JPH0234565A - Method of in fusibilising organic silazane polymer - Google Patents
Method of in fusibilising organic silazane polymerInfo
- Publication number
- JPH0234565A JPH0234565A JP63186324A JP18632488A JPH0234565A JP H0234565 A JPH0234565 A JP H0234565A JP 63186324 A JP63186324 A JP 63186324A JP 18632488 A JP18632488 A JP 18632488A JP H0234565 A JPH0234565 A JP H0234565A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- polymer
- silazane polymer
- infusible
- gas
- 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.)
- Granted
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims description 51
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 10
- 238000000465 moulding Methods 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 125000003118 aryl group Chemical group 0.000 claims abstract description 4
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 4
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 4
- 229910052787 antimony Inorganic materials 0.000 claims abstract 2
- 229910052758 niobium Inorganic materials 0.000 claims abstract 2
- 229910052718 tin Inorganic materials 0.000 claims abstract 2
- 229910052721 tungsten Inorganic materials 0.000 claims abstract 2
- 229910052726 zirconium Inorganic materials 0.000 claims abstract 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 36
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 6
- 150000003377 silicon compounds Chemical class 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 3
- 150000001639 boron compounds Chemical class 0.000 claims description 3
- 150000002736 metal compounds Chemical class 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims 1
- 239000000835 fiber Substances 0.000 abstract description 43
- 239000000919 ceramic Substances 0.000 abstract description 21
- 229910052794 bromium Inorganic materials 0.000 abstract description 6
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 3
- 239000011574 phosphorus Substances 0.000 abstract description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052796 boron Inorganic materials 0.000 abstract description 2
- 229910052719 titanium Inorganic materials 0.000 abstract description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract 1
- 229910052782 aluminium Inorganic materials 0.000 abstract 1
- 229910052733 gallium Inorganic materials 0.000 abstract 1
- 229910052732 germanium Inorganic materials 0.000 abstract 1
- 229910052742 iron Inorganic materials 0.000 abstract 1
- 229910052710 silicon Inorganic materials 0.000 abstract 1
- 239000010703 silicon Substances 0.000 abstract 1
- 229910052720 vanadium Inorganic materials 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 24
- 239000000047 product Substances 0.000 description 22
- 239000007789 gas Substances 0.000 description 20
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- 229910021529 ammonia Inorganic materials 0.000 description 10
- 238000010304 firing Methods 0.000 description 9
- 239000011261 inert gas Substances 0.000 description 9
- 238000005915 ammonolysis reaction Methods 0.000 description 8
- 239000012700 ceramic precursor Substances 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 5
- 239000005052 trichlorosilane Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229910010293 ceramic material Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052863 mullite Inorganic materials 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- KTQYJQFGNYHXMB-UHFFFAOYSA-N dichloro(methyl)silicon Chemical compound C[Si](Cl)Cl KTQYJQFGNYHXMB-UHFFFAOYSA-N 0.000 description 3
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 3
- 230000008014 freezing Effects 0.000 description 3
- 238000007710 freezing Methods 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000005055 methyl trichlorosilane Substances 0.000 description 3
- 239000005048 methyldichlorosilane Substances 0.000 description 3
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 150000003961 organosilicon compounds Chemical class 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- -1 B CQ Chemical class 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000002074 melt spinning Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 2
- 229910000105 potassium hydride Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- VFURVLVRHAMJKG-UHFFFAOYSA-N dichloro-[2-[dichloro(methyl)silyl]ethyl]-methylsilane Chemical compound C[Si](Cl)(Cl)CC[Si](C)(Cl)Cl VFURVLVRHAMJKG-UHFFFAOYSA-N 0.000 description 1
- YLJJAVFOBDSYAN-UHFFFAOYSA-N dichloro-ethenyl-methylsilane Chemical compound C[Si](Cl)(Cl)C=C YLJJAVFOBDSYAN-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
産２分Ｍ＝
本発明は前駆体法でセラミックスを製造するに当り、そ
の前駆体を所望の形状に保持した状態で熱分解する為に
必要な不融化処理方法に関する。[Detailed Description of the Invention] Production 2 minutes M = The present invention relates to an infusible treatment method necessary for thermally decomposing the precursor while maintaining it in a desired shape when manufacturing ceramics by a precursor method. .
の び が しよ゛とする
セラミックスは、耐熱性、耐摩耗性、高温強度等に優れ
た材料として注目を集めているが、固く、そして脆いた
め、セラミックスを加工することは極めて困難である。Ceramics, which tend to stretch, are attracting attention as materials with excellent heat resistance, abrasion resistance, high-temperature strength, etc., but because they are hard and brittle, it is extremely difficult to process them.
従って、セラミックス製品を製造する場合、セラミック
ス材料の微粉末を加圧等の方法により予め所望の形状に
成形した後、焼結する方法、或いはセラミックス前駆体
としての有機重合体を熔融若しくは溶剤に溶解し１、こ
れを所望の形状に加工した後、焼成して無機化する前駆
体法等が採用されている。上記前駆体法の最大の特徴は
、微粉末による焼結法では不可能な形状のセラミックス
製品を得ることができ、従って繊維状或いはシート状と
いった特殊形状の製品を製造し得ることである。Therefore, when manufacturing ceramic products, it is necessary to form fine powder of ceramic material into a desired shape by applying pressure or other methods and then sintering it, or by melting or dissolving an organic polymer as a ceramic precursor in a solvent. 1. A precursor method is employed in which the material is processed into a desired shape and then fired to become inorganic. The most important feature of the precursor method is that it is possible to obtain ceramic products in shapes that are impossible with the sintering method using fine powder, and therefore it is possible to produce products in special shapes such as fibers or sheets.
この場合、一般にセラミックスと呼ばれるもののうちＳ
ｉＣ及びＳｉ３Ｎ４は、それぞれＳｉＣが耐熱性、高温
強度に優れ、Ｓｉ、Ｎ４が耐熱衝撃性。In this case, among what is generally called ceramics, S
Regarding iC and Si3N4, SiC has excellent heat resistance and high temperature strength, and Si and N4 have excellent thermal shock resistance.
破壊靭性に優れるなど、高温での優れた特性を有するた
めに広く注目を集めているところであり、本発明者らも
先に特願昭６１−１３５４３７号、特願昭６１−２６１
６３４号、特願昭６２−２５７８６号、特願昭６２−３
１３２６４号に前駆体法による５ｉＣ−８ｉ、Ｎ、系の
セラミックスの製造に用いられる有機シラザン重合体の
製造法並びに該有機シラザン重合体からセラミックスを
得る方法を提案したものである。It has attracted wide attention due to its excellent properties at high temperatures, such as excellent fracture toughness, and the present inventors have previously published Japanese Patent Application No. 61-135437 and Japanese Patent Application No. 61-261.
No. 634, Japanese Patent Application No. 62-25786, Japanese Patent Application No. 62-3
No. 13264 proposes a method for producing an organic silazane polymer used in the production of 5iC-8i, N, ceramics by a precursor method, and a method for obtaining ceramics from the organic silazane polymer.
