JPH06287243A - Graft polymer composition - Google Patents

Abstract

PURPOSE:To obtain a polymer composition at a high graft efficiency without causing the gelation in the graft polymerization of a vinyl monomer. CONSTITUTION:This graft polymer composition is derived from a polymer having active hydrogen, an azo catalyst having a group reactive with the active hydrogen at the terminal, a vinyl monomer and dicyclohexylcarbodiimide.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a graft polymer composition. More specifically, it relates to a cellulosic composition.

[0002]

2. Description of the Related Art Conventionally, polymers having active hydrogen, particularly cellulose derivatives, have been grafted with acrylic or styrene vinyl monomers to improve their solubility in solvents, compatibility with other resins, physical properties of coatings, etc. It has been reported to improve. For example, (1) a method of polymerizing a vinyl monomer by using a peroxide catalyst for the purpose of grafting a cellulose derivative by hydrogen abstraction (for example, JP-A-48-80192, JP-A-50-80).
-48030), and (2) a method of introducing a polymerizable double bond into a cellulose derivative and copolymerizing it with a vinyl monomer (for example, JP-A-60-58415, JP-A-60-58415). 60-110
No. 712).

[0003]

However, the graft ratio is generally poor, gelation is likely to occur during the graft polymerization of the cellulose derivative, and the physical properties are not sufficiently improved.

[0004]

The present inventors have arrived at the present invention as a result of extensive studies to solve the above problems. That is, the present invention comprises a polymer (A) having active hydrogen, an azo catalyst (B) having a group capable of undergoing a dehydration reaction with active hydrogen at a terminal, a vinyl monomer (C) and dicyclohexylcarbodiimide (hereinafter abbreviated as DCC). It is a derived graft polymer composition (D).

In the present invention, the polymer (A) having active hydrogen is a polymer having a hydroxyl group, an amino group or a carboxyl group, for example, a polysaccharide (eg, cellulose, starch, chitin, chitosan, xanthan gum). , And their derivatives), polyvinyl alcohol, a hydroxyl group-containing (meth) acrylate copolymer (for example, a copolymer of hydroxyethyl methacrylate and methyl methacrylate, a copolymer of hydroxyethyl methacrylate and styrene, etc.), an amino group-containing (meth) ) Acrylate copolymer (for example, a copolymer of dimethylaminoethyl methacrylate and styrene), carboxylic acid-containing (meth) acrylate (for example, a copolymer of methacrylic acid and butyl acrylate), polyoxyalkylene polyol ( Those obtained by adding ethylene oxide or propylene oxide to a compound having more than five active hydrogen), a copolymer of styrene and maleic acid, and the like and mixtures thereof. Of these, preferred are polysaccharides, and particularly preferred are cellulose and cellulose derivatives.

Cellulose is usually cellulose obtained from pulp or cotton as a raw material, and preferred is one having an α-cellulose content of 85% or more.

Examples of the cellulose derivative include methyl cellulose, ethyl cellulose, cellulose acetate, cellulose acetate butyrate, amino cellulose, cellulose acetate phthalate and cellulose acetate butyrate phthalate.

It is preferable that the hydroxyl group and / or amino group and / or carboxyl group possessed by cellulose or a cellulose derivative are held in an amount of 0.001 mol or more per glucose ring of cellulose.

In the present invention, the azo catalyst (B) is DC
It has a group capable of undergoing a dehydration reaction with active hydrogen of cellulose in the presence of C, and examples thereof include a group having a hydroxyl group, an amino group, or a carboxylic acid group.

As the azo catalyst having a hydroxyl group, 2,2'-
Azobis [2- (hydroxymethyl) propionitrile], 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) -propionamide] and the like can be mentioned. Examples of the azo catalyst having an amino group include 2,2'-azobis [2-
(Imidazolin-2-yl) propane] and the like.
Examples of the azo catalyst having a carboxylic acid include 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis [2- (hydroxymethyl) propionitrile] and a dibasic acid anhydride (phthalic anhydride). , Succinic anhydride, maleic anhydride, etc.). Among (B), a preferable one is an azo catalyst having a carboxylic acid, and a particularly preferable one is 4,4′-azobis (4-cyanovaleric acid).

When (A) and (B) are reacted in the presence of DCC, the reaction substantially proceeds by a dehydration mechanism,
The combination of (A) and (B) is limited. That is, (A)
Is a polymer having a hydroxyl group and / or an amino group, (B) is an azo catalyst having a carboxylic acid group at the terminal, and (A) is a polymer having a carboxylic acid group,
(B) is an azo catalyst having a hydroxyl group and / or an amino group at the terminal.

