JPS58132024A - Organometallic copolymer - Google Patents

Abstract

PURPOSE:An organometallic copolymer capable of forming ZrC-SiC fiber having more excellent mechanical properties and higher oxidation resistance at high temperatures than the conventional ones, wherein the polycarbosilane portion is crosslinked with the polyzirconosilane portion in the midst of a main chain linkage. CONSTITUTION:The titled crosslinked block copolymer is obtained from (A) a polycarbosilane, number-average MW of 500-10,000, having a main chain selecton consisting mainly of formulaI, wherein Si has one or two side groups selected from the group consisting of H, a lower alkyl and a phenyl, and (B) a polyzicronosiloxane, number-average MW of 500-10,000, having a main chain skeleton consisting of randomly bonded units of formulas II and III, wherein total number ratio of formula II/ formula III is 30:1-1:30. The copolymer has a number average MW of 1,000-50,000. Part of the Si atoms of component A are crosslinked with part of the Si and Zr atoms of component B through oxygen atoms. The component A to component B rato is 100:1-1:100.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel organometallic crosslinked block copolymer consisting of a polycarbosilaf moiety and a polysilane moiety.

It is a polymer whose main chain skeleton consists of +Si-CM, ÷, and two side chain groups are bonded to each silicon atom. It is well known that SiC fibers with good mechanical properties and thermal properties can be produced by forming the fibers and firing them, and the present inventors have described such a technique in Japanese Patent Application Laid-open No. 1516300/1983. It was disclosed in Japanese Patent Application Laid-Open No. 151-139929.

The inventor then discovered that the main chain skeleton was ÷8l-OH.
, a polycarbosilane consisting of ten structural units, a butanoxane bonding unit ÷T1-0÷ and a noxane bonding rate of 18
ENO-TiO fiber obtained by spinning, infusible, and firing an organometallic copolymer with polytitanosiloxane having 1-0+ in its main chain skeleton has superior mechanical properties compared to 810 fiber. Special M#45 that it is Yuyari embroidery
No. 4-80, adapted in the specification of No. 93.

As a result of continued research on organic gold tII4-based electrocompounds, the present inventors discovered that the cross-linked polymetallic copolymer can be formed into 810 fibers obtained from conventional polycarbosilane by molding and firing. LrO-81G fiber 1 exhibits better mechanical properties and oxidation resistance at high temperatures than
It has been found that it is a useful polymer that can be crosslinked because it can obtain Ii-.

According to the present invention, the number average molecular weight is about 500 to 10,000.
The polycarbosilane moiety (A) and the number average molecular weight of about 50
0 to 10,000 polyzirconate; The polycarbosilane moiety (^) has the formula +8l-CtH as earth, and has a main chain skeleton consisting of ten structural units, and the silicon atom in the formula is a hydrogen atom, a lower alkyl group (carbon (preferably number 1-4) and phenyl groups.
The polyzircono Vct xane component (B)
and the ratio of the total number of zirconoxane bonds to the total number of siloxane bonds is within the range of 30:1:30, and most of the silicon atoms of the siloxane bonds are lower alkyl groups (preferably vertical di-4) and It has one or two @ groups selected from the group consisting of phenyl groups, and most of the zirconium atoms in the wI zirconoxane bond are lower alkoxy groups (preferably 1-4 carbon atoms) as side chain groups, Phenoxy V group or acetylacetoxy group t-1 box or 2
at least 41 parts of the silicon atoms of the polysilane moiety (A) are
At least 41 parts of the silicon atoms and/or zorconium atoms of the moiety (B) are bonded to each other via oxygen atoms, and the polycal silane moiety (,4) and the polysilconosiloxane moiety (B1) are bonded to fL. The ratio of the polycal to the silane moiety (A)÷Si-CM, +total number of structural units to +ZdeO÷bonding units and +5i-0÷total number of bonding units of the polysilconosiloxane moiety is 100:1 to 1
There is provided the above-described block copolymer which has a special feature of being melted by heating at 50 to 400° C. and capable of being grown on a shore.

