JPS63270767A - Carbon black graft polymer and production of the same - Google Patents

Abstract

PURPOSE:To obtain the title polymer which is excellent in dispersibility in an org. polymer, water, an org. solvent, etc., and is suited for use as a colorant for an ink, a coating compsn., etc., a modifier for various polymers, etc., by reacting carbon black with a polymer having a particular reactive group. CONSTITUTION:A polymerizable monomer having in its molecule at least one reactive group selected from an aziridine group, in oxazoline group and an N-hydroxyalkylamide group (e.g., isopropenyloxazoline, optionally together with another polymerizable monomer (e.g., styrene), is polymerized to give a polymer (B) having said reactive group in its molecule. 100pts.wt. carbon black (A) is reacted with 1-3,000pts.wt. component (B) at room temp. - 350 deg.C under agitation.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a novel carbon black graft polymer and a method for producing the same. For more information, see Cardenbra,
(hereinafter referred to as CB) is reacted with a polymer having a specific reactive group, and is used as a coloring agent for inks, copying machine toners, paints, plastic molding materials, etc., or as a modification of various polymers. This invention relates to a useful new carmen black graft polymer and a method for producing the same.

(Prior Art) CB has excellent colorability, 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.
It is extremely difficult to mix or disperse uniformly under normal mixing or dispersion conditions.

In order to solve this problem, many studies have been conducted to improve the dispersibility of CB by coating the 08 surface with various surfactants and resins to increase its affinity with solid or liquid substrates. Among them, Cargen Black graft polymer, which is obtained by combining polymerizable monomers in the coexistence of CB, is SN.
Hydrophilicity and/or lipophilicity can be changed as appropriate by appropriately selecting the type of polymerizable monomer, which has attracted attention in recent years.

For example, Japanese Patent Publication No. 42-22047, Japanese Patent Publication No. 42-22047,
No. 4-3826, Special Publication No. 45-17248, Special Publication No. 4
6-26970, however, the yield of carbon plaque graft polymer obtained by these methods is low, ranging from a few coefficients to several tens of thousands, and the majority exists in the form of a vinyl homopolymer, and the surface treatment of CB The moving parts were extremely poor. For this reason, the affinity with other substances was not improved as much as expected, and the dispersion state often varied depending on the mixing or dispersion conditions.

(Problem to be Solved by the Invention) As a result of intensive studies in view of the current situation, the present inventors have found that the polymer contained in a specific reactive fund molecule reacts extremely efficiently with the surface functional group of CB. -The obtained carbon black graft polymer has extremely excellent dispersibility in various substances, and by specifying the reaction conditions, the carbon black graft polymer has further improved dispersibility. The present invention was completed after discovering that it can be easily obtained.

(Means for Solving the Problems) The present invention provides a polymer (hereinafter referred to as , a polymer having a reactive group). ) is a product that is characterized by its reaction.

The present invention relates to a method for producing a carbon black graft polymer, which comprises stirring and mixing a graft polymer, CB, and a polymer (A) having a reactive group under a reaction temperature condition of room temperature to 350°C.

The polymer (A) having a reactive group in the present invention is a vinyl polymer having one or more reactive groups selected from an aziridone group, an oxazoline group, and an N-hydroxyalkylamide group in the molecule. , polyester, polyether, etc. 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, depending on the type of CB that can be used. It is subject to limitations and requires a step of pre-treating CB prior to the reaction. The significance of using the monomer (4) having the above-mentioned reactive group in the reaction with CB is 1. Regardless of the type and state of CB used, CB and polymer (
A) reacts with very high grafting efficiency, resulting in the production of a carburine graft polymer with extremely excellent dispersibility in various substances.

For example, the method for obtaining the polymer (A) having a reactive group is as follows.
) (hereinafter referred to as monomer (a)) and other polymerizable monomer (b) (hereinafter referred to as monomer (b)).
(1) A method of polymerizing the compound (e) having the above-mentioned reactive group in the molecule with a polymer (d) having a group capable of reacting with the compound (C) (hereinafter referred to as compound (c) 1); (hereinafter referred to as polymer (d)) to introduce a polymer (d) other than the above-mentioned reactive groups, etc., and these methods may be adopted as appropriate depending on the purpose of use. be able to.