而して、セラミックス前駆体からセラミックスを製造す
る場合は、セラミックス前駆体を溶融、成型した後、こ
れを不融化処理することが必要であり、その後熱分解し
、セラミックス材料を得るものであるが、かかる製造方
法において、不融化処理方法として下記■〜■の不融化
処理方法が知られている。Therefore, when producing ceramics from a ceramic precursor, it is necessary to melt and mold the ceramic precursor and then subject it to an infusible treatment, and then thermally decompose it to obtain a ceramic material. In such a manufacturing method, the following infusibility treatment methods (1) to (4) are known as infusibility treatment methods.
即ち、■空気酸化する方法、■スチームあるいはスチー
ムと酸素を用いる方法、■紫外線照射による方法、■電
子線照射による方法、■各種有機珪素化合物による方法
などの方法が提案されている。That is, methods such as (1) air oxidation, (2) a method using steam or steam and oxygen, (2) a method using ultraviolet irradiation, (2) a method using electron beam irradiation, and (4) a method using various organic silicon compounds have been proposed.
しかし、これらはいずれも問題点を有するものであった
。即ち、■、■の方法は空気中で加熱するだけでよく、
簡便な方法として汎く採用されているが、必要とされる
熱エネルギーが大きく、また生成されるセラミックスは
酸素含量の多いものとなり、セラミックスの持つ高強度
、高弾性などの機能が大幅に減ぜられるという不利があ
る。However, all of these had problems. In other words, methods ① and ② only require heating in air;
Although this method is widely used as a simple method, it requires a large amount of thermal energy and the ceramics produced have a high oxygen content, which significantly reduces the high strength, high elasticity, and other functions of ceramics. There is a disadvantage of being exposed.
一方、■、■の方法は、■の方法と異なり、エネルギー
コストも低く、酸素の混入を回避できるという有利性は
あるが、この方法により不融化を行なうためには、多量
の紫外線や電子線の照射量が必要とされることと、この
ような装置は非常に高価なものであるという２点から工
業的方法として採用し難いものである。更に■の方法は
、米国特許第４，５３５，００７号明細書に開示されて
いるように、Ｒ，５ｉＮＨ−基を有するポリマーを各種
有機珪素化合物（例えば四塩化珪素、トリクロロシラン
）または金属塩素化物（例えばＢ ＣＱ、。On the other hand, methods ① and ② differ from method ③ in that they have the advantages of low energy costs and avoidance of oxygen contamination; It is difficult to adopt this method as an industrial method because of two reasons: it requires a radiation dose of 1,000 yen, and such equipment is very expensive. Furthermore, as disclosed in U.S. Pat. No. 4,535,007, the method (2) involves treating a polymer having R,5iNH- groups with various organosilicon compounds (e.g., silicon tetrachloride, trichlorosilane) or metal chlorine. compounds (e.g. B CQ,.
５ｎＣＱ４）により不融化する方法であるが、本発明者
らの知見によればＲ□５ｉＮＨ−基を有しない有機シラ
ザン重合体に対しては何ら有効でなく、後述する比較例
に示したように融着が甚しく。5nCQ4), but according to the findings of the present inventors, it is not effective at all for organic silazane polymers that do not have R□5iNH- groups, and as shown in the comparative example below. Severe fusion.
ポリマーの形状を留めることができないものである。な
お、この米国特許明細書中にはセラミックス前駆体法に
おいて最も重要視される熱分解後のセラミックス繊維の
強度等については全く記載がなく、不融化の有効性を明
かにしていない。The shape of the polymer cannot be maintained. Incidentally, this US patent specification does not mention anything about the strength of ceramic fibers after pyrolysis, which is the most important aspect in the ceramic precursor method, and does not disclose the effectiveness of infusibility.
従って、上述したように、従来提案されているセラミッ
クス前駆体の不融化処理方法は種々の欠点を有するもの
であった。Therefore, as described above, the conventionally proposed methods for making ceramic precursors infusible have various drawbacks.
本発明は、上記事情に鑑みなされたもので、有機シラザ
ン重合体（セラミックス前駆体）を容易かつ簡便にしか
も安価に不融化することができ、これにより高品位のセ
ラミックス繊維等を確実に製造することを可能にする有
機シラザン重合体の不融化方法を提供することを目的と
する。The present invention was made in view of the above circumstances, and it is possible to easily and simply make an organic silazane polymer (ceramic precursor) infusible at low cost, thereby reliably producing high-quality ceramic fibers, etc. An object of the present invention is to provide a method for making an organic silazane polymer infusible.
を るための び
即ち、本発明者らは有機シラザン重合体を溶融成形し、
更に不融化処理をするに当り、この不融化処理について
鋭意研究を行なった結果、式（１）
Ｒａ Ｓ ｉ Ｘ４−Ｂ
（但し、Ｒは水素原子、低級アルキル基、アルケニル基
又はアリール基、Ｘは塩素原子、臭素原子又は沃素原子
を示す。ａはＯ〜２であるが、ａが２の場合、Ｒは互に
同一でも異なっていてもよい。）
で示されるケイ素化合物、
式（２）
（但し、Ｘは上記と同様の意味を示す。）で示されるホ
ウ素化合物、
式（３）
（但し、又は上記と同様の意味を示し、ｂは３又は５で
ある。）
で示されるリン化合物、及び
式（４）
％式％
Ｂｉを示し、Ｃは該金属の原子価である。Ｘは上記と同
様の意味を示す。）
で示される金属化合物
を不融化処理剤として使用し、その１種又は２種以上の
蒸気を含む気体を用いて有機シラザン重合体の成型物を
処理すること、しかもかかる処理を行なった後にアンモ
ニアガスで処理することにより、上述した従来の不融化
方法の問題点を解決し、不融化が簡単に達成されると共
に、この不融化処理によって、高強度、高弾性のセラミ
ックス材料が製造できることを見い出し、本発明をなす
に至ったものである。In order to achieve this, the present inventors melt-molded an organic silazane polymer and
Furthermore, as a result of intensive research on this infusibility treatment, we found that the formula (1) Ra Si X4-B (where R is a hydrogen atom, a lower alkyl group, an alkenyl group, or an aryl group, represents a chlorine atom, a bromine atom, or an iodine atom. a is O-2, but when a is 2, R may be the same or different.) A silicon compound represented by the formula (2) (However, X has the same meaning as above.) Boron compounds represented by formula (3) (However, or has the same meaning as above, and b is 3 or 5.) Phosphorus compounds represented by formula (3) , and formula (4) % formula % Bi, and C is the valence of the metal. X has the same meaning as above. ) is used as an infusibility treatment agent, and a molded article of an organosilazane polymer is treated with a gas containing one or more vapors thereof, and furthermore, after such treatment, ammonia It was discovered that by treating with a gas, the problems of the conventional infusibility method described above can be solved, and infusibility can be easily achieved, and that high strength and high elasticity ceramic materials can be manufactured by this infusibility treatment. , which led to the present invention.
