JPS58145728A - Alcohol polymerization catalyst - Google Patents

Abstract

PURPOSE:A polymerization catalyst useful in the polymerization of an alcohol such as furfuryl alcohol or benzyl alcohol, comprising ''sampi''. CONSTITUTION:A catalyst for the polymerization of an alcohol of the formula (wherein R is an aromatic group), e.g., furfuryl alcohol or benzyl alcohol, comprising ''sampi'' (e.g., porous acicular clays such as sepiolite or attapulgite). When the above alcohol is brought into contact with a catalyst comprising ''sampi'' under heating, the reaction proceeds in such a way that one water molecule is eliminted from two alcohol molecules, and the resulting product condenses further. Finally, a resinous polymer can be obtained. A furan resin prepared by polymerizing furfuryl alcohol has excellent chemical resistance and can be utilized as a molding material for tanks or plants, and is particularly useful as a sand binding resin in the foundry industry. Polybenzyl has a possible use as an electrical insulating material.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention (r:i) relates to a catalyst for the polymerization of alcohol.
The present invention relates to a catalyst for polymerizing an alcohol represented by (R is an aromatic group).

It has been known that furan resin or polybenzyl can be obtained by condensing furfuryl alcohol or some pencil alcohol in the presence of a mineral acid. The inventors
As a result of many years of research into the catalytic effect of mountain bark, we found that when mountain bark is exposed to alcohols such as methanol and ethanol/L/L/L/2 under heating, hydrocarbons such as olefins and diolefins are released. In anticipation of this, W1 Shi has already issued a patent (for example, 3 Mori Kaisho 56-169629 = Public Corporation), but this time, Yamahata unexpectedly announced that furfuryl alcohol and benzyl alcohol. It has been found that these alcohols have a texture-strengthening effect and that a tree IJM-like substance is formed from these alcohols. Based on this knowledge, the present inventors conducted a historical and in-depth study and arrived at the present invention.
Polymerization of alcohols substituted with H (wherein R represents an aromatic group) (111 catalyst).

Mountain bark, which is the r'+11-active component of the present invention, is a group of porous needle-shaped clays called mountain cork, mountain leather, mountain wood, etc. Examples include sepiolite as a magnesium compound, acpulgite and palichorskite as aluminum magnesium compounds. Among these, sepiolite is a general type Mg
8S1. ,03,)(OH)4 (H2())4・81
(This clay is represented by No. 20, and is the most preferred active ingredient of the present invention.) These mountain barks are usually prepared by crushing 111 leather raw stone in a dispersion medium containing water to disperse the mountain bark. It can be obtained by collecting the dispersed mountain bark with a filter and drying it.To use the mountain bark obtained in this way as a catalyst, it can be used as a powder or shaped into a pellet or sphere as appropriate. If necessary, a heteropolyacid or a metal such as titanium, tin, antimony, or zirconium dioxide may be supported on the skin of the tomato by a conventional method.

The alcohol that can be polymerized using the mountain bark catalyst of the present invention as described above is a compound represented by the general formula RCH20H (R aromatic group), [? Examples of the aromatic group represented by include allyl groups such as phenyl and naphthi/l/, and heterocyclic aromatic groups such as furyl and pyridyl. Among these alcohols, furfuryl alcohol/l/sylbenzyl alcohol can be suitably polymerized using the catalyst of the present invention. .

In order to polymerize such an alcohol, it is usually necessary to apply it to a catalyst made of mountain bark under heating.

The reaction proceeds while the raw alcohols are combined in the form of two molecules of alcohol with one molecule of water removed, and a corresponding resin-like polymer is obtained. In order to proceed with the small batch 6 for one successive time, it is usually necessary to heat the eel at a temperature of 40°C or higher, preferably at a temperature in the range of about 90°C to 850°C.

For example, when furfuryl alcohol is used as the IIIt material, approximately 90°C to 350°C1-! When benzyl alcohol is used, the reaction can proceed smoothly at a temperature of 150[delta] to 350[deg.]C.

Alcohol usually remains in liquid form or in gas form.
Contact with Ilt medium. Specifically, for example, there is a method in which a medium is directly added to and mixed with alcohol, or a method in which a catalyst is fixed in a container and liquid or gaseous alcohol is passed through it and brought into contact with it.
The reaction is not limited to these, and the reaction proceeds sufficiently by allowing the catalyst to coexist in the alcohol. The amount of catalyst used is 1! Although it depends on the contact temperature, it is generally preferable to use about 0.1% to 50% by weight, more preferably about 0.05% to 5% by weight, based on the alcohol.