The organometallic co-unit body of the present invention has the following features: (1) A main chain skeleton 1 mainly consisting of the formula +5i-CH,+ at the 1st structural ratio, with a number average molecular weight of about 500 to toooo;
, and the silicon atoms in the formula have substantially 8 side chain groups selected from the group consisting of hydrogen atoms, lower alkyl groups (preferably 1 to 4 carbon atoms), and phenyl groups, and (2) the number average molecular weight is about 500 to 10,000, and the ratio of the total number of zirconoxane bonding units to the total number of siloxane bonding units is within the range of 30:1 to 1:30;
Most of the silicon IF and m molecules of the siloxane bonding unit have one or two side chain groups from the group consisting of a lower alkyl group (preferably having 1 to 4 carbon atoms) and a phenyl group. , most of the zirconium atoms in the zirconochitin bonding unit are lower alkoxy groups (1-carbon atoms).
4 is preferred), a polyzirconosiloxane t having one or two phenoxy groups or acetyl ayatoxy groups,
÷8l-OHI÷width 1tljlL of the polycarbosilane
The ratio of the total number of positions to the +zr-o+ bonding rate of the polyzirconosiloxane and the total number of units 1-〇+bonding units is 10
The resulting mixture was mixed in a quantitative ratio within the range of 0:1 to 1:1OO, and the resulting mixture was heated in an all-organic solvent and under an atmosphere inert to the reaction (-) to form a wrinkled polycarbonate. A crosslinked polysilane moiety characterized by at least 1 part of the silicon atoms of the silane being bonded via oxygen atoms to at least 41 parts of the silicon atoms and/or Fielconicum atoms of the polynorconosiloxane. and the polysilconosiloxane portion, the number average molecular weight is 1000 to 50000.
It can be produced by the method for producing an organic gold m-crosslinked block copolymer.

Hereinafter, the organic gold 11 near-lock copolymer (hereinafter sometimes simply referred to as organometallic copolymer) of the present invention and the method of the present invention for producing it will be explained in more detail.

The organometallic comonomer of the present invention is a crosslinked block copolymer obtained by crosslinking polycarsilane and polysilconosilane through block copolymerization KL. Normal block copolymers have each block at each end! IL/-
1, and thus has fUl that it consists of a series of blocks connected by head-to-tail connections. On the other hand, in the organometallic copolymer of the present invention, a part of the silicon atoms of the structural unit +5i-CH,÷, in which the polycal is present in the middle of the main chain skeleton of the silane moiety, is The structural unit (-Fl
l-0- and/or -Zr-0-) silicon atoms and/or
The father has a structure in which it bonds with a part of the zirconium atom. Uchi, the organic gold-coelectric composite of the present invention is
It is a crosslinked block copolymer with a unique structure in which the polycarbosilane moiety (A) and the polyzirconosiloxane moiety (B) are crosslinked in the middle of the main chain bond, rather than in a single bond.

Although polycarposikune itself and polyzirconosiloxane themselves are known polymers, a copolymer consisting of carbosilane and zirconozoloxane has not been known so far.

Needless to say, a crosslinked block copolymer formed by combining polycarbosilane and polydylphosiloxane in the above-mentioned unique bonding manner has not been known at all, and this is the fourth feature of the present invention. Polymers are new polymers.

The organometallic coelectrolyte of the present invention is
Gel permeation chromatography (GPC) and infrared absorption spectrum (Ia
) can be confirmed by C. Figure 1 shows a GPO of 9-polycarbosilane, which was added using the #multiplication method 1 described later.
The figure shows the GPO of polyzirconosiloxane obtained by the method of Reference Example 2 described later, and Figure 3 shows the weight ratio of the polycarbosilane and polyzirconosiloxane obtained according to the η method of Example 1 described later. GPO of the organometallic symmetries of the present invention obtained by reacting at l:1 (in each case, 50 kits of polymer, lOsg of tetrahydrofuran)
c) The dissolved solution was subjected to all measurements). Dear friend, Figure 4 shows the GPO of a simple mixture of the above-mentioned polyzircone loxane (weight ratio 1:1). Polymer mixture dissolved in tetrahydrofuran (10). #! The epo of the mixture of two yuzu polymers shown in Fig. 4 is a part of the good one by superimposing the GPC of Fig. WJ1 and the Gpo of Fig. #S2. However, in the GPO of the copolymer shown in Figure 3, a new peak that is not seen in either ()Pot: in Figures 1.2 and 4 appears at the elution amount of 8.1- on the horizontal axis. ing. This means that polycarbosilane and polyzirconosiloxane are block copolymerized (: therefore, the molecular weight has increased). In addition, the peak ζ at elution 1110- seen in GPO in Figures 1 and 2; the height of this peak is very small in CPO in Figure 3. means that the content of low molecular weight substances in the block copolymer (2) has decreased considerably.As mentioned above, the GPO experimental results show that the organometallic polymer of the present invention This shows that it is not a mixture of zirconosiloxanes, but a block copolymer whose molecular weight has been increased by combining the two polymers mentioned above.

