JPS58222101A - Polymer particle containing filler - Google Patents

Abstract

PURPOSE:Polymer particles having a high particle strength and hardly swelling even in a good solvent, prepared by dispersing a filler in a vinyl (co)polymer containing at least 15wt% polyvinyl compound component. CONSTITUTION:Use is made of fine powder, particle diameter of about 30- 5,000Angstrom , of titanium oxide, magnesium carbonate or the like (preferably, one which is rendered oleophilic by a surface treatment with a fatty acid-based surfactant, silane coupling agent or the like). Namely, filler-containing polymer particles having a particle diameter of about 0.1-300mu and a polyvinyl compound component content >=15wt% are formed by suspension-polymerizing a mixture of (i) 100pts.wt. polyvinyl compound, e.g., divinylbenzene or vinyl methacrylate (an oleophilic vinyl compound, e.g., methyl methacrylate, may be used in conjunction) and (ii) about 0.1-200pts.wt. above filler in an aqueous phase in the presence of an initiator and a suspension stabilizer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to polymer particles of vinyl compounds containing fillers.

Polymer particles containing fillers can be used as electronic pages, paints, inks, ion exchange resins, resin molded products, carriers for biological substances, immobilized enzyme carriers, immunoserological diagnostic agents, or carriers for medical administration. It is used in many fields, such as:

Traditionally, filler-containing polymer particles are made by mixing the filler into polymers made by conventional polymerization methods. For example, one method is to mix a filler into a bath liquid of an organic bath medium, stir the solution well to make it homogeneous, and then spray dry it, or mechanically disperse a polymer solution in water containing a filler. After that, there is a method of recovering the organic heating medium or a method of kneading the polymer and filler and then pulverizing them. These methods require equipment to remove the solvent, energy to remove the solvent, and the dispersion state of the filler in the polymer particles is not uniform, resulting in irregular morphology and particle size of the polymer particles. It has disadvantages such as:

To avoid such drawbacks, it has been proposed to add fillers to the monomers and prepare the polymers by suspension polymerization.

However, this method has a problem in that it is not possible to obtain single integrated particles containing the filler in a uniformly dispersed state.

An object of the present invention is to provide polymer particles containing a filler in a well-dispersed state and having an increased particle strength, which hardly swells even in a good solvent, and containing a filler having a true spherical shape. There is a particular thing.

According to the present invention, it is characterized in that it is a monomer particle of a vinyl compound in which 5% or more of a polyfunctional vinyl compound is polymerized or copolymerized, and a filler is dispersed in the polymer particle. Polymer particles containing filler are provided.

Next, the present invention will be explained in detail.

Examples of the polyfunctional vinyl compound used in the present invention include compounds having two or more α,β-ethylenically unsaturated bonds in the molecule, such as divinylbenzene, vinyl methacrylate, ethylene glycol, polyethylene glycol, Examples include acrylic acid polyesters, methacrylic acid polyesters, and allyl polyethers of polyols such as globylene glycol, polypropylene glycol, trimethylolpropane, and glycerin. The amount of polymerization or coelectrolysis of these polyfunctional bi='): 1-child compounds is 15 to 100% by weight, preferably 20 to 100% by weight.
100 weight range, more preferably (3) 30 to 100 weight range. If the weight ratio is less than 15, the strength of the obtained polymer particles is insufficient, the degree of swelling by a good solvent is too large, and the polymer particles may be destroyed when subjected to ultrasonic treatment in step 1.2 during use. The filler contained in the polymer particles becomes localized in the polymer particles7, resulting in non-uniform color tone of the polymer particles.

Other vinyl compounds that can be copolymerized with the polyfunctional vinyl compound are lipophilic vinyl compounds, such as aromatic vinyl compounds such as styrene, α-methylstyrene, ethylstyrene, vinyltoluene, and chlorostyrene; unsaturated carboxylic acid ester compounds such as methyl methacrylate and methyl acrylate, unsaturated dichloromethane compounds such as methacrylonitrile and acrylonitrile, and lipophilic α compounds such as vinyl halide compounds such as vinyl chloride and vinyl bromide; Mention may be made of β-ethylenically unsaturated phase compounds.

