JPH0374414A - Polyfunctional diacetylene composition - Google Patents

Abstract

PURPOSE:To obtain the title composition having excellent wetting properties to a metal sulfide, good drape to the surface thereof, controlling abrupt reaction and decomposition reactivity caused by the reaction, having improved shrink characteristics of curing during molding, containing a polyfunctional diacetylene compound and a metal sulfide. CONSTITUTION:The objective composition containing a polyfunctional diacetylene compound (e.g. compound shown by formula II) shown by formula I [R and R' are 2-8C double bond-containing organic group; X and X, are-OC(O)- or-O-; A and A' are 1-6C organic group] and a metal sulfide (preferably Cu2S, CuS, ZnS, CdS, HgS, MoS2 or FeS).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a composition of a polyfunctional diacetylene compound and a metal sulfide.

[Conventional technology]

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

In order to express 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. Researchers have so far demonstrated that diacetylene compounds with high crosslinking group density and high crosslinking group reactivity can be combined with amide groups or ester groups and diacetylene groups or carbon-carbon/double bonds. We have achieved high elastic modulus by utilizing the excellent solid-state reactivity of these materials.

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

However, due to the good reactivity of the diacetylene compound, depending on the molding conditions and reaction conditions, the reaction may proceed rapidly and decompose, resulting in a serious problem in terms of safe molding. Of course, if the molding conditions were relaxed, decomposition reactions would be less likely to occur (but productivity would drop significantly. Therefore, a solution was needed that would enable stable molding without sacrificing productivity. In particular, when the diacetylene compound is liquid, it often oozes out of the mold, making it difficult to obtain a homogenized molded product.

[Problem to be solved by the invention]

The purpose of the present invention is to have excellent moldability, a small curing shrinkage rate during molding, and less likely to cause decomposition reactions during molding, and to have excellent properties (high elastic modulus, good dimensional stability) It is an object of the present invention to provide a composition of a polyfunctional diacetylene compound which can provide a polyfunctional diacetylene compound.

[Means to solve the problem]

The present inventors have already discovered that by mixing a polyfunctional diacetylene compound and an inorganic filler and molding the mixture, the polyfunctional diacetylene compound can be molded without decomposing under molding conditions that would decompose it alone. 0 who discovered and disclosed possibilities
The present inventors further found that, depending on the type of inorganic filler, it has good wettability or affinity with certain polyfunctional diacetylene compounds, which greatly improves mixing operability and stability during molding. As a result of discovering this and studying various factors related to these, the present invention was arrived at.

That is, the present invention provides a composition containing a polyfunctional diacetylene compound represented by the -111a formula (I) and a metal sulfide.

R-X-A-C-C-CmC-A'-X'-R'
(I) (Here, R and R' are organic groups having a double double bond with 2 to 8 carbon atoms, x and x' are -○C- or -○-, and A and A' represents an organic group having 1 to 6 carbon atoms.

In the present invention, the polyfunctional diacetylene compound is a polyfunctional diacetylene compound having a double bond represented by the general formula (I).

In the general formula (I), R and R' are organic groups having a double bond having 2 to 8 carbon atoms, examples of which include C
HlCH-, CHt=C-CH.

C111CHCHzCHx-, CHz=ICCHz-C
HgllCHCHgCHmCHg- CB, CH, CB, CH- CHgllCH-CI-CB- CHsCH-CI(CHg(Hg- cux*c- CI, CH bulk CHtCFls CHs-CH-CH-Ctl=CI(- In the present invention, x, x' is -0C-1-〇-, and -0C- is particularly preferred from the viewpoint of reactivity, resistance to rapid decomposition, and good properties after curing; in this case, R, A, and R' There are special bonding modes with A', and among these bonding modes are preferable in that they have good reactivity and excellent properties after curing.

A and A' represent an organic group having 1 to 6 carbon atoms, examples of which are -CHg-, +CH+I +r.

+CH8+T, +CH! -h-, +C118-)-r,
+C118+rCRvCHCHt- is preferred, especially C
) I-C) I-, CH Tomi-C- are preferable because they cause a rapid reaction during molding and curing, and especially increase the reactivity of the diacetylene group, and -CI(,-) is preferable. be.

In the present invention, for the synthesis of the diacetylene compound represented by the general formula (I), the synthesis methods shown in JP-A-62-267248, JP-A-62-267251, etc. can be applied. .

In the present invention, metal sulfides include Cu, Ag, Z
n.

