JP3362438B2 - Method for obtaining block copolymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the acquisition of a block copolymer.
About the law. [0002] 2. Description of the Related Art Conventionally, isobutylene and aromatic vinyl
Various methods for producing block copolymers with compounds have been reported.
I have. For example, isobutylene and an aromatic vinyl compound
The followingGeneral formula 1Organic compounds having the functional groups shown in
Polymerization in the presence of an initiator system consisting of an isocyanate catalyst
The law has been reported. The target solution is contained in the polymerization solution after the reaction.
Since the catalyst residue coexists in addition to the lock copolymer,
It is necessary to remove the medium residue. However, in the method described above
The polymerization solution has a high viscosity, and the catalyst is filtered from the polymerization solution.
Was difficult to remove. Therefore, add a solvent
To lower the viscosity of the polymerization solution by adding
Requires a large amount of solvent, and is inefficient and productive
However, there is a drawback that is reduced. In contrast, the block
A solution that solidifies the copolymer and dissolves the catalyst
A method of removing a catalyst residue using a medium has been adopted.
However, in this method, part of the catalyst is contained in the block copolymer.
And the purity of the block copolymer must be
Was also unsatisfactory. [0003] SUMMARY OF THE INVENTION The present invention has been developed in view of such circumstances.
It is based on removing catalyst residues from the polymerization solution.
To obtain the desired block copolymer with high purity
It is intended to provide. [0004] According to the present invention, there is provided:
For example, (A) isobutylene and an aromatic vinyl compoundunder
General formula 1Organic Compounds Having Functional Groups and Lewis Acids
Polymerizing in the presence of an initiator system comprising a catalyst,
(B) The solubility coefficient in the polymerization solution is 14 to 17 (MPa).
^1/2To form a block copolymer by adding
Dissolving step and (C) solubility coefficient is 24-30 (M
Pa)^1/2Add a polar solvent to remove catalyst residues
A block copolymer, characterized by comprising
An acquisition method is provided.General formula 1: Embedded image (Where R¹Is a hydrogen atom, an alkyl groupOrAryl group
And R²Is an alkyl groupOrAn aryl group is represented by R³Is halo
Gen atom, alkoxy groupOrShows an acyloxy group. ) In the present invention, first, as step (A),
Sobutylene and an aromatic vinyl compound,General formula 1Shown in
Opening of organic compound with functional group and Lewis acid catalyst
Polymerize in the presence of the initiator system. As an aromatic vinyl compound
For example, styrene, α-methylstyrene, β-meth
Tyl styrene, dimethyl styrene, t-butyl styrene
, Monochlorostyrene, dichlorostyrene, methoxy
Styrene or the like is used. In the present invention,
Ten, pentene, hexene, butadiene, isoprene,
Other cationically polymerizable monomers such as methyl vinyl ether
Can be used. [0006] The initiator system comprises a specific organic compound and a Lewis acid.
Consists of Organic compoundsGeneral formula 1With the functional groups shown in
For example, 2-chloro-2-phenylp
Lopan, 1,4-bis (2-chloro-2-propyl) be
Benzene, 1,3,5-tris (2-chloro-2-prop
B) benzene, 2-chloropropane, t-butyl chloride
And halogen compounds such as α-chloroethylbenzene;
2-methoxy-2-phenylpropane, 1,4-bis
(2-methoxy-2-propyl) benzene, 2,4,6
-Trimethyl-2,4,6-trimethoxyheptane, t
-Butyl methyl ether, isopropyl methyl ether
Compounds having an alkoxy group such as 2-acetoxy-
2-phenylpropane, bis (2-acetoxy-2-p)
Ropyl) benzene, 1,3,5-tris (2-acetoxy
(S-2-propyl) benzene, 2,4,6-trimethyl
-2,4,6-triacetoxyheptane, triphenyl
Acylo such as methyl acetate and t-butyl acetate
A compound having a xy group is used. Organic compounds
The amount used is usually 0.00 mol per mol of isobutylene.
The range is from 0.01 to 0.002 mol. Metal halides are used as Lewis acids.
