JPH02281002A - Polymerization of anionic polymerizable monomer - Google Patents

Abstract

PURPOSE:To obtain a polymer useful as a modifier or emulsifier for resins by polymerizing an anionic polymerizable monomer in the presence of an epoxy group-contg. compound and tertiary amine. CONSTITUTION:The objective polymer can be obtained by polymerizing an anionic polymerizable monomer [e.g. (meth)acrylonitrile, methyl vinyl ketone] in the presence of (A) an epoxy group-contg. compound (e.g. bisphenol-based epoxy resin) and (B) a tertiary amine (e.g. N,N'-dimethylpiperazine, N- methylmorpholine). The amounts of the compounds A and B are pref. such as to be 0.001 to 1wt.% in total.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel polymerization method, and more particularly to a method for polymerizing an anionically polymerizable vinyl monomer in the presence of an epoxy group-containing compound and a tertiary amine.

[Conventional technology and issues]

Tertiary amines are used as curing agents for epoxy resins. It is known that the curing mechanism of this curing reaction of epoxy resins with tertiary amines is a continuous reaction of epoxy groups to alkoxy anions produced by the reaction between epoxy groups and tertiary amines (Muroi, Ishizai, Polymer added etho, 22 (/9♂6
)). Furthermore, tertiary amines are known to be anionic polymerization initiators (Teiji Tsuruta, Synthesis of Polymers, Kagaku Special Edition 7, PJ-g/91.￥ Kagaku Doujin).

However, there are no known examples of attempting anionic polymerization in the presence of an epoxy group-containing compound and a tertiary amine.

[Means to solve the problem]

The present inventors focused on the alkoxy anion produced by the reaction between an epoxy group and a tertiary amine, and as a result of intensive research on the ability of this alkoxy anion to initiate anionic polymerization, the present invention was achieved.

That is, the gist of the present invention is a method for polymerizing an anionically polymerizable vinyl monomer, which is characterized in that the anionically polymerizable vinyl monomer is polymerized in the presence of an epoxy group-containing compound and a tertiary amine.

The epoxy group-containing compound used in the present invention is not particularly limited as long as it has at least one epoxy group in the middle of the molecule. For example, Bisfe/-k A,! : Bisphenol-based epoxy resin produced by reacting epichlorohydrin in the presence of an alkali, monoepoxy compounds such as styrene oxide, butyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, glycidyl methacrylate, diglycidyl ether, glycol diglycidyl Ether, vinyl cyclohexene dioxide, epoxidized vegetable oil, etc. Q polyepoxy compounds, epoxy group-containing radically polymerizable monomers such as glycidyl methacrylate, and other vinyl monomer tonocopolymers such as styrene, methyl methacrylate, etc. Epoxidized products of natural products such as cellulose etc. can be mentioned.

The tertiary amine used in the present invention is N.

Those commonly used as curing agents for epoxy resins include N'-dimethylpiperazine, N-methylmorpholine, hexamethylenetetramine, triethylenediamine, pyridine, pyrazine, benzyldimethylamine, and dimethylaminopyridine.

Examples of anionically polymerizable vinyl monomers that can be used in the present invention include vinyl monomers such as acrylonitrile, methacrylonitrile, methyl vinyl ketone, nitroethylene, methylene ethyl malonate, vinylitine cyanide, and methyl methacrylate; caprolactone, and low molecular weight cyclic polydimethylsiloxane. Examples include cyclic monomers such as (for example, Da + D4).

The ratio of the epoxy group-containing compound and the tertiary amine used in the present invention is usually equivalent.

The amount of (epoxy group-containing compound + tertiary amine) to be used with respect to the anionic polymerizable monomer is not particularly limited, but is usually 0. The ratio is θθ/−/% by weight.

Polymerization reactions are usually carried out in organic solvents. Preferred organic solvents include polar solvents such as tetranohydrofuran, dimethylsulfoxide, dimethylacetamide, dimethylformamide, and N-methylpyrrolidone.

The polymerization temperature is not particularly limited, but usually ranges from room temperature to 200°C.
It is preferably carried out in the range up to 'C.

During polymerization, the epoxy group-containing compound and the tertiary amine may or may not be reacted in advance, but the polymerization reaction rate tends to be faster if they are reacted in advance.

The present invention can be easily carried out by, for example, dissolving an epoxy group-containing compound and a tertiary amine in an organic solvent, adding an anionically polymerizable monomer to a pre-reacted reaction solution, and stirring and mixing for a predetermined period of time. ] Hereinafter, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to these embodiments unless it departs from the gist thereof.

Example 1 Epoxidized cellulose θ, 909t was mixed with sulfoxide (DMSO)/! at, gauge methylaminopyridine 0. /2 Add f.

Acrylonitrile (A
N) JATJ was added and reacted at 4tO 0 C for 2 hours.

Next, it was washed with primary methanol and dried under reduced pressure. The nitrogen content of the product was 7.60% by weight and contained 27.4% by weight of polyacrylonitrile.

