JPH03281605A - Production of polymer - Google Patents

Abstract

PURPOSE:To produce a high-molecular polymer having a narrow mol.wt. distribution at an arbitrary rate of polymerization by polymerizing a cationically polymerizable vinyl monomer in the presence of a specified initiator system and a specified oxygenous compound. CONSTITUTION:A process for polymerizing at least one cationically polymerizable vinyl monomer in the presence of an initiator system comprising an organic compound having a functional group of the formula (where in R<1> is H, alkyl or aryl; R<2> is alkyl or aryl; and X is halogen, alkoxy or acyloxy) and a Lewis acid, wherein the polymerization is performed in the presence of an oxygenous compound selected from among a ketone, an ether and an acid anhydride. Examples of the organic compounds used include halogen compounds (e.g. 2-chloro-2-phenylpropane), alkoxylated compounds (e.g. 2- methoxy-2-phenylpropane) and acyloxylated compounds (e.g. 2-acetoxy-2- phenylpropane).

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a method for producing a polymer by improved cationic polymerization of a cationically polymerizable vinyl monomer, and more specifically, a method for controlling the polymerization reaction rate in a cationic polymerization method. production of polymers, block copolymers, terminally functional polymers, or macro-septamers whose molecular weights and structures are controlled arbitrarily from low to high molecular weights by narrowing the molecular weight distribution of the polymer. It is about the method.

(Prior art) Generally, when a Lewis acid is used to perform cationic polymerization of a cationically polymerizable vinyl monomer, chain transfer reactions and termination reactions easily occur because carbenillam ions, which are propagating species, are unstable. However, it has been difficult to arbitrarily control the molecular weight and obtain a polymer with a narrow molecular weight distribution, and furthermore, it has been difficult to obtain a block copolymer.

5. From the viewpoint of controlling the molecular weight of the polymer. Conventionally, when performing cationic polymerization in combination with proton-donating compounds such as high alcohols and Lewis acids, compounds such as Schiff 5, amides, esters, and pyridines were present in the polymerization system, thereby achieving higher polymerization. However, it is difficult to control the molecular weight and obtain a polymer with a narrow molecular weight distribution.
Since the polymerization reaction is completed within several tens of seconds, it is practically possible to sufficiently remove the polymerization heat.

In addition, attempts at block polymer synthesis have been published in TLS 3.994.993 and US 4,276.39.
However, according to these methods, not only the block copolymer but also each homopolymer is formed in a non-negligible amount), so a fractionation operation is necessary, and the polymerization method also It's complicated.

Since living polymerization does not cause transfer reactions or termination reactions, it is easy to control the molecular weight, and it is possible to synthesize Zoroku copolymers. Since it is also possible to control the polymerization rate, numerous attempts have been made to discover a living polymerization system in cationic polymerization as well.

In recent years, examples of so-called living cationic polymerization have been reported, which suppress the gastric conversion of 4L-long cationic polymers, the chain transfer anti-L1, □1, and termination reactions.

For example, Azuma et al. (Macromolecules, 1
7.265 (1984)) reported that cationic living polymerization was possible by polymerizing divinylnityl using an initiator containing 11 combinations of hydrogen Tatsuhydride and iodine. However, this polymerization using initiator C is not possible with Denshi! There were various problems such as being limited to a cationically heavy intermediate having a highly reactive alkoxyl group, and the initiator being unstable and complicated to handle5. , Kennedy et al.
4, JP-A-64-6230B) uses an organic carboxylic acid, esgol, or ether as an initiator and combines it with a Lewis acid to polymerize olefin monomers such as isobutylene. It was shown that polymerization is possible. However, there are many problems in using the second method directly7.
Ta.

Kennedy et al. prefer boron trichloride, which has low polymerization activity, as the Lewis acid. This is thought to be because when the polymerization activity of the Lewis acid is high, various side reactions occur, making it difficult to control the molecular weight of the polymer.In fact, when titanium tetrachloride, which has a high polymerization activity, is used, the molecular weight and It is difficult to control the polymerization rate.

