JPS60228449A - Azo compound having monomer structure and its preparation, preparation of graft copolymer and block copolymer to be used for it - Google Patents

Abstract

NEW MATERIAL:An azo compound having a monomer structure shown by the formula I (R1 and R2 are lower alkyl, or phenyl; R3 and R3 are H, lower alkyl, or phenyl). EXAMPLE:2,2'-Dimethacryloyloxy-2,2'-azobispropane. USE:Useful as an initiator or a monomer in a polymerization or copolymerization reaction. Having both polymerization properties as a monomer and characteristics as an azo polymerization initiator. PREPARATION:A halo-substituted azo compound shown by the formula II (X is halogen) is reacted with a metallic salt of an acrylic acid monomer shown by the formula III (M is alkali metal ion, or heavy metal ion; n is 1, or 2) in a solvent such as benzene, acetonitrile, etc. at room temperature - under heating in the presence of a phase transfer catalyst (e.g., crown ether), to give a compound shown by the formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel azo compound having a monomer structure and a method for producing the same.
4. Concerning the production method of i/and block copolymers: Traditionally, as a means of imparting useful properties to polymers, general-purpose polymers have been subjected to modification treatments or functional groups or reactive groups have been added. Various methods have been proposed and implemented, such as polymerizing or copolymerizing monomers that have functional or reactive groups from the beginning, or adding grafting or block modification to the polymer chain. The most common method is to add craft-like or block-like modification to polymer chains, and many proposals have been made regarding these techniques. For example, methods for radically obtaining a graft copolymer include a method in which radicals are generated and branched in the side chain of the main polymer by a chain transfer reaction of the radical onto the polymer, and a method in which a peroxy group is introduced by oxidation of the side chain. A method of diazotizing the amine group of the side chain to use as a polymerization initiation point, a method of initiating branched polymerization by radiation irradiation, photochemical reaction, oxidation reaction, etc. Attempts have been made to carry out polymerization using polymers (such as groups). In addition, as a method to radically obtain a block copolymer, the first monomer is polymerized in the presence of a telogen, and a functional group with photopolymerization initiation ability is introduced at the molecular end, and copolymerization with oxygen This can be done by introducing peroxide bonds into the main chain and then polymerizing the second monomer from these sites, by using Bopkor/Polymer, or by cutting the main chain with high speed agitator and shear force. Various methods have been tried.

However, when using these methods, for example, when obtaining a kraft copolymer, the main chain is limited because it is necessary to create a reactive site in the main chain, or after copolymerization, a reactive site is formed on one of the monomers. In the case of obtaining a block copolymer, it is necessary to have reactive sites at both ends of the monomer, and in the case of cutting the main chain. For example, it is necessary to use materials that are easy to cut, etc., and the technology is limited to only special systems and is difficult to commercialize. This is the actual situation.

As a result of intensive research into methods for easily and effectively obtaining raft copolymers and block copolymers, the present inventors created an azo initiator that itself can be a monomer, and polymerized it. Thinking that the purpose could be achieved by using it as an initiator or monomer, we synthesized a new compound that has both a monomer structure and an azo polymerization initiator structure in the molecule, and used this as an initiator. However, a new ``macromer type'' polymer having a monomer structure at the end was obtained, and when this was used as a monomer, a new ``macromer type'' polymer type opening initiator having polymerization initiation activity within the molecule was obtained. Furthermore, by using polymers with these functionalities, it is possible to obtain craft-like polymers from the former in block form or depending on the conditions, and craft-like polymers from the latter under conditions intermediate between the conditions for obtaining the former and the conditions for obtaining the latter. Based on the results obtained, the present invention has been completed in which a polymer having both of these structures can be obtained.

That is, the present invention relates to the general formula (1) (22 (wherein, R4 and R2 represent a lower alkyl group or a phenyl group which may have a substituent, and R3 and R4 represent a hydrogen atom or a lower alkyl group). , or represents a phenyl group.

), the invention relates to an azo compound having a monomer structure, a method for producing the same, and a method for producing a kraft copolymer and/or a block copolymer using the same.

