JPS6396144A - Diacetylene compound having double bond - Google Patents

Abstract

NEW MATERIAL:A diacetylene compound having a double bond and composed of one or more hydrocarbon groups containing diacetylene group of formula I or formula II (R is H or univalent organic group; R<1>, R<2>, R<3> are bivalent organic group; the linking group is ether bond, ester bond, amino bond, imino bond or urethane bond) bonded with one or more hydrocarbon groups having carbon-carbon bond through one or more linking groups. EXAMPLE:The compound of formula III. USE:Useful as a crosslinkable material having excellent curing reactivity and useful in the fields of precision machinery and electronics. It has high rigidity, heat-resistance and curing reactivity. PREPARATION:The objective novel compound can be produced e.g. by condensing the compound of formula IV with the compound of formula V to obtain an ester compound having terminal ethynyl group and subjecting the ester compound to oxidative coupling reaction.

Description

Detailed Description of the Invention (Technical Field of Application of the Invention) The present invention is a novel crosslinkable material type with excellent curing reactivity (= excellent
Diacetylene compound D containing a double bond as
(This is doubled.

2 (Prior art) Haru In recent years, the synthesis of single-crystalline polymers using topochemical reactions through solid-state polymerization has attracted attention, and this method has been used to develop various highly crystalline polymers with high elastic modulus. is being attempted. (For example, R1, "Organic nonlinear optical materials", CMC (/9zaj), -Macromolecule Chemistry Volume 739, Evening Volume 72, 7th edition//@(/974t).) Intended to improve Various materials with crosslinking groups such as acetylene groups, norbornene rings, and combinations of maleimide and cyanate have been developed.

(Problems to be Solved by the Invention) However, these new crosslinking groups have drawbacks such as high reaction temperature and long molding time. Therefore, severe molding conditions are required in order to sufficiently carry out the crosslinking reaction and obtain a good molded product. The present inventors have focused on a diacetylene group as a highly reactive functional group and have studied its properties as a crosslinking group. As a result, it was discovered that a material containing diacetylene groups and double bonds in seven molecules is a material with excellent curing reactivity, and as a result of further intensive studies, the present invention was achieved.

(Means for Solving the Problems) That is, the present invention provides one or more constituent units of diacetylene group-containing hydrocarbon groups represented by the general formula +11 or [1), and a carbon-carbon double A diacetylene compound R-C≡C-C having a double bond, in which one or more structural units of a hydrocarbon group having a bond are connected via /Enoki or two or more connecting groups. ≡C-R1-...(I
1-R2-C=≡C-C≡C-R3-.-(If) (where R is a hydrogen atom or a heptavalent organic group, R1, R2, R
3 represents a divalent organic group, and the linking group is an ether bond, ester bond, amino bond, imino bond, or polyurethane bond. ).

In the present invention, R in the general formula +11 is a hydrogen atom or 7
is a valent organic group, for example, CH3-1C2H5-1
In addition, the hydrogen atom or hydrocarbon group in R may be substituted with another bond (=substituted), and the bond may be an ether bond, ester bond, amide bond, imide bond, amino bond, imino bond, valethane bond, etc. In this case, some of the hydrogen atoms of R are -tro group, hydroxyl group, ano group, carboxyl group, amino group, etc.
It may be substituted with a 10-gen atom or the like.

In the present invention (2), R1, R2, and R3 are the same or different types of divalent organic groups, and examples thereof include a complex group of alicyclic groups, and these R1, R2, Even if some of the hydrogen atoms in R3 are substituted with a 710 gen 1 atom, a nitro group, a hydroxyl group, an ano group, a carbo, xyl group, an amino group, an amide group, an ester group, a carbonyl group, an ether bond, etc. good.

In addition, the organic group may include an ether bond, a sulfonyl bond,
It may be an organic group connected by a destyl bond, a carbonyl bond, etc., and specific examples thereof will be given below.

Among these R1, R2, and R3, synthesis is preferred.

