JPH0391515A - Molding of grafted inorganic substance - Google Patents

Abstract

PURPOSE:To obtain a molding having a high velocity of propagation of ultrasonic waves, high elasticity high hardness and excellent strengths, abrasion resistance and heat resistance by molding a grafted inorganic substance prepared by grafting a specified diacetylene compound onto an inorganic substance. CONSTITUTION:A grafted inorganic substance prepared by grafting a diacetylene compound of formula I (wherein R and R' are each a 2-8C double bond- containing organic group; X and X' are each formula II or O; A and A' are each a 1-6C organic group), e.g. 1,6-diacrylato-2,4-hexadiyne) onto the surface of an inorganic substance (e.g. titanium oxide) is molded. Because the diacetylene compound is grafted onto the surface of the inorganic substance, the obtained molding is controlled in rapid decomposability and curing shrinkage which are problematic in a diacetylene compound, the molding has a high velocity of propagation of ultrasonic waves, high elasticity, high hardness, excellent strengths, abrasion resistance and heat resistance, and is very useful for precision machine parts, parts related to friction or abrasion materials ultrasonic machines, electronic field, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a grafted inorganic molded article that provides a material with excellent rigidity, elasticity, hardness, coefficient of linear expansion, thermal conductivity, etc. that can be used in precision mechanical parts and electronics fields. .

[Prior Art] The present inventors have so far developed high-modulus molded bodies that are three-dimensionally crosslinked with high density using various multifunctional diacetylene compounds.

In order to express a high elastic modulus three-dimensionally by crosslinking using covalent bonds, the density of crosslinking groups must be made as high as possible, and the crosslinking groups must be reacted regularly and in high yield. The present inventors have previously developed diacetylene compounds that have a high density of crosslinking groups and are highly reactive, by combining amide groups or ester groups with diacetylene groups or carbon-carbon double bonds. By utilizing the excellent solid-phase reactivity of these materials, we have achieved high elastic modulus.

Among these, the present inventors have particularly found that the diacetylene compound having the structural formula shown in the claims has good reactivity in both the double bond and the diacetylene group.

(Problems to be Solved by the Invention) However, due to the good reactivity of the diacetylene compound, depending on the molding conditions and reaction conditions, there may be sudden changes in the field, and a big problem has arisen in terms of safe molding.

Furthermore, when the diacetylene compound is in a liquid state, it often oozes out of the mold during molding, making it difficult to provide a homogenized molded product.

An object of the present invention is to provide a molded article of a diacetylene compound that can be molded without causing such problems and that provides a material with excellent rigidity, elasticity, hardness, coefficient of linear expansion, thermal conductivity, etc. .

[Means to solve the problem]

In order to solve such problems, the present inventors have studied various inorganic substances, believing that the problem can be solved by grafting the diacetylene compound onto the surface of the inorganic substance. As a result, it was confirmed that the diacetylene compound was grafted onto various inorganic substances. Furthermore, it was discovered that an inorganic molded article grafted with the diacetylene compound provided high physical properties, and was therefore defeated by the present invention.

That is, the present invention provides a grafted inorganic molded article R-X-^-c, cc, c-^'-X"-R' in which a diacetylene compound represented by format (1) is graft-polymerized on the surface of an inorganic material. −・−
------- (I) (Here, R and R'' are organic groups having a double bond of 2 to 8 carbon atoms, x, x'
is 10C- or -0-, and A and A'' represent an organic group having 1 to 6 carbon atoms.

In the present invention, the inorganic substances used include metals, metal oxides, sulfides, carbonates, phosphates, carbon black such as carbon black, carbon fiber, graphite, carbon whiskers, etc., and these have functional groups. It is more preferable if it has a functional group, such as a hydroxyl group, a carboxylic acid group, a sulfonic acid group, etc., and examples of inorganic substances having a functional group include metal oxides, sulfides, carbon black, Carbon fiber, carbon whiskers, etc.

In the present invention, when a diacetylene compound is graft-polymerized onto the surface of an inorganic material, it is possible to perform graft polymerization directly from the surface of the inorganic material using a catalyst or activator, or by using a functional group on the surface of the inorganic material. A method in which the material is graft-polymerized, and a method in which the material is once treated with a functional coupling agent such as a silane coupling agent or a titanium-based coupling agent, and then graft-polymerized.
Particularly preferred is a method in which a radical initiator such as an azo group is added and graft polymerization is carried out therefrom.

