JPS6262801A - Production of macromonomer - Google Patents

Abstract

PURPOSE:To obtain a macromonomer having narrow molecular weight distribution and high purity, by carrying out the ionic polymerization of a carbonyl- containing monomer, etc., using vinylphenyl ketene methyl trimethylsilyl acetal as a polymerization initiator and an F compound as a cocatalyst. CONSTITUTION:The objective macromer having a styryl group at a terminal can be produced by carrying out the ionic polymerization of a vinyl monomer having carbonyl group or cyano group (e.g. methyl methacrylate) in anhydrous tetrahydrofuran in the presence of vinylphenyl ketene methyl trimethylsilyl acetal as a polymerization initiator and an F compound [e.g. tris(dimethylamino) sulfonium difluorotrimethyl silicate] as a cocatalyst and adding the reaction mixture to a methanol-containing hexane.

Description

Detailed Description of the Invention (a) Purpose of the Invention (Field of Industrial Application) The present invention relates to a method for producing a macromonomer with a narrow molecular weight distribution and high purity in the synthesis of functional graft polymers. It is.

<Conventional technology and its problems> The use of block polymers and graft polymers to improve the functionality of polymeric materials has been used for some time, but block polymers made by ionic polymerization have many manufacturing constraints, so Advances in graft polymers have been required for the development of flexible polymer materials.

Macromonomer means a relatively high molecular weight monomer having a certain repeating unit with a polymerizable functional group at the end.
It is an abbreviation of r.

Twenty years ago, research on oligomers with a double bond at one end was conducted, but the topic was that of Milkovich.
This is after the research by et al. Their method uses e.g. 5ec-
Methacrylic acid chloride, allyl chloride, etc. are made to act on living anions such as styrene, α-methylstyrene, butadiene, and isoprene using butyl Li as a catalyst.
This method obtains a macromonomer having a methacryloyloxy group, an allyl group, etc. at one end (Japanese Unexamined Patent Publication No. 47-21
No. 486, JP-A-50-116586, etc.).

Macromonomers were given industrial importance by the British ICI.
This began after research at the company as a dispersant for the production of high-solid paints.

ICI's method involves polymerizing a radically polymerizable monomer such as methyl methacrylate with a carboxylic acid-containing polymerization initiator such as azobiscyanovaleric acid in the presence of mercaptoacetic acid as a chain transfer agent to obtain a polymer with a terminal carboxylic acid. It is made to react with methacrylate to form a macromonomer (Japanese Patent Publication No. 11224/1973,
-16147, etc.).

As a method similar to this ICI method, a polymer with terminal hydroxyl groups is obtained using mercaptoethanol as a chain transfer agent.
du Pont's method (USP 568) in which this is inocyanated with toluylene diisocyanate and then macromonomerized with hydroxyethyl methacrylate.
No. 9595 (1972)).

In addition, in Japan, Yamano et al. have created comb-shaped graft polymers using various macromonomers synthesized using the above-mentioned ionic polymerization method of Milkovich et al. and radical polymerization method of ICI, and have used them to improve the surface of polymeric materials. (Japanese Unexamined Patent Publication No. 57-179246, Macromolecule 13 216 (198
0) etc.).

In this way, the necessity of TL for macromonomers is clear,
It is expected that further progress will be made in the development of applications.

However, each of the above-mentioned methods for producing macromonomers has advantages and disadvantages. For example, the anionic polymerization method of Mikovich et al. can produce a macromonomer with a molecular weight distribution of 1.1 or less, which is close to monodisperse, and has good purity; however, applicable monomers include styrene, etc. It is limited to non-polar olefinic monomers, and it is difficult to use highly polar α,β-unsaturated nibonyl monomers such as acrylates and methacrylates.

In addition, with the radical polymerization method developed by ICI or du Pont, it is possible to produce macromonomers of acrylate, methacrylate, and various other α, β-, and β-carbonyl monomers; This method has the disadvantage that the molecular mass distribution is wide and the purity of the macromonomer is poorer than that of the anion 1 method.

(b) Means for solving the problems of the structure of the invention
, a β-unsaturated unsaturated nylbonyl monomer with a molecular weight close to the set molecular weight and a molecular weight distribution close to monodisperse,
As a result of intensive research into methods for producing highly pure macromonomers, we discovered that it is possible to produce the desired macromonomer by synthesizing a new compound with a specific chemical structure and using this as an initiator. completed.

That is, the present invention provides a method for producing a macromonomer, which is characterized in that a vinyl monomer having a carbonyl group or a cyan group is ionically polymerized using vinyl phenylketene methyltrimethylsilyl acetal as a polymerization initiator and a fluorine compound as a cocatalyst. It is.