When the compound of the present invention is used for polymerization, by appropriately selecting polymerization conditions, it is possible to form a compound having a monomer structure at the end.
Macromer-type polymers or "holimer-type" initiators having polymerization initiation activity within the molecule are obtained; from the former, depending on flocs or conditions, craft polymers can be obtained, and from the latter, craft polymers can be obtained. If the polymer is not obtained under conditions intermediate between the conditions for obtaining the former and the conditions for obtaining the latter, a polymer having both of these structures can be obtained.

The compound of the present invention is characterized by having both a monomer structure and an azo polymerization initiator structure in the molecule.
In producing such a compound, the present inventors found that the polymerizability of the monomer is mainly determined by the substituents on the double bond, and that the decomposition rate of the azo compound, which is a typical polymerization initiator, is as follows:
Based on the knowledge that -N=N~ depends on the substituent bonded to it, it is possible to bond the two without significantly affecting the reactivity of the two, and an initiator that can become a monomer can be produced. From this point of view, the azo compound having a seven-mer structure of the present invention.

That is, as a result of synthesizing an azo initiator that is an unsaturated carbo/acid ester and conducting research on the possibility of using it in polymer synthesis by radical polymerization, we found that this compound has high polymerizability as a monomer and azo polymerization initiation. The compound was found to have properties as a drug, and the desired purpose was achieved.

The azo compound having the monomer structure of the present invention has the general formula (
II) A halo-substituted azo compound represented by 1
(In the formula, M represents an alkali metal ion, an alkaline earth metal ion, or a heavy metal ion, R3 and R4 represent a hydrogen atom, a lower alkyl group, or a phenyl group, and n represents 1 or 2.) It can be produced by reacting an acrylic acid monomer represented by the following with a metal salt.

That is, a halo-substituted azo compound of the general formula (It) obtained by reacting a halogen/ with a ketone having an R1 group and an R2 group by a method known per se, and an acrylic acid of the general formula (nI). and the metal salt in an organic solvent without active hydrogen such as benzene, acetonitrile, acetone, ethyl acetate, or carbon tetrachloride at room temperature or at elevated temperature, if necessary in the presence of a phase transfer catalyst such as crown ether, After reacting for several hours to several days, the desired product can be obtained by processing by a known post-treatment method and, if necessary, purifying by means such as recrystallization or column chromatography.

In general formulas (1) and (ID), examples of the lower alkyl group represented by R1' and R2 include a methyl group, an ethyl group, a propyl group, a butyl group, etc. Examples of substituents on the phenyl group include lower alkyl groups such as methyl and ethyl groups, lower alkoxy groups such as methoxy and ethoxy groups, chlorine, bromine, iodine, etc.
Examples of the rogen group represented by X include chlorine, bromine, iodine, and fluorine.

In the general formulas (1) and (g), examples of the lower alkyl group represented by i(3, R4 include methyl group, ethyl group, propyl group, butyl group, etc.) The alkali metal ions that occur are Na" + K",
Li+ etc., but as alkaline earth metal ions, Ca”
, Mg", 13a2+, etc., and heavy metal ions such as Ag+I CU" + zn2+ l P
b"" + Cd" + Mo1kiself, etc. are listed respectively.

The reaction solvent used in the method for producing the compound of the present invention is usually an organic solvent without active hydrogen, such as acetonitrile, benzene, toluene, acetone, ethyl acetate, carbon tetrachloride, etc. However, the phase transfer catalyst that may be used if necessary includes Clara/ether, quaternary ammonium salt, etc., but is not limited thereto. The reaction temperature is usually room temperature, but if necessary, the reaction may be carried out with heating, for example at 50 to 60°C. The reaction time varies depending on the type of compound and the reaction temperature, but it is generally one to several days at room temperature, and several hours to 24 hours under heating. As a method for purifying the product, an appropriate method may be selected from among known purification methods such as recrystallization and column chromatography, taking into consideration the physical and chemical properties of the compound.

