JPS58132025A - New polytitanocarbosilane - Google Patents

Abstract

PURPOSE:The titled carbosilane capable of forming good inorganic moldings such as continuous fiber and coating films by a baking treatment and useful as a sintering binder or an impregnant, derived from a polycarbosilane and titanium alkoxide. CONSTITUTION:A new polytitanocarbosilane is obtained from (A) a polycarbosilane, number-average MW of 200-10,000, having a main chain skeleton of formulaI(wherein R is H, a lower alkyl or a phenyl) and (B) titanium alkoxide of formula II, wherein R' is a 1-20C alkyl. Said polytitanocarbosilane has a number-average MW of 700-100,000, and is in a crosslinked state in which part of the silicon atoms are bonded to the titanium atoms through oxygen atoms, has a ratio of the total number of SiCH2 units to that of TiO units of 2:1- 200:1, and includes a monofunctional polymer (e.g., formula III) through a tetrafunctional polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel polytitanocar-silanes in which the polycal is derived from a silane and a titanium alkoxide.

Silane is a polymer whose main chain skeleton consists of +5i-CH1+ and two side chain groups are bonded to each silicon atom. It is known that SiC fibers with good mechanical and thermal properties can be produced by melt-melting carbosilane in the form of fibers. It was disclosed in Japanese Patent Application Laid-open No. 126300, Japanese Patent Application Laid-open No. 139929/1980, and the like.

The present inventors subsequently discovered that the main chain skeleton is mainly composed of coupling units ÷ 8
An excellent 81C-TIO fiber is produced by firing a bound metal copolymer with a polytitanosiloxane having M in the main chain skeleton as a lII feed, resulting in an excellent 81C-TIO fiber which is even more mechanically resistant than a 810 brewer. I learned that the repair work was of excellent quality.

Therefore, the present inventors have diligently continued their research on the former F and Yu 1a Kinho co-maro combinations, and as a result, have now reached 101. The main skeleton mainly consists of 1- and 8l-OH structural units. T? 1
A novel polytitanocal silane formed from a 7 carbosilane and a titanium alkoxide having a +Ti-0+ bonding unit and its structural method were discovered and developed in the present invention.

According to the invention, as raw general formula (However, R in Formula 9 is a hydrogen atom or a lower alkyl group.

200~
Polycarmedilan of t o, o o o and the general formula T i (OR').

(However, R' in the formula represents an alkyl group having 1 to 20 blown atoms.)
The silane is a 4-titanol silane, in which at least a portion of silicon atoms are bonded to titanium atoms via oxygen atoms, thereby forming a VT bridge in which a delicalgesilane block is cross-linked with titanium atoms via oxygen atoms. is a block conjugate, and the polycal is +5i-O of the silane block.
A polytitanocal silane is provided, characterized in that the ratio of the total number of H,+ structural units to the total number of +Ti-0)- structural units is in the range of 2:1 to 200:1.

Furthermore, according to the present invention, the polycarmedylane and the titanium alkoxide are each -fSi-CH,
In addition to the quantitative ratio such that the ratio of the total number of structural units of Ti to the total number of structural units of +Ti-0 is within the range of 2:l to 200:1,
By heating the reaction in an atmosphere inert to the reaction,
The number average molecular weight, where aS means that at least a portion of the silicon atoms of the polycal silane are bonded to the butane atoms of the titanium alkoxide via oxygen molecules, is approximately? o
.

-100,000 novel methods of making polytitanocarbosilanes are provided.

The present invention will be explained in more detail below.

As the two-dimensional force of the present invention, the function vI as illustrated in the first order! Polymer, dual-functional polymer.

3-blind polymer and 4-blind polymer.

(1-functional polymer) (21-functional polymer) 1 I M mouth 1 (3-functional polymer) (4-functional polymer) (Also, R
Sharpness R′ has the same meaning as WItj arrangement), that is,
1IHff! Titanium alkyloxy r is bonded to the merimer fi of Fi-ricarbisilane in a functional electrolyte as shown in *2'[functionality, trifunctionality and 41iT.
*! There are 8 or more i IJ Cal

d? Although polyl silane itself and decune alkoxy r itself are known, a polymer composed of Iv carboxylate and titanium alkoxylate has not been known so far.