In addition, acrylic acid, methacrylic acid, itacone (4) acid, acrylamide, methacrylamide 7':C may be copolymerized to the extent that the vinyl compound does not inhibit the polymerization reaction, for example, below the IO weight ratio, and Conjugated diene compounds such as butadiene, isoprene, piperylene, etc. may be copolymerized to the extent that the filler-containing polymer particles do not stick to each other and agglomerate.

Examples of the filler used in the present invention include metals such as iron, cobalt, nickel, copper, and aluminum, alloys of these metals with each other or with other metals such as lanthanum series elements such as lanthanum and gadolinium, and oxidized fillers. Metal oxides such as iron, cobalt oxide, lead oxide, aluminum oxide, zinc oxide, silicon oxide, titanium oxide, magnesium carbonate, calcium carbonate, aluminum silicate, barium sulfate, lead carbonate, lead chromate, cobalt aluminate,
Metal salts such as mercuric chloride, metal sulfides such as zinc sulfide and cadmium sulfide, nickel metallized azo yellow, Red Lake R, permanent red, 2B, 2G,
Pigments such as copper phthalocyanine blue and copper phthalocyanine clean, or fillers such as metal chelate compounds can be mentioned. The particle size of the filler needs to be smaller than the polymer particles containing the target filler, and
It is desirable that it be about A~5000A.

The surface of these fillers is often hydrophilic, and if left as is, the fillers often aggregate together in the lipophilic vinyl compound, making it difficult to uniformly disperse them into polymer particles. . In the present invention, the surface of the filler is treated to have lipophilic properties so that the filler is uniformly dispersed in the lipophilic vinyl compound and the filler does not aggregate or precipitate even if left for a long time. Fillers are preferably used.

Any treatment method may be used to impart lipophilicity to the surface of the filler, but for example, the filler is treated in a medium containing a surfactant whose main component is a fatty acid, and then the filler is treated with pn 7.
A method of imparting lipophilicity to the surface of the filler by washing with an acidic solution having a concentration of less than 5, preferably 5 or more and less than 7 can be mentioned. In this case, surfactants containing fatty acids as main components include, for example, alkali metal salts of unsaturated fatty acids such as rosin acid, dodecenoic acid, tetradecenoic acid, hexadecenoic acid, myristic acid, valmitic acid, stearic acid,
Examples include alkali metal salts of saturated fatty acids such as alagic acid, alkaline earth metal salts of rosin acid, and the like.

In addition, as an acidic bath solution with a pH of less than 7, lower alcohols such as methanol and ethanol, lower ketones such as acetone and methyl ethyl ketone, water, etc. are prepared by preparing I) II M with mineral acids such as hydrochloric acid, GLT acid, nitric acid, and phosphoric acid. I can mention bath liquid.

The temperature for treating the filler in a medium containing a surfactant 1 whose main component is a fatty acid is usually 30 to 100 liters.
5 (1°C, preferably 70 to 110°C, and the treatment time is usually 0.5 to 2 hours, preferably 0.5 to 1 hour. The concentration of the surfactant is not particularly limited, but is usually 2 parts by weight or more, preferably 1 to 20 parts by weight.

Fillers treated by this method form a monomolecular layer of fatty acids on the surface, and the hydrophilic groups of the fatty acids are adsorbed onto the surface of the filler, with the lipophilic groups facing outward, making the surface of the filler lipophilic. It is considered that this will be granted.

