JPH0337213A - Diacetylene composition - Google Patents

Abstract

PURPOSE:To produce a diacetylene composition which excels in stability, moldability, etc., and can give a molding excellent in modulus, strengths, dimensional stability, etc., by mixing a specified diacetylene compound with a whiskery polymer. CONSTITUTION:A diacetylene compound of formula I (wherein R and R' are each a 2-10C double bond-containing organic group; X and X' are each a bonding group selected from among amide, ester, ether, amino, imino and imide bonds, and A and A' are each a 1-8C organic group) (e.g. formula II or III) is mixed with whiskers of a polymer (e.g. polyoxymethylene or 1,6- bisethylurethane-2,4-hexadiyne polymer) to produce a diacetylene composition. The obtained composition can be desirably used for precision machine parts, coating materials, adhesives, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a diacetylene compound that has excellent moldability and is less susceptible to decomposition reactions during molding.

(Prior art and its problems) As a curable diacetylene compound that exhibits a high level of performance, a compound represented by -Monken (I) is currently known (Japanese Patent Application Laid-Open No. 63-9144). .

These compounds have a high density of crosslinking groups and are characterized in that both the double bond and diacetylene group of the crosslinking groups have good reactivity.

However, due to the good reactivity of these diacetylene compounds with a high density of crosslinking groups, rapid decomposition may occur depending on the molding conditions and reaction conditions, which poses a serious problem in terms of stable molding.

Of course, if the molding conditions are made milder, decomposition reactions will be less likely to occur, but productivity will drop significantly. Therefore, a solution was needed that would enable stable molding without sacrificing productivity.

(Problems to be Solved by the Invention) An object of the present invention is to provide a diacetylene composition that has excellent moldability, is difficult to cause a decomposition reaction during molding, and has stable moldability.

(Means for Solving the Problems) That is, the present invention provides a diacetylene composition 1? comprising a diacetylene compound represented by the symbol (I) and a polymer whisker-like substance. -X-A-CEC-C≡C-A'-X'-R'...
...(I) (Here, R and R' have carbon numbers of 2 to IO
is an organic group having a double bond, X, A' represents an organic group having 1 to 8 carbon atoms. ).

In the present invention, X and X' are one or two linking groups selected from an amide bond, an ester bond, an ether bond, an amino bond, an imino bond, and an imide bond;
Amide bonds are preferred in terms of heat resistance, resistance to rapid decomposition, and excellent properties after curing, and are preferred in terms of operability, reactivity, resistance to rapid decomposition, and properties after curing. is preferably an ester bond.

In the present invention, when X and X' are an amide bond, an ester bond, an ether bond, an amino bond, or an imino bond, R,
R' is a monovalent organic group having 2 to 10 carbon atoms and having the same or different double bonds; examples thereof include C1l□
=CH-, Cl5CII=CH-.

CH3C1hCII=CH-, CIhCHzCHzCH
=CII-, cHz・C~.

C) 13 CHzCll-C-, CI (z=C-, Cl1z=C-
, C11z=C-C11-CI-.

CH3C2H5C3H? C4H9 is preferable in that it has good reactivity, is unlikely to cause rapid decomposition, and has excellent properties after curing, and furthermore, considering ease of synthesis, Clz=CH- and CHz.C- are preferable.

CHl In the present invention, when x and x' are imide bonds, R and R' are divalent organic groups having a double bond having 2 to 1 carbon atoms, examples of which include. When a high degree of heat resistance of the cured product is required, it is preferable to use such an imide bond.

In the present invention, A and A' each represent a divalent organic group having 1 to 8 carbon atoms, such as -C1,-.

+CHrh-, +CHr)y, +CHz+T-
, +CHt+T.

CH.

In particular, -CI! increases the reactivity of the diacetylene group and is easy to synthesize! -, -CH- In the present invention, the method for synthesizing compound (I) used is a method already disclosed by the present inventors (for example, JP-A-6
2-267248, Japanese Unexamined Patent Publication No. 62-267251, etc.) can be applied.

Specifically, if a compound contains an ester bond as a linking group (X or The acid chloride (e.g. 1, Cf -C-HC=CH) is subjected to a condensation reaction to synthesize an ester compound having an ethynyl group at the end (e.g. ○1, CHmiCCHz OCHC=CH2), and then this A compound can be converted into a diacetylene compound by an oxidative campling reaction. The number of moles of the metal catalyst used in this oxidative coupling reaction is 0.01 with respect to the substrate.
~1 equivalent, and the flow rate of oxygen is preferably 10 to 1000 d/min. Pyridine is preferred as the solvent used in this reaction, but other solvents may also be present.

