JPS58213026A - Organometallic crosslinked polymer containing silicon and titanium or zirconium and its production - Google Patents

Abstract

PURPOSE:To obtain the titled crosslinked polymer amenable to an insolubilization treatment and advantageously used in the production of fiber, etc., by mixing a specified organosilicon polymer with an organometallic compound and reacting by heating in an inert atmosphere. CONSTITUTION:A mixture is prepared by mixing an organosilicon polymer consisting mainly of units of formulas I and II (having H in at least part of the side chains attached to a silicon atom; having a lower alkyl, aryl, phenyl or silyl in other side chains attached to the silicon atoms; having a ratio of the total number of units of formula I to that of units of formula II in the range of from 20:1 to 1:20; and having a number-average MW of 200-10,000) with an organometalic compound of formula III (wherein M is titanium or zirconium and X is a 1- 20C alkoxy, phenoxy or acetylacetoxy) in a predetermined ratio. This mixture is reacted by heating in an atmosphere inert to the reaction to bond at least part of the silicon atoms of the organosilicon polymer to the metal atoms of the organometallic compound through oxygen atoms to thereby obtain an organometallic crosslinked polymer, number-average MW about 500-100,000, having silicon and titanium or zirconium.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an organometallic crosslinked polymer containing novel silicon derived from an organosilicon polymer and an organotitanium compound or an organozirconium compound, and titanium or zirconium, and a method for producing the same. It is.

Polycarbosilane, which is a polymer with a main chain skeleton of +31 0H2÷ and two side chain groups bonded to each silicon atom, is converted into SiC, an inorganic carbide, by firing, so polycarbosilane can be used as a fiber. It is well known that S and C fibers with good mechanical properties and thermal properties can be produced by firing the fibers in the form of a carbon fiber. JP-A-51-139929 (3) Disclosed in the official gazette, etc. 7'7. ing.

The present inventor then discovered that the 1-so chain skeleton was mainly (-si
-C++□→- structure Q'i position, next polycarbosilane, titanoxane bond middle ÷'[・1-0÷ and siloxane bond? 1'L position -F r; polytitanosilogysan having i-0+ in the 1-chain skeleton or zirconoxane bonding unit +7. The organometallic copolymer with polyzirconosiloxane having r-0+ and n[1 Gizan bond unit (-si-o÷ in the main chain'1''1 case) was formed by firing the union into a fiber form. i 'If! 'l'
iC fiber or SiC-ZrO fiber is! 3i0#
It has been reported in Tokkai No. 56-5828 and JP-A-56-1 that it is a fiber with even better mechanical properties compared to other fibers.
Publication No. 31628, JP-A-56-! It was disclosed in J20 September Publication and Special Publication No. Sho 55-182817.

Further, the present inventor has discovered that polycarbosilane whose main chain skeleton mainly consists of +5i-CH2 structural units and +Ti-0±
Titanium alkoxide or +Zr-0 at bond tIi position
-3- Polytitanocarbosilane or polyzirco (4
) Nocarbosilane and its manufacturing method were discovered, and from these polymers Sj, 0-TiC fiber, 5iC-ZrO
JP-A-56-'74126 discloses that fibers can be obtained.

It was disclosed in Japanese Patent Application Laid-Open No. 56-92923.

In order to produce the above-mentioned 5ic-Tie fiber Mk or SiO-ZrO fiber from these polytitanocarbosilanes or polyzirconocarbosilanes, the fibers obtained by spinning are kneaded and heated to maintain their shape. It needs to be mineralized. For this purpose, the thread-like polymer obtained by spinning must be pretreated to make it infusible by curing. One of the most suitable methods for this infusibility treatment is to gradually heat the polymer in air to near its softening point, but careful attention must be paid to the rate of temperature rise, etc. .