Next, to explain the infrared absorption spectrum (IR),
Figure 6 shows XVt% of the polycarbosilane described in Reference Example 1.
Figure 6 shows I of the polyzirconosiloxane described in Reference Example 2.
The R% diagram is the IR of the organometallic coelectrolyte of the present invention described by Fljlt 2. And the absorptions of IRi:, 1250 cm-" and U 2100 on-" in FIG. 5 are respectively 81. These absorptions correspond to -0HI and 81-H (these absorptions do not exist in the IR of polyzirconosiloxane in FIG. 6). Even in the IH of copolymers, which is small due to the bulk, the above two absorptions of 8l-OH and absorption intensity (12
50m-'') ratio 1: Comparing Figures 5 and 7, the ratio of Upper-C is 0.608 in the IR of Figure 5, while it is 0.456 in Figure 7. This is due to the reaction between polycarbosilane and polyzirconosiloxane.
It is shown that some of the H bonds disappear, thereby resulting in a block copolymer of polycarmedylane and polyzirconosiloxane. That is, the organometallic copolymer (block copolymer) of the present invention has a structural unit ÷8l-0) present in the main chain skeleton of polycarbosilane. , some of the hydrogen atoms bonded to the 41'l group to the silicon atoms of 10 are eliminated, and the silicon atoms form the structural unit (-al-O- and/X is-
Zr-0-) is formed by cross-linking with the silicon atom and/or zirconium atom III via the oxygen atom. Based on the above IR data.

Actual - Calculating the crosslinking rate of the organometallic copolymer of Example 1, it is 25
．． 011G (assuming that crosslinking occurs only by the disappearance of the 81-H bond).

The method of the present invention for producing the organometallic copolymer of the present invention comprises heating a mixture of polycarbosilane and polyzirconosiloxane in an organic solvent and in an atmosphere inert to the reaction; At least 11fISt of silicon atoms in polycarbosilane? This is a method in which at least a part of the silicon atoms and/or zirconium atoms of polyzirconosiloxane are bonded via acid An atoms. The organic solvent is used to carry out the reaction smoothly and to prevent the formation of by-products such as gel-like substances. Preferred solvents include benzene, toluene, xylene, tetrahydrofuran, etc. Monkey.

In addition, it is necessary to carry out the reaction in an atmosphere of an inert gas (for example, phoneme, argon, hydrogen), and if it is carried out in an oxidizing atmosphere such as air, the raw material This is not preferred because it causes oxidation of carbosilane and polyzirconosiloxane.

The reaction temperature can be varied over a wide range (for example, IMWtC may be heated below the boiling point of the organic solvent used; however, when a copolymer with a high crosslinking rate is used, the organic solvent It is preferable to carry out the crosslinking reaction by heating the organic solvent to a temperature higher than the boiling point of
It is preferable to keep the temperature below 00°C. The reaction time is not particularly critical, but is usually 1 to 10 hours #A degrees. It is generally preferable to carry out the reaction near normal pressure, and it is not preferable to carry out the reaction in a vacuum or in a reduced ratio because low molecular weight components will distill out of the system and the yield will decrease. 10,000 ff of the present invention: t-
In order to carry out the reaction, it is preferable to carry out the reaction while feeding an inert gas into the reaction section as a gas stream.

The reason is that this keeps the pressure inside the reactor at normal pressure, which prevents temperature rise and hydrocarbon gases released during the reaction.
For example, this is because it can prevent pressure increases caused by gases such as methane.

In the method of the present invention, the polycarbosilane used as one of the starting materials for constructing the Aromakin wI4 copolymer has a number average molecular weight of about 500 to 10,000 and a formula +8l-OH, +. It is a polycarbosilane having a chain skeleton consisting of structural units, and the silicon atoms in the formula substantially have 2flI side chain groups selected from the group consisting of hydrogen atoms, lower alkyl groups, and phenyl groups. In addition to the side chain groups mentioned above, the silicon atom of the terminal group of polycarbosilane has
An OH group may also be attached.

The method for producing polycarbosilane itself is known, and the above-mentioned polycarbosilane used in the present invention can be prepared by such a known method.

