JPH0224868B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a novel carbon black graft polymer and a method for producing the same. For more details,
Carbon black (hereinafter referred to as CB) is reacted with a polymer having a specific reactive group, resulting in ink,
The present invention relates to a new carbon black graft polymer useful as a coloring agent for copying machine toners, paints, plastic molding materials, etc., or as a modification of various polymers, and a method for producing the same. (Prior Art) CB has excellent coloring properties, electrical conductivity, weather resistance, chemical resistance, etc., and is therefore widely used for various purposes such as reinforcing agents and fillers for plastics and elastomers. However, since CB is in the form of powder or granules, it is rarely used alone; it is usually dispersed uniformly in a solid base material such as rubber or resin, or in a liquid such as water or a solvent. Demonstrate characteristics. However, CB has a weak affinity with other substances such as organic polymers, water, and organic solvents compared to the cohesive force between particles, so it is extremely difficult to mix or disperse uniformly under normal mixing or dispersion conditions. It was difficult. To solve this problem, many studies have been conducted to improve the dispersibility of CB by coating the CB surface with various surfactants and resins to increase its affinity with solid or liquid substrates. ing. Among them, carbon black graft polymers obtained by polymerizing polymerizable monomers in the coexistence of CB can be modified to have hydrophilicity and/or lipophilicity by appropriately selecting the type of polymerizable monomers.
It has attracted attention in recent years because it can be changed. As a method for producing this carbon black graft polymer, for example, Japanese Patent Publication No. 42-22047,
Special Publication No. 44-3826, Special Publication No. 17248, Special Publication No. 45-17248, Special Publication No. 17248, Special Publication No.
No. 46-26970, however, the yield of carbon black graft polymer obtained by these methods is low, ranging from several percent to several tens of percent, and the majority exists in the form of a vinyl homopolymer, and the carbon black graft polymer obtained by these methods is in the form of a vinyl homopolymer. It was extremely inefficient. For this reason, the affinity with other substances was not improved as much as expected, and the state of dispersion often differed depending on the mixing or dispersion conditions. (Problem to be Solved by the Invention) The present inventors have conducted extensive studies in view of the current situation, and have found that a polymer having a specific reactive group in its molecule can interact with the surface functional groups of CB extremely efficiently. The carbon black graft polymer obtained by the reaction has excellent dispersibility in various substances, and by specifying the conditions during the reaction, a carbon black graft polymer with even higher dispersibility can be easily obtained. The present invention was completed based on the discovery that this can be done. (Means for Solving the Problems) The present invention involves reacting one or more types selected from the group consisting of an aziridine group, an oxazoline group, and an N-hydroxyalkylamide group in the molecule with respect to 100 parts by weight of CB. A carbon black graft polymer characterized in that it is formed by reacting a polymer having a reactive group (hereinafter referred to as a polymer having a reactive group (A)) in a proportion of 1 to 3,000 parts by weight, and CB and a reactive group. The present invention relates to a method for producing a carbon black graft polymer, which comprises stirring and mixing a polymer (A) having the following properties at a reaction temperature of room temperature to 350°C. The polymer (A) having a reactive group in the present invention is a vinyl polymer having in its molecule one or more reactive groups selected from an aziridine group, an oxazoline group, and an N-hydroxyalkylamide group;
These include polyester and polyether. Groups that can react with the functional groups present on the surface of CB are not necessarily limited to these reactive groups, but when using a polymer having groups other than these reactive groups, the type of CB that can be used It is subject to limitations and requires a step to pre-treat CB prior to the reaction. The significance of using the polymer (A) having the above-mentioned reactive group in the reaction with CB is that
Regardless of the type and state of CB, CB and polymer (A) react with extremely high grafting efficiency even under mild reaction conditions, yielding carbon black grafted polymers with outstanding dispersibility in various substances. It's there. As a method for obtaining the polymer (A) having a reactive group, for example, if necessary, the polymerizable monomer (a) having the above-mentioned reactive group in the molecule (hereinafter referred to as monomer (a)) is used. A method of polymerizing the compound (c) with another polymerizable monomer (b) (hereinafter referred to as monomer (b)); The reactive group is reacted with a polymer (d) (hereinafter referred to as polymer (d)) having a group capable of reacting with the compound (c).