The hydrocarbon group having a carbon-carbon double bond in the present invention (= is generally a heptavalent or divalent or more hydrocarbon group having two carbon atoms/~20, examples thereof include -HC, ≡ C-1
-HC≡CH-CH≡CH-1-CH, -HC=HC-
":i>" composed of a carbon-carbon double bond such as CH2-1-occupied H3 and a hydrogen atom, or a carbon-carbon double bond such as an aliphatic group and an aromatic group.

':, ii ″''H2c=cH-1H, C≡C-1H2C≡CH-C
H, -1-HC≡CH-1-H3 The diacetylene compound of the present invention has a connecting group that connects a diacetylene group-containing hydrocarbon group and a hydrocarbon group having a carbon-carbon double bond as a constituent unit. It does not matter if the oxygen atom in the molecule is replaced by a sulfur atom. Any of these linking groups may be used, and not only seven types but also two or more types may be combined.

Furthermore, it may partially contain (=, amide bond) other than these linking groups.

As described above, the diacetylene compound of the present invention is a compound in which a diacetylene group-containing hydrocarbon group and a hydrocarbon group having a carbon-carbon double bond are bonded in one molecule (2). However, there is no limit to the number of diacetylene group-containing hydrocarbons present in the molecule. Well, again,
When included as a repeating unit, the diacetylene group-containing hydrocarbon groups may be of the same type or different types.

The diacetylene compound of the present invention has, in addition to a diacetylene group-containing hydrocarbon group and a hydrocarbon group having a carbon-carbon double bond, some of these hydrocarbon groups in addition to the hydrocarbon groups other than the constituent elements. - May be substituted with a tro group, a cyano group, a hydroxyl group, a carboxyl group, an amino group, a halogen atom, etc. Introducing hydrocarbon groups other than these constituents may have an effect in balancing curing reactivity and moldability.

In the diacetylene compound of the present invention (2), there is no particular restriction on the ratio of the diacetylene group-containing hydrocarbon group to the carbon-carbon double bond-containing hydrocarbon group, but the preferred range is that the curing reactivity is microscopic. The molar ratio is 0.2~!
It is f. Furthermore, the most minute effect is seen when the ratio is 0.3-2, which is especially preferable.

To illustrate the diacetylene compound of the present invention, HC≡
CHx CH-CH3 (OH1)HC= CH-CH2-N-CH2-C≡C
-C= C-CH2-N -CH2-HC≡CH(CH
3) -c=c-C)(,-o@Hc=cH.

Examples include oligomers and polymers having the following repeating units.

+CH2-CH≡C)l-CH2-0-CI-1, -page-C≡C-CH, -0±+CH2CH≡C)I CH2
0@Hoko c-C=≡C00-)CH,-HU=L;H.

The diacetylene compound of the present invention can be synthesized by applying and improving known organic synthesis reactions. To give an example of the synthesis method, for example, in the case of a compound containing an ester bond as a connecting group as a structural unit, an alcohol having an ethynyl group at the end (for example, HC≡C-CH
, -OH) and acid chlorides with double bonds (e.g. 1
1) is subjected to a condensation anti-CL-C-HC≡CHz reaction to synthesize an ester compound having an ethynyl group at the end (for example, H-C-CH2-O-C-HC≡CH,), and then this compound is an oxidative coupling reaction (=Therefore, a diacetylene compound can be obtained.The number of moles of the metal catalyst used in this oxidative coupling reaction (= is θ6θ7 to 7 equivalents to the substrate, and the oxygen flux is 70 to 70%) θ
θθφ is preferable. Pyridine is preferred as the solvent used in this reaction, but other solvents may also be present. There are no particular restrictions on the reaction temperature and reaction time, but preferably the reaction temperature is between -2θ and /θOC and the reaction time is in the range of 20 minutes to 72 hours. In addition, in the acid chloride having a double bond to be used, a compound having a recognized functional amyl chloride group (for example, an alcohol having a chloride group (e.g. HC≡C-CH, -OH) can be reacted with -equivalents). By this, ester compounds having ethynyl groups at both ends (e.g. HCEEC-CH, -0-C-HC=
≡CH-C-0-CH, -C≡CH) is obtained, so
If this is subjected to an oxidative coupling reaction, a polymer containing diacetylene bonds can be synthesized. In addition, a diacetylene compound (
For example, 8O-CH2-C'≡C-C≡C-CH2-O
H) Compounds having a double bond (for example, H2C≡CHc-C
t) can also be used for a condensation reaction.