C+L Fig, Sn+ Pb, Sb, Ta,
Cr+ Mo, W, Mn+ Fe, Co, Ni
IB, 2B, 4B, 5B, 6A, 7 of the periodic table of elements such as t
One or more sulfides of metals belonging to Group A, Group 8, etc., preferably CuzS, CuS, AggS, Z
nS, CdS, IIgS, 5nSz, PbSSb! S
3+ Cr S lMo5t l WS z + M
nS, FeS, CoS, etc., particularly preferably Cu, S, CuS, ZnS, CdS+)I
gs, MoS, and FeS. These metal sulfides have good wettability with the polyfunctional diacetylene compound of the present invention, and the metal sulfide can be dispersed in a large amount of the polyfunctional diacetylene compound, or conversely, the polyfunctional diacetylene compound can be dispersed in a large amount. It has excellent workability when attached to metal sulfides, and when it is processed into molded rods, the polyfunctional diacetylene compound is less likely to leak out or be unevenly distributed.

In the m-acid of the present invention, the ratio of metal sulfide is 2 to 98% of the total amount of metal sulfide and polyfunctional diacetylene compound.
% by weight, and in order to significantly suppress the rapid reaction and accompanying decomposition, the metal sulfide preferably contains 5% by weight or more,
Furthermore, the amount of the metal sulfide is preferably 10% by weight or more, particularly preferably 20% by weight or more.On the other hand, when obtaining a dense molded piece as a cured molded article by curing the polyfunctional diacetylene compound, the metal sulfide is preferably 90% by weight or more. % or less, particularly preferably 85% by weight or less.

The composition of the polyfunctional diacetylene compound and metal sulfide can be dispersed, mixed, or deposited using various existing mixing devices and techniques. A method of kneading with a kneading machine with a kneader or mixing while crushing with a kneader, or a method of dissolving a polyfunctional diacetylene compound in a solvent, emulsifying or suspending it, and mixing it with the metal sulfide. A method in which the metal sulfide is dispersed in a liquid dispersant and a polyfunctional diacetylene compound is added thereto and mixed. How to keep sulfides present,
Conversely, a method can be used in which a polyfunctional diacetylene compound is present or mixed into the production system when producing a metal sulfide.

In particular, since metal sulfides tend to coalesce as extremely fine suspensions, one of the excellent methods is to mix them with a polyfunctional diacetylene compound in the production system.

In the composition of the present invention, as components other than the polyfunctional diacetylene compound and metal sulfide, stabilizers against heat and light,
Reaction initiators and inhibitors for promoting or inhibiting the reaction of polyfunctional diacetylene compounds, additives for improving the fluidity and processability of the assembled product, and adjusting the properties of formed rods, For example, plasticizers, thermoplastic polymers, solvents and dispersants,
Ceramic or metal powders other than sulfides may be blended.

〔Effect of the invention〕

The polyfunctional diacetylene composition of the present invention has good wettability with metal sulfides, blends well with the surface thereof, and can suppress rapid reactions and accompanying decomposition reactivity, which are problems of polyfunctional diacetylene compounds. When the composition (2) and (20) is cured and molded, the curing shrinkage during molding is greatly improved, and the resulting molded rod is a bottom-shaped material with good elastic modulus and excellent homogeneity.

For this reason, it can not only be used for precision machine parts, coating agents, etc., but also the inherent properties of metal sulfides can be effectively utilized. , and m-acids have improved friction and wear resistance, making them extremely useful as industrial materials.

〔Example〕

The present invention will be explained below with reference to examples, but it goes without saying that the present invention is not limited to the following examples.

Example 1 (I) CH*-CHC00CIb=C[I 1+
+oj! with CuC10,1-01 and pyridine 300
After the reaction was carried out for 5 hours while blowing oxygen in d, the reactant was poured into cold concentrated hydrochloric acid, extracted with ether, dried with sulfur salt, concentrated, and a liquid polyfunctional diacetylene compound was obtained. (CHz-CIICOOChC mid-h was obtained. The structure of the obtained compound was confirmed by IR and NMR spectra.

(2) Cadmium sulfate (CdSO4・-11,O) 7
When 20.5 g of ammonium sulfide is added to 6.8 g of an aqueous solution, cadmium sulfide (CdS) precipitates. After washing it with water, it is dispersed in water and passed through Has gas to become a transparent glue-like liquid.

(3) (C11g-CRCOO obtained in (I)
A methanol solution of 20 g of CH*-C+r- was vigorously stirred with a homogenizer, and this and the C obtained in (2)
Mix the dS solution little by little and precipitate. After all the amounts were mixed, the mixture was further stirred for 1 hour while blowing in nitrogen to obtain a homogeneous powder mixture precipitate, which was separated from the supernatant liquid and dried under reduced pressure.

A portion of the resulting composition was separated and weighed, extracted with chloroform to remove the polyfunctional diacetylene compound, and then the chloroform was removed under reduced pressure and the remaining CdS was measured. It was found that the amount was about 69% by weight, which is almost the same as the value, and that the adsorption and mixing were good.

This composition was suddenly heated to 200 k by using a heat press machine.
Compression molding was carried out at 170° C. for 4 hours under a pressure of g/cj, but a good molded product with no rapid decomposition and no cracks was obtained.