This time, the present inventors have diligently continued research on organometallic polymers in order to obtain polymers that can be easily subjected to the above-mentioned infusibility treatment compared to conventional polymers. 5) An organosilicon polymer consisting of +Sj, Si÷bond +1'I- position, and (-Ti-0+organotitanium compound with structure 'l'-(i>) or an organic zirconium compound with +Zr-0÷structure 4+ position Novel silicon derived from
The present invention has been accomplished by discovering an organometallic crosslinked polymer containing titanium or zirconium and a method for producing the same. The organometallic crosslinked polymer of the present invention obtained by the above method is
Unexamined Japanese Patent Publication No. 1974 G-'74.126, Unexamined Japanese Patent Publication No. 56-
4) Compared to the polymer disclosed in Publication No. 2923, the polymer contains +S I S 1+ bonding units, so it is easily made infusible and is extremely advantageous for use in the production of fibers, for example. I found it.

According to the present invention, -L consists of a 1000i -OH2÷ bonding unit and a +t31 Si child bonding unit, and the side chain of silicon is a hydrogen atom, a lower alkyl group, or an aryl group.

It has a phenyl group or a silyl group, (-5i-CH2+
an organosilicon polymer portion in which the ratio of the total number of bonding units to +Si Sj +total number of bonding units is in the range of 20:l to 1:20, and at least a portion of the silicon atoms of the organosilicon polymer portion (6) are oxygen halved. +5j-OH□ of a portion of the organosilicon polymer, consisting of a portion bonded to a titanium or zirconium metal atom via n
÷ bonding unit +Si −Sj+total number of bonding units +M−
The ratio of the total number of 0+ structural units is within the range of 2:l to 500:l, and the average molecular weight is about 500 to 100,000.
An organometallic crosslinked polymer containing silicon and titanium or zirconium is provided.

Furthermore, according to the present invention, it mainly consists of +811 0H2+ bond units and +5i-Si+ bond units, and at least a portion of the silicon side chains has a hydrogen atom, and the nine silicon side chains include lower alkyl groups and aryl groups.

It has a phenyl group or a silyl group, (-Si, -CH
An organosilicon polymer having a number average molecular weight of 200 to 10,000, in which the ratio of the total number of 2+ bonding units to the total number of +Si-Si+ bonding units is in the range of 20:l to 1:20.

An organometallic compound represented by general formula (7) (Mid in formula 9 represents titanium or zirconium mura, χ represents an alkoxy group having carbon number] = 20, a phenoxy group 1ITJ, and an antylacetoxy group) +:3] of the organosilicon polymer, C112+ bond +l′1 position and +Si
-Si÷total number of bonding units 21+fl'4 organometallic compound+M-0+total number of structural units ratio is 2:1 to 5
11) The resulting mixture is heated and reacted in an inert atmosphere 1) to remove at least one of the silicon atoms of the organic polymer. 3. Z average molecular weight is about 500~], OO, OOO novel silicon, titanium, zirconium, etc. Provided is a method for producing an organometallic crosslinked polymer containing.

The present invention will now be described in more detail.

The organometallic crosslinked polymer containing silicon and titanium or zirconium of the present invention includes l-functional polymers, difunctional polymers, 3(8) functional polymers, and tetrafunctional polymers as shown in the following figure. Is there a polymer?

(l-functional polymer) RHRR 11I 1 〜〜〜〜5i-Chehehehe N SI Si he8-q (1111 0HOR X-M-X X-M-X lI X Union) RHRRRH II II II ~~~~~ To 5i-C ~~~Si -Si~~~~5i
To -0～～X-M-X X-M-X X
-M-Xl 1 1 0HOR0R (9) (trifunctional intermediate combination) (+41113 ((f'! l, H is a water bed 1 white light, lower alkyl group,
represents an aryl group, phenyl group or silyl group, M,
has the same meaning as above) In other words, in the functional combination, + s ],
ClI2+ bond Q'1. (+n: & U (-s
], -s]-)- An organotitanium compound or an organozirconium compound is bonded as a pendant side chain to the polymer chain of an organosilicon polymer consisting of bonding units, and bifunctional, trifunctional and tetrafunctional 1/1: In the intermediate a: two or more of the above-mentioned organic polymers are crosslinked with an organic titanium compound or an organic zirconium compound.