The monomers of the azo compound having a monomer structure of the present invention include styrene, methyl methacrylate, ethylene, vinyl chloride, vinyl acetate, acrylamide, acrylic acid, methacrylic acid, vinyl and vinylidene monomers such as vinylizo 7 chloride, and fumaric acid. ester, maleimide,
Vinyl/based monomers such as maleinoic anhydride, and butane/
, These functional polymers are further copolymerized with other monomers as the isop parent polymer to produce a block copolymer, a graft copolymer, or a copolymer having the structure of these two types of copolymers. In this case, the partner monomers include methyl methacrylate, styrene, acrylamide,
Monomers normally used in copolymerization, such as vinyl acetate, ethylene, vinyl chloride, acrylic acid, methacrylic acid, vinylite/chloride, fumaric acid ester, maleimide, maleic anhydride, butadiene, isopre 7, etc., are used without exception. Reaction conditions and method for obtaining a "macromer type" polymer having a monomer structure at the terminal using an azo compound having a monomer structure as an initiator, and a method for obtaining a polymerization initiation activity in the molecule using the azo compound as a monomer. The reaction conditions and methods for obtaining the polymer initiator may be carried out in accordance with known polymerization reaction conditions and methods, such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. In addition, the polymerization conditions and methods for producing the thus obtained block copolymer or graft copolymer may also be based on known reaction conditions and methods for block copolymerization or graft copolymerization, such as bulk polymerization, solution polymerization, It may be carried out according to the method and conditions of suspension polymerization, emulsion polymerization, etc.

In addition, reaction conditions intermediate between the reaction conditions for obtaining a ``macromer type'' polymer and the reaction conditions for obtaining a perpolymer type'' initiator If the reaction is carried out at a temperature (which can be adjusted by the reaction conditions such as reaction temperature and reaction time), a polymer having both of these properties can be obtained, but this can be used as a parent polymer and copolymerized with other monomers. For example, a copolymer having the structures of both a kraft type copolymer and a block type copolymer can be obtained.

Using the compound of the present invention, graft polymers with special physical properties, such as comb-shaped graft polymers, can also be easily obtained.

The present invention has both a seven-mer structure and an azo polymerization initiator structure in the molecule, and when this is used as an initiator, a new "macromer type" polymer having a monomer structure at the end can be obtained, and also as a monomer. If used, a new "'holimer type" initiator having polymerization initiation activity in the molecule can be obtained,
Furthermore, by using polymers with these functionalities, the former can be obtained as a block polymer or a graft polymer depending on the conditions, and the latter as a craft polymer. The present invention provides an azo compound having a monomer structure, which is a novel functional initiator, from which a polymer having the structure of these two types of copolymers can be obtained, and a method for producing the same. The contribution it makes to the industry is extremely significant.

Examples are shown below, but the present invention is not limited thereto.

Example 1, 2.2'-dimethacryloyloxy-2,
Preparation of 2'-azobispropa/To 100 m/l' of acetonitrile,
Ru 2.2'-Azohisisoprop;/5. @(
0,027 mol), potassium methacrylate 10 g (
0,081mal), 18-Clara 7-6 6. ! Dissolve 7 and stir at room temperature for 2 days. At the beginning of the reaction, flaky crystals of potassium methacrylate are observed, but at the end of the reaction +
CV'i disappeared and powdered potassium chloride was produced instead. After the reaction is completed, the reaction mixture is poured into 500 ml of water, and the insoluble portion is filtered off. After thorough washing with water and drying, the obtained product is recrystallized from methanol. Yield 5
g (65%).

mp 91.5~92.0°CO11R(KBr): ν(c+n-1)~1718
(-C-0-), 1630-1623 (C=C, N=N
), 145° Example 2, Preparation of 2,2'-dimethacryloyloxy-2,2'-azobispropane To 100 rnl of acetonitrile, add 2,2'-dichloro-2,2'-azobisyne chloropropane 7 5 ．． ! i'(0
,027mal), barium methacrylate A 12.5
g (0,041 mob) and 6 g of tetra-n-butylammonium bromide were dissolved and stirred at room temperature for 4 days. After the reaction is completed, the reaction mixture is poured into 500 ml of water, and the insoluble portion is filtered off. After thorough washing with water and drying, the obtained product is recrystallized from methanol. Yield 5.9 (6
5%). Example 1. mp+IR and NMR match the product.