Example 2 Using the same method as in Example 1 (I), a polyfunctional diacetylene compound (C old-C-COO-CHm-C-
C+rHs was synthesized.

Using 25 g of this polyfunctional diacetylene, (
2). The same operation as in (3) was carried out to obtain a powdered m-acid containing about 64% by weight of CdS, and in this case, a good molded product was obtained without any rapid decomposition reaction or cracking due to curing shrinkage. Obtained.

Examples 3 to 6 The polyfunctional diacetylene compounds of Example 1 were synthesized.

The same composition as in Example 1 was prepared by changing the amount of this polyfunctional diacetylene compound to 10 g, 20 g, 30 g, and 50 g, and a uniform powdery composition was obtained in each case.

The Cd50 compositions are almost the same as the theoretical values of the preparations, which are 81% by weight, 69% by weight, 59% by weight, and 45% by weight, respectively, and all of them do not decompose rapidly even if suddenly exposed to high temperatures of 170°C. Hardening occurred without any hardening. Breath molding was carried out under a pressure of 500 kg/d, and good molded rods with no cracks were obtained in all cases.

Example 7 (I) Zinc sulfate (ZnSOa 4 former 0) 100
ZnS was precipitated by adding 25 g of ammonium sulfide to the aqueous solution. After removing the supernatant liquid of the precipitate and washing it, Has gas was introduced to obtain a gelatinous solution of ZnS.

(2) Polyfunctional diacetylene compound synthesized in (I) of Example 1 (Cl1g -CHCOOCH*-CmiC-h-
Dissolve 30g in acetone and add this and the ZnS obtained in (I)
The mixture was mixed with the gelatinous liquid using a homogenizer while being stirred, and stirring was continued for 1 hour while passing N-rich gas through the mixture.

The resulting precipitate was separated from the supernatant and dried under reduced pressure.

After separating and weighing a portion of the composition obtained in this way, the polyfunctional diacetylene was extracted and removed with chloroform, the chloroform was evaporated under reduced pressure, and the remaining CdS was weighed. When the CdS content was determined, it was found to be 53% by weight, which is almost the same as the theoretical value based on the amount charged.

20 Composition is 170″C1200kg by heat press
Even when pressure molding was performed at /cJ, no rapid decomposition occurred and a good molded product without cracks was obtained.

Example 8 As a polyfunctional diacetylene compound (CHm-CI-Coo-CHm-C”C→7 20
The same operation as in Example 7 was performed using g and. The resulting composition was a semi-solid substance with some stickiness, and Zn
The S content was about 30% by weight. This is 120”C2
00kg/190 after compressing for 1 hour with CIJO heat press
After pressing at 'C for 2 hours, a good molded product could be obtained without decomposition.

Example 9 100 g of sulfuric acid steel (CuSO4.5 Hg0) is dissolved in water and vigorously stirred with a polyfunctional diacetylene compound nizer. In this forcedly dispersed system, NatSgOs j 58!0 is dissolved. 110
An aqueous solution of g is gradually added to generate CuS. After the addition was completed, the mixture was stirred for an additional hour, and then the precipitate was separated and dried under reduced pressure. This precipitate contained 60% by weight of CuS, which was approximately the theoretical value based on the charged amount. This is 1
When molded using a hot press at 70℃ and 200 kg/C4,
A good molded product was obtained without decomposition.

Examples 1O to 13 As a polyfunctional diacetylene compound (CHs-CH-COOCHt-C-C
81, another polyfunctional diacetylene compound shown in Table 1, metal sulfide powder, and toluene as a dispersion medium were mixed to form a slurry, and this was kneaded in a Nigu. Thereafter, toluene was removed under reduced pressure, and the resulting compositions were hot-pressed for 4 hours, and as a result, it was confirmed that any of the compositions could be molded without decomposition.

Comparative Example 1 When the polyfunctional diacetylene compound used in each Example was immediately heated to 150° C. or higher, a violent reaction occurred and decomposition occurred.

(Left below) Comparative Example 2 The polyfunctional diacetylene compound used in Example 3 was dissolved in chill and silica gel 42.6% was used as an inorganic substance for comparison.
After mixing g, the ethyl ether was distilled off. Press molding of this composition (81% by weight of silica gel) was attempted in the same manner as in Example 3, but the resulting product was brittle and crumbled when pressed with a little force with fingers.

Comparative Example 3 The same operation as in Example 8 was carried out using silica gel 34 instead of ZnS.
(in this case, the composition was 30% by weight of silica gel), but after the sample was placed on a press heated to 120°C, it began to decompose after a while and molding could not be performed.

Claims (1)

[Claims] A composition containing a polyfunctional diacetylene compound represented by the general formula (I) and a metal sulfide. R-X-A-C_mC-C_mC-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 numerical formulas, chemical formulas, tables, etc.▼ or -O- , A, and A' represent organic groups having 1 to 6 carbon atoms.)