For example, a method for preparing polycarbo V-lantern by combining monosilane with its components has been described by Fritt; A.
ngew, Chem,, 7Q p, 657 (19
6)), and the method of manufacturing polycarbosilane by once converting monosilane into polyvrane and then combining the same is disclosed in Japanese Patent Application No. 126300/1983, filed by the applicant of the present invention. Publication, JP-A-52-1
This is disclosed in Japanese Patent No. 12700 and the like. +f with this invention! Among the polycarbosilanes used, the King 1 skeleton is
Polycarbosilane qualitatively consisting only of structural units of ÷81-OH,+ can be produced by the above-mentioned known method.

Polycarbosilanes particularly suitable for use as starting materials in the present invention are disclosed in JP-A-54
A modified polycarbosilane produced by the method J described in Japanese Patent No. 61299, ie, a polycarbosilane partially containing a loxane bond. This modified polycarbosilane is
(A) and (B) were the kings from the early inscriptions (herein, R, R, and R are each independently a hydrogen atom, an alkyl group, or a phenyl group) ( A) and (B) O are polycarbosilanes having a specific gravity of 5:l to 200:l and partially containing silokinane bonds with a number average molecular weight of 500 to 10,000. This modified polycarbosilane has R.

- (-St +, polysilane with a structure of 0.01 to 15 iL of polyborosiloxane having a phenyl group in at least a portion of the ring of 81 is mixed, and in an atmosphere inert to the reaction, the mixture of the polymers is usually heated to 250 μL. 'C1l above, preferably 300
It can be produced by heating at ~500°C and producing a sweet aroma for S48~10 hours.

In the method of the present invention, 1f! The polyzirconosiloxane used has a number average molecular weight of about 500 to 10,000, a skeleton consisting of zirconoxane osseous units + Zr-0÷ and V-loxane bonds +81-〇+, and a zirconoxane bonding rate bγ. The ratio of all the siloxane bonding units is within the range of 30:1 to 1:30, and most of the silicon atoms in the siloxane bonding units are selected from the group consisting of lower alkyl groups and phenyl groups. @ chain t 1
-Manyuki has two zirconium atoms, and most of the zirconium atoms in the wI zirconoxane bonding unit have a lower alkoxy group, phenoxy V group, or acetylacetoxy group as a control group.
or polyzirconosiloxane having 2411.

Kei exists as 4 groups of polydyl fluorosiloxane trees
In addition to the above-mentioned side chains, an OH group may also be bonded to the atom or zirconium atom.

The method for producing polyzirconosiloxane itself is known, and the above polyzirconosiloxane used as a starting material in the present invention can be produced by such a known synthesis method. Typical synthetic methods include (a) Synthesis method 1 by cohydrolysis of organochlor ν and zirconium alkoxide, zirconium phenoquine or zirconium acetylacetonate (b) Synthesis method 1 by co-hydrolysis of organochlorine and zirconium alkoxide; Synthesis method using acid condensation reaction or (c) Synthesis method using dealcoholization condensation reaction C of organosilanol and zirconium alkoxide, zirconium phenoxide, and zirconium acetylacetonate.

When synthesizing the polyzirconosiloxane conveniently used in the present invention by the synthesis methods (a) to (c) above, -81-0
If the generation of the -TI-0- bond is reduced by the formula, it will look like the above.

(a) -8101+ -TiORHRO-Ii
+l -81-0-Ti-+ROM (b) -810)1+ -TiOj --
→-81-0-Ti −+ HOj (c) -R1OH+ -TiOR-1→8l-
0-Ti-+ROI
ganlc poxymere (y, a, A,
8tOn6Aaadem1c Press, 1
! J62), and is also described in Japanese Patent Application No. 58004/1989 filed by the present applicant.

In the present invention, starting = h and the polyzirconosiloxane used in "C" has a number average molecular weight of 500 to 1 ootJ.

It is made of polymers that are soluble in organic solvents (eg, benzene, toluene, xylene, acetone, tetrahydrofuran).

In this specification, the siloxane bonding unit present in the oxane skeleton is expressed by the simplified formula ÷81−〇+ in accordance with the conventional notation method, but as is well known to those skilled in the art, the siloxane bond unit present in the The bonding unit is a trifunctional group R trifunctional group -0-81-0-.

