JP2000053716A - Macroazo compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a macroazo compound having a specific chemical structure and capable of easily and efficiently catalyzing the production of a block copolymer having polyorganosiloxane unit(s) and polyoxyalkylene unit(s) as a polymerization initiator. SOLUTION: This macroazo compound has a chemical structure expressed by formula I [R1-R4 are each a lower alkyl or cyano; R5 and R6 are each a lower alkyl or an aryl; X and Y are each a lower alkylene; (m), (n), (p) and (q) are each >=1 integer]. The compound of formula I is obtained e.g. by reacting (A) 1 mol azodicarboxylic acid of formula II [e.g. 4,4'-azobis(4- cyanopentanoic acid)] with (B) 0.1-4 mol polyorganosiloxane modified with polyoxyalkylene at both ends, expressed by formula III [e.g. α,ω-bis(polyoxyethylene)polydimethylsiloxane] in the presence of a condensing agent and, if needed, a basic catalyst in a solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel macroazo compound having both a polyorganosiloxane unit and a polyoxyalkylene unit in one molecule.

[0002]

2. Description of the Related Art Silicon compounds are characterized by having excellent water repellency and low coefficient of friction. The method of adding polysiloxane to the resin or spraying the resin with silicone makes the resin water repellent. Is known. However, the method of mixing a polysiloxane with a compatible or incompatible resin and the method of spraying the resin with the polysiloxane have a problem that the polysiloxane floats on the resin surface. As a means for solving this problem, a method of polymerizing a polymerizable monomer in the presence of a polyorganosilsesquioxane macromonomer or a polydialkylsiloxane macromonomer to form a graft polymer or the presence of an azo group-containing polyorganosiloxane compound Below, a method of polymerizing a polymerizable monomer to form a block copolymer is being studied.

[0003] However, the polysiloxane-containing resin thus prepared does not contain a polyoxyalkylene unit or contains a polyoxyalkylene unit but does not have a polymer unit of an ethylenically unsaturated monomer. Most are things. Therefore, it has a drawback that it has poor affinity for polyethylene terephthalate (PET) and acrylic resin and has insufficient hydrophilicity.

[0004] Further, in a treatment method in which polyethylene glycol which is incompatible with a polysiloxane resin is mixed or reacted, affinity between the resins is low, and one of the resins emerges on the surface to deteriorate weather resistance and chemical resistance. Alternatively, there is a problem that the chemical resistance and the abrasion resistance are reduced due to insufficient adhesion to the base resin.

[0005]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above situation. For example, when used as a polymerization initiator, both a polyorganosiloxane unit and a polyoxyalkylene unit can be easily and efficiently used. It is an object of the present invention to provide a novel macroazo compound capable of producing a block polymer having a molecule.

[0006]

The present invention provides a compound represented by the general formula [1]:

Embedded image (Wherein, R ^{1 to} R ⁴ each independently represent a lower alkyl group or a cyano group, R ⁵ and R ⁶ each independently represent a lower alkyl group or an aryl group, and X and Y each independently represent a lower alkyl group or an aryl group. Represents a lower alkylene group, and m, n, p and q each independently represent a positive integer.)

The present invention is also directed to a polymerization initiator comprising the above-mentioned macroazo compound.

In the general formula [1] of the present invention, R ¹
The lower alkyl group represented by R ⁶ to R ⁶ may be linear or branched and includes, for example, an alkyl group having 1 to 6 carbon atoms, specifically, a methyl group, an ethyl group, an n-propyl group,
Isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, isohexyl, 1-methylpentyl , 2-methylpentyl group and the like.

The aryl group represented by R ⁵ and R ⁶ includes, for example, phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,3-xylyl group, 2,4-xylyl group, 2, Examples thereof include a 5-xylyl group, a 2,6-xylyl group, a 3,5-xylyl group, and a naphthyl group.

