JPH036234A - Method and apparatus for producing modified polymer - Google Patents

Abstract

PURPOSE:To effectively carry out a small-lot production of many kinds of polymers with a reduced changeover loss by taking a part of an oligomer out of the main production line, depolymerizing the taken-out oligomer, adding modifiers to it, and polymerizing it. CONSTITUTION:A modified polymer is produced with an apparatus equipped with: a flow channel 2 which leads an oligomer to a main polymerization vessel 1 (e.g. 1a-1c); a branch flow channel 3 to take a part of the oligomer out; a depolymerization vessel 4 which is equipped with a total reflux means 4a (e.g. a condenser) and in which the oligomer taken out by the branch flow channel 3 is depolymerized; a polymerization vessel 5 (e.g. 5a, 5b) in which the oligomer depolymerized in the depolymerization vessel 4 is polymerized; and a modifier- injecting means 6 (e.g. 61a-61d) which injects a modifier into the depolymerized oligomer before it is polymerized in the polymerization vessel 5.

Description

Detailed Description of the Invention [Industrial Field of Application] This invention relates to the production of a modified polymer, which is produced by combining a modified polymer with a modifier added to the polymer when producing a polymer such as polyester. The present invention relates to a method and an apparatus for manufacturing the same.

[Prior art and its problems] Conventionally, in the production of polymers such as polyester, when producing a modified polymer by copolymerizing this polymer with various modifiers, it is usual to produce a modified polymer by copolymerizing the polymer with various modifiers. The production line that had been used for this process was used as is, and a modifier was added to it and copolymerized to produce a modified polymer.

However, if a modified polymer is manufactured by using the production line used to manufacture the previous polymer as is, the quality will be constant due to the mixing of the previous polymer and the modified polymer at the time of switching. There was a problem in that the part where the previous polymer and the modified polymer were mixed had to be removed in order to prevent the polymer from becoming oxidized.

Particularly, as is the case today, when it is necessary to produce small quantities of various modified polymers with various modifiers added, each time a changeover is made, the previous polymer and the modified polymer mix. There was a problem in that the matching portion had to be removed, resulting in a large amount of loss, as well as a lot of unnecessary operation of the device, and a significant drop in production efficiency.

[Problems to be Solved by the Invention] This invention solves the above problems when producing a polymer such as polyester by copolymerizing such a polymer with various modifiers and combining the modified polymer with the product. The objective is to solve such problems.

In other words, in the process of producing polymers such as polyester, in the process of producing a modified polymer by copolymerizing such a polymer with various modifiers, the present invention eliminates the large amount of loss that occurs during switching as in the conventional method. The purpose of this invention is to make it possible to efficiently produce various modified polymers even in small quantities without causing any problems.

[Means for Solving the Problems] In order to solve the above-mentioned problems, the present invention, in producing a modified polymer, extracts a part of the oligomer in its oligomer state before polymerization, and After depolymerizing the extracted oligomers, various modifiers are added before the extracted oligomers are polymerized.

In addition, the apparatus for producing the modified polymer as described above includes a channel 2) that leads the oligomer to the main polymerization tank (1).
A depolymerization tank (4a) is provided with a branch path (3) for extracting a portion of the oligomer, and a total reflux means (4a) for depolymerizing the oligomer extracted through the branch path (3).
4), a polymerization tank (5) for polymerizing the oligomer depolymerized by this depolymerization tank (4), and this polymerization tank (5).
In this method, a modifier injecting means (6) for injecting a modifier into the oligomer at a stage before the oligomer extracted by the above is polymerized is used.

In this invention, known modifiers can be used as the modifier to be injected into the extracted oligomer, such as cationic dye dyeability, easy dyeability, flame retardancy, alkaline Easily soluble, hygroscopic, water absorbent, heat retaining, heat permeable and waterproof, anti-static conductivity, antifouling, antibacterial and aromatic, high heat shrinkability.

Modifiers with various properties such as elasticity, fusion properties, anti-build properties, and gloss can be used, and specifically, for example, lower alkyl modifiers such as phthalic acid, isophthalic acid, and 5-metal sulfoisophthalic acid. Esters or aromatic esters, polyethylene glycol, lithium acetate, titanium oxide, pigments, dyes, etc. can be injected.