It contains a 3dlI siloxane bonding unit (wherein R is a side chain group and Z). All of these three danroxane bonding units can serve as structural units that form the skeleton of the polyzirconosiloxane used in the present invention. However, as the content of four-blind functional siloxane linking units increases, the polymer generally becomes cross-linked,
In the polyzirconosiloxane used in the present invention, most of the siloxane bonding units are difunctional or trifunctional siloxane bonding units because the polyzirconosiloxane used in the present invention has a rich structure and is insoluble in solvents. Therefore, the polyzirconosiloxane used as a starting material in the present invention is
Most of the silicon atoms in the siloxane bonding unit ÷81-〇+ should bond to one or two @ chain organic groups R (lower alkyl group or phenyl group). In addition, the polyzircono(/Clxane) used in the present invention may contain functional siloxane bonding units, but its content is uncertain within the limits that do not harm the dissolution of the polymer in the solvent and the solvent. It is preferred that the polyzirconosiloxane bonding units useful in the present invention consist essentially of difunctional and/or trifunctional siloxane bonding units.

Similarly to the above, the zircoscan bonding unit represented by the formula +Zr-0+ also includes a bifunctional group, a 3'1 functional group, and a quadrifunctional group, but for the same reason as mentioned in 9 above, In the polyzirconosiloxane used in the present invention, most of the zirconoxane bonds are @ chain m groups (lower alkoxyl group, phenoxy & or acetylacetoxy group) t-2
Is it unique (trifunctional group) or is the father lii#N
It is preferred that the zirconoxane bonding unit is substantially trifunctional and/or that the parent is a trifunctional zirconoxane bonding position.

In the polyzirconosiloxane used in the present invention, the ratio of the total number of zirconoxane bonds to the total number of siloxane bonds is in the range of 30:1 to 1:30.

The polyzirconomi 10xane used in the present invention is a polymer consisting of a skeleton in which siloxane bonds +81-0÷ and zirconoxane bonds Zr-0+ are randomly bonded with two ζ bonds as described above. It can take on the structure of a dandelion or a mesh-like structure.

In the method of the present invention, the above polycarbosilane and polyzirconosiloxane are mixed at +81
- Mixing at a ratio of the total number of CM1 structural units to the total number of ÷Zr-0+ bonding units and ÷81-〇+ bonding units of polyzirconosiloxane, which is within the range of 100:1 to 1:100, The resulting mixture is reacted, thereby creating crosslinks between the two polymers. As explained above, the crosslinking reaction is carried out using the structural unit ÷8l-CH! in the main chain skeleton of polycarbosilane. Among the + silicon atoms, the silicon atom from which the hydrogen atom bonded as the @- group has been removed is the siloxane bond unit in the main mt case of polyzirconosiloxane and/or the silicon at the zircotsca single bond rate position. The reaction is such that the atom and/or parent are bonded to a portion of the zirconium atom via oxygen, thus producing the enriched metal polymer of the present invention, which is a crosslinked block copolymer. Therefore, when focusing on the polycarbosilane moiety of the block copolymer, the silicon atoms in the main chain skeleton involved in crosslinking may have two @ship groups before the crosslinking reaction, but in the Shibahashi reaction Later on, the silicon atoms in the main chain skeleton that carry one side group and are not involved in cross-linking are substantially hydrogen atoms, selected from alkyl groups and phenyl groups. Two 111Il at - I like it.

Method 1 explained above: The organogold-111 electropolymer of the present invention thus produced is a block copolymer with a molecular weight of 1000 to 5QOOO, which is a combination of the polycarbosilane and polyzirconosiloxane specified in the present invention. It is a thermoplastic material that normally undergoes ff1-setting when heated at 50 to 400°C, and can be dissolved in solvents such as benzene, toluene, xylene, and tetrahydrone.

FIG. 7 shows the infrared absorption spectrum (IR) of the organic mounted copolymer of the present invention obtained by the method of Practical Example 1. A block copolymer consisting of a polycarbosilane partially containing a V-loxane bond obtained from dimethylsilane and polyborodiphenylsiloxane, and a polyzirconosiloxane obtained from diphenylsilanediol and zirconium tetrazate. . The starting materials shown in Figure 5 and Factor 6 (
IR of polycarbosilane and polyzirconosiloxane)
Taking into account, the I of the block copolymer in the m'F diagram is
Judging whether or not R has disappeared is like a long time ago.

