JPH03137114A - Star-shaped multi-branched polymer - Google Patents

Abstract

PURPOSE:To obtain the subject novel polymer useful as a reinforcing agent for multiple-phase polymer, an adsorbent for low-molecular compound and ion, etc., by bonding plural branches composed of a polymer of an alkenyl ether to a core composed of a crosslinked polymer of a dialkenyl ether. CONSTITUTION:The objective polymer has a structure produced by using a polymer of formula II (m is integer) produced by polymerizing an alkenyl ether of formula I (R<1> is H or methyl ; R<2> is univalent organic group) as a branch and bonding >=2 branches to a core composed of a polymer of formula IV (n is integer) consisting of a crosslinked polymer of a dialkenyl ether of formula III (R<3> and R<5> are R<1>; R<4> is bivalent organic group). The polymer is preferably synthesized by polymerizing the monomer of formula I by cationic polymerization to synthesize the polymer of formula II to form a branch and adding the monomer of formula III to be used as a raw material for the core to the above reaction solution without terminating the former reaction.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to star-shaped hyperbranched polymers, and more specifically, the present invention uses a polymer of alkenyl ether as a technique and a crosslinked polymer of dialkenyl ether as the core. The present invention relates to star-shaped multibranched polymers that can be used as reinforcing agents for multiphase polymers, adsorbents for small molecules and ions, metal ion carriers, reaction catalysts, etc.

[Conventional technology]

Star-shaped multibranched polymers can generally be synthesized by reacting a linear living polymer with a trifunctional or polyfunctional monomer.

On the other hand, when alkenyl ether is homopolymerized, a high polymer is produced only by cationic polymerization, but in general, migration and termination reactions are likely to occur, so living polymerization thereof has been difficult.

Therefore, star-shaped hyperbranched polymers using alkenyl ether polymers have not been previously obtained.

However, the present inventors have recently discovered that alkenyl ethers undergo living polymerization when an initiator consisting of hydrogen iodide and iodine or zinc halide is used (Proceedings of the Society of Polymer Science and Technology, Vol. 32, 187.188 ,190,1
439.1443 (1983); Macromolec
ules.

Volume 17, 265 (1984), etc.).

(Problem to be solved by the invention) Since living cationic polymerization of alkenyl ethers has been difficult, star-shaped hyperbranched polymers made from alkenyl ether polymers are expected to have many useful applications from an industrial standpoint. However, until now it has not been synthesized at all.

The present invention aims to solve the above-mentioned conventional problems and to provide a star-shaped hyperbranched polymer using an alkenyl ether polymer using the living cationic polymerization recently discovered by the present inventors. do.

[Means for Solving the Problems] The present inventors have conducted extensive research to achieve the above objects, and as a result, have arrived at the present invention.

That is, the present invention is represented by the formula CI) CHR'=CH(OR'')...CI) (wherein R1 represents a hydrogen atom or a methyl group, and R2 represents a monovalent organic group) Polymer (n) of alkenyl ether (wherein R' and R2 are the same as the general formula [II, m is 1
(indicates an integer greater than or equal to
...(Illi) (wherein R3 and R5 represent a hydrogen atom or a methyl group, and R4 represents a divalent organic group)
) (wherein R'', R' and R5 have the same meanings as in general formula (III) and 1.n represents an integer of 1 or more), and to this nucleus, the above alkenyl ether polymer (II) is added. 2 branches
The subject matter is a star-shaped multibranched polymer characterized by having a structure with more than one bond.

The present invention will be explained in detail below.

The alkenyl ether used in the present invention has the general formula C
I), in which R' represents a hydrogen atom or a methyl group. Further, in the formula, R2 represents a monovalent organic group, for example,
Alkyl group, acyloxyalkyl group, cycloalkyl group, aryl group, aralkyl group, alkoxyalkyl group,
Indicates an aryloxyalkyl group, etc., which may be substituted with a hydroxyl group, a halogen atom, an alkoxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, or a phthalimide group, and the carbon chain may have a hetero group. good. Preferred examples of Rt include an aralkyl group, an acyloxyalkyl group, and a hydroxyalkyl group, and particularly preferred are these three types of substituents consisting of a lower alkyl group having 1 to 6 carbon atoms.

Specific examples of the above-mentioned alkenyl ethers include compounds shown in 1 to 5 in Table 1 below.

Note that alkenyl ethers in which R2 is a hydroxyalkyl group can be easily obtained by alkaline hydrolysis of an acyloxyalkyl group, as described below, so for convenience,
It is omitted from the table below.

The alkenyl ether polymer of the present invention has the general formula (
II) and is synthesized by living cationic polymerization.