Although the organosilicon polymer itself and the organometallic compound are known, an organometallic crosslinked polymer composed of the organosilicon polymer and the organometallic compound is unknown.

That is, 1. The novel organometallic crosslinked polymer of the present invention containing silicon and titanium or zirconium, J: 1 and 1. +Ff,'1. O [12-member combination unit and +
It can be confirmed by gel permeation chromatography (GPC) and infrared absorption spectrum (IR) that the polymer has a structure different from that of an organosilicon polymer consisting of S]-81+ bond units. FIG. 1 shows an organosilicon polymer OPc obtained by the method described in Reference Example 1 below.

FIG. 2 shows the novel silicon and titanium composition of the present invention obtained by reacting the organosilicon polymer and titanium alkoxide at a ratio of 2:1 (weight ratio) according to the method described in Example 1 below. o of the organometallic crosslinked polymer
pa (in each case, a solution of 0.145' of the polymer dissolved in 10 me of tetrahydrofuran was used for the measurement). In Figure 2, compared to Figure 1, the elution amount on the horizontal axis is 60 ~
At 80 me, a new broad peak that is not seen in FIG. 1 appears. This means that the novel polymer obtained by the method of the present invention is not a mere mixture of the organosilicon polymer and titanium alkoxide, but has a higher molecular weight than the organosilicon polymer because the two are combined through reaction. It means that it is an organometallic crosslinked polymer [in GPC, the horizontal axis of pi (
(13) The lower the numerical value (elution amount), the higher the corresponding molecular release. Next, the organosilicon polymer obtained by the method described in FIG. This is I 11 of the novel organometallic crosslinked polymer containing silicon and titanium of the present invention obtained by reacting with alkoxide at a ratio of 2:1 (weight ratio).
The absorptions of 1250 w' and 2100 tyn-'' at
Absorption corresponding to i-CHa and Sj, -TI. Comparing FIG. 35 and FIG. 5 at the ratio shown in FIG. 5, 1. l' (then this ratio is 0.795
In contrast, in Fig. 5, it is 0.441, which is indiscernible. This is due to the reaction between the organosilicon polymer and the titanium alkoxide, resulting in
Some of the H-bonds disappear, thereby causing the organosilicon polymer to react with the titanium alkoxide.

(14) and shows that organosilicon polymers are crosslinked by titanium alkoxide.

That is, the novel organometallic crosslinked jr1. containing silicon and titanium of the present invention manufactured by the method of Example 1. The coalescence is mainly +5i-OH2÷bonding unit and +S],
Some of the hydrogen atoms bonded as side chain groups to the silicon atoms of the organosilicon polymer consisting of S i ÷ bonding units are detached, and the silicon atoms form bonding units of titanium alkoxide +Ti, -0+ titanium atoms and oxygen atoms. It is generated by combining via.

In order to produce the novel organometallic crosslinked polymer of the present invention, the method of the present invention mainly involves the use of
An organosilicon polymer and an organotitanium compound or a polyzirconium compound consisting of Si Si + bond units,
The reaction is carried out by heating in an atmosphere inert to the reaction without a solvent or in an organic solvent.

This is a method in which at least a portion of the silicon atoms of the organosilicon polymer are bonded to titanium atoms or zirconium atoms of the organometallic compound via oxygen atoms. Even if the organosilicon polymer is reacted without a solvent, it is desirable to carry out the reaction slowly and to suppress the formation of by-products such as gel as much as possible. It is more advantageous.

Preferred solvents include n-hexane, benzene, I-luene, quinolene, tetrahydrofuran, and the like. - It is necessary to carry out the reaction in an atmosphere that is still inert to the reaction, such as nitrogen, gas, hydrogen, etc., and in an oxidizing atmosphere such as air. If it is carried out, the organosilicon polymer and the organogold compound 1, .

The reaction temperature can be varied over a wide range; for example, when a organic solvent is used, it may be heated to a temperature above the boiling point of the organic solvent.