Furthermore, in general, in cationic polymerization, the polymerization rate is greatly influenced by the state of dissociation of ion pairs of growing species, and if a nonpolar solvent such as butane or pentane in which ion pairs do not dissociate is used, the polymerization rate decreases. Therefore, if boron trichloride, which has low polymerization activity, is used, polymerization will not proceed unless a polar solvent such as methyl chloride is used as a solvent.

In the case of Kennedy et al., the polar solvent that gave good polymerization results was a poor solvent for the polyisobutylene produced, so the molecular weight of the polyisobutylene was 5000.
If it becomes 1-, the polymer will precipitate in the system, and the reactivity of the active species will be extremely low. Therefore, in order to obtain a polymer with a high molecular weight while controlling the molecular weight, it is necessary to carry out the polymerization at an extremely high polymerization rate so that the polymerization is completed before the polymer precipitates. However, this involves a large amount of outside generation in a short period of time.

Moreover, it is impossible to obtain a block copolymer by successively adding the it form in a poor solvent system because of precipitation of the main polymer.

An example of carrying out living cationic polymerization in a specific mixed solvent is described in JP-A-63-205304K.

However, in this case as well, there are problems similar to those of Kennedy et al.'s 7j method, and AL is not a method to easily obtain a polymer with a controlled molecular weight.

(Problems to be Solved by the Invention) The present inventors have discovered that when polymerizing one cationically polymerizable vinyl 1lff, it is possible to control the molecular weight over a wide range, and that it is possible to control the molecular weight over a wide range between 4 and 7. As a result of intensive research to find a method that allows polymerization at any polymerization rate, in the presence of an oxygen-containing compound selected from the group consisting of ketones, ethers, and acid anhydrides, the formula (
It has been found that by using an initiator system consisting of an organic compound having a functional group shown in No. 11 and a Lewis acid, a polymer with a narrow molecular weight distribution and a controlled molecular weight and terminal structure can be obtained. Furthermore, after the first stage polymerization is completed, a block copolymer can be synthesized by successively adding other vinyl monomers to this polymerization solution, and based on this knowledge, the present invention was completed. I came to the conclusion.

(Means for solving problems) According to the present invention, the following 1, 2 and 3 are provided.

1. A method of polymerizing at least one cationically polymerizable vinyl monomer using an initiator system consisting of an organic compound having a functional group shown in formula (11) and a Lewis acid, in which the polymerization is carried out using ketones, ethers and 1. A method for producing a vinyl monomer polymer, characterized in that the method is carried out in the presence of an oxygen-containing compound selected from the group consisting of acid anhydrides.

1 - C-X (11 2 2) The manufacturing method according to claim 1, wherein the polymer is a block copolymer.

3. After the polymerization of one type of cationically polymerizable vinyl monomer is substantially completed, another type of cationically polymerizable vinyl monomer is subsequently added to complete the polymerization. A method for producing a block copolymer.

As an initiator used in the present invention, an organic compound having a functional group shown in formula +11 (hereinafter referred to as an initiator compound) is a halogen compound such as 2-chloro-2-
Phenylpropane, bis(2-chloro-2-propyl)
Benzene, tris(2-chloro-2-propyl)benzene, bis(2-chloro-2-propyl)-1-butylbenzene, bis(2-chloro-2-propyl)biphenyl, bis(2-chloro-2-propyl) Flobil) phenanthrene,
Bis(2-chloro-2-propyl)phenylethane, bis(2-chloro-2-propyl)phenylpropane, 2
-Chloro-2,4,4-trimethylpentane, 2,4,
4.6-tetramethyl-2,6-dichlorohebutane, 2
, 4.6-) dimethyl-2,4,6-trichlorohebutane, 2,4-dimethyl-2,4-dichloropentane,
2,5-dimethyl-2,5-dichlorohexane, 2,5
-dimethyl-2,5-dichloro-3-hexyne, 2,5
．． 8-1-dimethyl-2,5,8-)lichlorononane,
triphenylchloromethane, 2-chloroo7'roban, 2
-chlorobutane, t-butyl chloride, l-chloroethylbenzene and the like.