Examples of the monomer (a) that can be used in the method (2) include CH2-CH-C0O-CH(CH3)-cn2-N3
CH2-C(OH3)-Coo-CH(CH3)-CH
2-N@CH2 size H-C00yun CH2CH2Osu CH2
CH2-N(CH2-C(OH3)-Coo-+CH2
CH2O crucible CH2CH2-Ngca2=cH-coo(
cu2ca2oi co-cht2Cn2-N@CH2
-C(CH,)-Coo→cH2cH2oq co-e
lr2cn2-NqCH2-CH20-Co-CH-C
H7CH2-CH20-Co-C(CH3)=CH2C
H2=CH-Coo-CH2CH2-NHCO-N, D
CH2-C(CH3)-Coo-CH2CH2-NHC
Aziridine group-containing polymerizable monomer represented by O-N etc.; 2-H=)v-2-oxazoline, 2-vinyl-
4-Methyl-2-oxazoline, 2-bi-5-methyl-2-oxazoline, 2-vinyl-4-ethyl-2-
Oxazoline, 2-vinyl-5-ethyl-2-oxazoline, 2-impropenyl-2-oxazoline, 2-impropenyl-4-methyl-2-oxazoline, 2-impropenyl-5-methyl-2-oxazoline, 2 - Oxazoline group-containing polymerizable monomers such as isopropenyl-4-ethyl-2-oxazoline, 2-impropenyl-5-ethyl-2-oxazoline, and 2-impropenyl-4,5-tumethyl-2-oxazoline Class; N-hydroxymethyl acrylamide, N-hydroxyethylacrylamide, N-hydroxybutylacrylamide, N-
Hydroxyisobutylacrylamide, N-hydroxy-2-ethylhexylacrylamide, N-hydroxycyclohexylacrylamide, N-hydroxymethylmethacrylamide, N-hydroxyethylmethacrylamide, N-hydroxybutylmethacrylamide, N-hydroxyisobutylmethacrylamide, N-hydroxy -N-hydroxyalkylamide group-containing polymerizable monomers such as -2-ethylhexylmethacrylamide and N-hydroxycyclohexylmethacrylamide, etc.; selected from these groups, nine 1aI or two or more are used. can do.

The monomer (b) that can be optionally used in the method (2) is not particularly limited as long as it can be copolymerized with the monomer (a), such as styrene, 0-methylstyrene, m
- Styrenic monomers such as methylstyrene, p-methylstyrene, α-methylstyrene, p-methoxystyrene, p-LerL-butylstyrene, p-phenylstyrene, 0-chlorostyrene, m-chlorostyrene, p-chlorostyrene, etc. Acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, stearyl acrylate, acrylic #R2-ethylhexyl, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate Acrylic acid or methacrylic acid monomers such as n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, methacrylate, 2-ethylhexyl phosphate, stearyl methacrylate; ethylene, propylene, butylene, vinyl chloride , vinyl acetate, acrylonitrile, acrylamide, methacrylamide, N-vinylpyrrolidone, etc. One or more of these can be used.

In order to obtain the polymer α) having a reactive group by the method (2), monomer (a) is combined with monomer (b) using the monomer (b) as required, and conventionally known polymerization methods such as bulk polymerization, suspension 1 The polymerization may be carried out by a method such as a method, an emulsion polymerization method, a precipitation #1 method, or a solution polymerization method.

Compounds (c) that can be used in the method (2) include f
(2-) Compound having two or more of the above reactive groups 1ffI in the molecule (2-2) Compound having two or more of the above reactive groups in the molecule (2-3) The above reaction Compounds having one or more reactive groups and a group other than the above-mentioned reactive groups in the molecule can be mentioned.

However, the group other than the reactive group described in item (2-3) is a group other than an aziridine group, an oxazoline group, or an N-hydroxyalkylamide group, and is not a polymer (
d), such as incyanate groups, epoxy groups, amine groups, carboxyl groups, hydroxyl groups, vinyl groups, etc.

The polymer (d) in the method (2) refers to the above (2-1) to
These include vinyl polymers, polyesters, polyethers, etc., which have a vine group that reacts with the compound (c) described in section (2-3). Examples of groups that react with compound (c) include hydroxyl groups, carboxyl groups, amine groups, and epoxy groups, and polymers having these groups (
d) can be easily obtained by known polymerization procedures such as radical 1 polymerization and fII'i polymerization.

In order to obtain 18 prisoners having a reactive group by the method (2),
The compound (c) and the polymer (d) may be reacted under conditions such that at least one of the reactive groups remains unreacted.