(d), etc., and these methods can be adopted as appropriate depending on the purpose of use. Examples of the monomer (a) that can be used in the method include: An aziridine group-containing polymerizable monomer represented by;
2-vinyl-2-oxazoline, 2-vinyl-4
-Methyl-2-oxazoline, 2-vinyl-5-
Methyl-2-oxazoline, 2-vinyl-4-ethyl-2-oxazoline, 2-vinyl-5-ethyl-2-oxazoline, 2-isopropenyl-2
-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5
-Methyl-2-oxazoline, 2-isopropenyl-4-ethyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline, 2-
Oxazoline group-containing polymerizable monomers such as isopropenyl-4,5-dimethyl-2-oxazoline; N-hydroxymethylacrylamide, N-
Hydroxyethyl acrylamide, N-hydroxybutylacrylamide, N-hydroxyisobutylacrylamide, N-hydroxy-2-ethylhexylacrylamide, N-hydroxycyclohexylacrylamide, N-hydroxymethylmethacrylamide, N-hydroxyethylmethacrylamide, N-hydroxybutylmethacrylamide N-hydroxyalkylamide group-containing polymerizable monomers such as amide, N-hydroxyisobutyl methacrylamide, N-hydroxy-2-ethylhexyl methacrylamide, N-hydroxycyclohexyl methacrylamide, etc., and selected from these groups. One type or two or more types can be used. Monomers that can be used as necessary in the method of
(b) is not particularly limited as long as it can be copolymerized with monomer (a), such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-methylstyrene, - Styrenic monomers such as methoxystyrene, p-tert-butylstyrene, p-phenylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene; acrylic acid, methyl acrylate, ethyl acrylate, acrylic acid n-butyl, isobutyl acrylate, dodecyl acrylate, stearyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-methacrylate
- Acrylic acid or methacrylic acid monomers such as octyl, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate; ethylene, propylene, butylene, vinyl chloride, vinyl acetate, acrylonitrile, acrylamide, methacrylamide, N-vinylpyrrolidone, etc. are mentioned, and one or more of these can be used. In order to obtain a polymer (A) having a reactive group by the method described above, monomer (a) is combined with monomer (b) using the monomer (b) if necessary, and a conventionally known polymerization method, such as bulk polymerization method or suspension polymerization method. The polymerization may be carried out by emulsion polymerization, precipitation polymerization, solution polymerization, or the like. Compounds (c) that can be used in the method include, for example, (2-1) a compound having two or more of the above-mentioned reactive groups in the molecule (2-2) a compound having two or more of the above-mentioned reactive groups in the molecule; (2-3) Compounds having one or more of the above-mentioned reactive groups and a group other than the above-mentioned reactive groups in the molecule can be mentioned. However, the groups other than the reactive groups described in item (2-3) are groups other than aziridine groups, oxazoline groups, and N-hydroxyalkylamide groups, and are included in the polymer (d) described below. Examples of such groups include isocyanate groups, epoxy groups, amino groups, carboxyl groups, hydroxyl groups, and vinyl groups. The polymer (d) in the method of (2-
A vinyl polymer, polyester, having a group capable of reacting with the compound (c) described in items 1) to (2-3),
Polyether etc. Examples of groups that can react with compound (c) include hydroxyl groups, carboxyl groups, amino groups, and epoxy groups, and polymers (d) having these groups can be prepared by known methods such as radical polymerization and condensation polymerization. It can be easily obtained by the following polymerization procedure. In order to obtain a polymer (A) having a reactive group by the method described above, compound (c) and polymer (d) are reacted under conditions such that at least one of the reactive groups remains unreacted. do it. In the present invention, the polymer (A) having a reactive group is appropriately selected depending on the properties to be imparted to the carbon black graft polymer, such as hydrophilicity, lipophilicity, or other affinity. When it is necessary to impart oleophilicity, vinyl polymers or polyethers containing acrylic acid as a main component are preferably used, and when lipophilic properties are to be imparted, vinyl polymers or polyesters containing styrene as a main component are preferably used. There is no particular restriction on the molecular weight of the polymer (A) having a reactive group, but the average molecular weight is preferably 200 to 200 in terms of remarkable treatment effects on CB and workability during reaction with CB.