When obtaining an intermediate having a high number average molecular weight, it is preferable to conduct the reaction by subsequently heating the mixture to a temperature above the boiling point of the organic solvent to distill off the organic solvent. The reaction temperature is generally 500℃ or higher1.
It is preferable to The reaction time is particularly important, and is usually about 1 to 10 hours. Reaction Q
In general, it is preferable to carry out the reaction under normal pressure, but it is not preferable to carry out the reaction in a vacuum or under high reduced pressure because low molecular weight components will distill out of the system and the yield will decrease. In order to carry out the method of the invention.

It is preferable to carry out the reaction while feeding an inert gas into the reaction system as a gas stream, because this maintains the pressure inside the reactor at approximately normal pressure and reduces the temperature rise and hydrocarbon gas released during the reaction. This is because it is possible to prevent a pressure increase caused by a gas such as methane, for example.

In the method of the present invention, the organosilicon polymer used as one of the starting materials for producing the novel organometallic crosslinked polymer containing silicon and titanium or zirconium is mainly (~+5l-CI(2 Partial bond unit and +8
i-Si+ bond unit, has a hydrogen atom in at least one part of the silicon side chain, and has a lower alkyl group, aryl group, phenyl group, or silyl group in the side chain of the other silicon atoms, +48i-OH2 −)−Total number of pairs of bonding units +Si
The ratio of -Si÷bonding units is in the range of 20:1 to l:20, preferably in the range of lO:l to 1:lO, and the biuniform molecular weight of several parts is (17) 200 to L O,00 (l It is.

One of the methods for producing such a 41-organic silicon polymer is to convert an organic compound containing a nitrogen having the bonds of 1.nl: (1), (2), and (3) into Lj,Nl.
α, or a mixture of these 1, is reacted in the presence of iJ alloy, as above +! There is a method for obtaining an organosilicon polymer consisting of E1-CI□+ bond unit and +S] B-1 part bond 11'-f)'t-.

(1) X + r; 1-an,, +, x(2)
x + 81-),
=1 to 4. X represents 710 gen.

As the halogen, d: chlorine and bromine are preferable. R is a hydrogen lower argyl group, an aryl group, a phenyl group or a silyl group. ) An organosilicon compound having the bond in (2) has one hydrogen atom in at least a part of the silicon side chain, and a lower alkyl group, phenyl group, or halogen is bonded to the other silicon side chain. ing.

(1,8) At least two or more compounds k'-1-1N selected from the compound groups of (1), (2), and (3)
Changing the ratio of +5i-OH□÷ bond units and +5j-3j+ bond units by reacting in the presence of a + K or a mixture or alloy thereof.

In addition, it is possible to change the bonding ratio of hydrogen molecules by as much as 1 μm.
Specifically, (1) χ+s j-CH2+n X is (
CI(3)(CI(□cz)sicz2.c,es
i(aH3)2an2c, 1°Br5i(a■]3)2
0H□Br, czst(c2H5),,aH2a
z.

Cps i (CH3)2 CI(2Br, B
r (-s 1 (CH3)2- C) I2+n Br
(n=3.4,5.6) C horse, Six CI (20H2 1 (2) x +si +nx (OB,)
Old month c, p-,,,((month+3)u;;tc,p2,
(c0H5)H8iCf2゜(C11,)lli;
113r, , (C,ull)+++;i++r2
．． H3itM! 3°H81nr3. (n-C,
II,,)lHjjell,,,, (n-03H7
)H3i042(3) R4-n S]χ1, as ("3)281C'2+ ("II3) 'o
H5Sll;, M2 + (C)(3)3 SIC,l
.

CH3S], Of3, 02tl. i;j-0,N1
．． (n 03I-17) 25lcz□.

(CH3)25]Br2. (a river) 011115
S], rJr2.

(CH3)35IBr, DIIISI I(r
, 02H55IBr3.

(02H5)2 Si Br2, (0611JI
5i13r, (0113)3Sj, Si (OT
(3) 20J.