In the present invention, the monomer having a reactive group is appropriately selected depending on the properties to be imparted to the carplacunoraft polymer, such as hydrophilicity, lipophilicity, or other affinity. When water-growing properties are to be imparted, vinyl polymers and polyethers containing acrylic acid as the main component are used; when lipophilic properties are to be imparted, vinyl-based polymers and polyesters containing styrene as the main component are used. Suitably used. The molecular weight of the polymer (A) having a reactive group is not particularly limited, but the average molecular weight is 200 to 100,000 in terms of remarkable processing effects on CBK and workability during reaction with CB.
It is preferably in the range of 0, more preferably 300 to
The range is 100,000.

The carbon black graft polymer of the present invention is CBK
It is formed by reacting a reactive foundation stone 1 with a polymer, and the polymer is grafted to CB with extremely high efficiency. The reaction can be done by Yuzu's method. For example,
Alternatively, a method may be used in which the polymer (A) having a reactive group obtained by the above-mentioned methods (1) and (2) is reacted with CB.
The step of obtaining a polymer (A) having a reactive group by carrying out methods (1) and (2) in the presence of B and the step of reacting the polymer (A) with CB may be combined into one. However, the former method is preferred in order to obtain Curve/Gura and Ta graft polymers with high grafting efficiency.

During the reaction, the amount of monomer (A) having a reactive group can be set arbitrarily depending on the purpose of use of the obtained carbon black graft polymer, but it is sufficient to sufficiently improve the dispersibility in each pond material. In order to express this and not impair its characteristics as a CB, it is usually added 1 to 100 parts by weight of CB.
A suitable proportion is 3000 parts by weight.

The present invention also provides a method for easily obtaining a carbon black graft polymer (f) which has further improved dispersibility in various substances.

Such a production method involves the production of a monomer (A) having CB and a reactive group.
) and are stirred and mixed under temperature conditions of room temperature to 350°C to achieve V. According to the production method of the present invention, when the CB used as a raw material in a secondary agglomerated state is stirred and mixed and reacted, it is efficiently crushed into fine and uniform particle diameters, and the efficiency of the reaction is also improved. The obtained cardan black special graft polymer has further improved physical properties. If the temperature condition during the reaction exceeds 350°C, the quality of the polymer component will change, which is not preferable.

In the production method of the present invention, the reaction between CB and a polymer (having a reactive group) may be a method in which only these two components are reacted, and the reaction does not correspond to a polymer (having a reactive group). The reaction may be carried out in the presence of other substances such as polymer components, polymerizable monomers, organic bath agents, and water. As an example specifically showing the embodiment of the manufacturing method of the present invention, for example, C
Polymer (A) having a reactive group based on 100 parts by weight of B
1 part by weight to 3000ii parts, preferably 5 parts to 10 parts by weight
0100 O parts・Polymer oB parts without reactive groups~
A mixture of 100 oNf part, 1 - 200M coated part of the combined monomer ON spear, and 1 part - 1000 part of the compound OM is heated at room temperature to 350°C, preferably from 50°C to 25°C.
The carbon black graft polymer of the present invention is obtained by stirring and mixing under the conditions of 0° C. and m degrees.

(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 has a high concentration of C8
It is grafted onto the surface.

In the present invention, the composition, type, etc. of the polymer (A) can be arbitrarily selected as long as the polymer (A) has a certain reactivity fund.
It is possible to give it to The carmen black graft polymer obtained in this way has improved affinity with various substances, for example, it has extremely excellent dispersibility in substances such as organic polymers, water, and organic bath agents.
It can be suitably used as a coloring agent for inks, toners for copying machines, paints, plastic molding materials, etc., and as a modifier for each A11 moiety. In addition, according to the production method of the present invention, carbon graphite, which has further improved the above-mentioned characteristics including dispersibility, and a carbon fiber graft polymer having a reactive group on CB (A) can be simply heated under full heating. It can be manufactured simply by stirring and mixing. 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. still,
In the examples, part indicates 1 part and 1 part, and q indicates weight %.

EXAMPLE 400 parts of deionized water containing 0.2 parts of polyvinyl alcohol was charged into a flask equipped with a stirrer, an inert gas introduction tube, a reflux condenser, and a thermometer.

A mixture of 16 parts of benzoyl peroxide and a polymerizable monomer consisting of 196 parts of styrene and 19 parts of impropenyl oxa prepared in advance was added thereto, and the mixture was stirred at high speed to form a uniform suspension. did. Next, the mixture was heated to 80° C. while blowing nitrogen gas, and stirred under this condition 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 molecule t of this polymer was Mn=5.800 by GPC measurement.

40 parts of a polymer having an oxazoline group as a reactive group and Carpin Black MA-600 (Mitsubishi Chemical Corporation f)
f) 20 parts and rub blast mill (manufactured by Toyo Seiki Co., Ltd.)
The mixture was kneaded and reacted at 160° C. and 100 rpm, and then cooled and pulverized to obtain a carbon black graft polymer (1).