Another treatment method for imparting lipophilicity to the filler is to bring into contact with the filler a compound that has in its molecule a portion with poor affinity for the filler and a lipophilic portion. A method may be mentioned in which a portion with high affinity is bonded to the filler by adsorption or chemical bonding, and the filler is treated so that the lipophilic portions are aligned outward. Examples of such compounds include, for example, F (silane coupling agent (8) such as a trialkoxysilane compound as shown in formula 11) (RO)g SIR' curve...curved surface...
1) (R is an alkyl group having 1 to 3 carbon atoms, R' is an alkyl group with or without a substituent, an alkenyl group, or an allyl group, such as -(CH2)s N
H2, -(CH2)38H.

(CH2)s NH-C2Ha, -(CH,)s NH
-(CH2), NH, -CH=CH,, -(,CH2
)s 0-C-C(CH,)=C)l,,1), titanium cutting agents such as alkoxytitanium compounds as shown in the following formula (11), etc. .

(R")mT + R"4-m --
--(11) (R" is an alkoxy group or a carboxy group having no direct substituent, Example CH2-0
\(CH,0CH2CH=CH2).

1 CH2~O/, C2H, ~C-C120-, etc., and R/// is an alkylcarboxy group, a substituted benzenesulfoxy group, a substituted phenoxy group, an unsaturated carboxy group, an alkyl phosphate ester group, It is an alkyl phosphite group, for example 0 1 C,7H36CO-1C)(2=C(CH9)CO-
0 111 CH,=CHC0-1(C+gHnO)t PO-00 0 (Ca'H+70)t POP(OH)O-10 NHt (4H4NH(J HI O-,0 etc. can be mentioned, m is l , 2 or 3.

) A method for combining a silane coupling agent or a titanium coupling agent with a filler includes, for example, combining the filler and the silane coupling agent or the titanium coupling agent in an inorganic medium such as water, or alcohol, ether, ketone, or ester. 5. Mix in an organic medium such as, heat while stirring, separate the filler by decantation etc. after heating, and dry under reduced pressure etc. , , Inorganic medium or organic medium can be removed by several methods.

Alternatively, the silane coupling agent or titanium coupling agent may be bonded to the filler by directly mixing the filler and the silane coupling agent or titanium coupling agent without using an inorganic or organic medium and heating the mixture. good. The heating temperature in these methods is usually 30 to 100
℃, and the heating time is about 30 minutes to 2 hours. The amount of silane coupling agent or titanium coupling agent used for the filler is determined as appropriate depending on the surface area of the filler, but is usually 1 to 50 parts by weight per 100 parts by weight of the filler.
The amount is preferably 2 to 30 parts by weight. When an inorganic or organic medium is used, the concentration of the silane coupling agent or titanium coupling agent in the medium is not particularly limited, but is usually t3! The concentration is more than 100%.

Yet another method for imparting lipophilic properties to fillers is to crush the fillers, such as in a ball mill, in a hydrophobic medium containing compounds with surfactant effects such as fatty acids, alkyl chain acids, and alkylaryl sulfonic acids. A method of imparting lipophilicity to the filler by further pulverizing it using a device, and emulsifying by adding and mixing an aqueous dispersion of fine filler powder produced by a wet method etc. into a hydrophobic medium containing the above-mentioned surfactant. A method of imparting lipophilicity to the filler by distilling off the water using heating and pressure, or a hydrophobic medium containing the above-mentioned surfactant is heated in advance, and water of fine filler powder produced by a wet method etc. There is a method of imparting lipophilicity to the filler by adding and mixing a dispersion and simultaneously distilling off water.

There are various methods for separating the lipophilic filler obtained by these methods from the hydrophobic medium, such as ethanol, impropatol, propatool, etc. The lower alcohol can precipitate the filler by mixing a hydrophobic medium containing the lipophilic filler, and the filler can be collected by filtration or decantation.

Fillers treated to impart lipophilic properties by these methods can be dispersed very easily and stably in lipophilic vinyl compounds, and can undergo solid-liquid separation such as precipitation and aggregation by gravity, magnetic force, centrifugal force, etc. It is difficult to wake up. The filler is preferably 0.1 to 20 parts per 1 oz of vinyl compound.
0 parts by weight, particularly preferably 5 to 120 parts by weight.