The details of the polymerization are described in JP-A No. 60-228509 by the present inventors.
No. 62-109373 and patent application No. 63-239
As described in No. 400, any initiator that initiates living cationic polymerization may be used as the polymerization initiator (specifically, the following protonic acid Examples include initiators that combine (Hl and phosphoric acid ester derivatives) and Lewis acids (such as rz and zinc halides).

HI/I! , HI/Zn 1. , HI/ZnCL.

HT/5nCj! z, HOP (0) (○CbHs
)2/Zn I2. HOPH(OC,Hs), /Zn
C1 The above protonic acid/Lewis acid has a molar ratio of 500 to
It is used in a range of 0.01, preferably in a range of 100-0.1, more preferably in a range of 50-1. These Lewis acids may be used as they are or may be diluted with an inert solvent.

The polymerization reaction for synthesizing the polymer (n) may be carried out without a solvent, but usually aliphatic hydrocarbons such as n-hexane and cyclohexane; aromatic hydrocarbons such as benzene and toluene; carbon tetrachloride , halogenated hydrocarbons such as methylene chloride; ethers such as diethyl ether and tetrahydrofuran are used as reaction solvents. These solvents may be used alone or in combination of two or more.

The charging ratio of solvent and monomer is usually 1:1 to 100:1.
(weight ratio) is preferred, particularly preferably 5:1 to 30:l. The charging ratio (weight ratio) of monomer and initiator is usually 2.
:1~1ooo: i range, especially 5:1~
100:1 is preferred.

The polymerization temperature may be 60°C or lower, but preferably 40°C or lower, and of course a temperature of 0''CC or lower may be used without any problem.

Polymerization may be carried out by homopolymerizing alkenyl ether CI) using the above-mentioned initiators, or by copolymerizing two or more alkenyl ethers, or by copolymerizing one or more alkenyl ethers. After polymerizing the alkenyl ether By, one or more other alkenyl ethers may be added and further polymerized to form a block copolymer.

The side chain substituent of the polymer (n) thus obtained may be converted into another substituent by a polymer reaction after synthesizing the star-shaped multibranched polymer of the present invention. An example of conversion of such a side chain substituent is conversion of an acyloxy group to a hydroxyl group by alkaline hydrolysis.

The dialkenyl ether that is the raw material for the core of the star-shaped multibranched polymer of the present invention is represented by the general formula CI), in which Rf
f and R5 represent a hydrogen atom or a methyl group. Further, in the formula, R4 represents a divalent organic group, and preferred organic groups are, for example, a methylene group, a phenylene group, etc., and these may be substituted with a hetero group. As specific examples of such dialkenyl ethers, the following compounds are preferably mentioned, but the invention is not limited thereto.

C) h=CHOffcHa ding-OCH=(jlz(2:
(integer greater than or equal to 1) CHz=CH0C1hCIh R' C)lzcH
zo CH=CHx The star-shaped multibranched polymer of the present invention is produced by first synthesizing the living polymer (If) by cationic polymerization of the monomer (I), and then adding it to the solution without stopping the reaction. It is synthesized by immediately adding dialkenyl ether (I[), which is the raw material for the nucleus. The charging molar ratio of (III)/(n) is 1:1.
As long as it is in the range of ~100:1 (especially 3:1~10:
l is preferably 0. The reaction solvent and temperature are the same as the above-mentioned polymer (II
), but is not limited to this.

Generally, when dialkenyl ether (I[) is added to living polymer (II), one of the two vinyl groups of (III) is thought to be added to the active end of (It). Repeatedly ℃, (II)
A kind of AB block polymer is produced in which several (I[] are bonded to each other. In this block polymer, unreacted vinyl groups derived from (I[) exist as side chain substituents, and these vinyl groups It is thought that a cross-linking reaction occurs when the active terminals of the AB block polymer and AB block polymer react one after another intermolecularly, and the core of the star-shaped multibranched polymer is formed.In fact, (
When (I[) is added to n), both vinyl groups of (I[I) are completely consumed and the product is completely soluble in the organic solvent used in the reaction. , its weight average molecular weight is several times to 100 times that of [■].
It increases by about twice as much. These facts indicate that through the above-mentioned crosslinking reaction, crosslinked polymer (IV) of (III) is converted into polymer (II).
) are chemically bonded to form a star-shaped multibranched polymer.

FIG. 1 is a schematic structural diagram of the star-shaped multibranched polymer of the present invention obtained as described above, in which (1) is the nucleus of crosslinked copolymerization (IV), and (2) is a technique of polymer (n) bonded to nucleus (IV), and there are two or more.

〔Example〕

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

In addition, each measurement in the following examples was performed by the following method.

(1) The number average molecular weight Mn of the branching polymer is G
PC (JASCO Corporation “TRI ROTAR” chromatograph, column: Showa Denko polystyrene gel A302.A
303. A304 (total of 3 columns in series); each column had an inner diameter of 8 m and a length of 500 cm).