Example 2 200 parts of toluene and 200 i'i of methyl in butyl ketone were charged into the same flask as used in Example, and heated to 80° C. while blowing nitrogen gas. A mixture of 190 parts of styrene and 1/10 parts of 2-(1-azilinonyl)ethyl methacrylate and 4 parts of benzoylnon-oxide was added thereto for 2 hours. The mixture was poured down through a dropping funnel, and stirring was continued for an additional 5 hours to carry out a 1-coal reaction, followed by cooling to obtain a 1-coal bath liquid. 2,000 parts of methanol was added to 100 parts of this polymer solution, reprecipitation was performed, and the mixture was dried to obtain a polymer having an atorison group as a reactive group. The molecular weight of this monomer is determined by GPC
The measurement showed that Mn = 3,000.

20 parts of a polymer having an aziridine group as a reactive group and Styron-6, which is polystyrene without a reactive group.
66 (manufactured by Asahi Kasei Industries, Ltd., Mn = 4000) and a total of 20 parts of carbon black MA-600 were reacted in the same manner as in Example], then cooled and pulverized to obtain carbon black graft polymer (2)'. Ta.

Example 3 Into the same flask used in Example, 7 chlorohexane 4
60 parts and 2 parts of Rheodol 5P-8IO (manufactured by Kao Corporation) were charged, and the temperature was raised to 75° C. while blowing nitrogen gas. 60 parts of acrylamide prepared in advance,
A mixture of 15.2 parts of N-vinylpyrrolidone and 1.6 parts of N-hydroxyethylmethacrylamide to which 140 parts of deionized water and 2 parts of ammonium peroxide were added was added for 1.5 hours. The mixture was added dropwise from the dropping funnel, and stirring was continued for an additional 0.5 hours to carry out a one-time reaction. After cooling, the cyclohexane was removed and the polymer was dried at 80-100°C under reduced pressure to obtain a polymer having N-hydroxyalkylamide groups as reactive groups. The molecular weight of this monomer is G
Mn=12,000 was determined by PC measurement.

45 parts of a polymer having an N-hydroxyalkylamide group as a reactive group and 15 parts of carbon black MA-10OR (manufactured by Mitsubishi Chemical Industries, Ltd.) were reacted in the same manner as in Example], and then cooled and pulverized to form carbon. A black graft polymer (3) was obtained.

Example 4 217 parts of toluene was charged into the same flask as used in Example 2, and heated to 90° C. while blowing nitrogen gas. To the previously prepared polymerizable monomers consisting of 480 parts of styrene and 20 parts of acrylic [n-butyl], 5.44 parts of thioglycolic acid and 1 part of azobisisobutyronitrile were added.
．． 32 parts of the mixture was added dropwise through the dropping funnel over a period of 2 hours, and stirring was continued for an additional 5 hours to carry out a polymerization reaction. The molecular weight of this polymer was determined by GPC measurement: Mn=9
It was 500.

Next, 2.95 parts of 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).
The reaction was carried out at 0° C. for 2 hours to obtain a solution of a polymer having an oxazoline group as a reactive group at the end (non-volatile content: 70%).

57.1 parts of a solution of a polymer having an oxazoline group at the end (70% non-volatile content) and carbon black MA-1
Add 20 parts of 0OR to 160°C using a Meglast Mill.
After kneading at 00 rpm to react and remove the bath, the mixture was cooled and pulverized to form a carbon black graft polymer (
4) was obtained.

Example 1 Series 5 32 parts of methanol and 0.35 parts of sodium hydroxide were placed in an autoclave equipped with a vacuum cleaner, a thermometer, and an ethylene oxide supply device, and the temperature was raised to 0°C and stirring was continued. While maintaining the pressure at 5 to 8 klZ/Cm2, 88 parts of ethylene oxide was added dropwise, and after aging for 30 minutes, the reaction temperature was further raised to 150°C, and 352 parts of ethylene oxide was added dropwise over 5 hours. , and then aged for 1 hour to obtain a 10 mol adduct of ethylene oxide with methoxylated one end. 47.2 parts of this one-end methoxylated ethylene oxide 10 mole adduct and 0.62 parts of sodium hydroxide were placed in the same autoclave as above, the temperature was raised to 150°C, and 616 parts of ethylene oxide was added dropwise over 5 hours. Thereafter, the mixture was aged for 1 hour to complete the first reaction, thereby synthesizing polyethylene glycol with methoxylated one end.