In the method using a silane coupling agent, the silane coupling agent used may be a commonly used silane coupling agent, such as vinyltriethoxysilane, vinyltrimethoxysilane, T-methacryloxypropyltrimethoxysilane, These include cidoxypropyltrimethoxysilane, T-glycidoxypropylmethyljethoxysilane, and the like. In addition, when adding a radical initiator, for example, 4,4'-azobis(4-cyanovaleric acid), 1,1'-azobis(cyclohexane-1-
carbonitrile), 2,2'-azobis(2°4-dimethylvaleronitrile), and the like.

In the present invention, the diacetylene compound to be grafted onto the surface of an inorganic substance is a diacetylene compound represented by the -format (1), where R and R' are organic compounds having a double bond of 2 to 6 carbon atoms. Base CH.

CHg=CHGHz- CH, Cl=CH- CH:1C1l=CHCHI CHz=(IICHt-CHz- CH3 (Ih=CCHz C)lz=cHcHzclI□C1l!-C1hCH=
CHC1hCHz- CH,=C- C)IgcHzcHzcIhC)I, (Il□(I(=CH), etc., are preferred, and considering ease of synthesis, CH: I CB□・C) I-, CH2=C- are preferred.

0 111 Also, X and X' have -oc- and -0-te -0C-
In the case of , there is no particular restriction on the bonding mode between R and A and between R' and A'.

^, A' represents an organic group having 1 to 6 carbon atoms, examples of which are -CHz-, -C-Ctlz -)y,
+CHI +r+CHz+r, +CH2-)7-,-(
-cut+-r, -CH (-
C11□- is preferred.

In the present invention, for the base of the diacetylene compound represented by the form (1), for example, JP-A No. 62-267
The base can be easily produced in high yield using the synthesis methods disclosed in Japanese Patent Application Laid-open No. 248 and Japanese Patent Application Laid-Open No. 62-267251.

Further, purification can also be carried out by conventional chromatography, distillation, recrystallization, etc.

In the present invention, when graft polymerizing a diacetylene compound onto an inorganic substance, various known graft polymerization methods can be used. Graft polymerization can be carried out by heat treatment for a certain period of time in an atmosphere free of carbon dioxide.

As for the vacuum sealing method, the usual vacuum sealing tube method can be used.For small-scale experiments, put the inorganic substance and diacetylene compound into a glass ampoule tube, then vacuum seal it, and then transfer it to the glass ampoule tube. A method of welding is easily used. Industrially, it can be carried out using a stirring tank under vacuum or under an inert gas atmosphere such as nitrogen or argon.

The reaction temperature is not particularly limited and can be selected depending on the reaction mode, but is generally preferably in the range of 10'C to 200°C, more preferably 0'C to 130°C in view of the reactivity of the diacetylene compound. In addition, the reaction time is not particularly limited, but is preferably 0.5 to 24 hours.After the reaction is completed, the reaction product is repeatedly extracted and washed with an organic solvent such as methanol, ether, acetone, dimethyl sulfoxide, etc. After drying, the grafted inorganic substance can be obtained.

The dried grafted inorganic material may be used as it is or mixed with the diacetylene compound, other resins, rubbers, etc., and then subjected to compression molding, injection molding, or after shaping, vacuum bag method, autoclave method, etc. A molded article of the grafted inorganic material can be obtained by a method of molding after post-treatment with.

The obtained molded article has an elastic modulus of 15 GPa or more, preferably 20 GPa or more, and most preferably 30 GPa or more. The Vickers hardness of the molded article is 80 or more, preferably 120 or more, and most preferably 150 or more. Moreover, the ultrasonic propagation speed of the molded body is 3800 m/s
The above is extremely high, especially 4000 w/s or more.

〔Effect of the invention〕

By graft polymerizing a diacetylene compound onto the surface of the inorganic material, the grafted inorganic molded article of the present invention can suppress rapid decomposition and curing shrinkage, which are problems of diacetylene compounds, and further improve the quality of the molded article. Features include extremely high ultrasonic propagation speed, high elasticity, and high hardness.
In addition, since it has excellent strength, wear resistance, and heat resistance, it is extremely useful for precision mechanical parts, parts related to friction and wear materials, ultrasonic-related mechanical parts, parts related to the electronics field, etc.

〔Example〕

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.

Example 1 Using titanium oxide manufactured by Wako Pure Chemical Industries as an inorganic material and a 5% toluene solution of T-glycidoxypropyltrimethoxylane as a silane coupling agent, treatment was performed by stirring at a temperature of 120"C for 8 hours. did.

Furthermore, after washing with methanol, it was dried at 100°C for 24 hours. Next, an azo group was introduced. 4 as an azotizing agent
, 4′-azobis(4-cyanovaleric acid),
Using a small amount of α-picoline and dimethyl sulfoxide as a solvent, the mixture was reacted with stirring at a temperature of 50'C for 6 hours. After the reaction was completed, it was washed with methanol and vacuum dried at room temperature for 48 hours. 25g of titanium oxide surface treated in this way
and 1-6 diacrylate 2 as a diacetylene compound.
-4 Hexadiine 50g was placed in a flask, and under vacuum, 7
The reaction was carried out at a temperature of 0'C for 2 hours. After the reaction was completed, it was washed with acetone and vacuum dried at room temperature for 48 hours.