That is, the novel d IJ Titanocal-1 of the present invention? The fact that silane is a polymer with a structure different from that of polycarbosilane can be confirmed by Del. The figure shows GPO of I-licarbisilane prepared by the method described in Example 1 described later, and the figure 2 shows GPO of 2-licarbisilane of Aji F and titanium alkoxy P according to the method described in Actual example 1 described later. apo of the novel polytitanocarbosilane of the present invention obtained by reacting at lO:
．． Solution t of 0064 dissolved in tetrahydrofuran 5-
Compared with the t#1 diagram, the 111@2 diagram (subjected to S + constant) is
A new peak that cannot be seen in Figure 1 appears near elution 3110- on the horizontal axis, which indicates that the new polyt-tanocarbo-vrane obtained by the method of the present invention is a combination of polycarmedylane and titanium alkoxide. This means that it is not just a mixture, but an organic metal polymer with a higher molecular weight than polycarbosilane due to the combination of the two through a reaction. (In GPO, the horizontal axis of the peak (elution amount) The lower the numerical value, the higher the corresponding molecular weight.] 6 Next, Figure 3 shows the IR of polycarbosilane obtained by the method of Reference Example 1 described below, and Figure 4 shows the IR of the polycarbosilane obtained by the method of Reference Example 1 described later.
1 (: XR of the novel rititanocarbosilane of the present invention prepared by reacting a-configuration polycarmedylane and titanium alfuxite at lO:) (metallic weight ratio) according to the method described. The absorptions at 1250m-'' and 2100°C-1 in FIG. Nine-cut rules I
In Litetanocal, this ratio is 1.031, while #! ! The number has decreased to 0.549. This is the tV between polycarbosilane and titanium alkoxide.
, by h'l.

81- in polycarmedilan! Some of the i-bonds disappear - whereby the pricarbisilane reacts with the titanium alkoxide, and the polycarbosilanes have an electrical conductivity of +T~Q
This indicates that the fish are enriched by mackerel.

That is, in the OR method of Example 1 of the present invention, the novel polytitanocar/silane a of the present invention was added as a Confucian chain group to the structurally oriented +at-on, -)-, which exists in the main chain skeleton of the rf polycarbosilane. A part of the bonded hydrogen atoms are interdigitated, and the silicon atom is bonded to the titanium atom of the bonding unit +TI −0+ of the titanium alkoxide via the oxygen atom.

New 11+ of the present invention, ,j? ! The 15th method of the present invention for producing J titanocarbosilane is the combination of licarbisilane and dethane, and the solvent-free process is currently in progress.

and heat-react in an atmosphere inert to the reaction, and at least a portion of the polycarbosilane polycarbosilane,
It is possible to bond the titanium atom of f-tan alkoxy P via the #lI atom. Although it is possible to melt silane and react in a medium without TS, the reaction is normally performed more smoothly when using a medium with SS, and the formation of by-products such as %A and del-like substances is suppressed. Preferred solvents include, for example, n-hexane, benzene, toluene, and xylene.

Examples include TetrahyP Lofuran. Also, an atmosphere inert to the reaction 9, for example, argon.

It is necessary to carry out the reaction in an atmosphere such as hydrogen, and it is necessary to carry out the reaction in a saponifying atmosphere such as air.

This is not preferable because it causes saponification of the raw materials polycarbosilicate and gotitane alkoxide.

The reaction temperature can be varied over a wide range (= 1
For example, if an organic solvent is used, can it be heated to M degrees below the boiling point of the organic solvent?

When obtaining a polymer with a high number average molecular weight, it is preferable to conduct the reaction by subsequently heating the organic bonito to one or more points to distill off the organic solvent.
It is preferable to set it under CB. Although the reaction time is not particularly limited, it is usually about 1 to 10 hours.General reaction time: It is preferable to carry out the reaction near normal pressure.If the reaction is carried out in a vacuum or under a high reduced pressure, the reaction time is usually about 1 to 10 hours. In carrying out the method of the present invention, it is not preferable because the yield decreases due to distillation.

It is preferable to carry out the reaction while feeding an inert gas into the reaction system as a gas stream, because this keeps the pressure inside the reactor at almost normal pressure and reduces the amount of gas released during the reaction during the temperature rise. It may be possible to prevent pressure build-up due to hydrogen gas, such as gases such as methane.

In the method of this Qing, used as one of the ninth starting materials to produce the new polytitanocal/silane, /IJ Calmedilan has a number average molecular weight of 200~l Olo 0
0, mainly the general formula % formula % (However, 8 in formula 1 is a hydrogen deuteron or a lower alkyl group.

The father has a main chain skeleton represented by a phenyl group). In addition, the terminal group of /Rikarousilane JIJI
In addition to the side chain of Yariki, a hydroxyl group may be bonded to the child.

The method for producing Ilicarpo ν run itself is well known.

The polycarbosilane used as a starting material in the present invention can be constructed by such known methods.