The filler-containing polymer particles of the present invention are, for example, (1)
A manufacturing method by suspension polymerizing a mixture of the vinyl compound and the filler treated to impart lipophilicity in an aqueous phase in the presence of a polymerization initiator and a suspension protectant, (2)
) * Obtained by a manufacturing method in which a mixture of the vinyl compound dissolved in the non-bathable polymer and the filler is subjected to suspension polymerization in an aqueous phase in the presence of a polymerization initiator and a suspension protectant. Can be done.

In the method (1) or (2) above, the 1-polymer initiator is an organic compound commonly used in the radical polymerization of the vinyl compound.
Select and use a heavy initiator with six medium bath properties. For example, acyloyl peroxides such as benzoyl peroxide and lauroyl peroxide, aralkyl hydroperoxides such as cumene hydroperoxide, varamenthano hydroperoxide, t-butyl perbenzoate, i-
Alkyl peracetates such as propyl peracetate,
Dialkyl peroxides such as dialkyl peroxide, azobisacylonitrile such as azobisisobutyronitrile, and azobiscyclohexanecarbonitrile can be used. These polymerization initiators are usually used in an amount of 0.1 to 5 parts by weight per 100 parts by weight of the above vinyl compound.
Preferably [) is used in an amount of 5 to 3 parts by weight. In the method (1) or (2) above, in order to adjust the molecular profile of the polymer, captan, halogenated carbon (i: hydrogen, etc.) can be used, and usually per 100 parts by weight of the above-mentioned nitrogen compound. Add up to 5% by weight.

The suspending agent used in the method (1) or (2) above is used to maintain the suspended state of the vinyl compound in the aqueous phase. As an organic suspending protectant,
For example, polyvinyl alcohol, polyvinylpyrrolidone,
Hydrophilic synthetic polymer bonds such as polyethylene glycol,
Natural hydrophilic polymeric substances such as gelatin and bath starch, hydrophilic semi-synthetic polymeric substances such as carboxymethyl cellulose, etc. may be mentioned, and inorganic suspension protectants include, for example, magnesium, barium or calcium. phosphates, calcium carbonate, magnesium carbonate, zinc white, aluminum oxide, aluminum hydroxide, etc.

Furthermore, these suspending protectants have nonionic, anionic,
A combination of cationic and other surfactants can be used. These suspending protectants usually contain the above vinyl compound 1.
0tz! Use 0.05 to 30 parts by weight based on the amount, and if a surfactant is used in combination, add 10 parts by weight of the above vinyl compound.
It is preferably used in an amount of 2 parts by weight or less relative to 0 parts by weight.

In the method (2) above, the water-insoluble polymer is a polymer that is soluble in the vinyl compound and insoluble in water; for example, among the polymers of the vinyl compound, the water-insoluble polymer is soluble in the vinyl compound. Polymerized products can be mentioned. This Y-toxic polymer is dissolved in the vinyl compound at a concentration of preferably 5 to 60% by weight. In addition, when carrying out suspension polymerization of the vinyl compound in which the water-insoluble polymer is dissolved, the concentration of the polyfunctional vinyl compound in the vinyl compound in which the water-insoluble polymer is dissolved is 155 parts by weight or more. It is necessary to take this into account.

The suspension polymerization conditions in the method (1) or (2) above are not particularly limited. An organic phase consisting of a polymerization initiator and a fast chain transfer agent used as necessary and an aqueous phase consisting of water, a suspending protectant and a surfactant used as necessary are mixed and stirred at a humidity below the polymerization initiation humidity. t7. List a method in which the organic phase is suspended in the aqueous phase as fine droplets with a uniform particle size, and then the suspended system is brought to the outside with stirring to initiate polymerization of the vinyl compound. The particle size and particle size distribution of the filler-containing polymer particles obtained by this method depend on the stirring conditions before the start of polymerization, the type and amount of the suspending protectant and the surfactant used as necessary. By appropriately combining these, it is possible to obtain filler-containing polymer particles having the desired particle size and particle size distribution.