The range is preferably 1,000,000, more preferably 300 to 100,000. The carbon black graft polymer of the present invention is obtained by reacting a polymer (A) having a reactive group with CB, and the polymer (A) is graft-bonded to CB with extremely high efficiency. The reaction can be carried out in various ways. For example, if the polymer (A) having a reactive group obtained by the above-mentioned method is
A method of reacting with CB may be used, and a step of obtaining a polymer (A) having a reactive group by carrying out a method of reacting with CB in the presence of CB, and a step of reacting the polymer (A) with CB. may be combined into one. However, the former method is preferred in order to obtain a carbon black graft polymer with high grafting efficiency. In the reaction, the amount of the polymer (A) having a reactive group used is 1 to 3000 parts by weight per 100 parts by weight of CB. The present invention also provides a manufacturing method for easily obtaining a carbon black graft polymer with further improved dispersibility in various substances.
Such a production method is achieved by stirring and mixing CB and the polymer (A) having a reactive group at a temperature of room temperature to 350°C to react. According to the production method of the present invention, in the secondary agglomerated state used as the raw material,
When the CB is stirred and mixed and reacted, it is efficiently crushed and becomes fine and uniform in particle size, and the efficiency of the reaction is also improved, so the properties of the obtained carbon black graft polymer are further improved. If the temperature condition during the reaction exceeds 350°C, the quality of the polymer component will deteriorate, which is not preferable. In the production method of the present invention, the reaction between CB and the polymer (A) having a reactive group may be a method in which only these two components are reacted, or the reaction between the CB and the polymer (A) having a reactive group may be a method in which only these two components are reacted. The reaction may be carried out in the presence of other substances such as polymer components, polymerizable monomers, organic solvents, and water that are not applicable. As a specific example of the embodiment of the production method of the present invention, for example, 1 part by weight of the polymer (A) having a reactive group to 100 parts by weight of CB.
3000 parts by weight, preferably 5 parts by weight to 1000 parts by weight,
A mixture of 0 to 1000 parts by weight of a polymer having no reactive group, 0 to 200 parts by weight of a polymerizable monomer, and 0 to 1000 parts by weight of an organic solvent is heated at room temperature to 350°C. The carbon black graft polymer of the present invention is obtained by stirring and mixing preferably at a temperature of 50°C to 250°C. (Effect of the invention) The carbon black graft polymer of the present invention is obtained by reacting a polymer (A) having a reactive group with CB, and the reactive group in the polymer (A) interacts with the surface functional group of CB. Due to its high reactivity, the polymer (A) component is grafted onto the CB surface with high efficiency. Since the composition, type, etc. of the polymer (A) can be arbitrarily selected as long as it has the reactive groups defined in the present invention, various properties can be imparted to CB depending on the purpose. Is possible. The carbon black graft polymer obtained in this way has improved affinity with various substances, and has extremely excellent dispersibility in substances such as organic polymers, water, and organic solvents.
It can be suitably used as a coloring agent for inks, copying machine toners, paints, plastic molding materials, etc., and as a modifier for various polymers. Furthermore, according to the production method of the present invention, the carbon black graft polymer, which has further improved characteristics such as dispersibility, can be obtained by simply stirring and mixing the polymer (A) having a reactive group on CB with heating. It can be manufactured with a simple operation. Therefore, the method for producing a carbon black graft polymer of the present invention is extremely useful industrially. (Examples) Hereinafter, the present invention will be explained in detail with reference to Examples, but the present invention is not limited to the following Examples. In addition, parts in the examples indicate parts by weight, and % indicates weight %, respectively. Example 1 Polyvinyl alcohol was added to a flask equipped with a stirrer, an inert gas inlet tube, a reflux condenser, and a thermometer.
400 parts of deionized water dissolved in 0.2 parts was charged. A mixture of 16 parts of benzoyl peroxide dissolved in a polymerizable monomer consisting of 196 parts of styrene and 4 parts of isopropenyloxazoline prepared in advance was added thereto, and stirred at high speed to form a uniform suspension. Next, the mixture was heated to 80° C. while blowing nitrogen gas, and stirred at this temperature for 5 hours to carry out a polymerization reaction, and then cooled to obtain a polymer suspension. This polymer suspension was filtered, washed, and dried to obtain a polymer having an oxazoline group as a reactive group. The molecular weight of this polymer was Mn=5800 by GPC measurement. Polymers with oxazoline groups as reactive groups
40 parts and Carbon Black MA-600 (Mitsubishi Chemical Industries)
Co., Ltd.) 20 parts and Laboplasto Mill (Toyo Seiki Co., Ltd.)