For example, there is a method to make monosilane very hot.
+1. Ang@v, CM
l+, , 79. 65'/ (196))
G, Frltm at al: Alv, I
norg, Chem.

Ral! 1001'l@111- *fu, 34
9 (1965), by first converting monosilane into /susilane and then polymerizing it (= a method of preparing polycarbosilane). JP-A-51-126300, JP-A-52-14000 Koji, JP-A-Sho δ2-11
2) It is shown in Koji No. 00 and Japanese Patent Application Laid-open No. 54-61!99. The polycarbosilane used in the present invention is.

Main chain skeleton is substantially +8l-OH, ten #I building sites t-
It has one-piece shape, Th-like shape and china-like shape 01 [combined].

In the method of the invention, novel d? IJ Titanocal? Teta-y alkoxy FhFi, which is used as another starting additive for producing silane, with the general formula % (where PI #-1 in formula 1 represents an alkyl group containing 1 to 2 carbon atoms) expressed.

In the method of the present invention, the above-mentioned Ilical lv run and titanium alphoxide are added to +8l-O of polycarbisilane.
B, total number of 11 units of + vs. +T of titanium Alfuki Vr
The ratio of the total number of 1-0+ structural units is 2:1 to 200
: In addition to the quantity ratio that falls within the range of l.

A heating reaction is performed to organize the polymer. Due to this reaction.

Structural unit in the main chain skeleton of I Ricardasilane - one of the chain groups λ is removed 1. The silicon atom is bonded to the butane atom of the titanium alkoxide via the I# atom tube.

The novel 11J Titanocal I silanes constructed by the method of the present invention are polymers with number average molecular weights of about 100 to 100,000 and are thermoplastics that melt by heating to typically 60 to 400°C. .

It is soluble in #111, such as dankurohekiichi, 4-benzene, toluene, chloride, and tetokuhid I-furan.

The new 11L/Lititano force report ν run of the present invention is carried out in vacuum.
It can be converted into an inorganic compound by firing in an inert gas atmosphere or in a non-oxidizing atmosphere.

Is this invention new? Rittanol Silane melts when heated, is soluble in organic solvents, and can be molded into molded products of various shapes.

By subjecting this to a heating and firing treatment, an inorganic molded body with poor performance can be obtained.

An example of such a molded body is a continuous fine body.

Examples include film, Ma11 genus, powder, etc. In addition, the new l-titanocal I silane of the present invention can be used as a sintering binder and an impregnating agent. Heating under a gas stream to the boiling point of xylene, dimedeldichloroν run lj!'i-
After completing the dropwise addition in 1 hour, the mixture was heated under reflux for 10 hours to form a precipitate. This precipitate was filtered, washed with methanol, and then washed with water.

A white powder of σMef-Lucilane 420f was obtained.

On the other hand, p-phenyl C chloro V Ran'F59 f and boric acid IJA f were heated in a nitrogen gas atmosphere in n-butyl ether at a humidity of 100 to 120°C, and the resulting white resinous material was further heated at 00°C under vacuum poisoning. A 530 f IlipocIσ phenylsiloxane was obtained by heating with l-Seki.

Next, the above /9
8.21 t of borodiphenylsiloxane was added and mixed in a 2 t quartz tube equipped with a reflux tube under a mass air flow for 350 t.
℃ and polymerized for 6 hours to form 1 of the starting material of the present invention.
A polycarbisilane was obtained.

After cooling at a temperature of 1 m, xylene was added thereto and liquid #7 was taken out, xylene was evaporated, and the mixture was concentrated at 320° C. under an open gas flow to obtain 14 solids. this? The number average molecular weight of Rimmer was determined to be 99 by the vapor pressure osmotic pressure method (VPO method). It was I. When the IR flux of this substance was kept constant, the results are shown in Figure 3.

Absorption of 81-C horse near 800ar-' and 1250m-'', 1400°2900, o- at 2950a11-1
Hoe absorption, absorption of 81-H at 2100m-''*1
81-1 snow-81 near 0102O” and 1355 country-1
The polymer obtained was introduced.

The element that forms l1lI Polycarbisilane, etc.

Reference Example 2 100f of tetramethylsilane was weighed out and heated at 2°C at rough 0°C in a nitrogenous atmosphere using a recyclable flow system.
The reaction was carried out for 4 hours to obtain polycarbosilane, which is one of the starting materials of the present invention. After cooling at a temperature of 1 m, normal hexane was added to form a solution, filtered to remove insoluble matter, normal hexane was evaporated, and normal hexane was heated at 180°C for 1 hour.
Concentration under reduced pressure of 5@aHt gave 14F sticky material. The number average molecular weight of this polymer was found to be asog when -J was added using the Fivpo method. IR of this substance
Measuring Susictor 1. As in Reference Example 1, various absorption peaks based on 1 rical rfv were recorded. Reference Example S 250 t of Isp methylsilane obtained in Reference Example 1 was placed in an autoclave in an argon atmosphere.

