JPS6020913A - Production of amine-modified wax - Google Patents

Abstract

PURPOSE:To facilitate the production of an amine-modified wax of excellent homogeneity, by grafting a tert. amino group-conaining vinyl monomer onto polyethylene wax under a specified condition. CONSTITUTION:40-0.3wt% tert. amino group-containing vinyl monomer (e.g., N,N-dimethylaminoethyl methacrylate) is grafted onto 60-99.7wt% polyethylene wax (number average MW of 800-6,000 and weight-average MW/number-average MW ratio >=1.05) in a nonaqueous system in the presence of 0.1-1mol, per mol of the vinyl monomer, of a radial generator (which generates no carboxyl radicals and has a decomposition temperature of about 60-120 deg.C), e.g., cyclohexanone peroxide. For example, a melt polymerization process, i.e., a process comprising melting the wax by heating and adding both a vinyl monomer and a radical generator to the molten wax to effect a reaction among them is preferable.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing an amine-modified polyethylene wax with excellent homogeneity.

Polyethylene wax generally has a number average molecular weight of 300.
~t o, o o o degree, and there are natural ones and synthetic ones. Due to its low molecular weight, this wax has, for example,
It has a low melting temperature and melt viscosity, high compatibility with various solvents and resins, and excellent workability such as impregnability, castability, and continuous processability, making it suitable for paints, printing inks, adhesives, plastic processing, etc. It can be applied to a wide range of applications such as auxiliary agents for fibers, fiber processing agents, pigment dispersants, processing aids for inorganic materials such as ceramics, and plasticizers, but it has the disadvantage that it cannot exhibit a wide range of functions because it does not have polarity.

On the other hand, unlike polyethylene wax, polymers with tertiary amine groups are polar, and due to the ionic properties of the tertiary amine groups, they are used as surface chemically active materials, such as ionic Binding adhesive, dispersant, flocculant, γ
It can be applied to a wide range of unique functions such as inorganic binders such as iron oxide powder, polymer electrolytes, and adsorbents.

If a resin were to appear that possesses the characteristics of both of these dissimilar resins, it would be highly useful and the range of applications would be expanded, so its appearance is eagerly awaited.

However, since these two resins have poor compatibility, it is not possible to obtain a finely dispersed homogeneous composition simply by blending the two resins.

As a way to improve this, ethylene and tertiary amine 7
A possible method is to copolymerize a vinyl monomer containing a group and then reduce the molecular weight of the copolymerized vinyl monomer. However, this method generally requires polymerization at high temperatures or high pressures and is not easy to implement, and the resulting copolymers lack the properties of homopolymers of various lengths. There is a strong possibility that you will be able to get what you are looking for.

Another improvement method is graft reaction.

It is true that if a vinyl monomer containing a tertiary amino group is completely grafted onto a polyethylene wax, a homogeneous modified resin can be obtained without phase separation during melting. It is not easy to do so, and the process is complicated and impractical, such as using a solvent to separate the homopolymer produced by the side reaction.

The inventors of the present invention have conducted extensive studies with the aim of solving these shortcomings and obtaining an industrially easy modification method. The present invention was completed based on the discovery that it is possible to easily obtain a finely compatible and homogeneous modified resin only by modification.

That is, in the present invention, 60 to 99.7% by weight of polyethylene wax having a number average molecular weight of 800 to 6,000 and 40 to 0.63% by weight of a tertiary amine group-containing vinyl monomer are added to 1 mole of the vinyl monomer. This is a method for producing an amine-modified wax, which is characterized by subjecting the wax to graft reaction conditions in a non-aqueous system in the presence of a radical generator that does not generate 0.01 to 1 mole of carboxy radicals.

The method of the present invention is remarkable in that a modified wax having the above characteristics can be obtained efficiently and in an industrially satisfactory manner, and that the modified wax is of excellent quality. It has a great effect.

The polyethylene wax used in the present invention has a number average molecular weight of 800 to 6,000, and can be used regardless of whether it is natural or synthetic.

If the above molecular weight is smaller than 800, the resulting modified wax will have poor homogeneity and cause separation during melting, while if it is thicker than 6,000, the viscosity at the time of melting during the modification reaction will increase. In addition to being difficult to lift, the resulting modified wax has poor homogeneity. A preferred number average molecular weight range is i,ooo to 5.000. The wax has a weight average molecular weight to number average molecular weight ratio of 1.05.
Above, more preferably 1.15 or above.