The whisker-like polymer of the present invention has a highly crystalline needle-like form such as single crystal or polycrystal, and although it cannot be generalized depending on the type and properties of the polymer,
Generally the length to diameter ratio (L/D) is at least 5
These are the above, and those of 10 or more are more preferable. As for the size of the whisker-like material, the smaller the whisker-like material is three-dimensionally, the easier it is to control the reaction during curing, and the better the improvement effect as a composition. For this purpose, the dimension in the minimum direction is preferably 0.5 ms or less, more preferably 0.2 wm or less, most preferably 0.0
This is a case where objects with a size of 5- or less are present in whole or in part. In addition, in order to utilize the reinforcing effect of the whiskers on the mechanical properties of the formed rod, it is better for the whiskers to have a certain size, and the maximum dimension is preferably 0.1
This is a case where there is a whole or a portion of objects with a size of 0.5 cm or more, more preferably 0.25 cm or more, and most preferably 0.5 cm or more. Also in this case, L/D is preferably 5 or more, more preferably 10 or more.

The whisker-like polymer of the present invention may have a chemical structure,
There are no restrictions on the preparation method, etc. Examples of whisker-like polymers include polyoxymethylene, polyoxybenzoate, poly(2-oxy-naphthoyl), poly(I,6-dicarbazol-9-yl-2,4-hexadiyne), poly(I, 6-bisethylurethane-2
Examples include diacetylene polymers such as 4-hexadiyne) and poly(I,6-bisphenylurethane-2,4-hexadiyne).

In the present invention, the preparation of polymer whiskers consists of
This can be done using generally known methods. That is, for whisker-like substances such as polyoxymethylene, polyoxybenzoate, and poly(2-oxy-naphthoyl), the whisker-like substances of the polymer are directly produced by solution polymerization. Regarding various polydiacetylene whiskers, since it is difficult to directly obtain polymers, polymer whiskers can be obtained by first preparing heptanomer whiskers and then polymerizing the obtained whiskers. It will be done.

Specifically, the whisker-like substance of polyoxymethylene is
It is obtained by cationic polymerization in a trioxane solution using BF3/H,O as a catalyst. Needle-shaped crystals of polyoxybenzoate can be obtained when liquid paraffin or triethyl biphenyl is used as a solvent. Moreover, poly(2-oxy-6-naphthoyl) can be obtained into a polymer whisker-like material by using liquid paraffin.

Several methods can be used to prepare monomer whiskers to produce various polydiacetylenes, but a typical method is recrystallization in a common solvent such as toluene, benzene, hexane, dioxane, or acetone. This is the way to do it.

The resulting monomer whiskers are polymerized by conventional methods using heat, ultraviolet light, ionizing radiation, and the like.

Among these, polyoxybenzoate and various polydiacetylenes are preferred from the viewpoint of adhesiveness between whiskers and the matrix. Among polydiacetylenes, whisker-like polydiacetylenes such as 1,6-(bisethylurethane)-2,4-hexadiyne, which do not have large side chains, are particularly preferred.

In the present invention, there is no particular restriction on the content ratio of the diacetylene compound represented by -pattern (I) and the whisker-like substance of the polymer, but if the content ratio of the whisker-like substance is small, the diacetylene compound There may be cases where the effect of suppressing rapid decomposition reactions is not sufficient. Also,
If the content of the diacetylene compound in the matrix is small, problems may arise in the adhesion between the diacetylene compound in the matrix and the whisker-like substances in the polymer. The content of whiskers is 2 to 95% by weight, more preferably 5 to 90% by weight, and most preferably 15% by weight, considering that the molded rod has excellent elastic modulus and strength.
~85% by weight.

In the present invention, there are no particular restrictions on the method for preparing the composition, but for example, the diacetylene compound and the filler are mechanically kneaded as they are, or the diacetylene compound is dissolved in a solvent, the filler is added, and the mixture is stirred. , a method of distilling off the solvent, etc.