[Operation: As described above, the flow path (which leads the oligomer to the main polymerization tank <1)
2) is provided with a branch path (3), a part of the oligomer before being polymerized is extracted from the flow path (2) through this branch path (3), and the extracted oligomer is transferred to the depolymerization tank (
4), and the oligomer is depolymerized while being totally refluxed by the total reflux means (4a) provided in the depolymerization tank (4).

The oligomers depolymerized in this way are then transferred to a polymerization tank (
Before the polymerization in step 5), a suitable modifier is added to the oligomer by the modifier injection means (6), and then various modifiers are added to the oligomer together with the oligomer in the polymerization tank (5). Copolymerization is used to produce modified polymers.

Therefore, when producing a modified polymer by copolymerizing various modifiers, there is no need to switch the production line for the previous polymer to the production of the modified polymer; There is no mixing with the modified polymer, the quality is stabilized, and there is no loss during switching.

[Example] Hereinafter, an example of the present invention will be specifically described based on the accompanying drawings.

In this example, a case will be explained in which a polyester is produced by a direct loading method using terephthalic acid and ethylene glycol as seven polymers.

In this example, first, terephthalic acid and ethylene glycol used as monomers are esterified in the first and second esterification tanks (7a) and (7b) to produce oligomers. I have to.

Then, most of the oligomers esterified in the esterification tanks (7a) and (7b) are transferred to the normal flow path (
2) through each of the first, second and third main polymerization tanks <la
>, (lb), (lc), and in these main polymerization tanks (la), (lb), (lc), the above oligomers are polymerized in order to produce polyester. However, the polyester produced as described above is extruded and cooled, then cut and dried to produce polyester chips.

On the other hand, in producing a modified polymer obtained by adding a modifier to polyester, the esterification tank (7a), (
A branch channel (3) is provided via a valve (3a) in the flow channel (2) that leads the oligomer esterified in step 7b) to the main polymerization tanks (Ia), (lb), and (lc). A part of the oligomer is extracted through the branch path (3),
The oligomer extracted in this way is led to a depolymerization tank (4).

Here, in this depolymerization tank (4), a total reflux means (4) for completely refluxing the oligomer extracted as described above is used.
As a), a condenser (4a) is connected to the depolymerization tank (4), and the oligomer is depolymerized while being totally refluxed by the condenser (4a).

Then, the oligomer depolymerized in this way is first
The polymer is introduced into the second polymerization tanks (5a) and (5b) in that order, and polymerized in these polymerization tanks (5a) and (5b).

In addition, before polymerizing the oligomer extracted through the branch path (3) as described above in the polymerization tanks (5a) and (5b), various modifiers are added to the extracted oligomer. The agent is added by means of an agent injection means (6).

Here, before the oligomer extracted through the branch path (3) is polymerized in the polymerization tanks (5a) and (5b), various modifiers are added by the modifier injection means (6). In this example, there are a pipe (3b) that leads the oligomer to the depolymerization tank (4), a depolymerization tank (4), and a pipe (3b) that leads the oligomer to the depolymerization tank (4), and a connection between the depolymerization tank (4) and the first polymerization tank (5a).
and the first polymerization tank <5a).
Modifier supply ports (61a
), <61b), (61c).

(61d), and each of these modifier supply ports (61a)
- (61d), various modifiers are supplied to the extracted oligomer.

Each of the above-mentioned modifiers is usually supplied as an ethylene glycol solution, but since the condenser (4a) is connected to the depolymerization tank (4) as described above, the ethylene glycol content is In the case of a large amount of modifier, a pipe (3b) leading the oligomer to the depolymerization tank (4) and a modifier supply port (61a) provided in the depolymerization tank (4), (
61b) for smooth mixing.

In order to supply various modifiers to each of the modifier supply ports (61a) to (61d), as shown in FIG. , (62
b), (62c), and (62d) contain various modifiers, and each of these storage tanks (62a) to (62d)
A stirring means (64) is provided in each of the storage tanks (62a) to (62d), and the various modifiers contained in the storage tanks (62a) to (62d) are stirred by the stirring means (64).