In the present invention, as the vinyl monomer (C), (meth) acrylic acid, (meth) acrylic acid alkyl ester (eg, butyl acrylate, lauryl methacrylate, etc.), styrenes (styrene, α- Methyl styrene, etc.), vinyl chloride, vinyl acetate, and mixtures thereof. Of these, preferred are (meth) acrylic acid alkyl esters and styrene.

In the present invention, (A), (B), (C)
And a graft polymer composition (D) derived from DCC is a reaction product of (A), (B), (C) and DCC, and a graft product of (C) onto (A), and (C) )
Of homopolymers and unreacted substances. Specific examples of (D) include (A) cellulose acetate and (B) 4,4′-
Azobis (4-cyanovaleric acid), a graft polymer composition of (C) butyl methacrylate, or (A) polyvinyl alcohol, (B) 4,4′-azobis (4-cyanovaleric acid), (C) ) Is a vinyl acetate graft polymer composition.

As a method of inducing (D), (A),
(A) in a solvent inert to (B) and DCC,
A method of mixing and heating (B), (C) and DCC can be mentioned. In this reaction, dicyclohexylcarbodiurea, which is a byproduct of the dehydration reaction of DCC, is preferably removed by a method such as filtration. The reaction is
When (A) and (B) react in the presence of DCC to obtain a cellulose derivative containing an azo group, polymerization of (C) occurs based on thermal cleavage of the azo group, and grafting occurs.
Polymerization of (C) may occur due to thermal cleavage of (B), and after obtaining a terminally reactive polymer, it may react with (A) in the presence of DCC to graft. Therefore, (A),
The mixing method of (B) and (C) is (A), (B) and DC.
A method of adding C after mixing C, a method of adding (A) and DCC after mixing (B) and (C), and a method of simultaneously mixing (A), (B), (C) and DCC And the like.

Examples of the inert solvent include aromatic solvents such as toluene and xylene, ketone solvents such as methyl ethyl ketone, ester solvents such as ethyl acetate, aliphatic hydrocarbon solvents such as hexane, halogens such as methylene chloride. Examples include system solvents and the like, and mixtures thereof.

The reaction temperature is usually from -5 ° C to 150 ° C.
The reaction of (A), (B) and DCC is preferably −5 ° C. to 20 ° C., and the polymerization of (C) accompanying thermal cleavage of the azo group is preferably 40 ° C. to 150 ° C. At -5 ° C or lower, the reaction rates of (A), (B) and DCC are slow, and at 150 ° C or higher, there are problems such as coloring during polymerization and a by-product of a crosslinked gel. The reaction time is usually 1 to 15 hours.

If desired, a catalyst may be used for the purpose of increasing the reaction rate of the dehydration reaction by (A), (B) and DCC. Examples of the catalyst include triethylamine and dimethylaminopyridine. The amount of catalyst used is 0.001 to 10% by weight based on (B).

Further, the constitutional unit of (D) is (A),
The amounts of (B) and (C) are based on the weight of (D).
(A) is 10 to 74% by weight, (B) is 0.1 to 7.5% by weight,
(C) is 89.9 to 18.5% by weight. DCC is usually used in 0.5 to 3 times the molar amount of (B). (D) is usually obtained as a solution, and the concentration of (D) in the solvent is 10 to 70% by weight.

[0019]

【Example】

The present invention will be further described below with reference to examples, but the present invention is not limited thereto. Parts in the examples are parts by weight. The polymerization rate and graft rate were determined by the following methods. Polymerization rate: Unreacted monomers were quantified and converted using gas chromatography. Graft ratio: The graft ratio for the polymerized monomer was calculated from the following formula. Grafting rate (%) = (ab) × 100 / a (where a is the amount of polymerized monomer, which is obtained from the amount of charged monomer × polymerization rate. B is the amount of homopolymer, and the reaction solution is petroleum ether) Obtained by extraction.)

Example 1 20 parts of cellulose acetate, 0.6 part of 4,4'-azobis (4-cyanovaleric acid) and 0.5 part of DCC were added to 300 parts of methylene chloride and reacted at 0-5 ° C for 20 hours. . The by-produced urea compound was filtered and the solvent of the filtrate was removed to prepare 20 parts of cellulose acetate (A-1) having an azo group. (A-1) 10 copies,
Mix 10 parts butyl methacrylate and 40 parts dioxane to 70
It was made to react at 10 degreeC for 10 hours, and the cellulose composition (D-1) was obtained. The polymerization rate was 98% and the graft rate was 56%. While the dioxane solution of cellulose acetate and polybutyl methacrylate was separated, the solution of (D-1) was uniformly transparent.