The amount of the aqueous phase to be used relative to the organic phase is not particularly limited, but is usually 100 to 200 parts by weight per 100 parts by weight of the organic phase.
0 parts by weight, preferably 200-1000 parts by weight.

In addition, the temperature of the suspension system is increased 1. - The polymerization temperature when polymerizing the vinyl compound can be determined as appropriate depending on the vinyl compound to be polymerized and the type and amount of the polymerization initiator used, but it is usually 50 to 15 (Ic, preferably 6
0-1 (100)

After completion of polymerization, the filler-containing polymer particles can be separated by an operation such as centrifugation, and the separated polymer particles are washed with water, ethanol, acetone, etc., if necessary.

According to the method (]) or (2) above, it is possible to easily obtain polymer particles containing a filler having an average particle diameter of () and a narrow particle size distribution of about 1 μm to 5 mm.

The preferred average particle diameter of the polymer particles containing the filler of the present invention is 1 to 300 μm, and those having an average particle diameter of this range are easiest to use.

Since the polymer particles containing the filler of the present invention have a polyfunctional vinyl compound polymerized or copolymerized with a weight ratio of 15° or more, the polymer particles have a highly crosslinked three-dimensional structure. However, the physical strength is significantly increased (2 times) compared to conventional single-unit particles containing fillers, and the degree of swelling can be reduced even when immersed in a good solvent. The polymer particles containing the filler of the present invention are hardly crushed by various treatments, such as ultrasonic treatment, and are immersed in a scientific material having a functional group to further modify the surface of the polymer particles. It is also possible to polymerize different types of monomers on the surface of polymer particles without dissolving or swelling.

In particular, the filler-containing polymer particles of the present invention are characterized by containing the filler in a well-dispersed state 2 and having a true spherical shape. In addition, the method (1) or (2) above is a production method in which very few polymer particles containing no filler are produced during suspension polymerization.

The filler-containing polymer particles of the present invention are extremely useful because the physical properties of the filler contained therein can be utilized. For example, when a colored material or filler is used, the filler is uniformly dispersed in the polymer particles, making it possible to obtain a product with no uneven color when molding the polymerized (11) particles. , it is possible to solve the difficulties of the coloring process of plastic products all at once.

Furthermore, when a filler with extremely high density is used, the polymer particles become dense, and the polymer particles can be easily separated from the liquid medium by gravity, centrifugal force, or the like.

It also has the advantage that uniform high-density molded products can be easily manufactured. Furthermore, when a magnetic filler is used, it becomes possible to move the polymer particles within a liquid medium, an organism, or a container by magnetic force. Further, polymer particles containing the filler of the present invention having a small particle size have a very small surface area per unit volume, and are therefore suitable as a carrier that utilizes the surface of the polymer particles.

The filler-containing polymer particles of the present invention as described above are
By combining the types of polymer and the type of filler, various chemical or physical properties can be provided, making these polymer particles extremely useful (911 (20)).

The present invention will be explained in more detail with reference to Examples below.

Example 1 400 ml of a 20% by weight water bath solution of potassium oleate is added to 1z of water containing 100r of ~01 particles with an average particle diameter of 110A prepared by a wet method, and the mixture is stirred at 90°C for 30 minutes. After cooling, the mixed solution was adjusted to p6 using dilute hydrochloric acid.

几、04 Particles will aggregate, so they should be filtered out and soaked in 80°C water 30°C.
Wash twice with 0 ml and twice with 300 ml of ethanol, and dry under reduced pressure. 400 ml of a 3-weight water bath solution of polyvinyl alcohol is added to a four-liter flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer.