The various modifiers contained in the storage tanks (62a) to (62d) are then stored in the storage tanks (62a) to (62d).
Pass each supply pipe (65) through these supply pipes (65).
While adjusting the supply direction and supply amount with each valve (66) provided in each of the above-mentioned modifier supply ports (61).
An appropriate amount of an appropriate modifier is supplied to a) to (61d).

Next, a more specific example will be described in which modified polyester is produced by adding various modifiers to polyester using the above-mentioned apparatus.

(Example 1) In this example, a case will be described in which a modified polyester dyeable with cationic dyes is produced.

First, terephthalic acid and ethylene glycol are added to each of the first and second esterification tanks (7a).

After being esterified in (7b), a part of the thus esterified bis-β-hydroxyethyl terephthalate having an esterification rate of 90% or more is passed from the flow path 2) through the valve (3a). It was led to a branch path (3) and supplied to the depolymerization tank <4) through this branch path (3).

Here, a 5% by weight ethylene glycol solution of lithium acetate is stored as a modifier in the first storage tank (62a), and this modifier is poured into the valve (66) as described above.
) through the supply pipe (65) while adjusting the
The oligomer was introduced into a modifier supply port <61a) provided in the pipe (3b) leading to the depolymerization tank (4), and was continuously supplied from this modifier supply port (61a).

In addition, in the second storage tank (62b), as a modifier,
A 35% by weight ethylene glycol solution of 5-Na sulfo-bis(β-hydroxyethyl)isophthalate is accommodated and this modifier is fed through the feed pipe (65), regulated by the valve (66) as described above. Depolymerization tank (
4), and was continuously supplied from this modifier supply port (61b>).

In addition, in the third storage tank (62c), as a modifier,
A 30-fold ignited ethylene glycol solution of titanium oxide is stored, and this modifier is passed through the supply pipe (65) while adjusting the temperature with the valve chloroform as described above, and is then connected to the depolymerization tank (4) and the first polymerization tank. Pipe (3c) between tank (5a)
The modifier 1 was introduced into the modifier 1 supply port (61c) provided at the top of the modifier 1, and was continuously supplied from this modifier supply port (61c).

Then, as described above, the modifier supply ports (61a) (61b
The oligomer of bis-β-hydroxyethyl terephthalate to which each of the above-mentioned modifiers has been added is refluxed in the depolymerization tank (4
), the above-mentioned modifier is further added from the above-mentioned modifier supply port (61c), and the above-mentioned oligomer to which each modifier has been added is transferred to the above-mentioned first and second oligomers. Polymerization was carried out in polymerization tanks (5a) and (5b), and the absolute viscosity thereof was increased to 0.550.

The modified polyester thus obtained showed good dyeability with cationic dyes.

(Example 2) In this example, a case will be described in which a modified polyester dyeable with normal pressure cation dyes is produced.

In this example, as in the case of Example 1 above, terephthalic acid and ethylene glycol were esterified in the first and second esterification tanks (7a) and (7b). A part of the bis-β-hydroxyethyl terephthalate having an esterification rate of 90% or more is led from the flow path (2) to the branch path (3) via the valve (3a). (3) through the depolymerization tank (4
).

Then, as in the case of Example 1 above, the first storage tank (
62a) contains a 5% by weight ethylene glycol solution of lithium acetate, and the modifier is supplied to the modifier supply port (61a) provided in the pipe (3b) leading the oligomer to the depolymerization tank (4). ), and the second storage tank (62b) also contains 5-Na sulfobis (β
A 35-fold boiled ethylene glycol solution of -hydroxyethyl) isophthalate is stored, and this modifier is introduced into the modifier supply port (61b) provided in the depolymerization tank (4), and this modifier supply port (61b).

In this way the first and second storage tanks <62a>).

The bis-β-hydroxyethyl terephthalate oligomer supplied with each modifier from the depolymerization tank (62b) is completely refluxed through the condenser (4a).
4) to cause depolymerization.

On the other hand, in the third storage tank (62c), as a modifier,
Polyethylene glycol with an average molecular weight of 600 is contained, and this modifier is added to the depolymerization tank (4) and the first polymerization tank (5a).
) Modifier supply port provided in the vibrator (3c) between <
61c).

The oligomers to which each modifier has been added are then transferred to the first and second polymerization tanks (5a) and (5b).
The absolute viscosity was increased to 0.550.