以下、本発明につき更に詳しく説明する。The present invention will be explained in more detail below.
本発明で用いられる有機シラザン重合体には特に制限は
ないが、既に本発明者らが特願昭６１−１３５４３７号
、特願昭６１−２６１６３４号、特願昭６２−２５７８
６号、更には特願昭６２−３１３２６４号で提案した有
機シラザン重合体が好適に用いられる。The organic silazane polymer used in the present invention is not particularly limited, but the present inventors have already reported it in Japanese Patent Application No. 61-135437, Japanese Patent Application No. 61-261634, and Japanese Patent Application No. 62-2578.
No. 6, and furthermore, the organic silazane polymers proposed in Japanese Patent Application No. 62-313264 are preferably used.
例えば特願昭６１−１３５４３７号の製造方法によれば
、メチルジクロロシラン、メチルトリクロロシラン、ジ
メチルジクロロシランの混合物とアンモニアを反応させ
てアンモノリシス生成物を得た後、該アンモノリシス生
成物を脱水素縮合可能な塩基性触媒により縮合させるこ
とによって有機シラザン重合体が得られる。For example, according to the production method disclosed in Japanese Patent Application No. 135437/1983, a mixture of methyldichlorosilane, methyltrichlorosilane, and dimethyldichlorosilane is reacted with ammonia to obtain an ammonolysis product, and then the ammonolysis product is subjected to dehydrogenation condensation. Organosilazane polymers are obtained by condensation with possible basic catalysts.
また特願昭６１−２６１６３４号、特願昭６２−２５７
８６号の方法によれば、一般式〔■〕及び（ＩＩ）
（但し、Ｒ２は水素、メチル基、エチル基、フェニル基
、又はビニル基、又は塩素又は臭素をそれぞれ示す。）
で示される有機珪素化合物との混合物を出発原料として
用い、特願昭６１−１３５４３７号の製造方法と同様に
アンモニアと反応せしめ、得られたアンモノリシス生成
物を更に脱水素縮合することによって有機シラザン重合
体が得られる。Also, Japanese Patent Application No. 61-261634, Japanese Patent Application No. 62-257
According to the method of No. 86, organic compounds represented by the general formulas [■] and (II) (wherein R2 represents hydrogen, methyl group, ethyl group, phenyl group, or vinyl group, or chlorine or bromine, respectively) An organic silazane polymer can be obtained by using a mixture with a silicon compound as a starting material and reacting it with ammonia in the same manner as in the production method of Japanese Patent Application No. 135437/1982, and further dehydrogenating the obtained ammonolysis product. .
更に、特願昭６２−３１３２６４号の製造方法によれば
、一般式（ｒＶ）
人
（但し、Ｒは水素、塩素、臭素、メチル基、エチル基、
フェニル基、又はビニル基、Ｒ工は水素、又はメチル基
、Ｒ８は水素、メチル基、エチル基、フェニル基、又は
ビニル基、Ｘは塩素又は臭素をそれぞれ示す。）で示さ
れる有機珪素化合物の少なくとも１種以上と、一般式（
ＩＩＩ）（但し、Ｒ１はメチル基、エチル基、又はフェ
ニル基、Ｘは塩素、臭素をそれぞれ示す。）で示される
有機珪素化合物の１種以上と、一般式Ｒ４
（但し、Ｒ１はメチル基、エチル基、又はフェニル基、
Ｒ４は水素原子又はビニル基、Ｘは塩素、臭素をそれぞ
れ示す。）
で示される有機珪素化合物の１種以上とを混合し、この
混合物をアンモニアと反応させてシラザン化合物を得た
後、該シラザン化合物をアルカリ触媒、例えばＫＯＨ，
ＮａＯＨ等により重合させることによって有機シラザン
重合体が得られる。Furthermore, according to the manufacturing method of Japanese Patent Application No. 62-313264, general formula (rV) (wherein R is hydrogen, chlorine, bromine, methyl group, ethyl group,
A phenyl group or a vinyl group, R represents hydrogen or a methyl group, R8 represents hydrogen, a methyl group, an ethyl group, a phenyl group, or a vinyl group, and X represents chlorine or bromine, respectively. ) and at least one organosilicon compound represented by the general formula (
III) (wherein, R1 is a methyl group, ethyl group, or phenyl group, and X is chlorine or bromine, respectively); and one or more organosilicon compounds represented by the general formula R4 (wherein, R1 is a methyl group, ethyl group or phenyl group,
R4 represents a hydrogen atom or a vinyl group, and X represents chlorine or bromine, respectively. ), and this mixture is reacted with ammonia to obtain a silazane compound, and then the silazane compound is treated with an alkali catalyst, such as KOH,
An organic silazane polymer can be obtained by polymerizing with NaOH or the like.
また、Ａｎｄｒｉａｎｏｖ Ｓ （Ｖｙｓｏｋｏ＋ｍｏ
１．５ｏｙｅｄ ４ 。Also, Andrianov S (Vysoko+mo
1.5oyed 4.
ＮＯＴ、１０６０〜１０６３ （１９６２）） による
ザン）をＫＯＨで加熱重合させた有機シラザン重合体も
好適に用いられる。An organic silazane polymer obtained by thermally polymerizing Zane) by KOH in KOH is also suitably used.
前記した有機シラザン重合体は、これをセラミックス前
駆体として用い、該有機シラザン重合体をＮ２を含む不
活性ガス中で熱分解することにより、５ｉＣ−３ｉ□Ｎ
４質のセラミックス材料が製造できる０例えば、セラミ
ックス繊維を製造する場合、まず有機シラザン重合体を
溶融紡糸方法により紡糸して繊維状に成型した後、熱分
解すればよい。The above-described organic silazane polymer is used as a ceramic precursor and is thermally decomposed in an inert gas containing N2 to produce 5iC-3i□N.
For example, when producing ceramic fibers, an organic silazane polymer may be first spun into a fiber shape using a melt spinning method and then thermally decomposed.
しかしながら、かかるセラミックスの製造方法において
、不融化処理を行なわず、ただ単に熱分解したのでは繊
維等の成型物の形状を保持できず、熱分解の段階で成型
物が全て溶融してしまうため、熱分解に先立って不融化
処理が不可欠となるものであるが、本発明はこの不融化
方法として、有機シラザン重合体を溶融、成型すること
により得られた成型物をまず不融化第１工程として下記
式（１）〜（４）で示される化合物を不融化処理剤とし
て用い、その１種又は２種以上の蒸気を含む気体で処理
し、次いで不融化第２工程としてアンモニアガスで処理
するという不融化方法を採用したものである。However, in such a method for manufacturing ceramics, if the infusibility treatment is not performed and the molded product is simply thermally decomposed, the shape of the molded product such as fibers cannot be maintained, and the molded product will completely melt during the pyrolysis stage. An infusibility treatment is essential prior to thermal decomposition, and in the present invention, as an infusibilization method, a molded product obtained by melting and molding an organic silazane polymer is first infusible as a first step of infusibility. A compound represented by the following formulas (1) to (4) is used as an infusibility treatment agent, and treated with a gas containing one or more vapors thereof, and then treated with ammonia gas as a second infusibility step. This method uses an infusible method.