Example 3, 2,2'-diacryloyloxy-2,2
Production of '-Azobispropane Acetonitrile 200+++1C12,2'-Dichloro-2,2'-Azobiswingrono: / 10ji(0
,054mail), potassium acrylate 18 g
(0,162 mol), 18-klau/-68 g was dissolved and stirred at room temperature for 4 days. After the reaction mixture is poured into a large amount of water, the insoluble portion is filtered and dried. The product is recrystallized from methanol and then from an ethyl acetate-0-hexane mixture. Yield 5.5g (40%) mp 49.0-4
9.5°Co O I IR (KBr): l' (cm-1) -1728 (-C-
0-), 0 111 1200 (-C-0-), 1150 (-C-0-)
.

'I-1-NMRl-1-N:cI)clz=1:
i): δ2H, J'= 17.2Hz, 10
．． 4I-1z), 5.72 (dd.

1.57 (s, (CH3)2C, 12H).

Example 4, 2.2'-disi/namoyloxy-2.2
Production of '-Azobispropa/To 30ml of acetonitrile, add 2.2'-Nchlor-2
．． 2'-Azobisisopropa: / 2I (0,011m
o6), potassium cinnamate 8g (0,036mol)
, 18-crown-63g was dissolved and reacted at room temperature for 3 days. After the reaction, the same treatment as in Example 1 is carried out, and the product is recrystallized from methanol. Yield 3g (68%).

mp　163.0-163.5°c.

I R (KBr): v (cm”) - = 3500
~34001 1145 (-C-0-), 775 (aromati
c C-H), 685 (aromatic C-H)
.

'HNMR(CC14)'δ(ppm) -7
,72~7.30 (m, aromatic H,
10H), 6.49 (s.

2H), 1.63 (s, (CH3)2C, 12H
).

Example 5, 1.1'-dimethacryloyloxy-1,
1'-Azophenylethane 300ml silver methacrylate 35g (0,
181mol! ) was dispersed, and 28 g of 1,1'-azo-1-chlorophenyl ether 7 (0,167 ma
il). After stirring at room temperature for 5 hours, heat to about 50°C and react for 30 minutes. After the reaction, the mixture is suction filtered, a polymerization inhibitor (t-butylcatechol) is added to the filtrate, and the mixture is concentrated using a rotary evaporator to precipitate a brown solid. The product was collected by filtration and purified by column chromatography using an alumina or silica gel column using benated/' as a solvent to obtain 105 g of colorless 1,1'-azo-1-methacryloyloxyphenylethane. Yield 15%.

mp 66-67°c.

IR (KBr): v (cml) ~ 3420 (
aromaticOO +I, 11 (-C-0-), 1 090 (-C-0-), 76
0 (aromatic C-H), 700 (aromatic
rnatic C-H) (.

1H-NMR(CDCl5)' δ(pI)m
) = 7.60 ~ 7.27 (m, aromaticH
, l0H), 6.18 (m.

13C-NMR (CDC13)' δ(1)pm)-
164,6 [Elemental analysis value] Calculated value a: c 70.94; H6,40; N 6.70
Actual value (to): C70,69; H6,51; N 6.4
4 Example 6, 2,2'-crotonyloxy-2,2
Production of '-Azobispropa/To 30 ml of acetonitrile, add 2,2'-Nchloro-2
．． 2'-7 zobisisoproba/2,! i'(0,01
1 mol), potassium chlorate/acid 4.9 (0,032
Example 1
．． The reaction is carried out in the same manner as above, the work-up is carried out, and the product is recrystallized from methanol. Yield 29 (65%).

mp 103.5~104.0°C IR (KBr): v (cIrL") -1720
~16901 (-C-0-), 1665 ~ 1660 (C=C, N=N
), 1190-1 1 40 (-C-0-), 11
00 (0 1 -C-Q-).

IH-NMR (CCl4): δ(pI)m>=
6.84 (dQ.

6H, J=7Hz, 1.7Hz), 1.46 (
8, (CH3)2C212H).

Example 7: Using 3 x 10-3 mall/l, be/ze/middle;
As a result of polymerizing Stire 7 (5,78 mol/l) and methyl methacrylate (5,88 mal/l) at 608C, the polymerization rates were 3.0%/hr and 9.6%, respectively.
/hr.