For example, BCl₃, BF₃, BF₃OEt₂,
TiCl₄, SnCl₄, AlCl₃Or its chlorine source
Whose mono- or di-substituted with an alkyl group, SbC
l₅, SbF₅, WCl₆, TaCl₅Etc.
You. The amount of Lewis acid used is as described above.Shown in general formula 1Functional group 1
It is usually at least equimolar, preferably 1 to 10
It is in the range of 0 mol. In the polymerization, ammonium salt, methylamino
Dimethylamine, triethylamine, aniline,
Amines such as peridine,
Ters and the like can be used. Ammonium salt,
The amount of the mins or esters used is as described above.Shown in general formula 1
YouUsually, 0.01 to 100 moles per mole of functional group
, Preferably in the range of 0.1 to 10 moles. [0009] The polymerization can be carried out in the presence of a solvent.
You. The solvent is not particularly limited as long as it is inert to the polymerization reaction.
No, for example, pentane, hexane, heptane, cyclo
Aliphatic hydrocarbons such as hexane and methylcyclohexane
Element: aromatic hydrocarbons such as benzene, toluene, and xylene
Nitrogen; nitro compounds such as nitromethane and nitroethane;
Methyl chloride, methylene chloride, 1,2-dichloroethane
Which halogenated hydrocarbons, nitromethane, nitroethane
Such as nitro compounds, or a mixed solvent thereof
Is mentioned. [0010] The polymerization temperature is usually from -120 to + 50 ° C,
Preferably it is -100 to + 20 ° C. Especially the polymerization time
Without limitation, types of organic compounds, Lewis acids, amines,
It can be adjusted by the amount used. The structure of the block copolymer is a branched block.
It may be a copolymer or a linear block copolymer
And a mixture thereof. Block
When the polymer is a linear block copolymer, for example,
Uses an initiator compound having two functional groups and a Lewis acid
And polymerize isobutylene until the reaction is substantially complete.
After that, an aromatic vinyl compound is added to the polymerization system to polymerize.
It can be produced by a method in which the reaction is continued. one
On the other hand, in the case of a branched block polymer, usually three or more
Using a Lewis acid with an initiator compound having the above functional group
Isobutylene polymerized until the reaction was substantially complete.
First, an aromatic vinyl compound is added to the polymerization system to cause a polymerization reaction.
Can be manufactured by using a method of continuing. After the completion of the polymerization reaction, as the step (B),
Solution has a solubility coefficient of 14 to 17 (MPa)^1/2Aliphatic
Hydrocarbon is added to dissolve the block copolymer. Book
The solubility coefficient in the present invention is POLYMER HAND
BOOK, THIRD EDITION, VII / 52
6 to VII / 533, δ (MP described in TABLE 3.1)
a)^1/2It is shown by. The solution used in the present invention
Resolution factor is 14 to 17 (MPa)^1/2Aliphatic hydrocarbons
Is for dissolving the block copolymer, for example,
Pentane, hexane, heptane, octane, cyclohexene
Examples thereof include sun and methylcyclohexane. in
Hexane, cyclohexane, methylcyclohexane
Preferably, methylcyclohexane is particularly preferred. Heel
The amount of the aliphatic hydrocarbon used is usually the amount of the block copolymer.
2 to 10 times by weight. When dissolving, stirring may be performed.
preferable. In addition, heat reflux to about 40-80 ° C.
May be preferred. Next, as a step (C), dissolution in the solution
Degree coefficient is 24 to 30 (MPa)^1/2Add the polar solvent
To remove catalyst residues. Adding such a polar solvent
The system is aliphatic carbonized with the block polymer dissolved
It consists of a hydrogen layer and a polar solvent in which the catalyst is dissolved.
The block copolymer and the catalyst.
Can be separated. In the present invention, the step (B)
And step (C) may be interchanged. That is,
(A) The polymerization solution obtained in the step has a solubility coefficient of 24 to
30 (MPa)^1/2Add a polar solvent to dissolve the catalyst
And then the solubility coefficient is 14-17 (MPa)^1/2Fat
Dissolve block copolymer by adding aliphatic hydrocarbon solvent
May be. A solubility coefficient of 24 to 30 (MPa)^1/2of
Examples of polar solvents include, for example, methanol and ethylene glycol.
