JPH0714979B2 - Diacetylene polymer - Google Patents

Description

TECHNICAL FIELD OF THE INVENTION The present invention relates to a diacetylene polymer,
More specifically, it relates to a soluble diacetylene-based polymer which can be a highly cross-linked material having a high elastic modulus.

[Prior art]

The inventors of the present invention have produced and developed a high elastic modulus molded product by three-dimensionally or two-dimensionally cross-linking it at high density using a compound having a diacetylene group, and have hitherto developed various functional diacetylenes. Have synthesized compounds.

In order to express a high elastic modulus three-dimensionally by cross-linking using a covalent bond, the cross-linking group density must be as high as possible and the cross-linking groups must be reacted regularly and in high yield. The present inventors have so far developed a diacetylene-based compound having a high cross-linking group density and a high cross-linking group reactivity without impairing the chemical stability of the compound. -It has been made possible by combining carbon double bonds, and high elastic modulus has been achieved by utilizing the excellent solid-phase reactivity of these materials. However, since the solid-state reactivity of the diacetylene compound is utilized, it is difficult to apply wet molding or melt molding as the molding method, and most of them are powder molding, and it is extremely difficult to improve moldability. It was very difficult.

On the other hand, in a liquid thermosetting resin represented by an epoxy resin, various molding methods can be used, and compounding can be easily performed. Therefore, if a liquid diacetylene compound is used, the moldability is improved, but it is generally known that the reactivity of the diacetylene compound in the liquid state is small (“polydiacetylene” NATO ASI series E Applied Science). .

Therefore, the present inventors have synthesized various liquid diacetylene compounds, and as a result of examining their moldability, reactivity, and mechanical properties,
It was found that the diacetylene compound having a double bond represented by the general formula (II) has high reactivity, but there was a problem that the reaction was too violent and decomposition was caused depending on the reaction conditions.

[Problems to be solved by the invention]

An object of the present invention is to provide a reactive diacetylene polymer having excellent moldability and free from problems such as decomposition during crosslinking and molding.

[Means for solving problems]

That is, the present invention provides a diacetylene polymer represented by the general formula (I) and having a number average molecular weight of 1100 to 5000.

(Where R, R ', R "are -H or -CH ₃ and R, R',
R ″ does not become −CH ₃ at the same time. X and X ′ are Or in --CH ₂ O--, in each case the oxygen atom is A,
Bind to A '. A, A _{'are, -CH 2 -, - CH 2} CH 2 - or -CH ₂ CH ₂ CH ₂ - in which).

In the present invention, R, R ', R "is an -H or -CH ₃ R, R', R" is not a -CH ₃ simultaneously. (R, R ′,
As the combination of R ″), (—H, —H, —H) and (—H, —H, —CH ₃ ) are particularly preferable in that they have high reactivity.

In the present invention, X and X ′ are Or -CH ₂ is O-, the oxygen atom in both cases, A,
Bind to A '.

In the present invention, A, A 'is _{-CH 2 -, - CH 2 CH} 2 - or -
CH ₂ CH ₂ CH ₂ -, and particularly enhance the reactivity of the diacetylene group, -CH ₂ in terms of easy synthesis - are preferred.

The polymer of the present invention can be synthesized by reacting one double bond of the diacetylene compound (II) as the raw material.

Regarding the synthesis of the diacetylene compound (II), for example,
It can be easily synthesized in a high yield by using the synthetic method described in JP-A-62-267248 and JP-A-62-267251. Further, the purification can be carried out by a usual chromatographic method, distillation and recrystallization.

The diacetylene-based polymer in the present invention is a polymer obtained by reacting the double bond of the diacetylene compound (II) with a double bond or more, and the synthesis method thereof is a normal bulk polymerization,
Solution polymerization, suspension polymerization, emulsion polymerization, solid phase polymerization, photopolymerization and the like can be applied.

In the bulk polymerization, the diacetylene compound (II) can be synthesized by, for example, heat-treating for a certain time in an inert atmosphere. The reaction temperature is preferably in the range of 50 to 250 ° C, more preferably 80 to 140 ° C. The reaction time is not particularly limited, but is preferably 5 minutes to 24 hours.

In solution polymerization, the diacetylene compound is added to water or a general-purpose organic solvent, and if necessary, in the presence of benzoyl peroxide, acetyl peroxide, α, α′-azodiisobutyl, t-butyl hydroperoxide, cumene hydroperoxide. , Can be synthesized by reacting. The reaction temperature and the reaction time are not particularly limited, but the reaction temperature is 50 to 200.
C, reaction time is between 5 minutes and 24 hours.

In suspension polymerization, it can be synthesized by reacting the diacetylene compound (II) in the presence of water and an organic solvent which does not mix with water, if necessary, in the presence of a peroxide, a perester or a redox type initiator. The reaction temperature and the reaction time are not particularly limited, but the reaction temperature is 0 ° C.
The reaction time is preferably 1 to 24 hours at -100 ° C.

Emulsion polymerization can be achieved by adding a fixed amount of anionic, cationic or nonionic surfactant to the suspension polymerization system. There is no particular limitation on the amount and type of surfactant added.

Further, for the synthesis of the diacetylene-based polymer of the present invention, an ionic polymerization method such as anionic polymerization, cationic polymerization and coordination polymerization can be applied.