Example 7. When polymerization was carried out in the same manner as above, the polymerization rate was 2.4%/h in the case of styrene.
In the case of methyl methacrylate, it was 7.5%/hr (see Figures 1 and 2). That is, no reduction in the decomposition rate as an initiator was observed due to the introduction of a double bond at the terminal.

Also, the activation energy for total polymerization in styrene polymerization is ^, F,, 1') 4h1319.4 Kcal
/mo/, 68F・'f319.6 Kcal/mol
There is no significant difference between the two in terms of polymerization activity. (See Figure 3).

Example 8゜Example 5. The 1,1'-enemethacrylate 7 (AP) obtained in (abbreviated as MMA) is 1
, 75 mol/l ([AP]/[MMA] molar ratio = 0.014), 2,2'-azobis(2,4-trimethylvaleronitrile) 5.4 x 10- as a polymerization initiator.
60° in benzene y 9 St using 3 mol/l
G. Allow polymerization reaction for 1 hour. Similarly, AP and MMA
Composition ratio o, ooisO, and composition ratio of AP and Stire/(hereinafter abbreviated as St) 0.011 and 0.0
When 16 copolymers were synthesized and used as parent polymers and MMA was used as the copolymer monomer, Vi
The table below shows the results of kraft copolymerization using St, Choda St, and MMA as the other monomer. The polymerization conditions were as follows: 0.15.9 ml of the parent polymer was added to 4 ml of the mating polymer, and the treatment was carried out at 80°C for 1 day.

Table 1 Graft copolymer production rate (total) - (graft copolymer/parent polymer)
．． It can be seen that craft polymerization occurred extremely efficiently in No. 01.

Example 9 1.1'-dimethacryloyloxo-1,1'-azophenyl xpy (AP) 0.010 g (3,01
”mail/l), methyl methacrylate (MMA)
5 ml (5,87 mail/l), pe/ze/3
ml was added and polymerized for 70 minutes at 60°C. As a result, a polymethyl methacrylate parent polymer having a heptad structure at the terminal was obtained at a production rate of 11.3%.

Similarly, AP O, 01M9 (4,58X10"-3m
ail/IJ), styrene (
St) 4mj' (5.78 mol/l) was added, 2 rug of Be/Cene was added thereto, and polymerization was carried out at 70°C for 70 minutes. As a result, the production rate was 7.4%, and polystyrene having the same terminal monomer structure was obtained. A parent polymer was obtained.

Block copolymerization was carried out in accordance with the following conditions by selecting St as the partner monomer for the polymethyl methacrylate parent polymer and polystyrene parent polymer for the former and MMA for the latter.

Polymethyl methacrylate 0.1533 as parent polymer
g or folystyrene 0.1346 g, 2,2'-azobisisobutyronitrile 0.005.9 as a polymerization initiator, 4 ml of the other monomer, and be/cene 5 ml as a solvent. Polymerization is carried out at 600C using In the former case, the yield is 1.085 in 27 hours.
In the latter case, 4 g (79% production rate) of the copolymer was added to 6
A block copolymer with a yield of 1.367 ig (production rate: 86%) was obtained in hours.

Example 10゜1.1'-dimethacryloyloxy-1,1'-azophenylethane (AP) 2.5xlO"mol/l, Styre 7 (St) 16.67x10"mol#
Polymerize in 9 ml at 60° C. for 70 minutes. Obtained A
When polymerizing P-8t copolymer as a parent polymer and MMA as a partner monomer at 80°C for 20 minutes, a graft-block copolymer is obtained at a production rate of 6885%.

Example 11゜Example 1. Table 2 shows the results of copolymerizing 2,2'-dimethacryloyloxy-2,2'-azobispropane (hereinafter abbreviated as AB) obtained with MMA or St as a hexamer. Shown below.

However, the polymerization conditions are as follows.

Polymerization initiator (2,2'-azobis(2,4-trimethylvaleronitrile): 1.85 x 10'' mol/ISt for MMA
For 2.01 X 10-” mal/IJ solvent:
P/Sen 4 ml Reaction temperature and reaction time: For MMA 60°C 250 minutes St 6
0°G, 11 hours Table 2 By using the above-obtained copolymer as a parent polymer and using a monomer that can be polymerized at high temperatures as a partner monomer, such as ethylene or diisopropyl fumarate, a graft copolymer of these can be obtained. can be easily obtained. (A B
Vi2.2'-diacetoxy-2,2'-azobispropane can be used as an initiator at 1150'o or more.