The modified polyester thus obtained was easily dyed with ordinary disperse dyes, and was also dyeable with cationic dyes under normal pressure.

(Example 3) In this example, a case will be described in which a modified polyester that is easily alkali soluble is produced.

In this example, as in Examples 1 and 2, terephthalic acid and ethylene glycol were esterified in the first and second esterification tanks (7a).

After esterification with (7b), a part of the bis-β-hydroxyethyl terephthalate of E was esterified in this way with an esterification rate of 90% or more.

The branch path (3) is connected to the flow path (2) via the valve (3a).
) and supply it to the depolymerization tank (4) through this branch (3).

In this example, a modifier having an average molecular weight of 4000 is added to the first storage tank (62a).
of polyethylene glycol with steam to 100-150%
A pipe (3b) that contains a liquid heated at ℃ and leads this modifier to an oligomer depolymerization tank (4).
5-Na is continuously supplied from the modifier supply port (61a) provided in the second storage tank <62b).
A 35% by weight ethylene glycol solution of sulfobis(β-hydroxyethyl) isophthalate was stored, and the modifier was supplied to the modifier supply port (6) provided in the depolymerization tank (4).
1b) was made to be continuously supplied.

Thus the first and second storage tanks (62a).

The bis-β-hydroxyethyl terephthalate oligomer supplied with each modifier from the depolymerization tank (62b) is completely refluxed through the condenser (4a).
After being depolymerized in step 4), this oligomer was polymerized in the first and second polymerization tanks (5a) and (5b) to increase its absolute viscosity to 0.70.

The modified polyester thus obtained had an alkali weight loss rate of 80 times that of ordinary polyester.

In this way, when each of the modified polyesters of Examples 1 to 3 above was manufactured one after another, the occurrence of loss when changing over each type was significantly reduced compared to the conventional continuous system. .

The types of modified polymers produced using the above-mentioned apparatus are not limited to those shown in Examples 1 to 3 above, and the types of modified polymers manufactured using the above-mentioned apparatus are not limited to those shown in Examples 1 to 3 above, and the types of modified polymers to be produced using the above-mentioned apparatus are not limited to those shown in Examples 1 to 3 above. By changing the type etc., various types of modified polymers can be manufactured.

[Effects of the Invention] As detailed above, in this invention, a branch path is provided in the flow path that leads the oligomer to the main polymerization tank, and a part of the oligomer before being polymerized is transferred from the flow path through the branch path. The oligomer thus extracted is led to a depolymerization tank, and the oligomer is depolymerized while being completely refluxed by a total reflux means provided in the depolymerization tank, and then the depolymerized oligomer is Before polymerizing with heavy metal species, the oligomer extracted as above is
A suitable modifier is added by a modifier injection means, and the various modifiers thus added and the above oligomer are copolymerized in a polymerization tank to produce a modified polymer. .

Therefore, in this invention, as in the conventional case,
There is no need to switch the previous polymer production line to the modified polymer production line, and at the time of switching,
The previous polymer and the modified polymer no longer mix.

As a result, in the present invention, when producing a modified polymer by copolymerizing various modifiers, there is no need for a lot of loss during switching, unlike in the past. Modified polymers can now be produced easily, with stable quality, and efficiently even in small quantities.

[Brief explanation of the drawing]

FIG. 1 is a schematic diagram showing an embodiment of the present invention, and FIG. 2 is a schematic diagram showing a modifier supply route in the same embodiment. Explanation of symbols

Claims (2)

[Claims] 1. A part of the oligomer is extracted in the state of the oligomer before being polymerized, and after depolymerizing the extracted oligomer, in order to polymerize it, at a stage before the extracted oligomer is polymerized. A method for producing a modified polymer, characterized in that various modifiers are added. 2. In the channel (2) that leads the oligomer to the main polymerization tank (1),
A branch path (3) is provided to extract a part of this oligomer,
A depolymerization tank (4) equipped with a total reflux means (4a) for depolymerizing the oligomer extracted through this branch path (3)
and a polymerization tank (5) in which the oligomer depolymerized by this depolymerization tank (4) is polymerized, and the oligomer extracted by this polymerization tank (5) is reformed into the above-mentioned oligomer at a stage before being polymerized. Modifier injection means for injecting the modifier (
6) A modified polymer production apparatus characterized by comprising: