JPH0430413B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel polymer compound characterized by a main chain consisting of a tert-butoxycarbonylmethylene chain and having low flexibility or rigidity (hereinafter simply referred to as rigidity). More specifically, a novel polymer having rigidity and consisting of tert-butoxycarbonylmethylene chains, which can be easily obtained by polymerizing di-tert-butyl fumarate as a monomer by a conventionally known suitable radical polymerization initiation method. Regarding compounds. Hitherto, various rod-shaped polymer compounds having rigid main chains and methods for providing them have been known. For example, natural polymer compounds such as cellulose;
Two or three isocyanate-based polymer compounds such as polybutyl isocyanate; many polyamides such as poly-p-phenylene terephthalamide-based polymer compounds, polypyromellitamide-based polymer compounds, polyamide hydrazide-based polymer compounds, etc. , polyimide-based polymer compounds, and the like. However, among these, natural polymer compounds are unsuitable as modifying materials for so-called general-purpose vinyl polymers, and other synthesized rigid polymer compounds also
Its disadvantages are that it requires complicated techniques to synthesize the monomer itself, and that the polymerization method is anionic polymerization or condensation polymerization, which requires ingenuity to remove low-molecular compounds such as water generated during polymerization. is commercially available, including many general-purpose vinyl polymers such as polyethylene, polyvinyl chloride, polystyrene, polyacrylic acid and its esters, polymethacrylic acid and its esters, ethylene-vinyl acetate copolymer, polyacrylonitrile, etc. It is not at all preferable because it requires a lot of effort to manufacture, such as not being able to use radical polymerization techniques that are industrially preferred for polymerizing various general-purpose resins. Furthermore, when modifying general-purpose vinyl polymers, it is undesirable for a large amount of nitrogen atoms to exist in the added modifier molecules, and in this sense, the polyamide and polyimide-based polymers mentioned above need improvement. It is said that The present inventors have found that improvements in these conventional techniques are desired, such as ease of synthesis of the monomer itself, and ease of synthesis under the conditions of the radical polymerization method often used for the polymerization of general-purpose vinyl polymers. The present invention aims to provide a polymer compound having a main chain with a rigidity that satisfies the above requirements, and further focuses on the fact that the main chain does not contain nitrogen atoms and preferably consists of only carbon-carbon bonds. As a result of extensive research, we found that when di-tert-butyl fumarate is used as a monomer and polymerized using an appropriate radical polymerization method, a rigid carbon-carbon bond that satisfies all of the desired improvements mentioned above has been created. The present invention was completed based on the discovery that a novel polymer compound having a main chain consisting of That is, the present invention provides the formula It has a repeating unit represented by , and the number average molecular weight is
5,000 to 300,000 and has a main chain consisting of a tert-butoxycarbonylmethylene chain. Various known polymerization techniques can be used to polymerize di-tert-butyl fumarate, but preferably in the presence of a selected radical polymerization initiator, in a solvent or without a solvent, at atmospheric pressure or under pressure. Alternatively, it is carried out under reduced pressure. Furthermore, a selected inert gas such as nitrogen, helium,
Substitution with argon, carbon dioxide, etc., or a method of passing a stream of these inert gases can also be carried out. In this case, it is desirable that di-tert-butyl fumarate be purified in advance by a known method such as recrystallization or vacuum distillation before being subjected to polymerization. Of course, various suitable reaction temperatures can be selected for polymerization, but if a high temperature is selected, the molecular weight of the polymer compound produced will be small, and if carried out at a low temperature, the molecular weight will be large. You can choose. In the present invention, the number average molecular weight is preferably 5000 to 300000,
