their preparation, and their application |
-
1989
- 1989-09-02 JP JP1227818A patent/JPH0393669A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0601407A1 (en) * | 1992-12-08 | 1994-06-15 | Bayer Ag | Silicon-aluminium nitride ceramics, their precursors, their preparation, and their application |
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