The lower alkylene group represented by X or Y may be linear, branched or cyclic, and includes, for example, an alkylene group having 1 to 10 carbon atoms, specifically, a methylene group and an ethylene group. , Propylene group, butylene group,
2-methylpropylene group, pentylene group, 2,2-dimethylpropylene group, 2-ethylpropylene group, hexylene group, heptylene group, octylene group, 2-ethylhexylene group, nonylene group, decylene group, cyclopropylene group, cyclopropylene Examples thereof include a pentylene group and a cyclohexylene group, and among them, an alkylene group having 1 to 6 carbon atoms is preferable.

M is usually an integer of 5 or more, preferably 5 to 2000, more preferably 5 to 300. n is an integer of usually 2 or more, preferably 2 to 100, more preferably 2 to 50. p
Or, q is usually an integer of 1 or more, preferably 1 to 200, more preferably 1 to 100.

The ratio between p and q is p: q = 10:
1 to 1:10, preferably 3: 1 to 1: 3, and represented by the general formula [1]
The number average molecular weight of the compound represented by is usually 5,000
300300,000, preferably 8,000-150,000.

The macroazo compound represented by the above general formula [1] of the present invention is, for example, a compound represented by the general formula [2]

[0014]

Embedded image

(In the formula, R ^{1 to} R ⁴ and X are the same as described above.)
And an azodicarboxylic acid represented by general formula [3]

[0016]

Embedded image

(Wherein R ⁵ , R ⁶ , Y, m, p and q are the same as described above) and a polyoxyalkylene-modified polyorganosiloxane at both ends represented by the formula It is obtained by reacting with a condensing agent in the presence of a basic catalyst.

Preferred specific examples of the azodicarboxylic acid compound represented by the general formula [2] include, for example, 4,4'-azobis (4-cyanopentanoic acid) and 5,5'-azobis (5-cyanohexanoic acid. ), 6,6'-azobis (6-cyanoheptanoic acid), 7,
7′-azobis (7-cyanooctanoic acid) and the like.

Preferred specific examples of polyorganosiloxanes having both ends polyoxyalkylene modified represented by the general formula [3] include α, ω-bis (polyoxyethylene) polydimethylsiloxane, α, ω-bis ( Polyoxypropylene) polydimethylsiloxane, α, ω-bis (polyoxyethylene) polymethylphenylsiloxane, α, ω
-Bis (polyoxyethylene) polydiphenylsiloxane, α, ω-bis (polyoxypropylene) polymethylphenylsiloxane, α, ω-bis (polyoxypropylene) polydiphenylsiloxane and the like.

The number-average molecular weight of the polyorganosiloxane modified at both ends represented by the general formula [3] is usually from 300 to 100,000, preferably from 500 to 20,000.
It is 0.

The amount of the polyoxyalkylene-modified polyorganosiloxane at both ends with respect to the azodicarboxylic acid compound in producing the macroazo compound of the present invention also differs depending on the type of polyorganosiloxane modified at both ends. Is usually 0.1 to 4 moles, preferably 0.3 to 4 moles with respect to the azodicarboxylic acid compound.
1.5 moles.

Examples of the reaction solvent include hydrocarbons such as toluene, xylene and benzene; esters such as ethyl acetate and butyl acetate; ketones such as acetone and methyl ethyl ketone; halogenated hydrocarbons such as methylene chloride and chloroform; Examples include dioxane, tetrahydrofuran, acetonitrile, dimethylformamide, dimethylsulfoxide and the like. These may be used alone or in combination of two or more.

Examples of the condensing agent include inorganic dehydrating condensing agents such as concentrated sulfuric acid, diphosphorus pentoxide, anhydrous zinc chloride and the like, for example, dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropylcarbodiimide) hydrochloride. Carbodiimides such as salts, polyphosphoric acid,
Examples thereof include acetic anhydride, carbonyldiimidazole, p-toluenesulfonyl chloride and the like.

When the amount of the condensing agent used is small, the reaction becomes slow, and when it is too large, it is not economical. ,Preferably
It is 2 to 3 times mol.