Grafting was confirmed by analysis using an IR, TG/DTA thermogravimetric analyzer, and the amount of deposits was observed at a yield of 56%.

Next, using a mold with a diameter of 60 mm, 25 g of grafted titanium oxide was charged into the mold, and 200 kg of the grafted titanium oxide was placed at room temperature.
It was compression molded at a pressure of /cd and shaped into a 60φ disc. Further, a disk shaped into a 60φ disk was impregnated with a diacetylene compound, and then heat treated in an autoclave at a temperature of 130° C. for 5 hours.

As a result of measuring the mechanical properties of the obtained molded body, high physical property values such as an ultrasonic propagation velocity of 4100 m 2 /s, an elastic modulus of 38 GPa, and a Vickers hardness of 200 were obtained.

Comparative Example 1 As an inorganic substance, titanium oxide manufactured by Wako Pure Chemical Industries, Ltd., which is the same as in Example-1, was left untreated without being grafted, and l-6 diacrylate 2-4 hexadiyne was added at a weight fraction of 20:80. Then, 25 g of the mixture was put into a 60 φ mold and compressed for 5 minutes at a pressure of 200 kg/aa at room temperature to form a 60 φ disc. This was further heat treated in an autoclave at a temperature of 130°C for 5 hours. As a result of measuring the physical properties of the obtained molded body, the ultrasonic propagation velocity 2
600ta/ss elastic modulus 15GPa, Vickers hardness 6
5, which was a lower physical property value than that of the grafted material.

Example 2 20 g of grafted titanium oxide obtained by using the same materials and the same grafting method as in Example 1 and 5 g of 1-6 diacrylate 2-4 hexadiyne were mixed with stirring using ether as a solvent. The ether was distilled off. A mixture of grafted titanium oxide and a diacetylene compound was compressed into a disk shape using a 60φ mold at a pressure of 50 kg/d. The obtained disc-shaped material is further added to lQQQkg/cJ.
Heat treatment was performed at 160°C for 1 hour under a pressure of . As a result of measuring the physical properties of the obtained molded body, the ultrasonic propagation velocity was 4740w/
s, elastic modulus of 45 GPa, and Vickers hardness of 250.

Comparative Example 2 A molded body was obtained using the same untreated titanium oxide as in Comparative Example 1 as the inorganic substance and by the same mixing and molding method as in Example 2.

As a result of measuring the physical properties of the obtained molded article, the physical properties were as follows: ultrasonic propagation velocity: 3100 m8, elastic modulus: 18 GPa, bit strength hardness: 78.

Example 3 The same grafting and molding method as in Example 2 was carried out except that zirconium oxide was used as the inorganic substance.

As a result of measuring the physical properties of the obtained molded article, high physical property values such as an ultrasonic propagation velocity of 4800+w/s, an elastic modulus of 54 GPa, and a Vickers hardness of 280 were obtained.

Comparative Example 3 The same molding method as in Example 3 was carried out, except that the same zirconium oxide as in Example 3 was used as an inorganic substance without being grafted and untreated. The physical properties of the obtained molded article were an ultrasonic propagation velocity of 2900 m/s, an elastic modulus of 20 GPa, and a Vickers hardness of 98.

Example 4 The grafting and molding methods were carried out in the same manner as in Example 2, except that aluminum oxide was used as the inorganic material. As a result of measuring the physical properties of the obtained molded body, high physical property values such as an ultrasonic propagation velocity of 468 m/s, an elastic modulus of 35 GPa, and a Vickers hardness of 260 were obtained.

Comparative Example 4 The same molding method as in Example 4 was carried out except that the same aluminum oxide as in Example 4 was used as an inorganic substance without being grafted and untreated. As a result of measuring the physical properties of the obtained molded body, the ultrasonic propagation velocity was 3100++/s, and the elastic modulus was 19 GPa.
, the physical property value was 90 in Vickers hardness.

Claims (1)

[Scope of Claims] A molded product of a grafted inorganic material obtained by graft polymerizing a diacetylene compound represented by the general formula (I) onto an inorganic material R-X-A-C≡CC≡C-A'-X'-R'... ......
(I) (Here, R and R' are organic groups having a double bond with 2 to 8 carbon atoms, and X and X' are ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or -O- (A and A' represent organic groups having 1 to 6 carbon atoms.)