500 cat-”, 81-0 near F00ω-1
6H@; around 800cm-”, 8 of 1250cIR
l-ORB; 950 (-PR's 81-υ-zr:
81-O81-0H of 1020-1030; 105
0m.

1120cIM's I'+1-0; 1430mer
st -0,H,; 81-H of 2100cya
Zr-00 of 2B50-2940C*, a-m in H.; 2900 mouths, 295 (O-H of LW-"1; 0- around 3050cR-") 1. The absorption corresponding to each C--H bond in is reduced to IR in FIG.

As explained above, 1: The a-metal copolymer of the present invention is a structural block copolymer with a novel structure, and this copolymer is prepared in an inert gas atmosphere and in a non-oxidizing gas atmosphere. By firing at , it is possible to convert it into a composite carbide which is mainly composed of ZrO and 810, and has a part of ZrO and 810 dissolved in solid solution, which has characteristics with mechanical strength ζ2 lower than that of conventional 810. can.

In addition, since it melts when heated (-) and is soluble in M solvent, it can be molded into a neat shape 1*. So, 10
By heating and firing at m degrees above 0° C., it is possible to obtain a composite carbide molded body having the above-mentioned structure with extremely excellent performance.

Examples of such molded bodies include slow-woven fibers, films, coated steel, powders, etc., made of this composite carbide. In addition, the organometallic copolymer of the present invention can be used as a binder for sintering and as a thinning agent in addition to the composite carbide article mentioned above. It is expected that it will have various uses.

Is this invention based on the actual examples below? al-to be happy.

Reference Example 1 A 5-ton three-lough flask (= 2.5 tons of anhydrous xylene and 400 tons of sodium 9m) was heated to the boiling point of xylene under a nitrogen gas stream, and 1 ton of dimethyldichlorosilane was improved in 1 hour.End under ?rlfI Thereafter, the mixture was heated under 11D heat reflux for 10 hours to form a precipitate.The precipitate was filtered once, first washed with methanol, and then washed with water to obtain a white powder of polydimethylsilane &20t.

On the other hand, diphenyldichlorosilane 159t and Hou@12
4 t in n-glyether under a phoneme gas atmosphere, 1
5301 (D; Jζriboro9-phenylonloxane was obtained by heating at a temperature of 00 to 120°C, and further heating the produced white resinous material at 400°C in vacuum for 1 hour.

Next, 8.2'lft of the above polyborodiphenylsiloxane was added and mixed with the above polydimethylsilane 250F,
In a 2t 6-pipe tube equipped with a reflux tube, 350
The mixture was heated to .degree. C. and enriched for 6 hours to obtain a polycarbosilane to be used as a raw material for the copolymer of the present invention. After cooling at room temperature, xylene was added and taken out as a solution, the xylene was evaporated, and concentrated under an air flow of 330 Ic for 2 hours.
A solid of t was obtained. The number average molecular weight of this polymer was determined by vapor pressure osmotic pressure method (VPO method) to be 1500.
Met. When we measured the IR spectrum of this substance, it was shown in Figure 5 (near 800m and 1250--1
Absorption of 8l-OH, 1400, 2900.2950
- O-H absorption at 1, 81- at 2100 cm-
Ho @ Shu, 1020, 1355 copies M-11'-81
Absorption of -04-81, 8 near l 100 ctx-1
Absorption of 1-0, f00°1120.1430 equipment-1 to 8
Absorption of 1-06H was observed, and the obtained polymer was
It is a polycarbosilane having 1 constituent element.

Reference Example 2 Diphenylsilanediol 864t and zirconium tetrabutylene Vd 3831Ft4'P were collected and subjected to reflux reaction at 150°C for 1 hour under MA gas with addition of xylene gold. After completion of the reaction, insoluble matter was filtered. After removing the solvent with a xylene polymerator, the resulting intermediate product was polymerized by heating at roughly 300° C. for 1 hour under nitrogen gas to obtain the polyzirconosiloxane used as a raw material for the copolymer of the present invention. A polymer was obtained in which the specific gravity of the total number of zirconoxane bonds to the total number of siloxane bonds was 1:4.The number average recruitment amount was determined to be 1650 by the vpo method.The infrared absorption spectrum of this material was measured, and the total number of siloxane bonds was 1:4. As shown in Figure 6, there is a slight absorption of 8l-OH near 3600 cll-'', absorption of benzene nucleus directly at 3050α-1, and 290
Absorption of 04H0 near 0 cm-”, 1600~l 3
Absorption% of ben4 nucleus at 50 tM-' 1150-100
Absorption of 81-O at 0 cm-'', absorption of Zr-0 at the bond of fi + 2 Zr-0-81 (attached to 950 crs-'') was observed, and the obtained polymer had Zr, 81. O
It is a polymer having the fC@ rating, with 81 phenyl groups in the order, and a butoxy group in the - group of Zr.