The tertiary amino group-containing vinyl monomer used in the present invention has the general formula (where R1 is hydrogen or lower alkyl, R2 is lower alkylene, R8 and R4 are lower alkyl, and 4 is aryl). ), specifically, for example, N, N-
Dimethylamine ethyl methacrylate, N,N-diethylaminoethyl methacrylate, N-ethyl-N-phenylaminoethyl methacrylate-1-, and the like are mentioned.

In addition to this monomer (main monomer), other monomers (
For example, vinylpyridine, vinylpipericisstyrene, acrylic acid, acrylonitrile, acrylic ester, methacrylic ester, vinyl acetate, etc. may be used in combination, but in that case, the submonomer The amount of should not exceed the amount of the main monomer. Of course, stabilizers,
There is no problem in adding additional components such as dispersants and colorants.

Furthermore, the radical generator used in the present invention does not generate carboxylic radicals.

If a substance that generates carboxy radicals is used, it will undergo a complex reaction with the above-mentioned vinyl monomers, resulting in significant coloration7, resulting in loss of commercial value, and the resulting modified wax has poor homogeneity. be. The normal reaction temperature is 150℃ or less,
Since the temperature is preferably 135°C or lower, the radical generator preferably has a decomposition temperature in the range of 60°C to 120°C.

The decomposition temperature here means the temperature at which the decomposition rate of the radical generator becomes 50 cm when 1 mole of the radical generator is added to benzene lt and left in a certain lagoon, tJf, for 10 hours.

Specific examples of such radical generators include cyclohexanone peroxide (97°C), 1,1
-Bis(t-butylperoxy) 3,3.5-trimethylcyclohexane (91°C), 1.1-bis(t-butylperoxy)cyclohexane (91°C), 2,2-
Bis(t-butylperoxy)butane (103°C), dicumyl peroxide (117°C), 2,5-dimethyl-2,5-di(1-butylperoxy)hexane (11
8℃), organic peroxides such as α,α′-bis(t-7′ thylperoxyisopropyl)benzene (113℃), azobisinbutyronitrile (65℃), azobis(2,
Examples include azo compounds such as 4-dimethylvaleronitrile (68°C). Numbers in parentheses indicate decomposition temperature. Among them, organic peroxides and azo compounds whose decomposition temperature is 100° C. or lower are preferred.

In the present invention, the above-mentioned components are used, and the ratio thereof is 60 to 99.7% by weight of polyethylene wax, 3% by weight of specific vinyl monomer, and 1 mol of vinyl monomer of radical generator. 0.1 to 1 mol.

If the wax is outside the above range, it becomes a modified product with poor homogeneity, which is not preferable. In addition, the amount of the radical generator must be determined in relation to other factors, i.e., polyethylene wax with a specific molecular weight, a specific vinyl monomer, and a radical generator with a specific reactivity. In addition to these factors, it is only possible to control the molecular weight of the modified product if the conditions of the amount used are met.

The preferred amounts of these components used are 70 to 99.7% by weight of polyethylene wax and 30 to 0.3% by weight of specific vinyl monomer.
0.15% by weight and per mole of this vinyl monomer
The amount of radical generator is ~0.9 mol.

The radical generator may be added in any manner, either directly or dissolved in a solvent or the vinyl monomer.

Next, the grafting reaction must be carried out in a non-aqueous system. When carried out in an aqueous system, it is difficult to graft a predetermined amount of vinyl monomer.

Examples of graft reaction methods include a method of dissolving in a solvent and reacting, a method of reacting in a suspension system, a method of reacting in a molten state, and any of these methods can be used.

As an example of a preferable method, for example, a melting method can be mentioned. This is done after heating and melting the wax above its melting point.
This is a method in which a vinyl monomer and a radical generator are added and reacted.

Another preferred example is to suspend wax particles in a solvent, then add a vinyl monomer and a radical generator, and uniformly impregnate the vinyl monomer into the wax at a temperature at which the radical generator does not decompose. , and then the reaction is completed by raising the temperature.

The reaction temperature is determined in relation to the decomposition temperature of the radical generating agent used, but is generally 50°C to 150°C, preferably 135°C or less. If the reaction is carried out for a long time at 135° C. or higher, side reactions such as thermal deterioration of the 4ft fat will become significant, which is not preferable. The reaction temperature does not need to remain constant throughout the reaction. The reaction time is usually about 0.2 to 8 hours. The reaction pressure is usually about normal pressure to 10 kg/CI#.