In addition, as compounds having an alkoxyl group, 2-methoxy-2-phenylpropane, bis(2-methoxy-
2-propyl)benzene, tris(2-me)xy-2-
propyl)benzene, bis(2-methoxy-2-propyl)-1-butylbenzene, bis(2-methoxy-2-
propyl)biphenyl, bis(2-methoxy-2-propyl)phenanthrene, bis(2-methoxy-2-propyl)phenylethane, bis(2-methoxy-2propyl)phenylpropane, 2.4.4-trimethyl-2
-methoxypentane, 2.4,4.6-tetramethyl-
2,6-dimethoxyhebutane, 2,4.6-dimethyl-2.4.6-1-dimethoxyhebutane, 2,4-dimethyl-2,4-dimethoxypentane, 2,5-dimethyl-2,5- dimethoxyhexane, 2,5-dimethyl-2
, 5-dimethoxy-3-hexyne, 2,5°8-trimethyl-2,5,8-)dimethoxynonane, t-butyl methyl ether, 5ec-butyl methyl ether, isopropyl methyl ether and the like.

Further, as compounds having an acyloxy group, 2-acetoxy-2-phenylpropane, bis(2-ace[·xy-2-propyl)benzene, tris(2-acetoxy-2-propyl)benzene, bis(2-· Acetoxy
2-propyl) dithylbenzene, bis(2-acetyl-2-propyl) biphene, bis(2-acetyl-2-propyl) phenane IL/ 7
, bis(2-acetoxy-2-propyl) 1. -ru J/', bis(2acetoxy-2-propyl), J", 2,4,4-trimethyl-2-
ace]-xypentane, 2゜3.3.6-titramethyl-2.6-diacetoxyhebutane, 2.4.6-trimethyl-2.4.6-triacetoxyhebutane, 24
4-dimethyl-2,4-di)'natoxybeni/tan,
2,5-dimethyl-2,5-diacetoxyhexane, 2
,5-dimethyl-2,5-diace1xy-3-hexyne,2,5.8-)limethyl'2+J18
Examples include triacetoxylin, triphenylmethyl acetate, t-butyl acetate, sec-binal acetate, and isopropyl acetate.

In addition, metal halides were used in Lewis acid, BCls, BF*, liver, OEt, T1C.
l! 4.5nCIla, AlCl, , A
IRCl, z, A J R2C1 (R is 1 carbon number
~5 lower alkyl group), SbC! ! , ,.

5bFS, Koshiki 15, MoCl5. . One example is TaCA3.

Furthermore, specific examples of oxygen-containing compounds selected from the group of getons, needles, and acid anhydrides, which are organic compounds having no functional group represented by formula (1,), and In the class, ace(n, siJ → rugetone, dipropyl utone,
Dibutyl ester, methyl enalgetone, methyl brovir getone, conidyl brovir getone, cyclopropa, non, Schiff 1.11 butanone, Schif rll bentenone, cyclo-xanone, methylcyclo-isanone, cycloheptanone, cyclohepta Non, cyclobrobyl methyl getone, 4 caclobyl 1 cobyl ethyl b'ton, caclobrobil brovir getone, chloroanatone, flomoacetone, yo 1! Acetone, dichloroacetone, acetylacetone 1, acetonylacetone, propionylacetone]・
N, -2 acetyl, acetone, ], non, b I: z biophenone, butilov I, noni/, barrel l''3 fu x noni/, biha'I'J'ノ, 16 no/゛, Methyl acetophenone, tumanil-, methylacetone, chloro'acetoph-non, fuyu,!-ruacetone, henzalacetone,
penzofunone, dibenzoyl, dibenzoylmethane,
Chloroa + tohenzoylphenone, phylomoacetobenzoyl phenone, non-1,-2/zo, quinone, naphthoquinone, 7-anthraquinone, chloranil, phenylhenzoquinone, etc. Examples include dimethylgo, -thyl, diethylni-thyl, di-n-propyl ether, di-n-futhyl ether, diisoamyl ether, dihydromethane, and tetrahydromethane. 8 Drobirane, Schifting, Nit], -ziru, methylylephenyl ethyl, engineering (ruphenyl x--n-ru, etc.) are 1, and acid anhydrides include acetic anhydride, propionic anhydride, isoacetic anhydride, etc. valeric anhydride, isovaleric anhydride, 3-succinic anhydride, ma-L/inic acid anhydride, citraconic anhydride, 1,2-Schiff V
Examples include hexynedicarboxylic anhydride, benzoic anhydride, phthalic anhydride, biromellitic anhydride, mellitic anhydride, and the like.

