JP2698676B2 - Macrocyclic polyolefin epoxide - Google Patents

Description

The present invention relates to a polymer having a novel structure. Specifically, it is a high molecular weight polymer which can react with various low molecular weight compounds or can react with high molecular weight compounds, and which can be mixed with other polymers while maintaining mechanical strength. The present invention relates to an epoxy group-containing macrocyclic polyolefin epoxide which is a united product.

[Conventional technology]

Epoxides having a structure similar to the epoxide of the present invention are disclosed in JP-A-63-105068. Meanwhile, the polyolefin used disclosed in this publication is
Polyoctenylene or cyclooctene-cycloene copolymer having an average molecular weight of 600 to 3000. It is considered that the reason why the low-molecular-weight polyolefin is used is that the purpose of use is an air-drying lacquer binder, and that the fluidity in a solution is taken into consideration. This publication does not disclose the high molecular weight polyolefin or its epoxide used in the present invention.

[Problems to be solved by the invention]

The present inventors have conducted various studies on a polymer compound capable of being mixed with other polymer compounds while retaining mechanical strength, and obtained by oxidizing a macrocyclic polyoctenelen having a molecular weight of 30,000 or more. The present inventors have found that polyepoxide has excellent properties which could not be expected before, and have completed the present invention.

[Means for solving the problem]

The present invention provides a novel epoxy-containing macrocyclic polyolefin epoxide obtained by oxidizing a macrocyclic polyolefin having a number average molecular weight of 30,000 or more and having at least one double bond regularly per 8 carbon atoms. Is what you do.

The preferred macrocyclic polyolefin used in the present invention is 25
It means a cyclic polyolefin having zero or more rings, and can be obtained by subjecting cyclopentene, cyclooctene, or the like to metathesis polymerization using a tungsten-based catalyst, particularly, tungsten hexachloride and a cocatalyst. This technique is disclosed in, for example, West German Patent Publication No. 2613999. At this time, the number average molecular weight changes depending on the polymerization conditions, but for the purpose of use in the present invention, the number average molecular weight needs to be 30,000 or more. When the molecular weight is less than 30,000, although the obtained epoxide has reactivity with a low molecular weight compound or a high molecular weight compound, miscibility with a high molecular weight compound, dispersibility is usually not good, and mechanical strength after mixing is low. There is a risk of significant damage.

In the macrocyclic polyolefin used in the present invention, it is desired that the double bond contained therein has a regular structure. The regularity of the double bond in the macrocyclic polyolefin is
It has a great effect on its physical properties. For example, in polybutadiene, two types of double bonds in the main chain and double bonds outside the main chain are generated during polymerization, so that the regularity in repeating the double bonds is extremely low. Such a polymer having low regularity is very difficult to estimate the state of mixing when mixed with another polymer, and this is an obstacle to designing stable functionality.

Examples of the macrocyclic polyolefin having a molecular weight of 30,000 or more and having at least one double bond per eight carbon atoms, such as Huls (H
ls) Those commercially available from the company (West Germany) can be used. With respect to the double bond in the macrocyclic polyolefin, two conformations (position configuration of chemical bond) of a cis form and a trans form are known. For the purpose of the present invention, any of the conformations may be used, but in consideration of the miscibility of the obtained epoxide with other polymers, the epoxide containing a large amount of the trans form, that is, 50% Desirably, the above-mentioned trans-polyoctenylene is used.

The macrocyclic polyolefin epoxide of the present invention may be synthesized by any oxidation method. For example, peracids such as hydrogen peroxide, peracetic acid, formic acid, pertrichloroacetic acid, meta-
A normal epoxidation method using chloroperbenzoic acid, perphthalic acid, perpropionic acid, perbutyric acid, perbenzoic acid, pertrifluoroacetic acid or the like can be applied.

