JPH0713085B2 - Sequential extraction and separation device for crystalline polymer - Google Patents

Description

TECHNICAL FIELD The present invention relates to an apparatus for sequential extraction and separation of polymers. More specifically, the present invention relates to an apparatus that can be suitably used for sequentially extracting a crystalline polymer and separating each component having different crystallinity, composition and the like.

[Conventional technology]

It is well known that a polymer is sequentially extracted with various solvents to separate each component having different crystallinity, composition, molecular weight and the like. Among them, it is widely practiced to sequentially extract crystalline polymers such as polypropylene and polyethylene to separate them into respective components, and a method of extracting in a reflux state of a hydrocarbon solvent having different boiling points (Bull.Chemica
l Society Japan, vol. 37, p. 909 (1964), Method of sequential extraction using a mixed solvent of a hydrocarbon compound which is a good solvent and alcohols which is a poor solvent (Chubu Chemical Association Society Branch Autumn) Conference 13th Lecture Proceedings 3A, 20 (1982
Year)) etc.

[Problems to be solved by the invention]

For the purpose of improving the physical properties of the polymer, it is important to examine the relationship among the three factors of the polymerization method-physical properties-composition, and it is widely practiced to carry out the above sequential extraction for this purpose,
The method using a mixed solvent has excellent separation performance but has a problem that it requires skill in operation. Also, the method using a hydrocarbon solvent having a different boiling point is simple, but accuracy such as reproducibility of extraction separation is difficult. There was a problem.

[Means for solving problems]

The present inventor has conducted intensive studies on an apparatus that solves the above-mentioned problems and that also enables automatic sequential extraction by utilizing a simple automatic conveying means, and completed the present invention.

That is, according to the present invention, at least a solvent storage tank section B comprising an extraction solvent storage tank, a meter connected to the storage tank and a conduit to the extraction section, a reflux condenser on the upper side, and a crystalline polymer to be extracted on the lower side of the reflux condenser are placed at least. A sequential extraction / separation apparatus for a crystalline polymer, characterized in that it comprises an extraction container having a filter in the lower part, and an extraction part A having a heating part and an extraction solvent extraction nozzle below the extraction container.

The outline of the device of the present invention will be described with reference to the drawings.

FIG. 1 shows an outline of the extraction section A and the solvent storage tank section B, and
The figure shows the details of the extraction container.

Glass or metal is preferably used as the material of the device.

The extraction unit A includes a reflux condenser 1, an extraction container 2, a heating unit 31, and
32 (31 is a portion into which a solvent is put, 32 is a heating device, for example, a heating medium containing jacket or an electric heater) and extraction solvent extraction nozzles 41 and 42 (this is a top extraction and a bottom extraction as necessary. 2 or one of them is attached.), The extraction solvent extraction nozzle is provided with a valve 5, and the reflux condenser is provided with a refrigerant inlet 11 and a refrigerant outlet 12. ing.

The extraction unit A has a structure in which the extraction container 2 can be easily put in and taken out by removing the reflux condenser 1.

In FIG. 1, the solvent storage tank portion B is provided with three storage tanks 61, 62, and 63 so that three kinds of solvents can be used. It is sent to the extraction unit A. The solvent is selected and measured by opening and closing the valve 5 provided in each storage tank. In addition,
An appropriate number of storage tanks may be provided according to the type of extraction solvent used, and the number of storage tanks is not limited to three.

Specifically, the extraction of the crystalline polymer is performed as follows.

The crystalline polymer is put in the extraction container 2 by the method described below,
The reflux condenser is removed and set at a position 2 below the reflux condenser 1 of the extraction section A. Next, with the valves 5 of the extraction solvent extraction nozzles 41 and 42 closed, a fixed amount of solvent measured by the measuring device 7 is introduced into the heating section 31 via the conduit 8 and heated by the heating device 32. The evaporated vapor is cooled and condensed by passing the refrigerant through the reflux device 1, and the condensed solvent is dropped into the extraction container 2 and continuously extracted. After being extracted for a certain period of time, the solution containing the extracted polymer is discharged from the nozzle 41 or
It is taken out of the system using 42 and heated with a solvent if necessary.
After 31 is washed, the solvent to be extracted next is supplied to the heating unit 31 via the meter 7 and the conduit 8, and the same operation as above is repeated.

The extracted polymer solution is separated by distilling off the solvent or by pouring it into a large amount of a poor solvent for the polymer, and used for various analyses.

By introducing the extraction solvent to and from the extraction section A by using the valve 5 as an electromagnetic valve and interlocking with a timer in the above-mentioned series of operations, the heating amount of the heating device 32 can be controlled by a timer and a temperature controller. It is possible to extract under a certain condition by controlling in conjunction. Furthermore, it is possible to completely automate the above series of operations by causing a simple robot to take out and set the extraction container 2.