The polymerization/f of the polymer thus obtained can be easily adjusted by appropriately selecting the amount of catalyst used and the contact temperature. If the reaction temperature is increased and brought into contact with f4+It at the internal temperature Jφ, a product with a low degree of polymerization can be obtained.The progress of the reaction can be monitored by measuring the viscosity g, liquid chromatography, etc. Desired When a polymerization level of After dissolving the substance in a suitable solvent, the catalyst can be precipitated, or
There are ways to filter this.

Relfuran resin obtained by polymerizing furfuryl alcohol has excellent chemical resistance, so it can be used as a molding material for tanks and plants, and is particularly useful as a BN for hardening sand in the foundry industry. In addition, polybenzyl has uses as an electrical insulating material 1, Example 1 /! 50 in 11 colbens with i1L meter and fractionator
Prepare 0f benzyl alcohol/L' and add 8fI to this.
Add sepiophyte powder (from Spain) and mix well. Thereafter, the temperature is gradually raised while heating, and when the internal temperature reaches approximately 90° C., bubbles are observed to be generated from inside the pencil alcohol. Further, the temperature was gradually increased until the temperature reached approximately 170°C, and the reaction was continued for 40 minutes, and the benzyl alcohol gradually changed into a yellow viscous substance while actively generating bubbles.

When the viscosity at 170° C. reached approximately 1000 cps, a portion of the reactant was collected to obtain a stringy candy-like viscous substance. The remaining residue was further reacted at 170° C. for 1 hour, generating exothermic heat and yielding a yellow-brown caramel-like solid substance.

The candy-like viscous substance was soluble in chloroform. This chloroform-fermentable IR specter e[iL? ! Shown in j.

When one caramel-like solid substance was dissolved in chloroform, the soluble portion was absorbed and the remaining portion was unfermented. When this iJ solution was dissolved in dichloro)VXtan and subjected to liquid A 11 chromatography, a large distribution was observed in the vicinity of a molecular weight of about 1000 (as shown in Figure 2). Similarly, the nuclear magnetic resonance (NMR) spectrum of the rll solution (in CC11, T) is shown in Figure 3. It turned out to be.

. The caramel-like substance chloroform was added to the glass plate in a chloroform solution. When the chloroform was evaporated in a heating tank at 100°C, a transparent coating was obtained at the temperature of the glass plate. . This coating did not peel off even in boiling water.

Example 2 Add 2g of Ceviolai 1 (produced in Spain) to 2001/Furfurifure alcohol and mix well. .

When heated gradually and kept at a reaction temperature of 90℃ for 60 minutes, the color changes to blackish brown while generating bubbles, and the viscosity is approximately 2000℃.
A tar-like substance of ops was obtained. The liquid phase chromatograph of this product q) is shown in FIG. 4, and the MNR spectrum is shown in FIG. By comparing these spectra with those of the standard product, it was found that unreacted furfuryl alcohol remained, but it was an initial polymerization product of furan resin.

This tar-like substance was well kneaded into glass fibers to form a sheet, and when heated in a heating phase of 100° C. for 1 hour, a hard resin plate was obtained.

Example 3 While keeping aOttl benzyl alcohol at a constant temperature of 180° C., 0.1 fI of sepiolite was added thereto and thoroughly stirred, and the relationship between reaction time and polymerization rate was investigated.

Note that the polymerization rate was determined by precipitating the polymer using dioxane.

The same experiment was repeated using o, ay Sevioly as catalyst. 3. Figure 6 shows the relationship between each reaction time and polymerization rate. In addition, in the same 1-1, ---- means the case where the catalyst amount is 0.1 fI, and ---- means the case where the catalyst amount is 03 g.

[Brief explanation of the drawing]

7- FIG. 1 shows the IR spectrum of the candy-like viscous substance obtained in Example 1. Figures 2 and 3 show the liquid chromatograph and NV'T (spectrum) of the caramel-like solid 'K (chloroform soluble content) obtained in Example 1. FIGS. 4 and 5 show liquid phase chromatography and NMR spectra of the tar-like substance obtained in Example 2. FIG. 6 shows the relationship between reaction time and polymerization rate in the reaction of Example 3. 8 - $40

Claims (1)

[Claims] Alcohol represented by the general formula RCH20H (in the formula, R represents an aromatic group) consisting of mountain bark