Examples of polymerizable vinyl monomers include isozotylene, pyrene, 1-butene, 2-butene, 2-butene, 3-methyl-Jl, pentene, 4-methyl -1-pentene 1.l\4cen, vinyl sif 1 fuhexane, suti!, 7, methylstyrene 1,t, -gunars 1,000l, , monochlorous f-L/
N, Jiku [10 Stire:・', Met1-Cysna L・;/
, α methylstyrene 5, β-methylstyrene 1/1, dame-3 styrene, butadiene 1, isoprene, cyclopenta・′,;Yun, methylpeel needle, 1:1F
Ruby, 6 Ruby, J-Delno, Isono Chiruji, Nil Engineering,
- Al, Me. 3, Ruso ° Robe - 1 and 9 - Le 1. ■Chill) tJ Benyl].

Examples thereof include -.

The mixing ratio of the initiator compound, the oxygen-containing compound selected from the group consisting of Lewis acids, ethers, ethers, and #anhydrides (hereinafter referred to as oxygen-containing compounds), and the vinyl monomer is such that the Lewis acid is the initiator compound. IJ, which is the starting point of the combination, is required to be equal to or more than the number of moles of the functional group of formula 4 (hereinafter referred to as -functional group temperature) and the number of moles of the oxygen-containing compound, and Lewis The acid has a molar ratio of 1 to 100 times the functional group concentration of the initiator compound, and the oxygen-containing compound has a molar ratio of 0.0 to the functional group concentration of the initiator compound.
1 to 100 times is preferable. Conditions in which the oxygen-containing compound is in excess of the Lewis acid are not preferred because the polymerization will actually stop. Moreover, the polymerization rate can be controlled by the Lewis acid concentration.

The organic solvent used in the present invention is not particularly limited as long as it does not adversely affect the polymerization activity of the initiator system, but includes aliphatic organic solvents such as butane, pentane, hexane, and heptane;
Examples include aromatic organic solvents such as benzene, toluene, and xylene, nitro compounds such as nitromethane and nitroethane, halogenated organic solvents, and mixed solvents thereof.

The polymerization temperature is not particularly limited as long as it is -120 to 50°C, and preferably -100 to 20°C.

The polymerization time is not particularly limited, and the polymerization rate can be controlled by the amounts of the initiator compound, Lewis acid, and oxygen-containing compound. Moreover, the molecular weight can be controlled by the ratio of the initiator compound concentration to the vinyl monomer concentration.

In addition, when producing a block copolymer, a type of cationically polymerizable vinyl monomer, an initiator compound, a Lewis acid, and an oxygen-containing compound are added to the polymerization system to substantially complete the polymerization. Thereafter, a block copolymer can be produced by subsequently adding another type of cationically polymerizable vinyl compound to the system and further polymerizing it.

(Effects of the Invention) Thus, according to the present invention, when polymerizing a cationically polymerizable vinyl monomer, an oxygen-containing initiator system consisting of an organic compound having a functional group shown in formula (1) and a Lewis acid is By carrying out polymerization in the presence of a compound, the polymerization rate can be controlled, and a polymer with a narrow molecular weight distribution, controlled molecular weight and terminal structure can be provided, compared to conventional techniques.

Further, according to the method of the present invention, a block copolymer whose molecular weight can be arbitrarily controlled is provided by sequentially polymerizing at least two different cationically polymerizable vinyl monomers. Further, by adding a compound having a functional group that reacts with the growing carbenilam ion, a functional group can be introduced at the end.

The present invention will be explained in more detail with reference to Examples below. Note that the percentages in Examples and Comparative Examples are based on weight unless otherwise specified.