(06H5)38131(C6115)2 Sl, (
061+5)2 CJ,.

CH2=CH-0H3Si012IO1l□-('3l
-1-(OH3)2Sill.

(OH3)3s ], 5i (c 13) C, A
2, Cl13S j II207, .

(c2o,),,5ir1c,ig,0113no
CP, 5jOj! 31 (+'II2 200) 2Sj, 0
Examples include f21 (C, ++, On, , )2sia, z21 and above.

Also as another method for producing organosilicon polymers.

(R is a hydrogen atom, a lower alkyl group.

It is an aryl group, a phenyl group or a silyl group. Note that the methyl group accounts for at least 5% of all side chains.

) A method of thermally decomposing poly7 run at 300°C to 500°C is mentioned. According to this method, +8j-C for yourself
Consisting of H2÷ bond unit and +5i-8i÷ bond unit,
An organic material that can be used as a starting material of the present invention, which has a hydrogen atom in at least a part of its silicon side chain and has a lower alkyl group, aryl group, phenyl group, or silyl group bonded to one silicon side chain. Silicon polymers can be obtained.

+5i-8i+bond qj due to thermal decomposition reaction of poly7rane
position and +Si -OH2÷ bond unit is generated by cleavage of the silicon-silicon bond +Si -Si÷, producing a silicon free radical, which extracts a hydrogen atom, and the silicon atom adjacent to the element free radical -to thus generated. is transferred, and a silicon-carbon bond+Si-Cl-12÷ is formed.

Let's explain this with a formula.

(21) Ill l
III Ill
11 1 1 (22) + + Sj-b ] + bonding unit, and +
Sj-CH2+ bonding units are formed, but if the side chain methyl groups in the polysilane are 5% or more, +81.
The proportion occupied by CH2+ bonding units is small, so
Since the number of hydrogen atoms as side chains of silicon decreases, it becomes disadvantageous for reactions with 9th-order organic titanium compounds and organic zirconium compounds, so it is desirable that the methyl groups in the side chains in polysilane be 5% or more. .

In the method of the present invention, the organometallic compound used as another starting material for producing the novel organometallic crosslinked polymer has the general formula (where M in formula 1 represents titanium or zirconium,
, x is an alkoxy group having 1 to 20 carbon atoms.

phenoxy group or acetylacetoxy group).

In the method of the present invention, the organosilicon polymer and the organometallic compound are combined into +5i-
0) ], , + bond bond table + Si Si + total number of bond units to organic total bending compound + M - 0 - (however, M represents the same meaning as above) ratio of the total number of structural units is 2:1 ~ f'g 500', in addition to the quantitative ratio within the range of 1,
A crosslinked polymer is produced by a heating reaction.

This reaction results in +01-r month 1□+ bonding unit and +
The hydrogen atom bonded to the silicon atom of the organosilicon polymer consisting of the S j, --S i bond Q' is detached.

The silicon atom is bonded to the titanium atom or zirconium atom of the titanium compound or organic zirconium compound via an oxygen atom.

The novel silicon and titanium polymer produced by the method of the present invention: the organometallic crosslinked polymer containing zirconium and gold has molecular weights in the order of tens of homogeneous molecules! 6 is a polymer of about 500 to 100,000, and 1 is a thermoplastic that is usually melted by heating to 50 to 400°C.

The novel organosilicon crosslinked polymer containing titanium or zirconium of the present invention has higher heat resistance than +Sj,O by firing in vacuum, in an inert gas atmosphere, or in a non-oxidizing gas atmosphere. 1. We paid special attention to the mechanical properties. S L-'I' ], -C system or 5l-
It can be converted into an inorganic substance consisting of Zr-C system.

In addition, the novel organometallic crosslinked polymer of the present invention is usually melted by heating, and in some cases, is soluble in organic solvents such as n-hexane, benzene, toluene, xylene, and tetrahydrofuran, and has various shapes. Since it can be made into a molded body, an inorganic molded body with good performance can be obtained by subjecting it to the above-mentioned heating and firing treatment. Examples of such molded bodies include, for example, continuous fibers.