Actual example l Polycarbosilane 4Of obtained in Reference 4 Example 1 and Reference V
Weighed and collected 40 tons of polyzirconosiloxane excellent in A12, added 400 tons of xylene to this mixture to make a mixed solution consisting of a homogeneous phase, and heated it under reflux reaction while stirring at 130°C for 3 hours in a threatening gas atmosphere. became. After completing the treatment, the temperature was further raised to 200° C. to release the xylene solvent, and then electrocoupling was carried out at 200° C. for 2 hours to obtain a 4 liter polymer composite. The average molecular weight of this polymer was determined to be 3600 by the vpo method. The results of the gel/%-i-yon chromatography of this material shown in Figure 3 and the percentages of the polycarbosilane of Example 1 and the polyzirconosiloxane of Reference Example 2 shown in Figure 4 1
As is clear from the comparison of the Gel Panney i7M chromatographic results of the partially mixed product, the polymer obtained here consists of the above-mentioned polycarbosilane and polyzirconosiloxane alone (= not a mixture of the raw materials, but both of the raw materials). It is a copolymer that has a high molecular weight by reacting with a polymer.The IR spectrum of this substance is shown in Figure 1, and Figure 5.
As is clear from the comparison of the XR spectra of polycarbosilane and polyzirconosiloxane shown in Figure 6,
The polymer obtained here consists of a polycarbosilane part and a polyzirconosiloxane part, and the 81-B bond in the polycarbosilane part partially disappears, and this part is replaced by the polycarbosilane part. The silicon atoms and/or atoms are bonded to at least a portion of the zirconium atoms via oxygen atoms, thereby forming a polycarbosilane moiety and a polyzirconosiloxane moiety in a copolymer.

+8l-CH of the polycarbosilane moiety, +Zr-0+ bond of the polyzirconosiloxane moiety and +
The ratio ◆ of 81-O÷total number of bonds is 7:2.

Here, the superior copolymer is 'm element'#, - 1
The mixture was heated to 700°C for 8.5 hours and calcined at 1700°C for 1 hour to obtain a black solid mass. When x, [i powder diffraction measurements were performed on this material, as shown in Figure 8, 2θ=
(111) diffraction line of β-810 at 35.8@, 2θ=
(220) diffraction of β-810 to 60.1”- and 2#
= 72.1'Eβ-810's (311) same town solution is
Ma7 (2fJ W 33.7' l: ZrO (11
1) Diffraction lines, (200) diffraction line of ZrO at 2σ = 39.1@, (220) diffraction line of ZrO at 2# = 56.3' and (311) diffraction leg of ZrO at 2σ = 67.0@ was recognized.

In particular, each frequency fr line of ZrO is the conventional zrc+:v
Since each diffraction line is shifted to a higher angle than 20, and the lattice constant is different from that of conventional ZrO, the obtained material mainly consists of β-810 and ZrO.
Moreover, it is presumed to be a composite ferrite in which β-810 and ZrO are dissolved in -S.

Practical Example 2 600f of diphenylsilanediol and 675f of tetrakisacetylacetonatozirconium were weighed (Nikivlene and ethanol [xylene/ethanol = 4/
1 (volume ratio)] and reacted at 250°C for 30 minutes after removing the solvent, the reaction was carried out in the same manner as in Reference Example 2.
A polyzirconosiloxane in which the ratio of the total number of zirconoxane bonds to the total number of siloxane bonds was 1:2 was obtained.

This polymer 954 and polycarbosilane 40f1 obtained in Reference Example 1 were weighed (-1) and 500 g of xylene was added to this mixture.
- was added to form a mixed solution consisting of a homogeneous phase, and the mixture was stirred at 130° C. for 2 hours in a -gas atmosphere to carry out the reaction at almost reflux fM. After the reflux reaction was completed, the temperature was further raised to 200°C for 1 m degree to distill off the xylene solvent, and then the temperature was increased to 200°C for 200°C.
Time polymerization was performed to obtain an fffe metal copolymer with a number average molecular weight of 15,670.