Coal, acetonitrile, N, N-dimethylformami
, Nitromethane, propylene carbonate, etc.
Is done. Among them, methanol and ethylene glycol
Preferably, methanol is particularly preferred. Such polar solvents
The amount used is usually 0.1 to 0.1 to the aliphatic hydrocarbon.
0.5 weight times. When dissolving, stir
Is preferred. By the above operation, the system was divided into two layers.
From the aliphatic hydrocarbon in which the block polymer is dissolved
Layer and separate it by, for example, steam coagulation.
Block copolymerization by removing aliphatic hydrocarbons
You can get the body. The block weight obtained in this way
The coalesce has an isobutylene content of 50 to 95% by weight, preferably
More preferably 55 to 90% by weight, and the styrene content is 5 to 5%.
0% by weight, preferably 10-45% by weight of the copolymer.
You. The number average molecular weight of the block copolymer is 10,10.
The range is from 000 to 500,000. [0017] Thus, according to the present invention, from the polymerization solution
Removes catalyst residues and purifies the target block copolymer with high purity.
Can be obtained. [0018] The present invention will be described in more detail with reference to the following examples.
Will be described. Note that, in the examples, comparative examples and reference examples,
% And% are by weight unless otherwise specified. Example 1 Isobutylene was added to the reactor at -70 ° C under dry nitrogen atmosphere.
126 grams, bis (2-chloro-2-propyl) ben
0.58 grams of Zen, 0.15 grams of triethylamine
708 g of methyl chloride, methylcyclohexane 7
Add 2 grams and 8.54 grams of titanium tetrachloride and add 1 hour
Polymerization was performed. Then add 41 grams of styrene,
Polymerization was performed for 0.5 hour. Add 15 grams of methanol
Thus, the polymerization was stopped. After the polymerization, 540 g of polymerization solution
Add 370 grams of methylcyclohexane to the ram and add
Stirred for 0 minutes. Then add 76 grams of methanol
After stirring for 10 minutes, centrifugation (2000
(Rev / min). Separate the cyclohexane layer and remove
When the block copolymer was solidified, 150 block
I got it. The bound styrene content of the resulting copolymer was 2
4.0% by weight (¹Calculated by H-NMR), number average
Molecular weight (for gel permeation chromatography
Calculated as polystyrene) 68,000
Was. In addition, the amount of catalyst residue in the block copolymer is inductively linked.
When measured by plasma emission spectroscopy, titanium
The amount was 10 ppm or less. Comparative Example 1 Polymerization was performed in the same manner as in Example 1, and the obtained polymerization solution was
The block copolymer was obtained by steam coagulation. block
Inductively coupled plasma emission spectroscopy is used to determine the amount of catalyst residue in the copolymer.
The titanium content was found to be 0.7% by the precipitation method.
Was.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-3-174403 (JP, A) JP-A-64-62308 (JP, A) JP-A-64-56713 (JP, A) 157418 (JP, A) JP-A-54-90391 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 297/00 C08F 6/08

Claims (1)

(57) [Claims] (A) Isobutylene and aromatic vinylation
With the compoundThe following general formula 1Organic compounds having the functional groups shown in
Polymerized in the presence of an initiator system consisting of a product and a Lewis acid catalyst
And (B) a solubility coefficient of 14 to 17 in the polymerization solution.
(MPa)^1/2Addition of aliphatic hydrocarbon blocks
Dissolving the copolymer and (C) having a solubility coefficient of 24
Up to 30 (MPa)^1/2Add a polar solvent to the catalyst residue
Removing the blocks.
Method for obtaining polymer.General formula 1: Embedded image (Where R¹Is a hydrogen atom, an alkyl groupOrAryl group
And R²Is an alkyl groupOrAn aryl group is represented by R³Is halo
Gen atom, alkoxy groupOrShows an acyloxy group. )