(Example 1-2) 0.0% of isobutylene was placed in a glass container under a dry nitrogen atmosphere.
56 g (10tmmo!>, 2-methoxy-2-
Phenylpropane (Ct+IIQMe) 1.5s+g
(11) I! moA'), ketone compound (30pIII
O! methylene chloride 4.0ml % n-hexane 4.0ts! ! was added and cooled to -50°C. Next, 0.3 M TiC1a, which had been cooled to -50°C in advance, was added.
Methylene chloride/n-hexane (volume ratio 1/1) solution Co
ail (TiCj!<0.3 tmol) was added to initiate polymerization. After the specified time, methanol 3.0
1 was added to stop the polymerization, and the solvent was removed to obtain the desired polymer.

Number average molecular weight (Mn) and Mw/Mn (M- is weight average molecular weight) were measured using GPC (HLC-8 manufactured by Tosoh Corporation).
020). Furthermore, assuming that all the initiators work effectively and that no chain transfer reaction or termination reaction occurs during polymerization, the theoretical molecular weight (MJ).

calcd,) was calculated using the following formula. In addition, conν, (
%) is the polymerization conversion rate.

Molecular weight of Doma starter compound Polymerization times and results are shown in Table 1.

With polymerization time, cot+v increases and Mn increases4
−′ It can be seen that

(Example 3) Polymerization was carried out in the same manner as in Example 1, except that diether was used instead of the compound in Example 1. The polymerization time and results were Shown in the table (.

(Example 4-5) 0.56 g (1,0m+noJ) of isoblur was added to a glass container under a dry nitrogen atmosphere, and 2-methoxy-27en/I/buff (CumOMe) 1.
5 mg (No, amor), 3.5 ml of medilene chloride
! ,, After adding 3.5 m/n of n-
m(() was added and cooled to -50°C.

Next, pre-cooled to -50℃], 0.3
M's Tic (! 4 ・Menacean chloride/11-hexane (volume ratio, 1/1) i liquid], o m12 (
TiC1,4,0,3nuno & ) was added to start polymerization. After a certain period of PJi, 3.0w+1 methanol was added to stop the polymerization, and the melt was removed to obtain the -ζ target polymer. The results are shown in Table 3.

(Example 6) Isobutylene (I) was placed in a glass container under a dry nitrogen atmosphere.
B) 0.56 g (10 mmol), 2-methoxy-2-phenylpropane (CumOMe) 1.
5 mg (10μmoj2), acetylacetone methylene chloride 4 ml! , n-hexane 4.0m! ! was added and cooled to -68°C. Next, the 0.0000.degree. 3 M TiCl 4 ・methylene chloride/n-hexane (volume ratio, 1/l) solution 1 tal (
Polymerization was started by adding 3 mmol of TiC14,Q. After 16 hours, 4.4M styrene, methylene chloride/n-hexane (volume ratio: 1/1) solution 1.
2 ml (5.4 mmol) was added.

13 hours after adding styrene, 5 val of methanol was added to stop the polymerization, and the solvent was removed under reduced pressure.
The desired polymer was obtained. Table 4 shows the results. Furthermore, in the molecular weights of the obtained polymers in Table 4, (11) is the molecular weight of the isobutylene homopolymer, and [2] is the molecular weight of the bronc copolymer.

Claims (1)

[Claims] 1. A method for polymerizing at least one cationically polymerizable vinyl monomer using an initiator system consisting of an organic compound having a functional group represented by formula (1) and a Lewis acid, 1. A method for producing a vinyl monomer polymer, characterized in that step 1 is carried out in the presence of an oxygen-containing compound selected from the group consisting of ketones, ethers and acid anhydrides. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(1) In formula (1), R^1 represents hydrogen, an alkyl group, or an aryl group, R^2 represents an alkyl group or an aryl group, and X represents a halogen,
Indicates an alkoxy group or an acyloxy group. 2. The manufacturing method according to claim 1, wherein the polymer is a block copolymer. 3. After the polymerization of one type of cationically polymerizable vinyl monomer is substantially completed, another type of cationically polymerizable vinyl monomer is subsequently added to complete the polymerization. A method for producing a block copolymer.