After reaction, the mixture was kneaded and reacted at 160° C. and 100 rpm using a commercially available product (manufactured by Alumni Co., Ltd.), followed by cooling and pulverization to obtain carbon black graft polymer (1). Example 2 Toluene was added to the same flask used in Example 1.
200 parts of methyl isobutyl ketone and 200 parts of methyl isobutyl ketone were charged, and the mixture was heated to 80°C while blowing nitrogen gas.
There, 190 parts of styrene prepared in advance and 2
-(1-aziridinyl)ethyl methacrylate 10
A mixture of 4 parts of benzoyl peroxide dissolved in a polymerizable monomer consisting of Obtained. 2000 parts of methanol was added to 100 parts of this polymer solution, reprecipitated, and then dried to obtain a polymer having an aziridine group as a reactive group. The molecular weight of this polymer is
Mn was found to be 3000 by GPC measurement. Polymer 20 with an aziridine group as a reactive group
Styron-666 (manufactured by Asahi Kasei Corporation, Mn = 4000), which is a polystyrene having no moieties or reactive groups, 20
and 20 parts of Carbon Black MA-600 were reacted in the same manner as in Example 1, then cooled and pulverized to obtain Carbon Black graft polymer (2). Example 3 Into the same flask as used in Example 1, 460 parts of cyclohexane and 2 parts of Rheodol SP-S10 (manufactured by Kao Corporation) were added.
The temperature was raised to 75°C while blowing nitrogen gas. A mixture of 140 parts of deionized water and 2 parts of ammonium persulfate was added to the previously prepared polymerizable monomers consisting of 60 parts of acrylamide, 15.2 parts of N-vinylpyrrolidone, and 1.6 parts of N-hydroxyethylmethacrylamide. was added dropwise from the dropping funnel over 1.5 hours, and stirring was continued for an additional 0.5 hours to carry out a polymerization reaction. After cooling, cyclohexane was removed, and the polymer was dried under reduced pressure at 80 to 100°C to obtain a polymer having N-hydroxyalkylamide groups as reactive groups. The molecular weight of this polymer is
Mn=12000 was determined by GPC measurement. 45 parts of a polymer having an N-hydroxyalkylamide group as a reactive group and carbon black MA-
15 parts of 100R (manufactured by Mitsubishi Chemical Industries, Ltd.) was reacted in the same manner as in Example 1, then cooled and pulverized to obtain a carbon black graft polymer (3). Example 4 Toluene was added to the same flask used in Example 2.
Pour 217 parts and heat to 90℃ while blowing nitrogen gas.
heated to. Styrene prepared in advance
A mixture of 5.44 parts of thioglycolic acid and 1.32 parts of azobisisobutyronitrile dissolved in a polymerizable monomer consisting of 480 parts of n-butyl acrylate and 20 parts of n-butyl acrylate was added dropwise from a dropping funnel over 2 hours, and then 5
The polymerization reaction was carried out by continuing stirring for a certain period of time. The molecular weight of this polymer was Mn=9500 by GPC measurement. Next, 2-p-phenylene-bis-2-oxazoline was added to 185.1 parts of this reaction product (a solution containing a prepolymer having a carboxyl group at the end).
2.95 parts were added and reacted at 80°C for 2 hours to obtain a solution (non-volatile content: 70%) of a polymer having an oxazoline group as a terminal reactive group. 57.1 parts of a solution of a polymer having an oxazoline group at the end (70% non-volatile content) and Carbon Black MA
20 parts of −100R was heated at 160°C using a laboplasto mill.
After kneading at 100 rpm to perform reaction and solvent removal, the mixture was cooled and pulverized to obtain a carbon black graft polymer (4). Example 5 32 parts of methanol and 0.35 parts of sodium hydroxide were placed in an autoclave equipped with a stirrer, a thermometer, and an ethylene oxide supply device, the temperature was raised to 110°C, and the pressure was increased to 5 to 8 kg/kg while stirring. ^cm2
88 parts of ethylene oxide was added dropwise while maintaining the temperature, and after aging for 30 minutes, the reaction temperature was further increased.