As the macrocyclic polyolefin epoxide of the present invention,
A macrocyclic polyolefin polyepoxide containing, for example, 0.5 to 30% by weight of oxygen as an epoxy group is desirable. The polyepoxide of the present invention is a novel one having a molecular weight of 30,000 or more. 1) The mechanical strength is improved because the crystallinity is not reduced. 2) The melting point can be controlled. 3)
It has effects such as improvement of weather resistance. Also, by appropriately changing the epoxy group content, the polarity of the macrocyclic polyolefin epoxide changes, so that it is possible to select the optimum epoxy content according to the purpose of use and use, and according to the type of the polymer to be mixed. it can.

〔The invention's effect〕

The macrocyclic polyolefin epoxide of the present invention, compared to conventionally known polyepoxides, is excellent in mixing and dispersibility with a high-molecular polymer, and therefore, even when mixed with another polymer, retains its strength, Can improve. Also, it has excellent reactivity with other substances, and can easily react with low molecular weight compounds and high molecular weight compounds. Therefore, the macrocyclic polyolefin epoxide of the present invention is very useful also as a modifier for the physical properties of a high molecular polymer and as a reaction material with a low molecular compound or a high molecular compound.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1 Macrocyclic polyoctenamer having a trans content of 76% (number average molecular weight measured by gas chromatography 94,000)
Dissolve 5.61 g in 100 ml of chloroform. Here, 5.01 g of meta-chloroperbenzoic acid is slowly added. After stirring for one day, the resulting white precipitate is removed by centrifugation and the solution is poured into a large amount of methanol to precipitate the polymer. 5.03 g (yield 84%) of the obtained polymer after drying
Met. FIGS. 1 and 2 show an infrared absorption spectrum and a nuclear magnetic resonance absorption spectrum before and after epoxidation.

The elemental analysis values of the polymer obtained by the above reaction were 81.2% for carbon, 12.07% for hydrogen, and 6.73% for oxygen, and it was calculated that about 49.6% of the double bonds in the macrocyclic polyoctenamer were epoxidized. The result was consistent with the result of NMR in FIG. Furthermore, when the thermal behavior of the macrocyclic polyolefin epoxide was measured by DSC (differential scanning calorimeter), FIG.
As shown in the figure, the main melting temperature of the epoxide increased and
Another new melting peak was observed around ° C.

(Measurement of molecular weight) The molecular weight was measured using gel permeation chromatography (GPC). Tetrahydrofuran was used as the eluate, and the number average molecular weight was determined using a refractometer as a detector. The chromatograms before and after the reaction are shown in FIG. FIG. 4 shows that the molecular weight hardly changed before and after the reaction.

Examples 2 to 5 Instead of the metachlorobenzoic acid used in Example 1, peracetic acid was added in the amount shown in Table 1 below, wherein the temperature was 0 to 80 ° C.
Is added so as to be in the range. The dissolution conditions for the starting macrocyclic polyoctenamer are the same as in Example 1. After the addition, stirring is continued at a temperature of 100 ° C. or less for 4 hours, and the solution is poured into a large amount of methanol to precipitate the polymer. Table 1 shows the physical properties of the obtained polymer, and FIG. 5 shows the melting behavior by the DSC method.
The S chart is shown in FIG.

[Brief description of the drawings]

FIGS. 1A and 1B show infrared absorption spectra of (a) a starting macrocyclic polyoctenamer and (b) a macrocyclic polyolefin epoxide of the present invention, respectively.
(B) is a diagram showing a nuclear magnetic resonance spectrum of (a) a starting macrocyclic polyoctenamer and (b) a macrocyclic polyolefin epoxide of the present invention, FIG. 3 is a diagram showing a thermal analysis curve by a differential scanning calorimeter, and FIG. FIG. 5 is a diagram showing gel permeation chromatography, FIG. 5 is a diagram showing a change in melting point of the epoxidized macrocyclic polyoctenamer by the DSC method, and FIG. 6 is a diagram showing wide-angle X-ray diffraction by WAXS.

Claims (2)

(57) [Claims] An epoxy group-containing macrocyclic polyolefin epoxide obtained by oxidizing a macrocyclic polyolefin having a number average molecular weight of 30,000 or more and having at least one double bond regularly per 8 carbon atoms. 2. The epoxy group-containing macrocyclic polyolefin epoxide according to claim 1, wherein the oxygen content of the epoxy group is 0.5 to 30% by weight.