(2) The weight average molecular weight (Mw) of the star-shaped polymer was determined by small-angle laser light scattering (KMX-6 model manufactured by Chromatix, light source: He-Ne laser (λ-633nlI), solvent: THF).

(3) The -NMR spectrum of the star-shaped polymer was obtained using a nuclear magnetic resonance spectrometer G5X-270 spectroscopy type of JEOL Ltd.
Measurements were made in room temperature CDCIls.

Example 1 To 10.5 liters of toluene sufficiently purified under a nitrogen atmosphere,
Isobutyl vinyl ether 475moj! Carbon tetrachloride, which is used as an internal standard for gas chromatography, is dissolved by adding 0.0% carbon tetrachloride. 75-
2 was added and cooled to -40°C.

Next, a toluene solution of hydrogen iodide (150mM) 1
．． 0 all and a diethyl ether solution of zinc iodide (1
．． 5mM) 2.0 all were added in this order to start polymerization, and the polymerization was continued for 40 minutes.

When the conversion rate of isobutyl vinyl ether was approximately 100%, the polymerization temperature was lowered to -78°C, and a toluene m solution (250 mM) of divinyl ether of the following formula (250 mM) 3.0 x 1 (5 equivalents to living carbon) was added. .

Immediately thereafter, the temperature was raised to -40°C and sufficient stirring was continued using a magnetic stirrer. Divinyl ether was completely consumed in 1 hour.

Thereafter, the reaction was further continued for 16 hours, and when the polymerization system was colored yellowish brown, the polymerization was stopped with methanol containing a small amount of aqueous ammonia.

Next, the mixture obtained by terminating the polymerization was washed with an aqueous sodium thiosulfate solution (approximately 10 tvt/νo1%) and then with water, and the solvent and the like were evaporated from the mixture to recover the product.

As a result, it is soluble in organic solvents such as hexane, toluene, methylene chloride, and chloroform, and has a polymerization degree of 38.
Mw=7.8×10' - 0.85 g of star-shaped polyvinyl ether with 14 branches per molecule was obtained. The yield of Ca was 100%. As a result of NMR analysis,
No vinyl groups were detected in the resulting polymer.

Example 2 0.75 tal (0°713 mof/f) of isobutyl vinyl ether was added and dissolved in sufficiently purified toluene 6.5a+1° under a nitrogen atmosphere, and carbon tetrachloride, which was used as an internal standard for gas chromatography, was dissolved. 0.75ml
and cooled to -40°C.

Next, a toluene solution of hydrogen iodide (150mM) 1
．． 0 ran and a diethyl ether solution of zinc iodide (2
, 0mM) were added in this order to initiate polymerization. Here, the concentration of living growing terminals [P2
] was set to be 1.5 times that of Example 1.

The following procedure was carried out in the same manner as in Example 1, except that the amount of divinyl ether used in Example 1 was changed to 7 equivalents relative to the living chain, and the reaction time after addition of divinyl ether was changed to 25 hours.

As a result, a star-shaped polymer with a branch polymerization degree of 38 and 59 Mw=3.8×10S branches was obtained (0.85 g, yield: Ca, 100%).

The solubility of the obtained polymer was similar to that of Example 1.

Example 3 The same procedure as in Example 1 was carried out except that the degree of polymerization of divinyl ether (ie, polyisobutyl vinyl ether) in Example 1 was changed to 76, and the reaction time after addition of divinyl ether was changed to 30 hours.

As a result, a star-shaped polymer with Mw=5.6×10′ and six branches was obtained (0.95 g, yield: Ca.

100%).

The solubility of the polymer was similar to Example 1.

Example 4 The same procedure as in Example 1 was carried out except that the branch in Example I was changed to polyethyl vinyl ether and the reaction time after addition of divinyl ether was changed to 35 hours.

As a result, a star-shaped polymer with an Mw of 5.41×10′ and 11 branches was obtained (0.70 g, yield: Ca,
LOO%).

Example 5 The divinyl ether forming the nucleus in Example 5 was changed to a compound of the following formula, and the polymerization solvent was changed to methylene chloride.
It was carried out in the same manner as in Example 1.

Nevertheless, it precipitated.

The divinyl ether was completely consumed in about 12 hours after addition, and the polymerization system became homogeneous. Thereafter, the reaction was continued for an additional 12' hours, and when the mixture was colored pale yellow, the polymerization was stopped in the same manner as in Example 1, and the same procedure was carried out thereafter.

Sono result, MW"=2.61 x 10', number of branches 5
A star-shaped polymer was obtained.

The solubility of the polymer was similar to Example 1.