The polycarbosilane portion of this polymer (-81-OH
, total number of child bonds versus +Zr of the polyzirconosiloxane moiety
The ratio of the total number of -0+ bonds and +81-〇+ axis bonds is approximately 7
:4.

Actual Example 3 Polycarbosilane 72F synthesized in Reference Example 1 and polyzirconosiloxane 8F synthesized in Reference Example 2 were weighed out, Penyne 4001w1/ was added to this mixture to form a mixed solution consisting of a homogeneous phase, and the mixture was heated in a nitrogen atmosphere. Then, conduct the 1itIIt reaction at 0°C for 6 hours with stirring.

After the reflux reaction was completed, the mixture was further heated to release benzene t-W, and then polymerization was carried out at 250° C. for 1 hour to obtain an organic gold steel copolymer having a number average molecular weight of 8,160. The obtained polymer was a uniform transparent resinous material. The ratio of the total number of +8l-CH and child bonds in the polycarbosilane moiety to the total number of ÷zr-o+ bonds and +81-O child bonds in the polyzirconosiloxane part of this @-like material is about 31:1.

[Brief explanation of the drawings] Figure #1 shows the gel pern knee chromatography (cipo) of the polycarbosilane of Reference Example 1, Figure 2 shows the Gpo of the polyzirconosiloxane of Consideration Example 2, and Figure 3 shows the real image of the polycarbosilane of Reference Example 1. Example 1O The epo of the organometallic copolymer of the present invention, FIG. 4, is determined by GPO of a mixture of the polycarbosilane of Reference Example 1 and the polyzirconosiloxane of Reference Example 2 in a weight ratio of 1:1. 1g
Figure 5 shows the infrared absorption spectrum (IR) of the polycarbosilane of Reference Example 1, and Figure 6 shows the IR% absorption spectrum of the polyzirconosiloxane of Reference Example 2. The combined IR is Ruru. Figure 8 shows the organic acoustic wind copolymer of the present invention of actual mfljl.
It is an Ox-axis powder diffraction diagram of a composite longitudinally solidified material obtained by C2, which is calcined at 1'700° C. in air. Patent applicant Special Inorganic Materials Research Institute Maza S Koshisan Co., Ltd. Engraving of drawings (no changes in content) S elution t (ml) Figure 3 Elution t (ml) Figure 3 Elution t (ml) Spontaneous writing of procedural amendments) February 17, 1980 Commissioner of the Japan Patent Office Kazuo Wakasugi 1, Indication of the case 1981 Patent Application No. 2816 2, Name of the invention Organometallic copolymer 3, 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 Baka 15, Date of amendment order None

Claims (1)

[Claims] A number average silane moiety (A) having a fine average molecular weight of about 500 to 10,000 and a polyzirconosilane moiety (B) having a number average molecular weight of about 100 to toooo. Molecular weight is approximately too-ieoo. Liorusilane moiety (A) mainly has the formula +Si-CM,
It has a main chain skeleton consisting of structural units of ÷, and the silicon atom in the formula has 1ml of side chain groups selected from the group consisting of water bulk atoms, lower alkyl groups, and phenyl groups, and 8 Fi; - Ri V Rucono Shiro Sun part (#) Ri Zorcono Su bonding unit ÷ Zday + IL' has a main chain skeleton that is The ratio of the total number of positions is within the range of aO: to 1:80, and most of the silicon atoms of the siloxane bonding unit are side chain groups selected from the group consisting of lower alkyl groups and phenyl groups t-1m In addition, most of the zolconium atoms in the zolconium bonding unit in the zorcono have t-1 to 9 groups as side chain groups in the lower alkoxy group, phenoxy group, or acetylaceto group. #l Rikal I
At least a portion of the silicon atoms of the silane moiety (A) are bonded to at least a portion of the silicon atoms and/or the FiG/luconium atoms of the patterned polyV luconosiloxane moiety (B) via oxygen atoms. , this makes the 4 rical the silane moiety (A)
and the polysilconosilane moiety (B) are crosslinked, and +5i-CH of the polycal I silane moiety (A),
+Total number of structural units vs. (j
The ratio of the total number of r-0 bond units and 1,000 S, i-0+ bond units is in the range of 100:1 to 1:loo Hso ~
The above-mentioned organic gold 11JI is characterized in that it is melted by heating at 400'C and cooled in an organic solvent. Foreign block copolymer.