式（１）
％式％
（但し、Ｒは水素原子、低級アルキル基、アルケニル基
又はアリール基、Ｘは塩素原子、臭素原子又は沃素原子
を示す。ａはＯ〜２であるが、ａが２の場合、Ｒは互に
同一でも異なっていてもよい。）
で示されるケイ素化合物、
式（２）
（但し、Ｘは上記と同様の意味を示す、）で示されるホ
ウ素化合物、
式（３）
（但し、Ｘは上記と同様の意味を示し、ｂは３又は５で
ある。）
で示されるリン化合物、及び
式（４）
％式％
Ｂｉを示し、Ｃは該金属の原子価である。又は上記と同
様の意味を示す。）
で示される金属化合物。Formula (1) % Formula % (However, R is a hydrogen atom, a lower alkyl group, an alkenyl group, or an aryl group, and X is a chlorine atom, a bromine atom, or an iodine atom. a is O-2, but when a is 2 In the case of , R may be the same or different.) A silicon compound represented by the formula (2) (wherein, X has the same meaning as above), a boron compound represented by the formula (3) (However, X has the same meaning as above, and b is 3 or 5.) A phosphorus compound represented by the formula (4) and the formula (4) represents Bi, and C is the valence of the metal. or has the same meaning as above. ) A metal compound represented by
ここで、上記式（１）〜（４）の不融化処理剤として、
具体的にはＣＨ３５ｉＣＱ、、 （ＣＨ３）、５ｉＣＱ
ｘ。Here, as the infusibility treatment agent of the above formulas (1) to (4),
Specifically, CH35iCQ, (CH3), 5iCQ
x.
（Ｃ，Ｈｓ）Ｓ ｉ ＣＨ３，（Ｃ，Ｈ，）２Ｓ ｉ
ＣＱ、、 Ｃ，Ｈ，Ｓ ｉ ＣＨ３゜（Ｃ６Ｈｓ）、Ｓ
ｉ ＣＱ、、 ＣＨ２＝ＣＨ５ｉ ＣＨ３゜（ＣＨ，
＝ＣＨ）、Ｓ １ＣＱ２． Ｈ３ｉｃＱ、、 Ｈ，５ｉ
Ｃ１１，。(C,Hs)S i CH3, (C,H,)2S i
CQ,, C, H, S i CH3゜(C6Hs), S
i CQ,, CH2=CH5i CH3゜(CH,
=CH), S 1CQ2. H3icQ,, H,5i
C11,.
Ｓ ｉ Ｃｆｌ、、 Ｈ（ＣＨ，）ＳｉＣＱ、 Ｈ（Ｃ
Ｈ，＝ＣＩ（）Ｓ ｉ ＣＨ２゜（ＣＨ，＝ＣＨ）Ｃ，
Ｈ５Ｓ １ＣＱ２． ＢＣＱ３． ＢＢ ｒ、、 Ｂ
Ｉ、。S i Cfl,, H(CH,)SiCQ, H(C
H,=CI()S i CH2゜(CH,=CH)C,
H5S 1CQ2. BCQ3. BB r,, B
I.
ＰＣＩｌ、、ＰＣＱ、、ＰＢｒ、、ＰＩ、、ＡＱＣＱ、
、Ｔｉ（１４゜ＦｅＣＱ、、Ｖ（、Ｈ４，ＧａＣＱ、、
ＧａＣＨ４，ＺｒＣＨ４゜ＮｂＣＱ、、５ｎ（１４，５
ｂＣＱ、、ＴａＣ１１！、、ＴｅＣＨ４゜ＷＣｌｌＩｓ
、 ＢｉＣＱ、などが例示され、これらの１種又は２種
以上が使用されるが、この中でも特にＨ（ＣＨ，）Ｓｉ
ＣＱ、、Ｈ８１ＣＱ、ＢＣＱ３）ＰＣＩｌ３．ＡｆｉＣ
Ｑ、、ＴｉＣＨ４などが好適に用いられる。PCIl,,PCQ,,PBr,,PI,,AQCQ,
, Ti(14°FeCQ, ,V(,H4,GaCQ, ,
GaCH4, ZrCH4゜NbCQ, 5n(14,5
bCQ,,TaC11! ,,TeCH4゜WCllIs
, BiCQ, etc., and one or more of these may be used, but especially H(CH,)Si
CQ,, H81CQ, BCQ3) PCIl3. AfiC
Q, TiCH4, etc. are preferably used.
これら物質を含む気体を用いて処理する方法に特に限定
はないが、例えば、Ｎ２．Ａｒ等の不活性ガスを用いて
、これら不融化処理剤に不活性ガスを通過させ、同伴す
る蒸気を成型物の存在する領域に流入させることによっ
て行なえばよい。この処理法において、これら不融化処
理剤のガス濃度は、不融化処理剤の温度を調整し、その
蒸気圧をコントロールすることにより、所望のガス濃度
に制御すればよく、濃度が高い場合は不活性ガスで所望
の濃度に希釈する方法も採用される。なお、一般に不融
化処理剤の蒸気濃度はＯ，ＯＯ１ｍｏｆｆｉ／ Ｑ ”
Ｏ、１ｍｏｆｆ ／ Ｑの範囲に制御することが特に好
ましい。処理温度、処理時間については、用いる有機シ
ラザン重合体によっても異なるが、処理中に不融状態が
維持できる十分に低い温度（即ち、ポリマーの融点より
十分低い温度）で不融化するに十分な時間（通常５〜２
４０分）処理すればよい。There are no particular limitations on the method of treatment using a gas containing these substances, but for example, N2. This may be carried out by using an inert gas such as Ar, passing the inert gas through these infusibility treatment agents, and causing the accompanying vapor to flow into the region where the molded article is present. In this treatment method, the gas concentration of these infusibilizing agents can be controlled to a desired gas concentration by adjusting the temperature of the infusibilizing agent and controlling its vapor pressure. A method of diluting to a desired concentration with an active gas may also be employed. Generally, the vapor concentration of the infusibility treatment agent is O,OO1moffi/Q”
It is particularly preferable to control it within the range of O, 1 moff/Q. The treatment temperature and treatment time will vary depending on the organosilazane polymer used, but the temperature is low enough to maintain the infusible state during the treatment (i.e., the temperature is sufficiently lower than the melting point of the polymer) and the time is sufficient to make it infusible. (Usually 5-2
40 minutes).
この第１工程の処理により、成型物は一般の有機溶剤（
例えばベンゼン、ヘキサン、トルエン。Through this first step, the molded product is treated with a general organic solvent (
For example, benzene, hexane, toluene.