α, β-, β-carbonyl compounds such as methyl methacrylate are converted into 1-methoxy-1-trimethylsiloxy-2-
It is known from Web
It was revealed in the study of S ter et al. (
JP-A-58-13603, A CBpolyme
rpreprints, 24 52 (1983), etc.)
. Webster et al. named this new polymerization method group transfer polymerization method.

This method is explained as follows. That is, strictly speaking, it is defined as a polymerization reaction that proceeds through repeated catalytic Michael additions of ketene silylacetal to α, β-, β-ester, nitrile, or carboxamide. Initiator with active trimethylsilyl group (1-methoxy-1
-trimethylsiloxy-2-methyl-1-propene, 1
etc.) and a catalyst (HF, etc.) necessary for the transfer of this group, an α,β-unsaturated carbonyl monomer such as methyl methacrylate (hereinafter abbreviated as MMA) is polymerized. A typical reaction formula is shown below.

(1) (MMA) That is, the initiator performs a Michael addition to the MMA monomer,
The trimethylsilyl group then connects the MMA end to the molecular content Ml.
12) t. Polymerization progresses successively by repeating both the addition and transfer reactions.

At this time, throughout the polymerization, the growing ends +21 and +31 always proceed while taking the same ketene silyl acetal end group structure as the initiator (11), producing a living polymer (3).

The molecular weight of the resulting slipping polymer can be controlled by adjusting the ratio of the initiator used in the polymerization to the concentration of the heptamer, and moreover, a nearly monodisperse polymer can be obtained.

Webster et al. have also synthesized living polymers using initiators in addition to the initiators shown in (1) above. However, in all of these initiators used by Webster et al., the other substituents (R+, Rt, Rs) of the general formula setal do not have polymerizable unsaturated groups such as styryl groups. When polymerizing using an initiator, it is difficult to directly introduce a polymerizable unsaturated group at one end, and in order to obtain a macromonomer with a polymerizable unsaturated group at one end, For example, when methanol and then acid are added to the initiator-generated or pinged polymer, a nearly monodisperse polymer (4) having an 10H group at one end can be obtained.

It is necessary to modify this OH group, for example, by the Du Pont method as exemplified in the above-mentioned macromonomer synthesis method to obtain a macromonomer having a terminal methacryloyloxy group, and a separate macromonomerization step is required.

The method for producing a macromonomer of the present invention basically follows this group transfer polymerization method. That is, for example, taking MMA as an example, the polymerization scheme of the present invention is as shown below.

CH,=CH Prisoner C) (No. 3 (MMA) 0S i (CH,)3 Living polymer (5) Macromonomer (6) In this way, the macromonomer (6) having a polymerizable styryl group at one end It is an industrially advantageous production method, as it can be obtained directly, has a molecular weight close to that of a macromonomer, and can produce extremely pure macromonomers.

That is, the fundamental difference between the method of the present invention and the method of Webster et al. is that a kedene silylacetal having a novel polymerizable unsaturated group called vinylphenylketene trimethylsilylacetal is synthesized. , which was used as an initiator.

This new initiator made it possible to directly produce macromonomers with a styryl group at one end. Naturally, according to the present invention, the produced macromonomer has a molecular weight close to the set molecular weight, a molecular weight distribution close to monodisperse, and high purity, as was obtained by Webster et al.

(Vinyl monomer having a carbonyl group or cyano group) The monomer used in the present invention is a vinyl monomer having a carbonyl group or a cyan group, for example, a vinyl monomer having a carbonyl group. Examples include acrylate or methacrylate (hereinafter collectively referred to as (meth)acrylate), ethyl vinyl ketone, etc., and examples based on vinyl having a cyano group include acrylonitrile, ethyl-2-cyanoacrylate, etc. (among them the general formula % aralkyl, and any of the above groups having one or more functional groups that are non-reactive during the polymerization conditions)
A (meth)acrylate represented by is preferred. Specific examples include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, inbutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and octyl (meth)acrylate. , isononyl (meth)acrylate, stearyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, phenyl (meth)acrylate, 2-acetoxyethyl (meth)acrylate, 3-methoxyglobil (meth)acrylate, allyl (meth)acrylate,
Examples include, but are not limited to, glycidyl (meth)acrylate, 2-(dimethylamino)ethyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, and ethylcarpitol (meth)acrylate.

More preferred monomers include methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate.
acrylate, 2-acetoxyethyl (meth)acrylate, and cyclohexyl (meth)acrylate. A particularly preferred monomer is methyl methacrylate.