Furthermore, as a reaction to generate a diacetylene group, a Cadiot-Chodkiewicz method involves brominating a compound having an ethynyl group and reacting it with another compound having an ethynyl group.
A z-coupling method can be used. This reaction is generally performed on compounds having an ethynyl group (e.g. H, C-C
When a solution of H-C-0-CH, -C≡CH) is mixed with excess amine (e.g. n-butylamine) and catalyst (e.g. 7 to 6% in molar ratio to suppress the reaction), the molar ratio is preferably 7 to 6%.

It is also necessary to add a small amount of hydroxylamine.

Furthermore, active hydrogen metalization of amino bonds and imino bonds,
A method of reacting a halide can also be used.

(Effects of the Invention) The diacetylene compound of the present invention has excellent curing reactivity due to the combination of diacetylene groups and carbon-carbon double bonds, and the cured product exhibits good heat resistance and mechanical properties.

By taking advantage of these properties, the diacetylene compound of the present invention can be used in the fields of electronic parts and precision mechanical parts that require high rigidity, heat resistance, and curing reactivity.

(Example) Next, the present invention will be specifically explained using examples.

Example / Synthesis of (H,C≡CH-CH, -0-CH2-C≡C-)2 Obtained H2C≡CH-CH, -0-CH, judicial C
H2θ1 (θhawkθJ' mot) with pyridine, 200m
1 as a solvent, cuprous chloride θ, y? (θ, θj mo
In the presence of t), oxygen was bubbled to react, and the target product was obtained.

IR: , 29! rOtyn-”, 2200 cyr-
", barOcm-", -/θriQcm-' In order to investigate the curing reactivity of this compound, in a nitrogen stream, 7
When differential thermal measurements were carried out at a heating rate of 0°C2-, a curing reaction (exothermic phenomenon due to -20°C) was observed from a low temperature.
A sample held at 0° C. for 7 hours was subjected to the same measurement, but no exothermic phenomenon due to the curing reaction was observed, indicating that curing of about 10θ had progressed.

Example H4C≡CH-CH2-0-CH, -C≡C-C≡C(
82C,, -CH-CH by the method of Synthesis Example/ of ◇
, -0-CH2-C≡CH was synthesized.

was synthesized. Next (=, this compound 20? (0, //mo
l) and Example/(=82C≡C)(-CH
,-0-CH2-C≡CH/ 0.7 f (0,/
/ mot) in ethanol solvent, cuprous chloride θ, e! ? (0,00!, t mot), NHzOH-H
C6/2.0? (0,7,2mot), n-butylamine! The target product was obtained by reacting in the presence of 2 ml.

IRH29jOcm-", 2200cm-', / '1
20cm-', /O0θcrn-'' This compound also showed almost the same curing reaction behavior as in Example.

Example 3 H2C≡CH-COO-CLJ, -C:≡C-C≡CK
◇Synthesis Propargyl alcohol and vinyl chloride are reacted in the presence of dimethylaniline to form H2C≡CH
-Coo-CH, -C''5CH is synthesized, and further Br-
C≡C (reacted in the same manner as in Example 1) to obtain the desired product.

IR:, 2? taOcm-', 220θ(m-', /7
This compound is the same as in Example (as a result of examining the second curing reactivity, the curing reaction starts at 200°C or lower, and further E It was found that by holding at 200°C for 7 hours, the reaction progressed by approximately 100 times.