If it is less than 5,000, the resulting polymer compound will have poor rigidity, and if it is more than 300,000, it will be difficult to produce. As the radical polymerization initiator, for example, various conventionally known organic peroxides, azo compounds, redox reagents, perhalogenates, etc. can be used, but polymerization initiation methods using light, oxygen, radiation, etc. can also be used. Furthermore, it is also possible to combine two or more of these types depending on the purpose. As the solvent, all conventionally known solvents that can be used in radical polymerization and combinations thereof can be used without any disadvantage. As the polymerization method, various known conventional techniques such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, and slurry polymerization can be applied. Furthermore, if necessary, the obtained polymer compound can be purified by a purification method suitable for each purpose. Of course, when polymerization is carried out using these methods, there is no generation of undesirable low-molecular compounds such as water or carbon dioxide, and
This is also one of the advantages of the present invention. The novel polymer compound obtained in this way has a main chain consisting of a tert-butoxycarbonylmethylene chain and has rigidity, and is a conventional polymer compound such as a known natural polymer compound, an isocyanate-based polymer compound, or a polyamide. Shows rigidity similar to polyimide polymer compounds. Furthermore, the tert-butyl ester group, which forms the side chain of the polymer compound, can easily decompose into isobutene and carboxylic acid at high temperatures, giving polycarboxylic acid, which can be used as a modifying material for general-purpose vinyl polymers. It can be fully applied. From these points of view, the novel polymer compound of the present invention is not only useful as a rigid polymer compound, but also has excellent properties as a modifier for other general-purpose vinyl polymers. . EXAMPLES The present invention will be specifically explained below with reference to Examples, but these are not intended to limit the scope of the present invention. Example 1 In a Pyrex glass polymer tube with an internal volume of 20 ml,
5 g of purified di-tert-butyl fumarate and 0.016 g of azobisisobutyronitrile (AIBN) as a polymerization initiator were taken, and after sufficiently repeating nitrogen substitution and deaeration inside the reactor, it was melt-sealed. This polymerization tube is 80
The tube was placed in a shaking water bath maintained at ±0.1°C and subjected to bulk polymerization for 1 hour, then the polymerization tube was opened, the contents were dissolved in benzene, and the contents were poured into a large amount of methanol to precipitate the polymer. The obtained polymer was then repeatedly purified by reprecipitation from a benzene-methanol system to obtain a white solid polymer. The results are summarized in Table 1. Example 2 Polymerization was carried out according to Example 1, except that 0.024 g of azobiscyclohexanecarbonitrile (ACN) was used as a polymerization initiator and the polymerization time was 4 hours, to obtain a white solid polymer. The results are summarized in Table 1. Example 3 Benzoyl peroxide (BPO) as a polymerization initiator
Except that 0.024 g was used and the polymerization time was 3 hours.
Polymerization was carried out according to Example 1. A white solid polymer was obtained. The results are summarized in Table 1. Example 4 Polymerization was carried out according to Example 1, except that 0.024 g of ACN was used as a polymerization initiator, the polymerization temperature was 90°C±0.1°C, and the polymerization time was 4 hours, to obtain a white solid polymer. The results are summarized in Table 1. Example 5 Into the same polymerization tube as in Example 1, 5.7 g of di-tert-butyl fumarate, 5 ml of benzene, and 0.052 g of AIBN were added.
After sufficiently repeating nitrogen purging and deaeration, the polymer was melt-sealed, and then bulk polymerization was carried out at 60°C±0.1°C for 10 hours to obtain a white solid polymer. The results are summarized in Table 1. Example 6 In a four-necked flask with an internal volume of 500 ml, 200 ml of a 0.2% by weight aqueous solution of partially saponified polyvinyl alcohol was added.
Take 2 g of calcium carbonate and 2.5 g of a 1% by weight aqueous solution of sodium dodecylbenzenesulfonate, and add 0.5 g of BPO to 50 g of di-tert-butyl fumarate.
A solution of g was added thereto, stirring was performed while introducing nitrogen gas, and suspension polymerization was carried out at 80°C±0.1°C for 24 hours. After polymerization, add hydrochloric acid to the reactor to make it acidic and dissolve calcium carbonate.
Separate the precipitated particulate polymer, wash thoroughly with water and hot water, and finally wash with methanol.
A white particulate polymer was obtained by drying under reduced pressure. The results are summarized in Table 1.