テトラヒドロフラン等）に不溶なものとなる。しかしな
がら、後述する比較例でも示したように、この第１工程
の処理のみではその後の熱分解工程において溶融してし
まうもので、不融化が完全でない、従って、本発明にお
いては次の第２工程、即ちアンモニアガス又は不活性ガ
スで希釈したアンモニアガスによる処理が不可欠である
。It becomes insoluble in tetrahydrofuran, etc.). However, as shown in the comparative example described below, the treatment in this first step alone will melt in the subsequent thermal decomposition step, and the infusibility is not complete. Therefore, in the present invention, the following second step That is, treatment with ammonia gas or ammonia gas diluted with an inert gas is essential.
この第２工程においても、その処理法に特に限定はなく
、ただ単に第１工程で得られた処理成型物をアンモニア
ガス又は不活性ガスで希釈したアンモニアガスに所定の
時間暴露することによって、不融化を完成することがで
きる。またこの第２工程の処理では、アンモニアガスの
濃度が０．０１〜１００容量％、好ましくは２〜ｂ
り好ましくは０．５〜ｂ
ましく、ガス濃度が高い場合はアルゴン、ヘリウム等の
希ガス、窒素ガスなどの不活性ガスでアンモニアガスを
希釈し、この希釈したアンモニアガスを成型物上に通過
させ、不融化するに十分な時間処理する方法が好適に採
用される。なお、処理温度、処理時間については、第１
工程と同様に使用する有機シラザン重合体により異なる
が、ポリマーの融点より十分低い温度で不融性にする十
分な時間（通常５〜２４０分）処理すればよい。In this second step, there is no particular limitation on the treatment method, and the treated molded product obtained in the first step is simply exposed to ammonia gas or ammonia gas diluted with an inert gas for a predetermined period of time. Melting can be completed. In addition, in this second step, the concentration of ammonia gas is 0.01 to 100% by volume, preferably 2 to 10% by volume, more preferably 0.5 to 100% by volume, and if the gas concentration is high, diluted with argon, helium, etc. Preferably, a method is employed in which ammonia gas is diluted with an inert gas such as nitrogen gas, and the diluted ammonia gas is passed over the molded product for a sufficient time to make it infusible. Regarding the processing temperature and processing time, please refer to the first
The process may vary depending on the organic silazane polymer used, but the treatment may be carried out at a temperature sufficiently lower than the melting point of the polymer for a sufficient period of time to make it infusible (usually 5 to 240 minutes).
このようにして不融化処理することによって得られた成
型物は、次いで常法により焼成、熱分解し、これによっ
てセラミックス成型体を得るもの゛である。例えば、上
記した本発明者らの提案した有機シラザン重合体を用い
て繊維を成型し、不融化した後、この不融化繊維を無張
力下又は張力下において高温焼成することにより、５ｉ
Ｃ１Ｓｉ、Ｎ４を主体とする強度１弾性率に優れたセラ
ミックス繊維を得ることができる６なお、この工程にお
いて、焼成は真空中あるいはＡｒなどの不活性ガス、Ｎ
２ガス、Ｎ２ガス、ＮＨａガス等の１種又は２種以上の
ガス中において７００〜２０００℃、特り、−７００〜
１５００℃で行なうことが好適である。この場合、繊維
は張力下で焼成することが特に好ましく、これによって
引張強度２００〜３００ｋｇ／Ｊ、弾性率１５〜２５ｔ
／−の物性を有する高品質のセラミックス繊維を製造で
きる。The molded product thus obtained by the infusibility treatment is then fired and thermally decomposed by a conventional method, thereby obtaining a ceramic molded product. For example, by molding fibers using the above-mentioned organic silazane polymer proposed by the present inventors and making them infusible, the infusible fibers are fired at a high temperature under no tension or under tension.
It is possible to obtain ceramic fibers with excellent strength and elastic modulus mainly composed of C1Si and N46. In this step, firing is performed in a vacuum or in an inert gas such as Ar, N
700 to 2000°C, especially -700 to 2000°C in one or more gases such as 2 gas, N2 gas, NHa gas, etc.
Preferably, the temperature is 1500°C. In this case, it is particularly preferred that the fibers be fired under tension, so that the tensile strength is 200-300 kg/J and the elastic modulus is 15-25 t.
High quality ceramic fibers having physical properties of /- can be produced.
Ａ１ｊυ弧釆
以上説明したように１本発明に係る有機シラザン重合体
の不融化方法によれば、簡便にがっ工業的に有利に不融
化が達成されると共に、セラミックス繊維、セラミック
シート等を容易に得ることができる。この場合、本発明
者らが先に提案した有機シラザン重合体を用いれば、高
強度、高弾性率をもつＳｉＣ，Ｓｉ□Ｎ４からなるセラ
ミックス材料を得ることができる。As explained above, according to the method for making an organic silazane polymer infusible according to the present invention, infusibility can be achieved simply and industrially, and it can also be easily made into ceramic fibers, ceramic sheets, etc. can be obtained. In this case, if the organic silazane polymer previously proposed by the present inventors is used, a ceramic material made of SiC or Si□N4 having high strength and high elastic modulus can be obtained.
以下、実施例及び比較例を示し、本発明を具体的に説明
するが、本発明は下記実施例に限定されるものではない
。EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.
特顕昭６１−１３５４３７号記載の方法に準じ。 According to the method described in Tokken Sho 61-135437.
撹拌機、温度計、ＮＨ，導入管、水冷コンデンサーを装
備し、乾燥した２Ｑの４つロフラスコにヘキサン１５０
０ｄを仕込んだ後、メチルジクロロシラン８０．５ｇ、
メチルトリクロロシラン１４．９ｇ、ジメチルジクロロ
シラン２５．ａｇを加え、常温にて過剰の気体状アンモ
ニアを９０Ｑ ／ Ｈｒの速度で１．２５時間この溶液
に加えた（アンモニア全添加量５．０モル）、この反応
混合物を室温下に放置し、その際未反応アンモニアが逃
げられるように冷却器を空冷凝縮鼎に変えた。Equipped with a stirrer, thermometer, NH, inlet pipe, and water-cooled condenser, add 150 ml of hexane to a dry 2Q four-bottle flask.
After charging 0d, 80.5g of methyldichlorosilane,
Methyltrichlorosilane 14.9g, dimethyldichlorosilane 25. Excess gaseous ammonia was added to this solution at a rate of 90 Q/Hr for 1.25 h at room temperature (total ammonia addition amount 5.0 mol). The reaction mixture was left at room temperature and its The condenser was changed to an air-cooled condenser so that unreacted ammonia could escape.
次に、ドライボックス中で反応混合物から副生じた塩化
アンモニウムを濾過により除去した。更にケークを１．
５Ωのヘキサンで３回洗浄し、濾液から減圧下（６０℃
／ １ ｔｒｙｓ Ｈｇ ）においてヘキサンをストリ
ップした。残留物（アンモノリシス生成物）は透明な流
動性の液体で、５２．５ｇを得た。Next, by-product ammonium chloride was removed from the reaction mixture in a dry box by filtration. 1 more cake.
Washed three times with 5Ω hexane, and the filtrate was washed under reduced pressure (60°C).
Hexane was stripped at 1/1 trys Hg). The residue (ammonolysis product) was a clear flowable liquid, 52.5 g was obtained.