(Polymerization initiator) The polymerization initiator used in the present invention (hereinafter simply referred to as 111 agent) is vinyl phenylketene methyl trimethyl silyl acetal, and the compounds include
There are three types of molds, and in the present invention, they can be used alone or in a mixture of two or more of them.

Synthesis examples of vinyl phenylketene methyltrimethylsilyl acetal are as shown in the reference examples below,
An example of the synthesis scheme is as follows.

11+ H2CL N搗CL (TMC) That is, using commercially available vinylbenzyl chloride as a starting material, vinylbenzyl cyanide, imide ester hydrochloride, vinylbenzyl acetate methyl ester l, vinyl phenylketene trimethylsilyl acetal ll.
The goal is to obtain O. In the above synthesis scheme,
For reactions similar to d), see C, Ainsworth g) J, Organome
tall icChemistry 4659 (197
2) has already been reported.

The method for producing the initiator vinyl phenylketene methyltrimethylsilylacetal of the present invention is not limited to this method, and the position of the ketenemethyltrimethylsilylacecool group substituted with the phenyl group is o- to the vinyl group as described above. , m-, and p-, and a mixture of each may be used, but m- or p- alone or a mixture thereof is preferable from the viewpoint of ease of production. In fact, as is clear from the starting material, the method of producing a macromonomer using the vinyl phenylketene methyltrimethylsilyl acetal thus obtained does not depart from the technical idea of the present invention.

(Catalyst) The catalyst used in the present invention is a fluorine compound, which is a known compound or produced by a known method. Catalysts useful in the process of the invention include fluoride ion CFs such as tris(dimethylamino)sulfonium difluorotrimethylsilicate, tris(dimethylamino)sulfonium difluorotriphenyl stanate, tetrabutylammonium fluoride, potassium ammonium bifluoride, and the like. A particularly preferred catalyst is tris(dimethylamino)sulfonium difluorotrimethylsilicate, which is a source of bifluoride ions (F2).

Tris(dimethylamino)sulfonium bifluoride can be easily produced by reacting tris(dimethylamino)sulfonium difluorotrimethyl hepta-silicate with ice or methanol.

(Production of macromonomer) In the present invention, the macromonomer refers to a relatively high molecular weight monomer having a polymerizable functional group at one end, and the molecular weight is preferably 1,000 to 100,000 as a number average molecular weight.

The number average molecular weight is a polystyrene equivalent molecular weight determined by gel permeation chromatography (hereinafter referred to as GPC), and the measurement conditions are as follows.

Apparatus: High performance liquid chromatography (for example, Toyo Soda Kogyo, reverse product name: HLC-802UR) Column: Polystyrene gel (for example, Toyo Soda Kogyo, product name: G4000H8 and G3000H8) Elution solvent: Tetrahydrofuran Eflux rate: j, Q rrtt / m column temperature:
40°C Detector: RI detector In the production of the macromonomer of the present invention, it is preferable to use a solvent in order to control the polymerization heat generated.
Not essential. Any solvent can be used as long as it is non-reactive with the monomer initiator and catalyst and has sufficient solubility, such as tJf, ethyl acetate, toluene,
Examples include xylenebenzene, tetrahydrofuran, acetonitrile, N,N-dimethylformamide, and tetrahydrofuran is most preferred.

The monomers used in the present invention are generally liquid and are used in an amount of at least 1 it% or more.

The preferred amount of the initiator to be used is determined by the target molecular weight of the macromonomer, and is difficult to determine in general, but it is used at a concentration such that the monomer/initiator molar ratio is 5 or more. Ru.

The catalyst usually has a molar ratio of initiator to catalyst of 1 to 500,
Preferably, it is used in the range of 10 to 200.

1 degree of lagoon is approximately -100°C to 100°C, preferably 0°
C to 50C, most preferably 00C to room temperature.

The final macromonomer obtained by the process of the invention is formed by contacting the living polymer with an active hydrogen field, such as water or alcohol.

The macromonomer produced by 4Q without invention has a molecular shape close to the set molecular weight (-5 main distribution of molecules, that is, Mw/M
Since it is HB-like for years with n equal to about 1 and has extremely high purity, if other known monomers that can be copolymerized with this macromonomer are subjected to radical copolymerization, for example, the branch segment of the present invention can be obtained. Comb-shaped graft polymers into which macromonomers are embedded are easily formed. At this time, by controlling the specificity of the comonomer and the charging ratio of macromonomer/comonomer, etc., it is possible to produce a functionally defined graft polymer with a clear structure.

[Reference Examples, Examples, and Application Examples Reference Examples, Examples, and Application Examples will be given below to more specifically explain the present invention. Parts and parts are by weight unless otherwise specified. Moreover, the molecule iMn of the obtained macromonomer.