Examples include film, coated odor, and powder. The novel polymers of the present invention can also be used in conjunction with sintering binders, impregnating agents or coating agents.

Reference Example 1 2.5 t of anhydrous xylene and 400 liters of sodium were placed in a 5 ton three-loaf flask, heated to the boiling point of xylene under a nitrogen gas stream, and 1 ton of dimethyldichloro 7-lane was added dropwise over 1 hour. After the dropwise addition was completed, the mixture was heated under reflux for 10 hours to form a precipitate. This precipitate was filtered, first washed with methanol and then with water, and white powder polydimethylsilane 42.
0tf obtained (25).

The above polydimethylsilane 400"i" was charged into a 3t three-bottle flask equipped with a gas inlet tube, a stirrer, a cooling tube, and a distillation tube, and was heated under a nitrogen stream while stirring. (50ml/min) and heat treatment at 420°C, a colorless and transparent slightly viscous liquid of 3507 was obtained in the distillation receiver. The number average molecular weight of this liquid was measured by vapor pressure osmosis method (＼ll・Oθmi), and the number average molecular weight was 4.
It was 70. When the IR spectrum of this substance was measured, as shown in Figure 3, absorption of 0i-0113 was observed at 650-900 tyn-'' and 1-2.50 on-'.

Absorption of +3j-If to 2100on-'+1020
81.-L month 1 near cm-1 and 1355 tyn-”
2-iji absorption, c-H at 2900°2950cm'
380t:
Since absorption of Sj -8i is observed in m-', the obtained liquid substance mainly consists of +si -Co2+ bond 11' and ÷5i-8i÷ bond units,
It is an organosilicon polymer that has hydrogen atoms and methyl groups in silicon side chains. Furthermore, from the measurement results of (26) NMR,1,R, this organosilicon polymer has +Si, -CH,, the total number of pairs of child bonding units (-
It was confirmed that the polymer had a ratio of Sj, -Sj÷total number of bonding units of approximately 1:3.

Reference Example 2 The organosilicon polymer 3002 obtained in Reference Example 1 was treated with ethanol to remove low molecular weight substances to obtain a polymer 402 having an average molecular weight of 1,200.

When measuring the IR spectrum and far-infrared absorption spectrum of this substance, absorption peaks similar to those in Reference Example 1 were observed. Become.

It is an organosilicon polymer that has hydrogen atoms and methyl groups in silicon side chains. In addition, from the measurement results of NMI'(, IR), this organosilicon polymer is.

+Si -CH2÷total number of bond units +S ], S
It was confirmed that the polymer had a ratio of 1÷total number of bonding units of approximately 7:1.

Reference Example 3 105f of metallic potassium and 800ml of anhydrous tetrahydrofuran ('Ht') were placed in a Yotsuro flask, and heated to approximately 70''C using a nitrogen gas flowmeter.
This 1m (a!Sj, (0113),, Cl120.M
'1. OV, (06H5)H8i042 75
2 and (CH3)2Sj, (E,, f'2 ri O
A mixture of f was added dropwise over 2 hours. Continuing after Droshishi 8
A reflux reaction was carried out by heating for a period of time. After the reflux reaction was completed, the reaction product was filtered off and the liquid (11) was distilled off (17) to obtain a white slurry-like substance 322 having a number average molecular weight of about 000.

Measurement of the lR spectrum and far-infrared absorption spectrum of this substance]7 showed that absorption peaks similar to those in Reference Example 1 were observed, and this substance was mainly composed of −: E, consisting of 1+ bonding unit.

It is an organosilicon polymer having hydrogen atoms, methyl groups, and phenyl groups in silicon side chains. Furthermore, N I
From the measurement results of vl R,l l(, this organosilicon polymer illusion:, -(-sco-eu,, →-total number of pairs of bond units +Sl-+3', + bond 'l'LO'f, (
It was confirmed that the polymer had a total number of h (7) and a ratio of 7>i if 1:8.