In the same autoclave used above, add 400 parts of distilled water,
100 parts of one-end methoxylated polyethylene glycol obtained by the above reaction, platinum/no! Charge 10 parts of rasium catalyst, maintain temperature at 90 to 95°C, and maintain pressure at 10 km/c.
The reaction was continued by stirring for 30 hours while adding compressed air from time to time so that the reaction time was maintained at m'' k m. The molecular weight of this polymer was found to be Mn=6600 by GPC measurement.The bath medium of the water bath solution of this modified polyethylene glycol was replaced with soethylene glycol, and the nonvolatile content was reduced to 33.3%.
A was set up. 300 parts of the diethylene glycol solution of the one-end carboxyl-modified polyethylene glycol thus obtained was charged into the same flask as used in Example 1, 50 parts were heated in the trench, and 1.70 parts of 2-(1-azilinonyl )-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 solvent containing a polymer having an oxazoline group as a reactive group and carbon black≠45 (Mitsubishi Chemical Corporation)
30 parts of Hibiscus Co., Ltd.) were transferred to the flask shown in Example 1, and 1
The reaction was carried out at 00°C for 5 hours to obtain a diethylene glycol bath solution of the carbon black graft polymer (5) ◇ Example 6 Into the same flask as used in Example 2, a linear saturated polyester Alogratz 0B-63 containing a terminal carboxyl group was added. (
Nippon Shokubai Chemical Co., Ltd. table, molecular weight Mn = 6000, non-volatile content 50%) 200 parts, 3.60 parts of 2-p-phenylene-bis-2-oxazoline were added, and the mixture was heated at 110°C.
The reaction was carried out for a period of time to obtain a solution (non-volatile content: 50 t) of the 'flf compound having an oxazoline group as a reactive group at the end.

80.0 parts of a solution (non-volatile content 50%) of a polymer having an oxacyl/group at the end and carbon black MA-10OR
20 parts were kneaded and reacted under the same conditions as in Example 4 to obtain a carbon black graft polymer (6).

Comparative Example: In a flask similar to the one used in Example 1, 4 styrene was added.
8 parts and 12 parts of carbon black MA-600 were charged, heated to 140° C. while blowing nitrogen gas, and stirred at this temperature for 5 hours to carry out a polymerization reaction, and then cooled.

After the reaction, 300 parts of toluene was added to the product, and the product was reprecipitated in 7000 s of methanol to obtain a comparative carbon black graft polymer (]). The composition of this comparative carbon black graft polymer (1) was 100 parts of CB component and 250 parts of polystyrene component.

Comparative Example 2 Polymethylenef 45 without reactive group used in Example 2
and 15 parts of carbon black MA-600t were kneaded in the same manner as in Example], then cooled and pulverized to obtain a comparative carbon black graft polymer (2) in which the CB acid component and the polymer component were not substantially bonded. 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 carpin black graft polymers (1) to (2),
Dispersibility in toluene and water was tested. The results were as shown in Table 1.

Table 1 Note 1) Evaluation of dispersion state is based on carbon plastic in the dispersion liquid.

It was conducted using straw containing 5% of ri.

Note 2) Of the total 200 parts of the polymer, 100 parts were the polymer having a reactive group.

Note 3) Comparative Example 3 shows the results of MA-10OR alone.

Claims (1)

[Claims] 1. Carbon black is reacted with a polymer having one or more reactive groups selected from the group consisting of aziridine group, oxazoline group and N-hydroxyalkylamide group in the molecule. A carbon black graft polymer characterized by: 2. 1 to 3,000 parts by weight of a polymer having one or more reactive groups selected from the group consisting of an aziridine group, an oxazoline group, and an N-hydroxyalkylamide group in the molecule per 100 parts by weight of carbon black. The carbon black graft polymer according to claim 1, which is obtained by reacting the carbon black graft polymer in a proportion of 1. 3. Carbon black and a polymer having one or more reactive groups selected from the group consisting of aziridine group, oxazoline group, and N-hydroxyalkylamide group in the molecule under temperature conditions of room temperature to 350°C. A method for producing a carbon black graft polymer, which comprises reacting by stirring and mixing. 4. For 100 parts by weight of carbon black, add 1 to 3,000 parts by weight of a polymer having one or more reactive groups selected from the group consisting of aziridine group, oxazoline group, and N-hydroxyalkylamide group in the molecule. 4. The method for producing a carbon black graft polymer according to claim 3, wherein the carbon black graft polymer is reacted in a proportion of 50%.