The MW was measured by GPC.

Reference Example 1 Synthesis of initiator vinyl phenylketene methyltrimethylsilyl acetal (hereinafter abbreviated as VPKTS) a> Commercially available m, p-vinylbenzyl chloride (
Methanol/water = 122 parts 150
of methanol under reflux (64°C) in a mixed solvent of 12 parts.
Allowed time to react. The reaction mixture was filtered to remove by-product common salt, and the solution was concentrated using a rotary evaporator. The residue was then distilled under reduced pressure to a boiling point of 87°C/2 ram H.
g of fractions were collected (70% yield). This one is m.

p-vinylbenzyl cyanide. It was confirmed by IR spectrum that the absorption of nitrile group (2250cm) and the absorption of -1,' vinyl group (1630α) were present.

b) Dissolve 64.4 parts of m,p-vinylbenzyl cyanide in 17.6 parts of anhydrous methanol/i/i, and cool the solution to 0°C.
Cool to 19 parts of dry hydrogen chloride are then absorbed with stirring. Seal the solution and leave it in the refrigerator overnight. The resulting precipitate of imidoester hydrochloride was pulverized, washed with anhydrous ether, filtered, and dried under vacuum (yield: 7(1)).

C) 66.7 parts of imidoester hydrochloride and 34.0 parts of water were stirred at room temperature for 15 minutes, then a large excess of 20 times the amount of petroleum ether was added and the mixture was stirred for 2 days. Obtained.

The yield based on vinylbenzyl cyanide is 58.8%. In the IR spectrum, the -tolyl group has an absorption of -1.

collection (2250α) has disappeared, while 1740cs
An absorption peak of ester group is seen near z-, and 16
The generation of vinyl phenylacetic acid methyl ester was confirmed because vinyl group absorption remained around 35m.

d) Add 268 parts of an 8% lithium diisopropylamide solution in tetrahydrofurin to a container purged with nitrogen. This container is ice-cooled, and 35.2 parts of m,p-vinylphenylrnrkl methyl is added dropwise over 5 minutes, and stirring is continued for 30 minutes while maintaining the temperature at 0°C. 54.3 parts of trimethylchlorosilane is added dropwise to this solution over 5 minutes, and the reaction mixture is allowed to return to room temperature. After stirring at room temperature for 30 minutes, the reaction solution was filtered once, and the solution (f) was evaporated using a rotary evaporator. The residue was washed with anhydrous ether and the t1 filtration was repeated several times. After removing the ether, the remaining oil is distilled under reduced pressure to obtain VPKTSA2, the target product at the node 110°C/3mxHg.
2.3 parts were obtained (45% yield).

15 p of 4-t-butylcatechol as a polymerization inhibitor
pm in a cool, dark place ((Stored. -VPKTSA
Identification of W(-) was carried out using f(-NMR (shown in Figure 1)) and IR spectra.
Since a strong peak due to C appeared at 850;1, it was fully confirmed that it had a ketene trimethyl acetal structure.

Example 1 1[10;J of anhydrous tetrahydrofluff (
tn, p-VPKTSA (1.385 parts (5.65 mmol) of a mixture of 60% meta and 40% bulk) and tris(dimethylamino)sulfonium difluorotrimethylsilicate (hereinafter referred to as TA S ": '2S) in THF).
iMe, abbreviated as) 0.03 part (0.11 mmol)
16.9 parts (0.17 mol) of Shiri MMA purified on calcium hydride (Ca H2) were added thereto, and the mixture was polymerized at room temperature for 6 hours. In addition to the hexane solution containing 5 timemethanol, Mn = 5500, Mw/Mn = 1. o q
A polyMMA macromonomer having a VC sufryl group at one end was obtained in a yield of 90.5 To.

A peak due to phenyl proton was observed, and as a result of comparing the integral value of this peak due to phenyl proton and the integral value of the peak due to methyl proton of methoxy group (6.6 ppm), it was found that one styryl group was introduced at the end of Bo'JMMA. I found out that

In addition, when the toughness of this polymer was examined by NMR, the syndiotactic was 58.6, and the toughness was 36. (l heterotactic, ri was 5.4 chi.

Examples 2 to 4 The charging molar ratio of the MMAIL body and the initiator VPKTSA was 30: IVPKTSA and the catalyst TASF2SiMe,
The molar ratio of 100:! 1, and polymerization was carried out in the same manner as in Example 1 at room temperature for a predetermined time. The obtained results are shown in Table 1. In all Examples, the molecular species of the macromonomer was 1.1 or less, which was close to monodisperse.