Comparative Example 1 AN was polymerized in exactly the same manner as in Example 1, except that regenerated cellulose containing no epoxy groups was used. The nitrogen content of the obtained product was 0.22% by weight, and the polyacrylonitrile content was 0.22% by weight. /% by weight, and almost no polymerization occurred.

Comparative example λ Epoxidized cellulose θ, 4tK, f’f’iDMs.

After adding 0.4t/2y of N-tetrabutylammonium iodide and pre-reacting at 700°C for 2 hours, AN! Add jlEl, 2'41 at gθ℃
Allowed time to react. The nitrogen content of the product was 0.22% by weight, indicating almost no polymerization.

Example λ Phenylglycidyl ether o, isθ1, triethylenediamine 0. //29 was heated at 100°C in DMSO 1urxl for 2 hours, and then Ar1t- was added for 4t.
Polymerization was carried out at 0° C. for an extended period of time. The polymerization rate was lθθchi.

Polymerization was carried out in the same manner as in Example C, and the polymerization rate was θ
It was Chi.

Example 3 Butyl glycidyl ether 00130t and triethylenediamine 70. //29 was dissolved in DMSO/4txj,
What was the polymerization rate when A N j nil was added without pre-reaction and polymerized at 410°C for a period of time? 3. It was θchi.

Example 3 The same procedure as in Example 3 was carried out except that AN was polymerized after the preliminary reaction was carried out at <10° C. for 2 hours, and the polymerization rate was 4.5 mm.

Example! Example 3 was carried out in the same manner as in Example 3, except that AN was polymerized after the preliminary reaction was carried out at 100°C for 2 hours, and the polymerization rate was 9 g! It was Chi.

Example 6 1 mmol of the epoxy group-containing compound shown in Table 1 and 0.0 mmol of triethylenediamine. //if (/mmol) DMS O/
After pre-reacting for 2 hours at 4tO℃ in 1ml, A
Nj and 0 rinj were added, and polymerization was carried out at θ°C for Z hours. The results are shown in Table 1.

Example 7 In Example 2, polymerization was carried out in exactly the same manner as in Example λ, except that methacrylonitrile was used instead of ANO.

The polymerization rate was 100%.

Example! Butyl glycidyl ether θ, ≦j/f and triethylenediamine θ, ttit in DMSO/4td at 700°C.
After pre-reacting for 2 hours at -1 caprolactone, θM
! (2.3% mol) was added and polymerized at 0° C. for 2 hours. The polymerization rate is 7r? It was Chi.

Example 1 Epoxidized cellulose o, 2t g) After pre-reacting 0.041417 f (0.4 tmmol) of lyethylene diamine at 4 to ℃ in the polar solvent (6g) shown in Table 1 for 1 hour, AN2d was added and the reaction was carried out at θ℃. 24 was polymerized for hours. The results are shown in Table-λ.

Table-2 Example 10 Phenyl glycidyl ether 0. /! 09 (/mmol) triethylenediamine 0. / / After preliminarily reacting 2 f (/mmol) in DMSO/4td at 0°C for 1 hour, methyl vinyl ketone j m/(3 mol) was added and polymerized for 30 minutes at 4t0°C, and the polymerization rate was ioo %Met.

Example/l Glycidyl methacrylate/methyl methacrylate copolymer 0. 3!2 (epoxy group: , 2.3 milliequivalents/
2) and triethylenediamine 0, / / 2 SF D
After pre-reacting in MSO/4tyxl for 4 tO'Cte/hour, j ml of methyl vinyl ketone was added and polymerization was carried out for 7 hours. The polymerization rate was 100%.0 Example 12 In Example //, C was used instead of methyl vinyl ketone.
- Polymerization was carried out in exactly the same manner as in Example /-/ except that caprolactone was used. The polymerization rate was 9%. The grafting rate determined by extracting the homopolymer with hot methanol is /! Example 13 Glycidyl methacrylate θ, 7//f and triethylenediamine o, rt, iy in DMSO/jmj at Zθ°C
After pre-reacting for 7 hours, ε-caprolactone! ml
was added and polymerized at 4tO°C for 2Z hours. The polymerization rate was 93. !
It was Chi.

Example/4t phenyl glycidyl ether θ, 7J-/f)
After preliminarily reacting IJ ethylenediamine 0.5≦/f in tetrahydrofuran/3ytl at 4t0°C for 1 hour,
1-Caprolactone! d was added, and 24 was polymerized at θ°C for an hour. The polymerization rate was ♂ and θ.

Example/j Polymerization was carried out in exactly the same manner as in Example // except that acrylonitrile 3yd was used instead of methyl vinyl ketone in Example 11. The polymerization rate was 100%. Also,
The craft rate was 230chi.

〔Effect of the invention〕

The polymerization method of the present invention is useful for the synthesis of block and graft copolymers, and is particularly useful as a method for producing resin modifiers, emulsifiers, and the like.

Claims (1)

[Claims] (1) A method for polymerizing an anionically polymerizable monomer, which is characterized in that the anionically polymerizable monomer is polymerized in the presence of an epoxy group-containing compound and a tertiary amine.