Example 6 Example 1 was repeated except that the divinyl ether was replaced with a compound of the following formula having a more flexible spacer.

Divinyl ether is completely dissolved at room temperature, but
When added to the polymerization system at -40°C, low concentration divinyl ether was completely consumed at a rate of 2 hours after addition, but
The reaction continued for 5 hours.

As a result, a star-shaped polymer soluble in common organic solvents was produced (50 wt%), but a large amount of low molecular weight products were produced as by-products (50 wt%). This low molecular weight product is believed to be an AB type block polymer of isobutyl vinyl ether and divinyl ether.

Example 7 7°2 t of methylene chloride thoroughly purified under nitrogen atmosphere
an, 2-vinyloxyethyl acetate having an ester group in the side chain) 0.39+ai! (0゜3'15 taol/
1) was added and dissolved, and 0.41 mff1i of bromobenzene was added as an internal standard for gas chromatography.
Cooled to -15°C.

Next, a hexane solution of hydrogen iodide (100mM) 1
．． A diethyl ether solution of Otan and zinc iodide (20
(mM) 1.0 ml were added in this order to start polymerization, and the polymerization was continued for 4 hours.

The following procedure was carried out in the same manner as in Example 1, except that the reaction time after addition of divinyl ether was changed to 3 hours.

As a result, a star-shaped polymer with a degree of polymerization of branches of 30, Mw = 8.9 x 104, and number of branches of 15, which is soluble in organic solvents such as toluene and methylene chloride, was obtained (0.5-8 g, yield :Ca, 100%).

The above polymer (0.3 g) was mixed with an acetone/water mixed solvent (1
: 1voj! /vof) 20 an! 5 equivalents of sodium hydroxide (2NNa
OHaq) 3.84 rsl was added and stirred at room temperature for 3 days.

As a result, the ester groups in the side chains were quantitatively converted to hydroxyl groups, yielding a hydrophilic star-shaped polymer that was soluble in water and methanol and insoluble in organic solvents such as toluene and methylene chloride.

Note that the polymer was purified by dialysis.

Example 8 The same procedure as in Example 1 was carried out except that the branch in Example 1 was changed to a block polymer of 2-, dioxyethyl acetate, and isobutyl vinyl ether (polymerization degree ratio: 10/30).

As a result, a star-shaped block polymer with Mw=5.02X10' and 8 branches was obtained (0.60 g, yield; Ca
, 100%).

The above polymer (0.6 g) was dissolved in dioxane (20 x 2) and reacted for 4 days in the same manner as in Example 7.

As a result, an amphiphilic star-shaped block polymer with branches consisting of hydrophilic and hydrophobic segments was obtained. The obtained polymer was soluble in toluene, methylene chloride, chloroform, methanol, and ethanol.

Example 9 The same procedure as in Example 1 was carried out except that the initiator in Example 1 was changed to a hydrogen iodide adduct of 2-vinyloxyethyl acetate.

As a result, Mw-7, 35xlO', number of branches is 13,
A star-shaped polymer was obtained in which only the surface was covered with functional groups (ester groups).

Furthermore, by performing hydrolysis in the same manner as in Example 8, a star-shaped polymer having hydroxyl groups on the surface was also synthesized.

〔Effect of the invention〕

As is clear from the above results, the present invention has the remarkable effect of providing a star-shaped hyperbranched polymer of alkenyl ether, which has not been obtained hitherto, and is of industrial value. These polymers have unprecedented structures and spatial morphologies, and are expected to be useful as reinforcing agents for multiphase polymers, adsorbents and carriers for small molecules and ions, and reaction catalysts. .

[Brief explanation of the drawing]

FIG. 1 is a schematic structural diagram of the star-shaped multibranched polymer of the present invention, in which (1) represents the core of the crosslinked copolymer (IV),
(2) represents a branch of polymer (II) bonded to core (IV).

Claims (1)

[Claims] (1) General formula [I] CHR^1=CH(OR^2)...[I] (In the formula, R^1 represents a hydrogen atom or a methyl group, and R^2
indicates a monovalent organic group) [II] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼... [II] (In the formula, R^1 and R^2 are the general formula [I ], where m represents an integer of 1 or more) is the branch, and the general formula [III] CHR^3=CH-O-R^4-O-CH=CHR^5
...[III] (In the formula, R^3 and R^5 represent a hydrogen atom or a methyl group, and R^4 represents a divalent organic group) [IV] Crosslinked polymer of dialkenyl ether [IV] ▲ There are mathematical formulas, chemical formulas, tables, etc.▼...[IV] (In the formula, R^3, R^4 and R^5 are general formulas [III]
(n is an integer of 1 or more) as a core, and the above alkenyl ether polymer [
A star-shaped multibranched polymer characterized by having a structure in which two or more branches of [II] are bonded together.