) Example 12゜Example 3. The monomer structure of 2,2'-diacryloyloxy-2,2'-azobispropa/ obtained in
Using 9 mail/l, this and MMA 6.86
When a polymerization reaction was carried out at 60°C for 1 hour in benzene/7 rug using 3.6 x 10-3 mail/l of azobisisobutyronitrile as a polymerization initiator, the polymerization rate was 6.0. % of a polymer-type initiator was obtained.

Example 13゜The 2,2'-disi/namoyloxy-2,2'-azobispropane obtained in Example 4 was used as a monomer to
Using 089 molt/l, this and stille 76.19m
When a polymerization reaction was carried out at 60°C for 3.5 hours in 7 ml of Pe/Cen using azobisisobutyronitrile 3.8 x 10-" mal/IJ as a polymerization initiator, polymerization occurred. A copolymer with a polymer type initiator was obtained with a yield of 5.8%.

[Brief explanation of drawings]

FIG. 1 and FIG. 2 both show Example 7. Figure 1 shows the one-hour curve of polymerization rate when styrene was used as the monomer, and Figure 2 shows the curve when methyl methacrylate was used as the monomer. - indicates 1,1'-dimethacrylate as the polymerization initiator. Cuturoyloxy-1゜1'-7sophenylethane (
AP) is used, and -Kyoichi shows the curve when 1,1'-diacetoxy-1,1'-azophenylethane (hereinafter abbreviated as AAP) is used as a polymerization initiator. In both FIGS. 1 and 2, the vertical axis represents the polymerization rate (%), and the horizontal axis represents time (minutes). Figure 3 shows an Arrhenius plot of the total polymerization rate of AP and AAP, where -1- is AP, +ViA A I)
Each represents the situation when using . The vertical axis is An[:
Rp (%/hr)], and the horizontal axis represents 10°0/T (absolute temperature). However, Rp represents the reaction rate. Patent applicant: Wako Pure Chemical Industries, Ltd. Figure 1 Time (6) Figure 3

Claims (1)

[Scope of Claims] (1) General formula (1) (In the formula, R and R2 represent a lower alkyl group or a phenyl group which may have a substituent, and R3 and R4 represent a hydrogen atom, a lower An azo compound having a monomer structure represented by (representing an alkyl group or a phenyl group). (2) General formula (■) RIR engineering 1 R2-C-N=N -C-R2(II)1 (represents a phenyl group which may optionally be and R4 represents a hydrogen atom, a lower alkyl group, or a phenyl group, and n
indicates 1 or 2. ) with the general formula (
1) A method for producing an azo compound having a monomer structure represented by the formula % (in the formula, R1+ R2+ R3 and R4 are as described above). (3) General formula (1) R3R4RIIR4R3 II l l 11 CH=C-CoO-C-N=N-C-OCO-C=CH
(1)1 1(21'(2 (wherein, R□ and R2 represent a lower alkyl group or a phenyl group which may have a substituent, and R3 and R4 are a hydrogen atom, a lower alkyl group, or A method for producing a kraft copolymer using an azo compound having a monomer structure represented by (representing a phenyl group). (4) General formula (I) Rs R4R+ RI R4R3 II l l 11 CIl=C-Coo-C-N =N'-(,0CO-C=
CH(1)1 1(2R2 (wherein, R and R2 represent a lower alkyl group or a phenyl group which may have a substituent, and R3 and R4 are a hydrogen atom, a lower alkyl group, or a phenyl group) ) A method for producing a block copolymer using an azo compound having a monomer structure represented by (5) General formula (1) % Formula % (1) (In the formula, R1 and R2Vi lower alkyl groups, or substituted Represents a phenyl group which may have a group, R3 and R4
represents a hydrogen atom, a lower alkyl group, or a phenyl group. ) A method for producing a copolymer having both the structures of a C-shift polymer and a block polymer using an azo compound having a monomer structure represented by