The shape and usage of the extraction container, which is important for effectively utilizing the apparatus of the present invention for the sequential extraction of crystalline polymer, will be described in detail below.

FIG. 2 shows a sectional view of an example of the extraction container 2.

Reference numeral 21 is a filter made of a sintered filter, a wire mesh or the like, which is usually circular and has a structure in which it is closely attached to a cylinder, and the filter can be attached to and detached from the cylinder by a filter retainer 22. Of course, it does not matter if they are fused together. twenty three
Indicates a rotary stirrer used when the crystalline polymer is dissolved. Further, 24 is a lid, 25 is a lid retainer, and 26 is a space for containing the crystalline polymer to be extracted.

The preferred practical use is shown below.

The crystalline polymer was placed in the 26 part of the extraction vessel 2 shown in FIG. 2 and then substantially dissolved under heating by a solvent capable of dissolving the crystalline polymer under heating, followed by cooling to crystallize and precipitate the polymer. Let it be a gel. In this state, it is set in the extraction unit A and subjected to sequential extraction operation.

Suitable crystalline polymers for applying sequential extraction using the apparatus of the present invention include, for example, poly α-olefins that are easily extracted and separated into components having different compositions by solvents having different boiling points, and the extraction solvent has a boiling point. Different hydrocarbon compounds or halogenated hydrocarbons having different solubility parameters, esters, ethers and ketones are used, and the extraction is carried out below the melting point of the crystalline polymer.

〔Example〕

 Hereinafter, the present invention will be further described with reference to examples.

Example A stainless steel container having the shape shown in FIG. 2 (inner diameter 30 mm, length
Two wire meshes of 60 mm and filter 200 mesh are stacked, and the lower lid is tapered and sealed with Teflon packing. In addition, the wire mesh is sealed by a screw-in type presser. 3) of a commercially available propylene block copolymer (Mitsui Toatsu Chemicals, Inc., Mitsui Noblene BJHH-G),
Kerosene (10 ml) was added, and the mixture was stirred at 130 ° C to completely dissolve it. Then, the mixture was kept at 25 ° C. for 24 hours to precipitate a gel.

The extraction section is a glass cylindrical container with an inner diameter of 60 mm and a length of 30 cm.A nozzle for extracting the extraction solvent is provided at a position 10 cm from the lower end, and the tip of the nozzle is 5 mm from the container bottom.
Is there. Further, a projection is provided on the inner side at a position 20 cm from the lower end so that the extraction container 2 can be attached with the filter downward. Further, it is connected to the reflux condenser made of glass with a slot. And 15 from the bottom
It has a structure in which a nozzle connected to the conduit from the solvent storage tank is provided at the position of cm. 1 volume for solvent storage
2 glass containers were used, the weighing machine was a 100 ml glass container, and they were connected with a Teflon tube and a cock as shown in FIG.

After setting the extraction container, put isopentane in the storage tank 61.
20 ml was put into the heating part 31 and subjected to reflux extraction for 6 hours, then the extraction solvent was taken out from the nozzle 41, and further 100 m of isopentane
washed with l. Next, the n-heptane from the storage tank 62 is heated by the heating unit 3
This was led to 1, and the extraction operation was performed in the same manner as below.

The obtained solution was poured into a large amount of acetone to precipitate and separate the polymer. The isopentane extraction part has an extraction amount of 8.3 wt%, 1
Intrinsic viscosity of tetralin solution at 35 ℃ 4.65, ethylene content 40.5
wt%, and the n-heptane extraction part is 7.8 wt.
%, 1.08, 13.2 wt%.

〔The invention's effect〕

INDUSTRIAL APPLICABILITY The apparatus of the present invention can be suitably used for sequential extraction and separation of crystalline polymers, and can be fully automated, which is extremely valuable industrially.

[Brief description of drawings]

FIG. 1 is a system diagram of the apparatus of the present invention, and FIG. 2 is a sectional view of an example of an extraction container.

Claims (2)

[Claims] 1. A solvent storage tank B comprising an extraction solvent storage tank, a meter connected to the storage tank, and a conduit to the extraction section, a reflux condenser on the upper side, and a crystalline polymer to be extracted at least on the lower side of the reflux condenser. An extraction container with a filter on the
A crystalline polymer sequential extraction / separation device, further comprising an extraction unit A having a heating unit and an extraction solvent take-out nozzle provided below. 2. The crystalline polymer according to claim 1, wherein the extraction container is provided with a detachable lid at one end of the cylinder and a filter closely attached to the cylinder at the other end or inside thereof. Sequential extraction and separation device.