The temperature was raised to 150°C, 352 parts of ethylene oxide was added dropwise over 5 hours, and the mixture was aged for 1 hour to obtain a 10 mole adduct of ethylene oxide with methoxylated one end. This one-end methoxylated ethylene oxide 10
47.2 parts of molar adduct and 0.62 parts of sodium hydroxide were placed in the same autoclave as above, and the temperature was raised to 150
The temperature was raised to .degree. C., 616 parts of ethylene oxide was added dropwise over 5 hours, and the mixture was aged for 1 hour to complete the polymerization to synthesize polyethylene glycol having one end methoxylated. Distilled water in the same autoclave used above.
400 parts, 100 parts of one-end methoxylated polyethylene glycol obtained by the above reaction, and 10 parts of platinum/palladium catalyst were charged, and the temperature was maintained at 90 to 95°C, and compressed air was supplied as needed to maintain the pressure at 10 kg/ ^cm2. The reaction was continued for 30 hours while stirring, and an aqueous solution of polyethylene glycol having an acid value of 8.4 and modified with a methoxy group at one end and a carboxyl group at the other end was obtained. The molecular weight of this polymer was determined by GPC measurement.
Mn=6600. The solvent of this aqueous solution of modified polyethylene glycol was replaced with diethylene glycol, and the nonvolatile content was adjusted to 33.3%. 300 parts of the diethylene glycol solution of the one-end carboxyl-modified polyethylene glycol thus obtained was charged into the same flask used in Example 1, heated to 50°C, and then 1.70 parts of 2-(1-
aziridinyl)-2-oxazoline was added dropwise over 30 minutes. After reacting for 5 hours, the mixture was cooled to obtain a solution (non-volatile content: 33.7%) containing a polymer having an oxazoline group as a reactive group at one end. 90 parts of a solution containing a polymer having an oxazoline group as a reactive group and 30 parts of Carbon Black #45 (manufactured by Mitsubishi Chemical Industries, Ltd.) were transferred to the flask shown in Example 1, and reacted at 100°C for 5 hours. A diethylene glycol solution of carbon black graft polymer (5) was obtained. Example 6 Into the same flask as used in Example 2, a terminal carboxyl group-containing linear saturated polyester alloplatz OB-63 (manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd., molecular weight Mn =
6000, non-volatile content 50%) 200 parts, 2-p-phenylene-bis-2-oxazoline 3.60 parts were added, 110
℃ for 2 hours to form a solution of a polymer having an oxazoline group as a terminal reactive group (non-volatile content: 50
%) was obtained. 80.0 parts of a solution of a polymer having an oxazoline group at the end (nonvolatile content 50%) and 20 parts of Carbon Black MA-100R were kneaded and reacted under the same conditions as in Example 4 to obtain a carbon black graft polymer (6). . Comparative Example 1 In a flask similar to that used in Example 1, 48 parts of styrene and 12 parts of carbon black MA-600 were added.
The mixture was heated to 140° C. while blowing nitrogen gas into the mixture, and stirring was continued at this temperature for 5 hours to carry out a polymerization reaction, followed by cooling. After the reaction, toluene is added to the product.
300 parts were added thereto, and reprecipitation was carried out in 7000 parts of methanol to obtain carbon black graft polymer (1) for comparison.
Carbon black graft polymer for comparison (1)
The composition is 100 parts of CB component and polystyrene component.
The proportion was 250 copies. Comparative Example 2 45 parts of the polystyrene without reactive groups used in Example 2 and 15 parts of carbon black MA-600 were kneaded in the same manner as in Example 1, then cooled and pulverized.
A comparative carbon black graft polymer (2) in which the CB component and the polymer component were not substantially bonded was obtained. Example 7 Using the carbon black graft polymers (1) to (6) obtained in Examples 1 to 6 and Comparative Examples 1 to 2 and the comparative carbon black graft polymers (1) to (2), Dispersibility was tested. The results were as shown in Table 1.

【table】

【table】

Claims (1)

[Scope of Claims] 1. 1 selected from the group consisting of aziridine group, oxazoline group and N-hydroxyalkylamide group in the molecule based on 100 parts by weight of carbon black.
The species or polymers having two or more reactive groups are 1-
A carbon black graft polymer characterized by being formed by reacting at a ratio of 3000 parts by weight. 2 Based on 100 parts by weight of carbon black, 1 selected from the group consisting of aziridine group, oxazoline group and N-hydroxyalkylamide group in the molecule.
1 to 1 polymer having a species or two or more reactive groups
1. A method for producing a carbon black graft polymer, characterized in that the reaction is carried out by stirring and mixing 3000 parts by weight at a temperature of room temperature to 350°C.