Example 1 The 11-organic silicon polymer 409 obtained in Reference Example 1 and titanium tetraisopropoxide 202 were weighed out, 400 ml of xylene was added to this mixture to form a mixed solution consisting of a homogeneous phase, and the mixture was heated under a nitrogen gas atmosphere. .

A reflux reaction was carried out with stirring at 130°C'''C for 1 hour. After the reflux reaction was completed, the temperature was further raised to distill off the solvent xylene, and then polymerization was carried out at 300°C for 10 hours to form silicon and titanium. An organometallic crosslinked polymer was obtained.The number average molecular weight of this polymer was 1165 as measured by the vpo method.

The results of the gel permeation chromatography of this substance shown in Figure 2 and the results of the gel permeation chromatography of the organosilicon polymer of Reference Example 1 shown in Figure 1 (organosilicon polymer of Reference Example 1) As is clear from the comparison of the gel permeation chromatograph of the material obtained by treating 2 under the same conditions as above in the absence of titanium tetraisogloboxoxide (same as in Figure 1), the The resulting polymer is not simply a mixture of the above-mentioned organosilicon polymer and titanium tetraisopropoxide (29), but is a polymer whose molecular weight is increased by the reaction of these two substances. As is clear from the comparison between the IR spectrum of this substance shown in Figure 5 and the IR spectrum of the organosilicon polymer of Reference Example 1, which is the raw material shown in Figure 1, the polymer obtained here The 81-H bond in the organosilicon polymer partially disappears, and the silicon J prince in this part bonds with the titanium atom of titanium tetrane propoxide through the oxygen atom, and as a result, a part of the organosilicon polymer It has three -o-q't (oa3o□) groups in its side chain, and a part of it is an organometallic crosslinked polymer in which organosilicon polymers are crosslinked with +Ti-0÷ bonds. Based on the above IR data, the reaction rate and/or crosslinking rate at the si-HM joint in this polymer is calculated to be 44.5%.
It is. +5 for the organosilicon polymer portion of this polymer
i-C112+bonding units+Si-Si+total number of bonding units vs. -0-TI(OC1119)3 and -Tj-0-
The ratio of the total number of bond mediums is approximately 6:1.

In addition, in the IR spectrum and far infrared absorption spectrum of this organometallic bridge 1j combination, an absorption peak equivalent to that of the organosilicon polymer of Reference Example 1 was observed as shown in Figs. 5 and 6 (30), indicating that this organometallic crosslinking The organosilicon polymer portion of the polymer is +81. CH2+ bonding unit O”:bi+5
It can be seen that it is composed of j-8i+ bonding units.

The polymer obtained here was heated in a nitrogen atmosphere.

Heat to 1700"C for 8.5 hours, then heat to 1700"C for 1 hour.
After calcination for an hour, a black solid was obtained. As a result of X-ray powder diffraction measurement of this material, the material obtained was mainly composed of Si.
It was found that it is an inorganic substance consisting of -Ti -0 system.

Example 2 Organosilicon polymer 402 obtained in Reference Example 2 and tetrakisacetylacetonatosilconium 64, B? 60ml of ethanol and 3001n of xylene were added to this mixture. , to make a mixed solution consisting of a homogeneous phase,
A reflux reaction was carried out under stirring at 60° C. for 8 hours under a gas atmosphere. After the reflux reaction was completed, the mixture was further heated to distill off ethanol and xylene, and then polymerization was carried out at 350°C for 8 hours.

The number average molecule 17i is 1.0. An organometallic crosslinked polymer containing 1:1 of silicon and silconium was obtained.

The organosilicon polymer portion of this polymer (-si-
DII2÷bond +81. S 1+total number of bond units to o −Zr(an;, CoC11Cor river, )3 and +Zr −0÷ratio of total number of bonds i:,+
n spectrum, far infrared absorption spectrum, +=I M
From the results of the I+ spectrum, it was found that Habo 4:IT was present. Based on the IR data of this material, the reaction rate at the Si H bonding part in this polymer: L-J: H/
Or, when the crosslinking rate is calculated, it is approximately 95%.