Example Synthesis of (H2C≡CH-COO-CH, -Cmi-c-)-2 CH2≡CH-Coo-CH2-C≡ obtained in Example 3
CH was synthesized by the oxidative coupling method using cuprous chloride and pyridine (= in Example/).

IR: 29 0 -l, 2200 α-1, /7 ta 0
Rho1,/co90an-'' This compound also showed the same curing reactivity as Example 3.

Example j CH of Example 3, = CH-COO-CH, -C≡CH
Synthesis (Example/oxidative coupling method (=
Therefore, the target product was synthesized.

IR: 29j Ocm-", 22θOcm-', /
7ta0(7)-1, /60θt-rn-”, /2
90 cm-'' - This compound also exhibited curing reactivity similar to that of Example 3.

Example B (-OC-CH≡CH-COO-CH2-C≡C-C≡
C-CH2-0-). Synthesis Example 3 CH2≡CH-
Coo-C) 12 Synthesis of C≡CH (= CH2≡
Instead of CH-CO-CI (2Cl0C-CH≡CH-C
By using O-CL, H(jC-CH, -00
C-CH≡CH-COO--C) 12-mouth≡CH was synthesized.

Next, this is carried out by the oxidative coupling method in Example/
Obtained the object.

IR,,2ri! rOcm-1,2200cm-', /7
TaOcm-”.

/29θWound-1 When this compound was maintained isothermally at 0°C, an exothermic phenomenon was observed and a curing reaction occurred.

Example 7 82C≡C)I-CH,- is 0. /, -CH2-CH≡
CH-CH2- is 0. -0H2-C≡C-C-≡C
-CH, -wo0. Synthesis of compounds linked by teurethane bonds Distillation-purified chlorobenzene and 0-dichlorobenzene were mixed in a volume ratio of ♂O:20 (==200-20% solvent),
HO-CH, -CH≡CH-CH2-OH 2.091
(0, θ237 j mot), HO-CH2-C≡
C-C≡C-CH2-OH3. -1! 7? (0
,0297mot), H2C≡CHCH20H is 0.
3≠fv (o, oo5ql(rnot) wokaeta.

The 100rd solvent (
A solution of hexamethylene diisocyanate of 2/θ, 02 was added dropwise, and reflux was continued for 27 hours while stirring vigorously. Thereafter, when the solution was cooled to room temperature, the target product precipitated.

IR:29jθlTll-1,2200cm-', /≦
θα-1,/, f, 20's -1 C (wt) HN O calculation j/, 3 K,, 2 /3j 30.0 actual value! θ,/! , θ /4t, 03θ, Riko's compound also had curing reactivity, and the curing reaction occurred even at temperatures below 200°C.

Example ♂ Heating propargylamine in acetic acid under reflux for j hours C≡CH
was isolated. Subsequently, this compound was oxidized and dissolved in methanol, and metal sodium was added to convert it into Na. Subsequently, CH3-Br was added to obtain precipitate H3 CH2-N-H. After converting this into Na again, H
2C≡CH-CH2-Br was added to obtain the desired product.

IR: 293θcIn-”, 2-0〇crIK-’, /
41/0cvt-",/2/Ocm-",
10♂Ocm-' This compound also showed the same curing reactivity as in Example.

Claims (1)

[Claims] 1. One or more structural units of a diacetylene group-containing hydrocarbon group represented by general formula (I) or (II);
A diacetylene compound R- having a double bond in which one or more structural units of a hydrocarbon group having a carbon-carbon double bond are connected via one or more connecting groups. C≡C-C≡C-R^1-...(I)-R^2
-C≡C-C≡C-R^3-...(II) (here, R
is a hydrogen atom or a monovalent organic group, R^1, R^2, R^3
, represents a divalent organic group, and the linking group is an ether bond, ester bond, amino bond, imino bond, or urethane bond. ) 2 A patent claim in which the molar ratio of the diacetylene group-containing hydrocarbon group represented by general formula (I) or (II) to the hydrocarbon group having a carbon-carbon double bond is in the range of 0.2 to 5. A diacetylene compound having a double bond according to item 1 in the scope of