The mixture was heated at 10° C. under about 100 atmospheres to obtain 14 Ftrltl silane, which is one of the starting materials of the present invention. Add normal hexane that has been allowed to cool at 300° C. to form a solution, and then subject the normal hexane to 11IR.

280°C T I H, 1 emHp F) 11
The solid obtained under pressure was treated with acetone to remove low molecular weight substances to obtain a polymer 6Of having a number average molecular weight of 8,750. When the IR spectrum of this substance was measured, it was found that it was the same as in Reference Example 1. Each collection peak based on v-run was observed.

Actual bag example 1 Obtained in reference example 1? Rica/L♂ silane 40f and titanium tetracytokire r2st were weighed, and xylene 400- was added to this mixture to form a homogeneous mixture #IPtII.
A reflux reaction was carried out under a nitrogen gas atmosphere at 130° C. with stirring for 1 hour. After the reflux reaction was completed, the humidity was further raised to 200°C to distill off the solvent and V, and then 1 JP-A polymerization was carried out at 200°C to obtain 1 organometallic polymer (polytitanocal-silane) containing titanium metal.
19. The number average molecular weight of this polymer was determined to be 1W8 by determining the number average molecular weight W'1vpoNorihito. The results of the gel Iξ--2 knee chromatography of this substance are shown in FIG. 2, and the gel-l! of Reference Example 1 is shown in FIG. - (Results of Nisilon chromatography (del/!-meation of the material obtained by treating the ?rical? silane of Reference Example 1 with the same number of columns as above in the absence of titanium tetracytoxy P) As is clear from the comparison of the chromatograms in Figure 1 and S), the polymer used here was not simply a mixture of the above-mentioned I Rical IV run and dethane tetraptoxide.

It is a polymer whose molecular weight is increased by the reaction of these two substances.

Furthermore, as is clear from the comparison between the IR shift of this material shown in Fig. 1 and the IR2R2 shift of the lrical〆ν run shown in Fig. 3, the polymer obtained here is
A part of the 81-H bond in Rikasibosilane disappears, and it bonds with the silicon atom of this part or the titanium atom of titanium tetrazotoxyv)' through the tII & elemental atom, thereby partially forming the Confucian chain of Fiiv carousilane. ni-o-rs(00,
B.) has an S group, and some I recarpo ν runs are 10T
This is an organometallic polymer photographed at 1-00. Based on the xR data above, the reaction rate and/or crosslinking rate at the R1-H bonding portion in this 2-rimer is calculated to be 46.
? -8 of the Ilicarposilane moiety of this polymer
1-0)1. -Total number of bonds -o-rs (0041@
The ratio of the total number of )s and -71-()- bonds is approximately 8:
It is l.

The electrolyte obtained here was placed in a 9-element atmosphere.

1'FOQC1, heated between 8.5uI and 1'F
A black solid was obtained by 1@1 φ in OOC. When this substance was subjected to X-ray powder diffraction #1, the results were as shown in FIG.

(Ill) diffraction line of β-810 on 2# 3i5.8',
2-■15(j,l' has the (220) diffraction line of β-810 and [?120m-12.1@ has the (3
11) Same fold line - 1, 20 again! 42.4 @ (:T10)
(200) 1! 11 fold Me 26 W 36. a”+(Ill) diffraction line of near 10, 2 f) e 61.
(220) diffraction line O and 2θx7 of 4″H'l'io
The (ll!S) diffraction line of TiO was introduced at 3.5°.

In particular, each of the T10 diffraction lines is I! The obtained product 5i is mainly composed of β-R10, TiC, and β-810 because the lattice constant changes from the T10 of the lattice constant. 710 l^] solution and TIO, -, (Kugashi O<x
It is estimated that it is a composite carbide consisting of <1).

Actual bag example 2 Obtained in reference example 1. 7 +J Mama - 31t at 330℃
Between 'y.