The above production method is preferably carried out in the presence of a basic catalyst. Specific examples of the basic catalyst include, for example, triethylamine, diisopropylethylamine, N, N-dimethylaniline, piperidine, pyridine, 4-dimethylamino Pyridine, 1,5-diazabicyclo [4.3.0] nona-5-
Ene, 1,8-diazabicyclo [5.4.0] undec-7-ene,
Organic amines such as tri-n-butylamine and N-methylmorpholine, for example, alkaline metal compounds such as sodium hydride and n-butyllithium, and the like can be mentioned.

The amount of the basic catalyst to be used is usually 0.005 to 3 times, preferably 0.01 to 2 times, the mol of the azodicarboxylic acid compound or the condensing agent.

If the reaction temperature is too high, the azo group is decomposed,
If the temperature is too low, the reaction rate becomes slow and the production takes time, so that the temperature is usually 0 to 40 ° C. The reaction time varies depending on the reaction temperature, the type of the azodicarboxylic acid compound used and the type of the polyoxyalkylene-modified polyorganosiloxane used at both ends, but is usually 1 to 24 hours.

The macroazo compound represented by the general formula [1] is obtained by first reacting an azodicarboxylic acid compound represented by the general formula [2] with, for example, phosphorus pentachloride to obtain an acid chloride. A polyoxyalkylene-modified polyorganosiloxane at both ends represented by the formula [3]:
It can also be produced by reacting in a suitable solvent in the presence of a base. The types of the basic catalyst and the solvent used here, the amounts used thereof, other reaction conditions, and the like are appropriately selected according to the above.

The desired product may be isolated by a conventional method according to the type and amount of the starting materials, basic catalyst, condensing agent, solvent, etc. and the state of the reaction solution. In such a case, the target macroazo compound can be obtained by diluting the reaction solution with an appropriate solvent, removing impurities by an operation such as filtration or washing with water, and then removing the solvent.

The macroazo compound obtained as described above is
The azo group is easily decomposed by heating or light irradiation to generate nitrogen gas and radical species. At that time, if various polymerizable monomers are present, polymerization is promptly caused. That is, a macroazo compound represented by the general formula [1],
A block polymer can be obtained by carrying out a polymerization reaction with a polymerizable monomer in a suitable solvent or without a solvent, if necessary, in an inert gas atmosphere according to a conventional method. Post-treatment after the reaction may be performed in accordance with a post-treatment method generally used in this field.

When conducting the polymerization reaction, a chain transfer agent (eg, lauryl mercaptan, octyl mercaptan, butyl mercaptan, 2-mercaptoethanol, butyl thioglycolate, etc.) is added as necessary to control the molecular weight. May go.

Examples of the polymerizable monomer used in the polymerization reaction include styrene, 4-methylstyrene, vinyl acetate, acrylic acid, methacrylic acid, methyl methacrylate,
Examples include methyl acrylate, acrylamide, N-vinyl pyrrolidone, vinyl pyridine and the like. These may be used alone or in combination of two or more.

As the above polymerization reaction, for example, solution polymerization,
It can be carried out by any polymerization method such as bulk polymerization, suspension polymerization, emulsion polymerization, dispersion polymerization and the like.

Examples of the solvent used in the solution polymerization include ethers such as tetrahydrofuran, diethyl ether and dioxane, for example, chloroform, methylene chloride, and the like.
Halogenated hydrocarbons such as 1,2-dichloroethane, for example,
Hydrocarbons such as n-hexane, petroleum ether, toluene, benzene, and xylene, for example, methanol, ethanol,
Alcohols such as isopropanol, for example, acetone,
Ketones such as methyl ethyl ketone and methyl isobutyl ketone, for example, acetonitrile, N, N-dimethylformamide, dimethyl sulfoxide and the like. These solvents may be used alone or in combination of two or more.

The polymerization reaction is desirably performed in an inert gas atmosphere. As the inert gas, for example, nitrogen gas,
Argon gas and the like can be mentioned.

The amount of the macroazo compound used in the polymerization reaction varies depending on the type of the polymerizable monomer used, but can be generally selected from a wide range, and is usually 0.01 to 100% by weight based on the polymerizable monomer. %, Preferably 0.05 to 50% by weight.