The diacetylene-based polymer of the present invention is not limited in its degree of polymerization, molecular weight, and molecular weight distribution as long as it is a dimer or more, but is not limited to methanol, acetone, tetrahydrofuran, chloroform, dimethylsulfoxide, N, N.
In order to be soluble in at least one organic solvent such as dimethylacetamide, the number average molecular weight Mn is preferably 11
It is better to set it to 00 to 5000, more preferably 1100 to 3000.

The diacetylene-based polymer of the present invention is required to be soluble in the organic solvent, and the advantage of being soluble is that the solvent or the monomer is contained, after casting, after molding such as film formation, By removing the solvent or the monomer, it is possible to provide an easily cured and strong film or molded product. Further, in the crosslinking step, since there are few active functional groups, rapid reaction such as decomposition is less likely to occur.

The diacetylene-based polymer of the present invention may optionally contain additives such as a stabilizer, a monomer, another polymer, a polymerization inhibitor, an initiator, a focusing agent and a solvent.

〔The invention's effect〕

Since the polymer of the present invention is a polymer of a diacetylene compound that is soluble in a specific organic solvent and has excellent cross-linking reactivity and moldability, the cross-linking yield and operability are extremely good, and a high degree of Expresses elastic modulus.

Therefore, the polymer of the present invention is extremely useful as a matrix resin, a sealant, a potting agent, a coating agent, a resist material and the like.

〔Example〕

Hereinafter, the present invention will be described with reference to examples, but needless to say, the present invention is not limited to the following examples.

[Example 1] 1 mol together with 0.01 mol of CuCl in 200 ml of pyridine for 4 hr,
The reaction was carried out at room temperature while introducing oxygen gas. After the reaction, the reaction product was poured into cold concentrated hydrochloric acid and extracted with ether. Then, it was dried with Glauber's salt to obtain the target compound (1) in a yield of 95%.

The structure of compound (1) was confirmed by IR and NMR.

IR (cm ^-1 ) ... 2939,2156,1727,1631,1166,985,810 When the obtained compound (1) was annealed at 100 ° C. for 20 minutes under N ₂ , the viscosity of the system was significantly improved. . GPC
When analysis (column: G-4000, developing solvent: tetrahydrofuran, detection: by refractive index) was performed, a polymer having a number average molecular weight of 1300 was obtained at a conversion rate of 6.2% in terms of polystyrene. When the reaction time was extended to 100 minutes, a polymer having a number average molecular weight of 1800 was obtained at a conversion of 26.3%.
The reaction product reacted for 100 minutes was poured into a large amount of ether, dimethyl sulfoxide was added to the precipitated polymer, and only the ether was distilled off, whereby a uniform solution was formed.

Next, this dimethyl sulfoxide solution was cast on a glass plate, and UV irradiation (245 nm) was performed while gradually washing with water,
A strong insoluble and infusible film was formed.

Further, the above dimethyl sulfoxide solution was poured into a large amount of water, and the precipitated polymer was placed in a mold while being wet, and the pressure was 30
When pressed in a vacuum of 0.02 torr at 00 kg / cm ² and a temperature of 150 ° C., an insoluble and infusible molded body could be obtained without decomposition.

When the flexural modulus of this cured product was measured, it was a good value of 13.8 GPa.

In the above experiment, completely deuterated dimethyl sulfoxide was used instead of dimethyl sulfoxide, and its NMR spectrum was measured. As a result, it was found that this polymer was a linear polymer (2) in which only one double bond reacted. Was estimated.

[Examples 2 to 7] Various monomers shown in Table 1 were used instead of CH ₂ = CHCOOCH ₂ C≡CH, and 5 g of the diacetylene compound obtained by oxidative coupling was added to 100 mg in the presence of 5 mg of benzoyl peroxide. At ℃
Annealed for 24 hours.

In the case of any of the compounds, the reaction product, after filtration, was put into a large amount of ether, N, N-dimethylacetamide was added,
Evaporation of only ether gave a homogeneous solution.
Table 1 shows the number average molecular weight of the polymer contained in this solution. The number average molecular weight was determined in the same manner as in Example 1.

[Example 8] (CH ₂ = CHCH ₂ OCH ₂ C≡C ₂ 500 mg was dissolved in 5 ml of anhydrous benzene, and allowed to react at 80 ° C. for 10 hours in a sealed tube in the presence of AIBN (azoisobutyronitrile) 5 mg. After the reaction, the reaction product was poured into a large amount of ether, and 230 mg of the precipitated polymer was isolated, and the obtained polymer had a double bond absorption (1630 cm ^-1 at about half) in the IR spectrum. From the fact that there is no change in the absorption of the diacetylene group (2223 cm ^-1 ), ¹ H-NMR, the absorption amount of bromine, elemental analysis, etc., the structure of the polymer is It turned out to be When this polymer was dissolved in tetrahydrofuran and subjected to GPC analysis, the number average molecular weight was 183.
It was 0.

This polymer was insolubilized by heat treatment at 150 ° C for 30 minutes, and a large decrease in the IR spectrum of the diacetylene group and double bond was observed.

Claims (1)

[Claims] 1. A diacetylene polymer represented by the general formula (I), having a number average molecular weight of 1100 to 5000. (Where R, R ', R "are -H or -CH ₃ and R, R',
R ″ does not become −CH ₃ at the same time. X and X ′ are Or in --CH ₂ O--, in each case the oxygen atom is A,
Bind to A '. A, A _{'are, -CH 2 -, - CH 2} CH 2 - or -CH ₂ CH ₂ CH ₂ - in which).