Examples 5 to 10 MMA f)gL synthesis was carried out in the same manner as in Example 1, except that the charging ratio of MMA and initiator was varied between 60 and 1000, and the polymerization temperature was 0°C and room temperature. I got the results in the table.

The GPC chart of the polyMMA macromonomer obtained in Example 6 is shown in Figure S. From FIG. 6, it can be seen that even with a molecular weight of 110,000 or more, the GPC chart shows excellent symmetry and is a macromonomer with good monodispersity.

Example 11 Initiator VPKTSA 1.23 parts (5 mmol) and TA in 2 Qrtzl of anhydrous tetrahydrofuran under dry nitrogen
SF, SiMe, cLo 5 parts (Q, 1 mmol) and 10 parts (100 mmol) of ethyl acrylate (hereinafter abbreviated as EA) purified with CaH were mixed and polymerized at room temperature for 24 hours. This was washed four times with a hexane solution containing 5-timeethanol to obtain a macromonomer of BoIJEA (yield 4B, 2%).

When the molecule t of this substance was examined by GPC, it was found to be Mn...
18QQ, Mw/Mn = 1.28, Example 1
2 Initiator VPKTSA 0.62 parts (2,5 mm/I/) and T
ASF, SiMe, [], 05 parts (0.1 mmol) and 5.66 parts (20 mmol) of cyclohexyl methacrylate 'purified on CaH2 were polymerized for 24 hours while being maintained at 0-55°C. After the polymerization was completed, this solution was added to methanol to precipitate the polymer, and when it was dried under reduced pressure, a poly(cyclohexyl methacrylate) macromonomer with Mn = 1280 and Mw/Mn = t15 was obtained in a yield of 9.
Obtained at 2.0%.

Example 16 Initiator VPKTS in anhydrous THF at 50°C under dry nitrogen
23 parts of At (5 mmol) and TASF.

Butyl methacrylate purified on Can2 was added to a solution of 0.03 parts (0.1 mmol) of SiMe.
4 parts (0.2 mol) was added dropwise little by little so that the temperature did not rise above 30° C., and the mixture was polymerized for 12 hours. The resulting solution was evaporated in vacuo, Mn = 4700, Mw/Mn =
1.11 of poly(butyl methacrylate) macromonomer was obtained in a yield of 896 cm.

Example 14 VP in 50 m anhydrous THF at 0° C. under dry nitrogen
KTSA t23 parts (5 mm! J moles) and TASF2
In a mixed solution of 0.03 parts (0.1 mmol) of SiMe, 5 parts (0.05 mol) of MMA purified on CaH2 and 71 parts of glycidyl methacrylate purified on alumina (
O, OS mol) was added at a humidity of 0 to 30°C
It was dripped while maintaining the temperature. After the addition was completed, the mixture was further stirred for 6 hours, and then the polymer was precipitated with hexane and dried under reduced pressure to obtain 12.05 g of poly(MMA/glycidyl methacrylate copolymer) macromonomer. This material had Mn=2500 and MW/Mn 1.15.

Application example 1 IJMMA macromonomer with terminal styryl group obtained in Example 1 (Mn=3500, M w /M n =1.0
9) 28 parts (8 mmol) and 125 parts (1.5 mmol) of the initiator AIBNO were dissolved in 100 t of benzene, and radical polymerization was carried out at 60° C. under vacuum.

Figure 4 shows the change in polymerization rate over time. As a result, Bo IJ
It was found that the MMA macromonomer has high radical polymerizability and purity of 95% or more.

(/1 Effect of the Invention According to the present invention, the molecular weight is close to the target molecular weight, and the molecular weight distribution is overlapping fractions (MW and Mn).

A macromonomer with a ratio close to 1) and high purity can be easily obtained, and the method for producing a macromonomer of the present invention is industrially useful.

[Brief explanation of the drawing]

Figure 1 shows the initiators m, p-V P K T S A
It is an H-NMR chart of. FIG. 2 is an H-NMR chart of the polyMMA macromonomer having a styryl group at one end obtained in Example 1. Figure 6 shows the GPCf of the polyMMA macromonomer having a styryl group at one end obtained in Example 6.
(UV is based on 245 BUV light, RI is based on refractive index). FIG. 4 is a graph showing the relationship between polymerization rate and time in Application Example 10.

Claims (1)

[Claims] 1. A method for producing a macromonomer, which comprises ionically polymerizing a vinyl monomer having a carbonyl group or a cyano group using vinyl phenylketene methyltrimethylsilyl acetal as a polymerization initiator and a fluorine compound as a cocatalyst.