[Table] Intrinsic viscosity is the value measured at 30°C using benzene as the solvent.
Identification of the polymer compound of the present invention and its properties will be explained below using instrumental analysis. Figures 1, 3, and 5 show infrared absorption spectra (IR) and nuclear magnetic resonance spectra ( ^1H and ¹³ Figures 2, 4, and 6 show the IR, ¹ H-NMR, and ¹³ C-NMR of the polymer compound of the present invention (hereinafter referred to as polymer) obtained in Example 1. NMR spectra are shown for each. Figures 1 and 2
In the IR spectrum, the absorption (1663 cm ^-1 ) based on the double bond of the monomer disappears in the polymer, and in the ¹ H-NMR spectra of Figures 3 and 4, the absorption (1663 cm -1 ) based on the double bond of the monomer disappears at 6.6 ppm of the double bond of the monomer. Proton absorption disappears in polymers
It appears as a very broad absorption around 3ppm. Furthermore, ¹³ C-NMR in Figures 5 and 6
In the spectrum, it can be seen that the double bond carbon absorption (134.39 ppm) that appears in the monomer disappears in the polymer, but the main chain carbon absorption
It seems that it is very small and is included in the noise. From the above, it can be seen that the polymerization of the monomer proceeds by cleavage of internal double bonds to yield a polymer consisting of tert-butoxycarbonylmethylene chains. Next, the results of thermogravimetric analysis of the polymer are shown in FIG. As is clear from Figure 7, the initial decomposition temperature of the polymer is 190℃, the maximum decomposition temperature is 205℃, and the
The residue at °C is 10.1%. The residue at 210℃ is
However, if the tert-butyl ester group of the polymer becomes a carboxylic acid while releasing isobutene, the value becomes 51%, and the decomposition at 205℃ corresponds to the decomposition of the tert-butyl ester group in the side chain. I know what you're doing. In addition, the polymer was tested under a nitrogen stream.
The mixture was thermally decomposed at 200°C for 2 hours, and the IR spectrum of the residue was measured, as shown in Figure 8. In FIG. 8, absorption of carboxylic acid and absorption of hydroxyl groups are observed, so it is clear that polycarboxylic acid is produced by thermal decomposition. The polymer compound of the present invention obtained in Example 6 was
The polymers were fractionated using a benzene-methanol system to obtain polymers with different molecular weights. The intrinsic viscosity of each polymer was measured, and the molecular weight was calculated by an osmotic pressure method, and the relationship between the molecular weight and the intrinsic viscosity was determined, and it was found that the following formula was followed. [η]=3.08×10 ^-3 M ^1.41 ([η]; intrinsic viscosity M; molecular weight) It is generally known that the relationship between the intrinsic viscosity and the molecular weight is expressed by the following formula. [η] = KM (K and α are constants) In general polymers, α is usually less than 1 and exhibits flexibility, but when α is greater than 1, it is considered to be a rigid polymer. In the polymer compound of the present invention in Example 6,
Since α is much larger than 1 as mentioned above,
It can be called a rigid polymer compound. From the above, it is clear that the polymer compound of the present invention is a rigid polymer compound whose main chain consists only of carbon-carbon bonds and has a tert-butoxycarbonylmethylene chain structure. Moreover, it is a polymer compound that can easily give polycarboxylic acid by heating, and is also useful as a modifying material for general-purpose vinyl polymers.

[Brief explanation of drawings]

FIGS. 1 and 2 are graphs showing infrared absorption spectra of di-tert-butyl fumarate monomer, which is a raw material of the present invention, and a rigid polymer compound of the present invention obtained therefrom, respectively. Figures 3 and 4 are graphs showing nuclear magnetic resonance spectra ( ^{1H-NMR) of di-tert-butyl fumarate monomer and the rigid polymer compound of the present invention, and Figures 5 and 6 are graphs showing nuclear magnetic resonance spectra (1H} -NMR), respectively. is a graph similarly showing a nuclear magnetic resonance spectrum ( ¹³ C-NMR). FIG. 7 is a graph showing the results of thermogravimetric analysis of the rigid polymer compound of the present invention, and FIG. 8 is a graph showing the infrared absorption spectrum of the thermal decomposition residue of the rigid polymer compound of the present invention.

Claims (1)

[Claims] 1 formula Number average molecular weight with a repeating unit represented by
5000~300000 rigid polymer compound. 2. The rigid polymer compound according to claim 1, which is obtained by radical polymerizing di-tert-butyl fumarate.