次いで、５００ｍ１ｌの３つロフラスコに撹拌機、温度
計、滴下ロートを取り付け、ドライボックス中で水素化
カリウム０．４ｇ及びＮａＨで脱水処理したテトラヒド
ロフラン（ＴＨＦ）２５０ｄをフラスコに注入した。こ
のフラスコをドライボックス中より取り出し、窒素管路
に連結した。常温下、混合物を撹拌して水素化カリウム
を分散させながら滴下ロートよりＴＨＦ １０ Ｑ＋ａ
Ｑに溶解した上記アンモノリシス生成物５２．５ｇを１
時間かけてゆっくりと加えた。この添加の間に大量の気
体の発生がみられ、２時間後に反応温度をＴＨＦの還流
温度とし、この状態で更に１．５時間保持した０反応開
始から３．５時間後に気体の発生が停止した。その後、
フラスコを室温に冷却し、沃化メチル４ｇを加えるとＫ
Ｉの白色沈殿が生じた。Next, a stirrer, a thermometer, and a dropping funnel were attached to a 500 ml three-bottle flask, and 0.4 g of potassium hydride and 250 d of tetrahydrofuran (THF) dehydrated with NaH were injected into the flask in a dry box. This flask was taken out of the dry box and connected to a nitrogen line. THF 10 Q+a was added from the dropping funnel at room temperature while stirring the mixture to disperse potassium hydride.
52.5 g of the above ammonolysis product dissolved in Q
I added it slowly over time. A large amount of gas was generated during this addition, and after 2 hours, the reaction temperature was raised to the reflux temperature of THF, and this state was maintained for an additional 1.5 hours. Gas generation stopped 3.5 hours after the start of the reaction. did. after that,
When the flask is cooled to room temperature and 4 g of methyl iodide is added, K
A white precipitate of I formed.
更に３０分間撹拌後、大部分のＴＨＦ溶媒を減圧で留去
し、残留する白色スラリーに１００１１１１Ｉのヘキサ
ンを加えた。この混合物を濾過し、濾液を減圧下（１＋
＋ａＨｇ）１８０℃にてヘキサンを除去すると４９ｇの
粘稠固体（シラザン重合体）が得られた。このものは融
点１２８℃、分子量１３６５（ベンゼンモル凝固点降下
法）であり、ヘキサン、ベンゼン、ＴＨＦ及びその他の
有機溶媒に可溶であった。また、ＩＲからは３４００（
ｍ−１にＮＨ１２９８０（２ｍ−’にＣ−Ｈ１２１５０
ｍ−’に５ｉ−Ｈ１１２６０ａａ−’に５ｉ−ＣＨ，の
各々の吸収が認められた。After stirring for an additional 30 minutes, most of the THF solvent was distilled off under reduced pressure and 1001111I hexane was added to the remaining white slurry. The mixture was filtered and the filtrate was collected under reduced pressure (1+
+aHg) Removal of hexane at 180° C. yielded 49 g of a viscous solid (silazane polymer). This product had a melting point of 128° C., a molecular weight of 1365 (benzene molar freezing point depression method), and was soluble in hexane, benzene, THF and other organic solvents. Also, 3400 (
NH12980 on m-1 (C-H12150 on 2m-'
Absorption of 5i-H11260aa-' and 5i-CH was observed in m-'.
このようにして得られたシラザン重合体（重合体Ａ）を
０．２ｍφの細孔を有する紡糸口金より１５０℃に加熱
して溶融紡糸した。得られた原糸は１３〜１４．の直径
であった。The thus obtained silazane polymer (polymer A) was heated to 150° C. and melt-spun using a spinneret having pores of 0.2 mφ. The obtained yarn was 13-14. It was the diameter of
次いで、得られた原糸（０，１〜０．２ｇ）をＡｆｌ、
Ｏ，ボートに乗せ、直径５０ｍｍφのムライト管型炉に
入れた。管型炉を不活性ガス（Ｎ２ｏｒＡｒ）で置換後
、第１工程としてトリクロロシランを入れたバブラー装
置を用いてＮ２ガスをこのバブラー装置を通し、一定濃
度のトリクロロシランガスを含むＮ２ガスを管型炉に通
過させた。なお、トリクロロシランガスの濃度は温度を
コントロールすることにより所望の濃度に調整した６次
いで第２工程として炉内を再び不活性ガス（ＮｚｏｒＡ
ｒ）で置換した後、Ｎ２ガスで希釈し、又は希釈せずに
第１表に示す濃度を有するアンモニアガスを炉内に流し
て処理し、不融化した。アンモニアガスにより所定の時
間処理した後、再び管機炉内をＮ２ガスにて置換し、Ｎ
３気流中で昇温速度１５０’Ｃ／ Ｈｒで１２００℃に
加熱し、この温度で繊維を３０分間熱分解した後、冷却
した。Next, the obtained yarn (0.1 to 0.2 g) was Afl,
O. It was placed on a boat and placed in a mullite tube furnace with a diameter of 50 mmφ. After replacing the tube furnace with an inert gas (N2 or Ar), as a first step, a bubbler device containing trichlorosilane is used to pass N2 gas through the bubbler device, and N2 gas containing a certain concentration of trichlorosilane gas is transferred to the tube furnace. passed. The concentration of trichlorosilane gas was adjusted to the desired concentration by controlling the temperature.6 Next, in the second step, the inside of the furnace was again filled with an inert gas (NzorA).
After substitution with r), ammonia gas diluted with N2 gas or without dilution having a concentration shown in Table 1 was flowed into the furnace to make it infusible. After treating with ammonia gas for a predetermined time, the inside of the tube furnace was replaced with N2 gas again.
The fibers were heated to 1200° C. at a heating rate of 150° C/Hr in 3 air currents, and the fibers were pyrolyzed at this temperature for 30 minutes, and then cooled.
第１表に上記トリクロロシラン処理条件、アンモニアガ
ス処理条件及び、焼成後の繊維の状態の結果を示す。Table 1 shows the results of the trichlorosilane treatment conditions, ammonia gas treatment conditions, and the state of the fibers after firing.
第１表の結果かられかる通り、Ｎｏ、１においては、焼
成後の繊維は密着部のみ融着した部分が存在したものの
、Ｎｏ、２〜６においては十分に不融化され、全く融着
のない非常に良好な繊維が得られた。As can be seen from the results in Table 1, in No. 1, the fibers after firing had some fused parts only in the adhesion part, but in No. 2 to 6, the fibers were sufficiently infusible and there was no fusion at all. No very good fibers were obtained.
なお、Ｎｏ、３で得られた繊維について物性を評価した
ところ、このものは繊維径１０．４μで引張強度２４０
ｋｇ／ｍｌ、引張弾性率２４ｔ／−であった、また、こ
の繊維の組成はｓｉ： ６１．４７％、Ｃ：１８．５６
％、Ｎ：１９．９７％であり、Ｓ ｘ Ｃ−Ｓ ｉ３
Ｎ ４を主体とするセラミックス繊維であることが確認
された。In addition, when the physical properties of the fiber obtained in No. 3 were evaluated, this one had a fiber diameter of 10.4μ and a tensile strength of 240.
kg/ml, tensile modulus was 24t/-, and the composition of this fiber was si: 61.47%, C: 18.56
%, N: 19.97%, S x C-S i3
It was confirmed that it was a ceramic fiber mainly composed of N4.