Example 1 Polyethylene wax (number average molecular weight Mn 1220, weight average molecular weight 15
50, crime/hase 1.27, melting point 104.5℃, density 0.9
s S+ / engineering) 7 was added to 5 and melted at 120° C. with stirring. To this, azobisin butyronitrile 82
y (o, s mol) in dimethylaminoethyl methacrylate 1572 (1 mol, 3% by weight of the total amount with wax) and acetonitrile 2002 was added dropwise over 45 minutes, and the mixture was kept at 120°C for an additional 15 minutes. Cooled, solidified, crushed and dried to form a white modified wax 5
．． Got 9 on 15.

The vinyl monomer content in the obtained modified wax was determined to be 3.0% by weight based on the determination of nitrogen by microcoulometric titration.
Met. Further, when this was kept in a re-melted state at 130° C. for 5 minutes and phase separation due to secondary aggregation was observed, no phase separation was observed and it was found to be excellent in homogeneity.

Comparative Example 1 The reaction was carried out in the same manner as in Example 1 except that the type of radical generator was changed to benzoyl peroxide (carboxy radical generation with a decomposition temperature of 74°C!!¥!2), but the reaction system turned brown. Due to discoloration and abnormal reaction, no claimable modified wax was obtained.

Comparative Example 2 The type of radical generator was t-butylperoxy-
The reaction was carried out in the same manner as in Example 1 except that 2-ethylhexanoate (a carboxy radical generating type with a decomposition temperature of 74°C) was used, but the resulting modified wax was brownish and had no gas or phase. When confirming the presence or absence of separation, agglomeration of brown wax was observed.

Comparative Example 3 Azobisin butyronitrile 14 as a radical generator
．． Example 1 except that B y (0.09 mol) was used.
When the modified wax obtained in the same manner as above was heated and melted at 130'C and the presence or absence of phase separation was confirmed, macroscopic phase separation was clearly observed.

Comparative Example 4 The amount of polyethylene wax was 2.75 to 9, the amount of azobisisobutyronitrile 117 sy (7.17 mol) and dimethylamine ethyl meta ZIJl/-t was 2
．． 25K9 (1, 4, 33 mol, 45% by weight of the total amount with wax) and the reaction was carried out in the same manner as in Example 1. As the reaction progressed, the brown wax began to phase separate. After the reaction, the brown wax was separated and qualitatively characterized by infrared spectroscopy, which revealed that it was a homopolymer of dimethyl-rminoethyl methacrylate (16'KX).

Example 2 Vinyl monomer (diethylamine ethyl methacrylate) 1
85F (1 mol, 3.6% by weight of the total amount with wax)
17 and vinyl monomer content 3 as in Example except that
, 6% by weight of modified wax was obtained.

This product showed no phase separation at all.

Example 3 Wax amount 4 to 9, azobisin butyronitrile
, o 4 a y (6,36 mol) and dimethylamine ethyl methacrylate in the amount of IK9 (6,36 mol, 200% by weight of the total amount with wax) Modified wax obtained in the same manner as in Example 1 The material was homogeneous with no macroscopic separation after melting.The content of vinyl monomer was 20 μl.

Example 4 2 kg of toluene and polyethylene wax (Mw108oX'Mh986, M
w/M+11.09, melting point 101.3℃, density 0.95
5'/CC) 2 and azobisisobutyronitrile 1
647 (1 mol) and dimethylamine ethyl methacrylate 3147 (2 mol, 13.6% by weight of the total amount with wax) were added, and the suspension was maintained at 55°C for 3 hours with stirring to form a vinyl monomer wax. After impregnation and diffusion into the solution, the temperature was raised and maintained at 90'C for 5 hours to complete the reaction. Methanol was added to the reaction solution, filtered, and dried to obtain a modified wax of approximately 2°IK7. The vinyl monomer content of this product was 3.1% by weight. Furthermore, when phase separation was observed, no separation was observed, indicating excellent homogeneity.

Patent applicant Mitsubishi Yuka Co., Ltd. Agent: Patent Attorney Hidetoshi Furukawa Agent: Patent Attorney Masahisa Nagatani

Claims (1)

[Claims] Number average molecular weight 800-6. 60 to 99.7% by weight of OO'0 polyethylene wax and 440 to 0.3% by weight of tertiary amino group-containing vinyl monomer are subjected to grafting reaction conditions in a non-aqueous system. A method for producing amine-modified wax.