Separately, 04 particles 152 were treated with styrene 50 F, divinylbenzene 1002, benzoyl peroxide 3R, t-dodecyl mercaptan 1.59, and potassium oleate obtained above to impart lipophilicity, or 04 particles 152 were preliminarily treated with water cooling (22 ) The mixed solution was uniformly mixed by stirring at 3.000 rpm, and the mixture was added dropwise to the polyvinyl alcohol aqueous solution inside the four-eye flask from the dropper while stirring. After the dropwise addition was completed, stirring was continued for 30 minutes, and when the particle size of the organic phase reached a uniform particle size of 25 μm, the temperature was raised to 85° C. for polymerization. After 12 hours of polymerization, unreacted monomers were collected under reduced pressure, and the polymer particles were separated by centrifugation and washed three times with 500 ml of warm water to obtain 140 tons of polymer particles containing 04 particles. . As a result of observing the polymer particles using an optical microscope with a magnification of 300 times, the particles were found to be perfectly spherical with a diameter of 25 μm and a uniform color tone throughout.

Furthermore, the polymer particles were attracted by a magnet and were not crushed by ultrasonic treatment, and the degree of volumetric swelling was 1.3 times even when immersed in toluene at room temperature for 5 hours.

Example 2 Styrene 50 in Example 1? Styrene 20 instead of
A polymerization reaction was carried out in the same manner as in Example 1 except that a mixture of 2 and methyl methacrylate 302 was used. Through this polymerization reaction, polymer particles 1402 containing Fi304 particles are obtained. The polymer particles had a true spherical shape with a diameter of 20±] and 0 μm, and had a uniform color tone throughout. Furthermore, the polymer particles were not crushed by being attracted by a magnet or by ultrasonic treatment, and the degree of volumetric swelling was 1.2 times even when immersed in styrene for 1 hour at room temperature.

(CH
,O), 5i(CH2)3 QC-C=CH,5me
A bath solution prepared by dissolving 11 cHg of ethyl alcohol in 3()- is added at room temperature with stirring. The mixture is then refluxed for 1 hour (7), cooled, centrifuged, washed twice with ethanol (20), and dried under reduced pressure. Fn20.1 which has been given lipophilicity by treating in this way
Particle 30f: styrene lof, divinylbenzene 902
, benzoyl peroxide 3f and t-dodecyl mercaptan (1,51i') were stirred in advance at 500 rpm under water cooling and mixed uniformly, and then added to a lt volume flask. Under water cooling, a 1.5 width aqueous solution of polyvinyl alcohol 40
0 ml was added and stirred at 2.00 Orpm for 15 minutes, and when the particle size of the droplets reached a uniform particle size of 12 μm, the temperature was raised to 80° C. to polymerize. After 16 hours of polymerization, unreacted monomers are collected under reduced pressure, and the polymer particles are separated by centrifugation to obtain polymer particles 100F containing Fg20 B particles. This polymer particle has a diameter of 14±5μ
It had a perfect spherical shape with a diameter of m, and had a uniform color tone throughout. Further, the polymer particles were not crushed even by ultrasonic treatment, and the degree of volumetric swelling was 1.1 times even when immersed in toluene at room temperature for 5 hours.

Comparative Example 1 Styrene 50t and divinylbenzene 10 of Example 1
A polymerization reaction was carried out in the same manner as in Example 1, except that 135f of substitute etethyrene and 15f of divinylbenzene were used for 0V. Through this polymerization reaction, polymer particles 140f containing 04 particles are obtained. This polymer particle has a diameter of 15±8μ
Although it had a perfect spherical shape, the h and 04 particles were localized in clusters within the polymer particles. Also, approximately 5 percent of the polymer particles contained no filler. Further, some of the polymer particles were crushed by the ultrasonic treatment, and the degree of volumetric swelling when immersed in toluene at room temperature for 1 hour was I 2 O,fi times.

Claims (1)

[Claims] A filler characterized in that it is a polymer particle of a vinyl compound in which 15 weight percent or more of a polyfunctional vinyl compound is polymerized or copolymerized, and a filler is dispersed in the 1° combined particles. Containing polymer particles.