(Effects of the Invention) The diacetylene compound or compound of the present invention is a composition that has both stability and good moldability. In addition, compared to compositions containing inorganic substances, the adhesion between the matrix diacetylene compound and polymer whiskers is excellent, and compared to compositions containing ordinary organic polymers, the elastic modulus and strength are improved. An excellent molded article can be obtained.

Therefore, the molded article obtained from the composition has strength,
It has excellent elastic modulus and dimensional stability, so it can be used in precision mechanical parts and electronics fields. Furthermore, since it has high hardness, it is extremely useful for coating materials, adhesives, sealants, resins for substrates, etc.

(Example 1) CIlz=CtlCOOCIIzC≡1 mol of CH was reacted with Cu C10,1o+ol in 300 mn of pyridine for 5 hours while blowing oxygen. After the reaction, the reaction mixture was poured into concentrated hydrochloric acid, extracted with ether, dried with sulfur salt, and concentrated to form a liquid (CHz=CllCOOCl).
lzC:C→T was obtained.

The structure of the obtained compound was confirmed using IR and NMR spectra.

The obtained (C)IZ=C1lCOOCH□C≡C)-
x and whisker-like polymers shown in Table 1 were mixed at a predetermined ratio to obtain the diacetylene composition.

Next, 5 g of the obtained composition was vacuum sealed and compressed in a press at 200 kg/cm at 150° C. for 14 hours to obtain a molded body.

Next, the obtained molded body was cut with a diamond cutter for 5
A rod-shaped object measuring 5 x 40 mm was cut out, and its elastic modulus was measured using DSS-500 manufactured by Shimadzu Corporation.

The presence or absence of decomposition during molding was also investigated.

The preparation of the polymer whisker-like material used here was as follows: 1
,6-dicarbazol-9-yl-2゜4-hexadiyne with acetone, 1゜6-(bisethylurethane)-2,4-hexadiyne with toluene, and 1.6-(bisphenylurethane)-2. ,4
-Hexadiyne was recrystallized with dioxane to obtain whisker-like monomers. The obtained monomer whisker-like material was polymerized by heating under a nitrogen stream to obtain a polymer whisker-like material.

The results are shown in Table 1.

Here, poly-DCHD in Table 1 represents a polymer whisker-like substance of 1.6 dicarbazol-9-yl-2,4-hexadiyne, and po131-EUHD represents 1
．． 6-(bisethylurethane)-2,4-hexadiyne polymer whisker-like substance, poly-PUH
D represents a polymer whisker of 1,6-(bisphenylurethane)-2°4-hexadiyne.

This is also expressed in the following examples.

Margin below Ne Decomposition occurred during molding.

nothing during molding No decomposition occurred.

(Example 2) As a diacetylene compound, CH:1 (CHz=CCOOC)lzcEc)r(DAc compound 2) (CHg=CHCOOCHzCHzC≡Ch (D
Ac compound 3) (CII, CHCII!0CH1C≡C
)r (DAc compound 4) (C1hCHI=CH
CHiOCHzC≡C+-r (DAC compound 5) (
C) r (D
An experiment similar to Example 1 was conducted using Ac compound 6). However, the temperature and molding time when molding the composition using a press were varied depending on the compound.

The results are shown in Table 2 along with temperature and molding time.

In some examples, experiments similar to those in Example 1 were conducted using 1% benzoyl peroxide. The results are also shown in Table 2.

The blank table * below shows a system in which lil % of benzoyl peroxide was added (Example 3). Hz
=CHCtbOC1lzC≡C)r(CHsCH=CH
CHzOCHzC=C-)r(CHz=CHCONHC
Using a mixture of HzC≡C+-r (DAc compound 1) (DAc compound 2) (DAc compound 3) (DAc compound 4) (DAc compound 5> (DAc compound 6) at a predetermined ratio, Example 1 and A similar experiment was conducted, except that the molding temperature and molding time when pressing the composition were varied.

The results are shown in Table 3 along with molding temperature, molding time, and mixing ratio.
It was shown to.

table

Claims (1)

[Claims] A diacetylene composition comprising a diacetylene compound represented by the general formula (I) and a polymer whisker. R-X-A-C≡C-C≡C-A'-X'-R'...
...(I) (Here, R and R' have 2 to 10 carbon atoms
is an organic group having a double bond, X and X' are one or two linking groups selected from amide bond, ester bond, ether bond, amino bond, imino bond, and imide bond; A' represents an organic group having 1 to 8 carbon atoms. )