〔実施例２〕
実施例１で製造した重合体Ａを溶融紡糸して得られた繊
維径１２〜１３μの繊維を用い、不融化処理第１工程の
不融化剤を種々変えた以外は実施例１と同様の方法で焼
成した。第１及び第２工程条件及び焼成後の繊維状態の
結果を第２表に示す。[Example 2] Example 2 except that fibers with a fiber diameter of 12 to 13μ obtained by melt-spinning Polymer A produced in Example 1 were used, and the infusibility agent in the first step of the infusibility treatment was variously changed. It was fired in the same manner as 1. Table 2 shows the results of the first and second process conditions and the fiber state after firing.
第２表の結果から認められるように、不融化処理第１工
程の不融化剤としてケイ素化合物以外にホウ素、リン、
チタン、アルミニウム化合物を用いた場合のいずれも良
好な結果が得られた。この中でもＮ０８９のＢＣｎ３を
用いて処理した繊維の繊維強度は繊維径９．２μ、引張
強度２５０ｋｇ／−１引張弾性率２３ｔ／−の良好な物
性を有していた。As seen from the results in Table 2, in addition to silicon compounds, boron, phosphorus,
Good results were obtained in both cases of using titanium and aluminum compounds. Among these, the fiber treated with N089 BCn3 had good physical properties such as a fiber diameter of 9.2 μ, a tensile strength of 250 kg/−1, and a tensile modulus of 23 t/−.
〔実施例３〕
出発原料にメチルジクロロシラン、１，２−ビス（メチ
ルジクロロシリル）エタン、メチルトリクロロシランの
３種のクロロシランを用い、各々混合割合を７５：１０
：１５モル％として、実施例１と同様にアンモニアと反
応させてアンモノリシス生成物を得た後、該アンモノリ
シス生成物をＫＨにて脱水素縮合して、シラザン重合体
（重合体Ｂ）を得た。このものは融点９０℃、分子量８
２０（ベンゼンモル凝固点降下法）であった。[Example 3] Three types of chlorosilane, methyldichlorosilane, 1,2-bis(methyldichlorosilyl)ethane, and methyltrichlorosilane, were used as starting materials, and the mixing ratio of each was 75:10.
: 15 mol%, reacted with ammonia in the same manner as in Example 1 to obtain an ammonolysis product, and then dehydrogenated the ammonolysis product with KH to obtain a silazane polymer (polymer B). . This product has a melting point of 90℃ and a molecular weight of 8.
20 (benzene molar freezing point depression method).
得られた重合体Ｂを実施例１と同様の紡糸装置を用いて
１１０℃にて溶融紡糸することにより、繊維径１３〜１
４μの繊維を得た６次いで得られた繊維をムライト管型
炉に入れ、実施例１と同様に不融化剤、各種処理条件を
変更して不融化処理したのち、同様に焼成した。第１及
び第２工程条件及び焼成後の繊維状態の結果を第３表に
示す。The obtained polymer B was melt-spun at 110°C using the same spinning device as in Example 1, so that the fiber diameter was 13 to 1.
The resulting fibers were then placed in a mullite tube furnace, subjected to infusibility treatment in the same manner as in Example 1 by changing the infusibility agent and various processing conditions, and then fired in the same manner. Table 3 shows the results of the first and second process conditions and the fiber state after firing.
第３表の結果かられかる通り、Ｎｏ、１４の焼成後の繊
維がわずかに融着した以外は非常に良好な結果が得られ
た。As can be seen from the results in Table 3, very good results were obtained except for the fibers of No. 14 that were slightly fused after firing.
〔実施例４〕
特願昭６２−３１３２６４号記載の方法に準じ、出発原
料のジメチルジクロロシランとメチルビニルジクロロシ
ランを用い、各々の混合割合を５０：５０モル％として
、ヘキサン溶媒中でアンモニアと反応させた。得られた
アンモノリシス生成物ａｏｇと触媒としてＫＯＨｏ、３
ｇｔｒ加え、２８０℃にて反応させることにより、シラ
ザン重合体（重合体Ｃ）２４ｇを得た。このものは融点
１１６℃、分子量１５２０ （ベンゼンモル凝固点降下
法）で、ＩＲからは３４００ａａ−’にＮＨ１２９８０
ｄｌ−１にＣ−Ｈ，１４２０ａｍ−”にＣＨ２＝ＣＨ，
１２６０ｃｍ−”に５ｉ−ＣＨ，の各々の吸収が認めら
れた。[Example 4] According to the method described in Japanese Patent Application No. 62-313264, dimethyldichlorosilane and methylvinyldichlorosilane were used as starting materials, and ammonia and ammonia were mixed in a hexane solvent at a mixing ratio of 50:50 mol%. Made it react. The resulting ammonolysis product aog and KOHo, 3 as a catalyst
By adding gtr and reacting at 280° C., 24 g of a silazane polymer (polymer C) was obtained. This material has a melting point of 116°C and a molecular weight of 1520 (benzene molar freezing point depression method), and from IR it is 3400 aa-' with NH12980.
C-H at dl-1, CH2=CH at 1420am-'',
Absorption of 5i-CH was observed at 1260 cm-''.
得られた重合体Ｃを用いて実施例１と同様に１３５℃に
て溶融紡糸し、繊維径１２〜１３μの繊維を得た１次い
で前記実施例と同様に繊維をムライト管型炉に入れ、各
種条件で不融化処理して１２００℃で熱分解した。第１
．第２工程条件及び焼成後の繊維状態の結果を第４表に
示す。The obtained polymer C was melt-spun at 135° C. in the same manner as in Example 1 to obtain fibers with a fiber diameter of 12 to 13 μm.Next, the fibers were placed in a mullite tube furnace in the same manner as in the previous example, It was subjected to infusibility treatment under various conditions and thermally decomposed at 1200°C. 1st
．． Table 4 shows the results of the second process conditions and the fiber state after firing.
第４表の結果から明らかなように、Ｎｏ、２０〜２５に
おいて、焼成後に全く融着なく、良好な状態の繊維が得
られた。As is clear from the results in Table 4, in Nos. 20 to 25, fibers in good condition were obtained with no fusion at all after firing.