9#4 Number average molecular weight obtained by dashed line under air flow is 299
0 I Recarbo V Run 40. Of and 5.3 t of detantetriline pro-I were punched, 500 m/m of 4-in was added to the mixture to form a mixed solution consisting of a homogeneous phase, and the mixture was heated at 70°C for 5 hours under an argon gas atmosphere. The reflux reaction was carried out while stirring. After the rapid flow reaction was completed, the insane was further heated to distill out the insane, and then polymerization was carried out at 150° C. for 2 hours to obtain Lridetanocal with a number average molecular weight of 8,900. I got silane. The obtained 4c remer was a **-like substance with an even-black color. − of the silane part of the **-shaped substance with
Total number of Pi-CHI-bond pairs -〇-T1(0-1eo
o, n, ), and the total number of -T1-〇- bonds, the ratio is about 3:1. Based on the IR data of this material, the reaction rate and/or the reaction rate at the 1-H bonding moiety in this polymer is between 1kII and 1kII.

Practical Example 3 Licarbisilane 40F and titanium tetoxotoxyr1o which were prepared in Reference Example 2 were weighed out, and this mixture 1:N-hexane 300- was added to form a mixture consisting of a homogeneous phase.
lll and 12. - A reflux reaction was carried out under a bulky atmosphere at 60° C. with stirring for 8 hours. After the reflux reaction was completed, the normal hexane was distilled off by further heating, and then polymerization was carried out at 0°C for 3 hours to obtain a number average molecular weight of 1450. Takes Shiran.

-81-CH of the Ilical I silane moiety of this polymer,
-Total number of bonds -o-Ts (004H,)s and d-
The ratio of the total number of 〒1-〇- bonds is about 23:l. Of this substance! 081 in this polymer based on the 7-ter
Calculating the reaction rate and d/or bridge rate at the -H@ joint part is close to #tItlOO.

Real-f14 Iv Cal I silane obtained in Reference Example S 40. Of and titanium tetrahedron o, 5x r1.6t and pestle It! IL
.

Add 200 sd of xylene to this mixture to make a mixed solution consisting of a homogeneous phase, and heat at 130°C under an Arzen gas atmosphere.
The reflux reaction was carried out with stirring for 2 hours. After the circulation reaction was completed, the temperature was further heated to distill off xylene, and then heated to 300°C.
Polymerization was carried out for 30 minutes with #! I average molecular weight is 1B! 5
00 2 Rizotatsukarushiran was obtained.

-R1-CH of the I rical mesilane moiety of this I remer,
-The ratio of the total number of bonds to -o-wl (o-i・00.Bma) and the total number of d-'I'1-0- bonds is about 122
: It is 1. Based on the IR meter of this 1 bond, the reaction fist and/or frame III rate at the 81-H bonding part in this I riff is calculated as tt, and the line number is t5%.

[Brief explanation of the drawing]

Figure 1 shows gel-no-ylon chromatography (ORC) of licarbisilane I in Reference Example 1, and Figure 142 shows the gelatin chromatography (ORC) of Ricarbisilane I in Reference Example 1. GPO of Riteta no Riki Rou 1v run. FIG. 3 shows the infrared absorption spectrum (IR) of the Ilical I silane of Reference Example 1, and the analogous number diagram shows the IR of the Pholitetanol Isilane of Example 1. Maku all! 5114 is Example 1
This is an X# powder diffraction diagram of a carbonaceous composite carbide obtained by firing 1g of Den9stanocardivran at 00°C in a 1111 atmosphere. Special non-living materials laboratory procedures
Amendment (spontaneous) February 17, 1980 Commissioner of the Japan Patent Office Kazuo Wakasugi1, Indication of the case 1981 Patent Application No. 28142, Name of the invention New polytitanocarbosilane3, Person making the amendment Relationship to the incident Patent applicant address: 873-3 Yamano, Shikata, Asahi Village, Kashima District, Ibaraki Prefecture
Name Special Inorganic Materials Research Institute Idiot 5, Date of amendment order None 6, Drawing subject to amendment 7, Contents of amendment: engraving of the drawing (no change in content)

Claims (1)

[Scope of Claims] Mainly the general formula + SEE C 鵡÷ (However, R in the formula is a hydrogen atom, a lower alkyl group, or Fi
Shows a phenyl group ) has a main chain skeleton represented by the number average molecular weight is! 0O-
10,000 4-licarpsilane and a titanium alkoxide represented by the general formula %) (wherein R' represents an alkyl group having 1 to 20 carbon atoms) The polytitanocal having a molecular weight of 700 to 100.000 is a silane, and the polytitanocal is a silane in which at least a part of the silicon atoms are bonded to titanium atoms via oxygen atoms, so that the polytitanocal has a silane block. It is a nine-crosslinked block copolymer that is crosslinked with titanium atoms through oxygen atoms, and the -lical is the +5t-C of the four silicone atoms.
A polytitanocal ? Silane.