Example 2 Cellulose acetate phthalate 20 parts, 2,2'-azobis [2- (hydroxymethyl) propionitrile] 0.6 part, DCC 0.5
Parts were added to 300 parts of methylene chloride and reacted at 0-5 ° C for 20 hours. The urea compound produced as a by-product is filtered, the solvent of the filtrate is removed, and an azo group-containing cellulose acetate phthalate (A-
2) Prepared 20 copies. In Example 1, (A-1) 10
As a result of carrying out graft polymerization on cellulose acetate phthalate in the same manner except that 10 parts of (A-2) was used in place of the parts, a cellulose composition (D-2) was obtained. Polymerization rate is 95
%, And the graft ratio was 54%. The solution of (D-2) is
It was uniformly transparent.

Example 3 20 parts of aminocellulose (A-3) having an azo group was prepared in the same manner as in Example 1 except that 20 parts of aminocellulose was used instead of 20 parts of cellulose acetate. 20 parts of (A-3), 20 parts of methyl acrylate and 40 parts of dioxane were mixed and reacted at 70 ° C. for 10 hours to obtain a cellulose composition (D-3). Polymerization rate is 92%, grafting rate is
It was 49%. Whereas the dioxane solution of aminocellulose and polybutylmethacrylate separates, (D-
The solution of 3) was uniformly transparent.

Example 4 Polyvinyl alcohol (PVA-217 manufactured by Kuraray) 20 parts, 4,
0.6 part of 4'-azobis (4-cyanovaleric acid) and 0.5 part of DCC were added to 300 parts of dimethyl sulfoxide and reacted at 0 to 5 ° C for 20 hours. The by-produced urea compound was filtered to prepare 320 parts of a solution of polyvinyl alcohol (A-4) having an azo group. 320 parts of the solution of (A-4) and 10 parts of acrylonitrile were mixed and reacted at 70 ° C. for 10 hours to obtain a solution of the graft composition (D-4). The polymerization rate was 92%.
Further, while the film obtained by casting the dimethyl sulfoxide solution of polyvinyl alcohol and polyacrylonitrile is cloudy, the film obtained by casting the solution of (D-4) is almost transparent. It was

Example 5 In Example 4, instead of 20 parts of polyvinyl alcohol, styrene / hydroxyethyl methacrylate (90/1
0) A solution of the graft composition (D-5) was obtained in the same manner except that 20 parts of the copolymer (weight average molecular weight 120,000) was used.
The polymerization rate was 98%. The film obtained by casting this solution was almost transparent.

Comparative Example 1 Styrene / hydroxyethyl methacrylate (90/10)
Copolymer (weight average molecular weight 120,000) 80 parts, 2,2'-azobisisobutyronitrile 0.8 part, dimethyl sulfoxide 100
And 20 parts of acrylonitrile were mixed and reacted at 70 ° C. for 7 hours to obtain a solution of the graft composition. The polymerization rate was 95%. The film obtained by casting this solution was cloudy.

Example 6 50 parts of pentaerythritol propylene oxide adduct (number average molecular weight 4,000), 0.6 part of 4,4'-azobis (4-cyanovaleric acid), 0.008 part of triethylamine and 0.5 part of DCC were added to 300 parts of methylene chloride. And allowed to react at 0-5 ° C for 20 hours. The by-produced urea compound was filtered and the solvent in the filtrate was removed to prepare 50 parts of a solution of pentaerythritol propylene oxide adduct (A-6) having an azo group.
(A-6) and 50 parts of acrylonitrile are mixed and mixed at 70 ° C for 10
The reaction was carried out for a time to obtain a graft composition (D-6). The polymerization rate was 95%, and the emulsion was stable.

[0028]

The present invention has the following effects. In graft polymerization of a vinyl monomer onto a cellulose derivative, high graft efficiency can be achieved without gelation. The obtained cellulose derivative is modified with grafted acrylic or styrene, has improved compatibility with acrylic resins and styrene resins, and solubility in solvents, and is suitable for applications such as paints and inks.

Claims (5)

[Claims] 1. A graft polymer composition derived from a polymer (A) having active hydrogen, an azo catalyst (B) having a terminal group capable of undergoing a dehydration reaction with active hydrogen, a vinyl monomer (C) and dicyclohexylcarbodiimide. Object (D). 2. The composition according to claim 1, wherein (A) is a polysaccharide. 3. The composition according to claim 1, wherein (A) is cellulose or a cellulose derivative. 4. The composition according to claim 1, wherein (A) is a polymer having a hydroxyl group and / or an amino group, and (B) is an azo catalyst having a carboxylic acid group at the terminal. 5. The composition according to claim 1, wherein (A) is a polymer having a carboxylic acid group, and (B) is an azo catalyst having a hydroxyl group and / or an amino group at the terminal.