実施例１，３．４で得られたシラザン重合体（重合体Ａ
、Ｂ、Ｃ）を用い、実施例１と同様の紡糸装置を用いて
溶融紡糸し、繊維径１２〜１４μの繊維を得た。次いで
、これら繊維（０，０５〜０．２ｇ）をＡｆｉ、０３ボ
ートニ乗せ、実施例ト１と同様にムライト管型炉にセッ
トし、各種不融化剤あるいは湿潤空気を用いて、種々条
件で処理した後、２００’Ｃ／Ｈｒの昇温速度で１２０
０℃にて３０分間焼成して、不融化性能を評価した。Silazane polymer obtained in Examples 1 and 3.4 (Polymer A
, B, and C) were melt-spun using the same spinning device as in Example 1 to obtain fibers with a fiber diameter of 12 to 14 μm. Next, these fibers (0.05 to 0.2 g) were placed on Afi, 03 boat, set in a mullite tube furnace in the same manner as in Example 1, and treated under various conditions using various infusibility agents or humid air. After that, the temperature was increased to 120°C at a heating rate of 200°C/Hr.
The infusible performance was evaluated by firing at 0° C. for 30 minutes.
第５表に第１工程を省略し、第２工程のアンモニアガス
のみの処理を行なった場合の結果を示す。Table 5 shows the results when the first step was omitted and only ammonia gas was used in the second step.
なお５アンモニアガスは希釈せずに、 ５ Ｑ ／’ｗ
ｉｎの速度で通気した。Note that 5 ammonia gas is 5 Q/'w without dilution.
Aerated at a rate of in.
また、第６表に第１工程のみを行ない、第２工程のアン
モニアガスによる処理を省略した場合の結果を示す。Further, Table 6 shows the results when only the first step was performed and the second step of treatment with ammonia gas was omitted.
第
表
第５，６表の結果から明らかなように、第２工程（アン
モニアガス）のみによる不融化、第１工程のみによる不
融化は、これらの処理条件を種々変えても達成できなか
った。As is clear from the results in Tables 5 and 6, infusibility by only the second step (ammonia gas) and infusibility by only the first step could not be achieved even if these treatment conditions were variously changed.
なお、Ｎｏ、３６で一部わずかに繊維形状をとどめたも
のの繊維強度を測定したところ、繊維径９．７μ、引張
強度５０ｋｇ／＋ｄ、引張弾性率６ｔ／−と低物性であ
った。In addition, when the fiber strength of No. 36, which partially retained its fiber shape slightly, was measured, the physical properties were low: fiber diameter 9.7 μ, tensile strength 50 kg/+d, and tensile modulus 6 t/−.
出願人 信越化学工業株式会社 代理人 弁理士 小 島 隆 司 手 続 補 正 昭和６３年特許願第１８６３２４号 ２、発明の名称 有機シラザン重合体の不融化方法 ３、補正をする者 事件との関係Applicant: Shin-Etsu Chemical Co., Ltd. Agent: Patent Attorney Takashi Kojima hand Continued Supplementary Positive 1986 Patent Application No. 186324 2. Name of the invention Method for making organic silazane polymer infusible 3. Person who makes corrections Relationship with the incident
Claims (1)
物を不融化処理するに当り、該成型物を下記式（１）〜
（４）で示される化合物から選ばれる１種又は２種以上
の蒸気を含む基体で処理し、次いでアンモニアガスで処
理して不融化することを特徴とする有機シラザン重合体
の不融化方法。 式（１） ＲａＳｉＸ＿４＿−＿ａ （但し、Ｒは水素原子、低級アルキル基、アルケニル基
又はアリール基、Ｘは塩素原子、臭素原子又は沃素原子
を示す。ａは０〜２であるが、ａが２の場合、Ｒは互に
同一でも異なっていてもよい。） で示されるケイ素化合物、 式（２） ＢＸ＿３ （但し、Ｘは上記と同様の意味を示す。） で示されるホウ素化合物、 式（３） ＰＸ＿ｂ （但し、Ｘは上記と同様の意味を示し、ｂは３又は５で
ある。） で示されるリン化合物、及び 式（４） ＭＸ＿ｃ （但し、ＭはＡｌ，Ｔｉ，Ｖ，Ｆｅ，Ｇａ，Ｇｅ，Ｚｒ
，Ｎｂ，Ｓｎ，Ｓｂ，Ｔｅ，Ｔａ，Ｗ又はＢｉを示し、
ｃは該金属の原子価である。Ｘは上記と同様の意味を示
す。） で示される金属化合物。1. After melting and molding the organic silazane polymer, the molded product is treated to be infusible by the following formulas (1) to
A method for making an organic silazane polymer infusible, comprising treating it with a substrate containing one or more vapors selected from the compounds represented by (4), and then treating it with ammonia gas to make it infusible. Formula (1) RaSiX_4_-_a (wherein, R is a hydrogen atom, a lower alkyl group, an alkenyl group, or an aryl group, and X is a chlorine atom, a bromine atom, or an iodine atom. a is 0 to 2, but when a is 2 In the case of , R may be the same or different.) A silicon compound represented by the formula (2) BX_3 (However, X has the same meaning as above.) A boron compound represented by the formula (3) ) PX_b (wherein, ,Ge,Zr
, Nb, Sn, Sb, Te, Ta, W or Bi,
c is the valence of the metal. X has the same meaning as above. ) A metal compound represented by
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63186324A JPH0234565A (en) | 1988-07-26 | 1988-07-26 | Method of in fusibilising organic silazane polymer |
| US07/371,716 US5008348A (en) | 1988-06-30 | 1989-06-27 | Infusibilization of organic silazane polymers |
| US07/404,584 US4948763A (en) | 1988-06-30 | 1989-09-08 | Preparation of hollow ceramic fibers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63186324A JPH0234565A (en) | 1988-07-26 | 1988-07-26 | Method of in fusibilising organic silazane polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0234565A true JPH0234565A (en) | 1990-02-05 |
| JPH0581556B2 JPH0581556B2 (en) | 1993-11-15 |
Family
ID=16186347
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63186324A Granted JPH0234565A (en) | 1988-06-30 | 1988-07-26 | Method of in fusibilising organic silazane polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0234565A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4959207A (en) * | 1987-03-02 | 1990-09-25 | Nippon Zeon Co., Ltd. | Deodrant composition, deodrant resin composition and deodrant resin shaped article |
| US5019599A (en) * | 1988-03-25 | 1991-05-28 | Nippon Zeon Co., Ltd. | Deodorizing urethane foam and process for its production |
| CN102375463A (en) * | 2010-08-13 | 2012-03-14 | 李尔公司 | System and method for controlling the output voltage of a power supply |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5612330B2 (en) * | 2010-02-15 | 2014-10-22 | 公立大学法人大阪府立大学 | Method for producing ceramic fiber and ceramic fiber obtained by the method |
-
1988
- 1988-07-26 JP JP63186324A patent/JPH0234565A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4959207A (en) * | 1987-03-02 | 1990-09-25 | Nippon Zeon Co., Ltd. | Deodrant composition, deodrant resin composition and deodrant resin shaped article |
| US5019599A (en) * | 1988-03-25 | 1991-05-28 | Nippon Zeon Co., Ltd. | Deodorizing urethane foam and process for its production |
| CN102375463A (en) * | 2010-08-13 | 2012-03-14 | 李尔公司 | System and method for controlling the output voltage of a power supply |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0581556B2 (en) | 1993-11-15 |
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