The concentration of the polymerizable monomer during the polymerization reaction varies depending on the type of the polymerizable monomer, but is usually 5 to 1
The amount is 00% by weight (no solvent), preferably 10 to 60% by weight.

The reaction temperature varies somewhat depending on the balance with other polymerization conditions, but is usually 30 to 130 ° C., preferably 40 to 130 ° C.
To 120 ° C, more preferably 60 to 90 ° C.

The reaction time varies depending on the reaction conditions such as the reaction temperature, the type of the polymerizable monomer, and the concentration.
Usually 2 to 24 hours.

Thus, by using the macroazo compound of the present invention as a macroazo initiator, a block polymer can be easily and extremely efficiently produced, and a conventional radical polymerization initiator used for polymerizing a polymerizable monomer can be obtained. It can also be used effectively. Specific examples of the polymerizable monomer in this case include all those exemplified above as the polymerizable monomer usable in the production of the block polymer.

Further, the polymer obtained by using the macroazo compound of the present invention contains a polyorganosiloxane unit and a polyoxyalkylene unit. Therefore, in addition to the water repellency and hydrophilicity derived from the macroazo compound of the present invention, Since it also has affinity for PET and acrylic resin, it can be used in a wide variety of applications.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[0043]

EXAMPLES Example 1. Synthesis of macroazo compound according to the present invention 4.6 g of 4,4'-azobis (4-cyanopentanoic acid), α, ω-bis
30 g of (polyoxyethylene) polydimethylsiloxane (trade name: SF8427, manufactured by Toray Dow Corning Silicone Co., Ltd., number average molecular weight: 2,400) and 0.2 g of 4-dimethylaminopyridine were dissolved in 50 ml of acetonitrile, and stirred under stirring. After adding 7.5 g of dicyclohexylcarbodiimide, the mixture was reacted at room temperature for 8 hours. After standing overnight, the precipitated crystals were removed by filtration, and the filtrate was concentrated to dryness to obtain 30 g of the desired macroazo compound (yield 87%). From the result of GPC measurement, the product had a number average molecular weight of 12,200 and a dispersity of 2.24. ¹ H-NMR δ ppm (CDCl ₃ ): 0.01 (s, 60 H, Si (CH ₃ ) ₂ O-), 0.48
_{~0.41 (t, 2H, -OCH 2} C H 2 Si -), 1.52~1.60 (t, 4H, -COOCH 2 C
H _2- ), 1.66 (d, 6H, = NC (CH ₃ ) CN-), 2.38 (br, 8H, -C H ₂ C H ₂ C
OO -), 3.34 (t, 2H, -OC H 2 CH 2 OSi-) 3.61 (s, 64H, -C H 2 C H 2 O
-), 4.19 (br, 4H, -COO-C H ₂ CH ₂ O-)

Example 2 12.5 g of the macroazo compound obtained in Example 1 and 50 g of styrene were dissolved in 50 g of toluene and polymerized at 80 ° C. for 8 hours under a nitrogen stream. The obtained polymerization solution was poured into 1000 ml of hexane to precipitate a polymer. The obtained polymer crystals were filtered and dried to obtain 46.2 g (polymerization rate: 74%) of a block polymer. The number average molecular weight was 38,000 from GPC analysis, and the composition of each unit calculated from NMR analysis was 9% of polyorganosiloxane units, 9% of polyoxyethylene units, and 82% of styrene units.

[0045]

As described above, the present invention provides a novel macroazo compound having both a polyorganosiloxane unit and a polyoxyalkylene unit in a molecule, and the macroazo compound is used as a polymerization initiator. In this case, a block polymer having both a polyorganosiloxane unit and a polyoxyalkylene unit in a molecule can be easily and efficiently produced.

Claims (2)

[Claims] 1. A compound of the general formula [1] (Wherein, R ^{1 to} R ⁴ each independently represent a lower alkyl group or a cyano group, R ⁵ and R ⁶ each independently represent a lower alkyl group or an aryl group, and X and Y each independently represent a lower alkyl group or an aryl group. Represents a lower alkylene group, and m, n, p and q each independently represent a positive integer.) 2. A polymerization initiator comprising the macroazo compound according to claim 1.