JPS6047005A - Modification of polymer - Google Patents

Abstract

PURPOSE:To effect the modification by facilitating the removal of an alkali (alkaline earth) metal by bringing a liquid product of an alkali (alkaline earth) metal-containing polymer into contact with a specified substance in the absence of water. CONSTITUTION:A liquid product of an alkali (alkaline earth) metal-containing polymer is brought into contact with at least one member selected from the group consisting of (A) at least one of oxides, hydroxides, or carbonates of Si, Mg, Al, or Ca, (B) a mineral having the above chemical component as an effective component (e.g., kaolin or bentonite) and (C) a cation exchange resin in the absence of water. It is possible to remove an alkali (alkaline earth) metal extremely easily and to obtain a highly pure polymer in good reproducibility.

Description

[Detailed Description of the Invention] relates to a method of modifying a polymer by removing alkaline earth metals, and more specifically, a method of bringing a specific substance into contact with a polymer liquid under specific conditions. The present invention relates to a polymer modification method characterized by:

Various polymers have recently been in increasing demand for various electronic materials or as sintering aids.

However, since these polymers are usually polymerized using metal salts or organometallic compounds, except when radical polymerization is used, they contain metal residues ranging from several tens to several hundred pln.

If metals, especially alkali metals and alkaline earth metals, remain in the polymer, they will remain in the sintered body, deteriorating the electrical properties and impairing the properties of the sintered body. There has been a demand for a practical supply of polymers with less residual metal.

The inventors of the present invention have been conducting various inspections regarding this point for some time, and have found that by the method specified in the above-mentioned claims, a polymer with extremely low residual impediment of these metals can be obtained. (Special application 1986-906)
47).

However, with the previously applied method, it is possible to remove metal residues, but when repeated, the metal residues can be removed almost completely (i pJ) I+] and in some cases cannot be removed very much (101) I) 111 above).

As a result of detailed study on a method that can remove the particles with better reproducibility, the present inventors have found that it is possible to remove them almost completely with good reproducibility by treating them under specific conditions112.
He discovered that this was the case, and completed the present invention.

An object of the present invention is to provide a method for efficiently removing alkali metals or alkaline earth metals.

The present invention is as described in the claims, but the gist of the invention is to treat a polymer in a liquid state, to treat the liquid polymer with a specific substance, and to treat the polymer in a liquid state with a specific substance. The essential condition is that 1) be carried out in the absence of water.
．． Next, it also includes the names of products made by melting specific substances. Naturally, the lower the viscosity, the easier the treatment in the case of stains.

The specific substances used in the reforming method of the present invention include those described in claim 1)(1) as chemicals and substances, as well as
It contains minerals containing these compounds as constituent components, and further contains a cation exchange resin. As can be easily understood, these may be a mixture. If you don't specify them, 8I, 02, M, o, Aノ203, aoo, My
(OH)2, Ai(o++)3, co, (011);
B, 8'ly O03, A12 (003) 3, aQ,
co, hydrotalcite, kaolin, montmorillonite, bentonite, etc., and these may be natural or synthetic. It is preferable to perform activation treatment upon use. As the cation exchange resin, commercially available products such as Amberlyst (trade name) and Diaion (trade name) can be used.

The amount of these liquids to be used is 10 to 1000 times the amount of alkali metals and alkaline earth metals contained in the object to be treated, but usually 10 to 100 times is sufficient. The present invention is applicable to a range in which the content of these metals contained in the polymer ranges from a few yen) to several tens of yen]11]. When processing highly diluted polymer liquids, liquid! Temperatures of 0001 to 01°C at 1F may be effective.

In the present invention, in the contact tank E! Ji is performed in the absence of water. The smaller the amount of water, the better, and preferably 0.1 wt% or less relative to the polymer bath solution. Specifically, it is necessary to keep the amount of water in the liquid polymer to a small amount and to ensure that water is not released from the above-mentioned specific substances during treatment, i.e., it is usually preferable to perform dehydration treatment before use. be.

In addition, in a preferred production form of the liquid polymer, IF u,
77, in the absence of water. Therefore, water is not used at the time of catalyst deactivation, and the treatment can be carried out under conditions where no water is mixed.

By using the method of the present invention, it is possible to produce polymers with less metal residue in an extremely simple JIH manner with good reproducibility of <8, which is industrially significant.

Hereinafter, the present invention will be explained in detail with reference to Examples.

Example 1 and Comparative Example 1 Styrene 50 prepared under nitrogen atmosphere in flask 1e
0.2.9 g of 7+-butyllithium (charged with 14.5% 7L-hexane m solution) was added to a mixed solution of g, toluene oom, and l, and the temperature rose to 80°C due to the heat of polymerization. did. Lower the temperature to 50'C, and add 1me of absolute ethanol (stir, leave half as is; 1j filtered, then half finely ground Kyowa~1.500 (synthesized by Kyowa Kagaku Co., Ltd.), Idrotalzite, 200℃ After stirring for 10 minutes, each polymer solution was filtered to obtain a polymer solution.Toluene and a small amount of unreacted monomer were distilled under reduced pressure from each polymer solution to obtain a polymer as a residue. 14 in the polymer
, 7 was analyzed by the flame light fraction initiator method, and the result was 0.51)l]+1 with the keyword added, and 420I)pIYl without the keyword added.

Comparative Example 2 The same procedure as in Example 1 was repeated except that 1 ml of water was used instead of 1 ml of ethanol as the deactivator in Rolling Example 1, and the amount of carbon in the obtained polymer was 42 ppm.

Example 2 50ml of toluene, α in a 1e flask under nitrogen atmosphere
-Methylstyrene'room1. ．． Diglyme 2m1.
．． 71. -Butyl lithium (0.39 g) was added, and the mixture was stirred at 60°C for 2 hours. Next, 1 ml of anhydrous methanol was added to deactivate the catalyst activity, and 2 g of finely ground silica gel was added, stirred for 10 minutes, and filtered through p-filter to obtain a polymer solution.Then, the polymer solution was poured into 24 methanol. to precipitate the polymer.

When the obtained polymer was analyzed in the same manner as in Example 1, it contained only 0.2 plMn of lithium.

Comparative Example The same procedure as in Example 2 was carried out except that 1 ml of water was used instead of 1 ml of methanol as a deactivator, and the lithium content in the polymer was 13 ppm.

Actual brM Example 6 In Example 1, thorium naphthalene 0 was used as a catalyst.
Polymerization was carried out in the same manner as in Example 1, except that the amount of polymer was 2 g and the firing time for Kyoward 500 was 60 minutes, and the same treatment was carried out, and the No. content in the polymer was 2 ppm.

Examples 4 to 7 In Example 1, finely ground Molecule Sieve 3A (Example 4), M,0 (Example 5), bentonite (Example 6), finely ground activated alumina (Example The process was carried out in the same manner as in Example 1, except that Example 7) was used. However, before addition, toluene 50
The polymer solution was diluted by adding 0ml. The Lj contents in the obtained polymers were 1 ppm and 0.4 p, respectively.
pm, 0.05 pp polishing 0.02 pI] η.

Claims (1)

[Scope of Claims] 1) A polymer liquid containing an alkali metal or an alkaline earth metal, (1) an oxide of sA, M,, A or Cα atoms;
(2) a mineral material containing substantially the above chemical component as an active ingredient; or (2) a cation exchange resin; A method for modifying a polymer, characterized in that the above-mentioned contact treatment is carried out in the absence of water. 2) The method according to claim 1, wherein the polymer is a polymer obtained from an olefin and/or diene compound using an organometallic compound.