The polymer obtained here was heated in a nitrogen atmosphere.

Up to 1700℃8.511. Heat between 'l' and 1'7
After firing at 00°C for 1 hour, a black solid was obtained. As a result of X-ray powder diffraction measurement of this material, it was found that the obtained material was a material mainly composed of 5j-Zr-0 system.

Example 3 Organosilicon polymer 301 obtained in Reference Example 3 and titanium tetraphenogyne 7d 2,7y were weighed.

Polymerization was carried out under an argon atmosphere at 330° C. for 10 hours with stirring to obtain an organometallic crosslinked polymer containing silicon and titanium and having a number average molecular weight of 2,450. +Si −082 ÷ bonding units of the organosilicon polymer portion of this polymer and +Si −Si + total number of bonding units −〇 −T
The ratio of the total number of i (OC,H,)s and +Ti-0+ bonds is determined by the IR spectrum, far-infrared absorption spectrum, N
From the results of the MR spectrum, it was found that the ratio was approximately 120:l. The reaction rate and/or crosslinking rate at the Si--H bond moiety in this polymer is calculated to be approximately 20% based on IR data of this material.

When examining the infusibility of this polymer, the temperature was raised from room temperature to 110°C in 30 minutes in air.

It is possible to make it infusible by simply holding it at 110℃ for 5 minutes,
It was found that infusibility treatment is extremely easy compared to conventional polymers.

[Brief explanation of the drawing]

Figure 1 shows the apC of reference example 1, and Figure 2 shows the opc of example 1.
, Is Figure 3 a reference? ! IR of I1, Figure 4 is for reference (33), far-infrared absorption spectrum of Example 1, Figure 5 is the far-infrared absorption spectrum of Example 1, Figure 6 is the far-infrared absorption spectrum of Example 1, respectively. Patent applicant: Ube Industries, Ltd. (:'S4.)

Claims (1)

[Claims] Mainly +Si -CH2÷bonding unit and +5l-
It consists of si+ bond units, has a hydrogen atom, a lower alkyl group, an aryl group, a phenyl group, or a silyl group in the side chain of silicon, and (-8i-OH2+ total number of pairs of bond units + Si
-The ratio of the total number of Si + bonding units is 20:1 to 1:2
0, and a portion in which at least a portion of the silicon atoms of the organosilicon polymer are bonded to titanium or zirconium metal atoms via oxygen atoms, +si −c)], the ratio of the total number of 10 bond units to the total number of +Si −Si+ bond units to the total number of structural units of +M−0+ is 2
The number average molecular weight within the range of :l to 500:1 is about 5
Organometallic crosslinked polymer containing 00 to 100,000 silicon and titanium or zirconium. (1) 21, as +++i −(+ll□÷bonding unit and (
-8i-81→- bond at the 11'i position, has a hydrogen atom in at least a part of the silicon side chain, and has a lower argyl group, aryl group, phenyl group, or silyl group in one silicon side chain. The ratio of the total number of + + i'31 082 ÷ total number of bonding units to +5j - 8j ÷ bond])) is 20:
Number average molecular weight within the range of 1 to 1:20 is 200 to
], 0.000 organosilicon polymer. General formula (however, M in formula 1 represents titanium or zirconium,
or 1 to 20 carbon atoms f: represents an alkoxy group, phenoxy group, or acetylacetoxy group) The mixture is mixed at a m ratio such that the ratio of total number to +M-0 of the organometallic compound ÷ total number of structural units is within the range of 2:1 to 500:1, and the mixture is inert to the entire reaction. React by heating in an atmosphere 1. (2J At least a part of the silicon atoms of the organosilicon polymer are bonded to the metal atoms of the organometallic compound via oxygen atoms, and the number average molecular weight is about 500 to
100,000 silicon and. A method for producing an organometallic crosslinked polymer containing titanium or zirconium.