JP2975084B2 - Oily component-containing solid resin composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a solid oily composition containing an oily component.

[Prior art] Conventionally, solid fuels have been used for camping and tabletop cooking, but most of them use low boiling alcohols such as methanol and ethanol as fuel components, and use metal soaps and sorbitol-based gelling agents. The gelation was carried out using a gel, and the gel was fluidized at a high temperature to become a liquid, and thus had the following disadvantages.

If exposed to high temperatures during combustion or at high temperatures during storage, harmful substances such as methanol and aldehyde may leak from the fluidized gel or volatilize into the air, causing ignition. High risk of doing.

Due to the above-mentioned leakage and volatilization of methanol and aldehyde, these fuels generate a small amount of heat and cannot obtain a stable and strong thermal power for a long time.

[Problems to be solved by the invention]

Therefore, an object of the present invention is to provide a novel oily component-containing solid resin composition that does not fluidize even when exposed to high temperatures. According to the present invention, the above-mentioned problems of the conventional solid fuel can be solved.

[Means and actions for solving the problem]

The present inventors have found that the above object can be achieved by absorbing and retaining a liquid oil component in a crosslinked polymer obtained by polymerizing a specific monomer, and have completed the present invention.

That is, the present invention relates to a method for preparing a monomer (A) having one polymerizable unsaturated group in a molecule containing a monomer having a solubility parameter (SP value) of 9 or less as a main component, from 96 to 99.999% by weight, and A single monomer comprising 0.001 to 4% by weight of a crosslinkable monomer (B) having at least two polymerizable unsaturated groups (the total of the monomers (A) and (B) is 100% by weight) An oily component-containing solid resin composition in which a crosslinked polymer (I) obtained by polymerizing a monomer component absorbs and holds a liquid oily component to prevent fluidization at a high temperature.

The solubility parameter (SP value) is generally used as a scale indicating the polarity of a compound. In the present invention, a value derived by substituting Hoy's aggregation energy constant into Small's calculation formula is applied, and the unit is ( cal / cm ³ ) ^Represented by ^1/2 .

The monomer constituting the main component of the monomer (A) used in the present invention is a monomer having a solubility parameter (SP value) of 9 or less and having one polymerizable unsaturated group in the molecule. . When a monomer having a solubility parameter (SP value) of more than 9 is used as a main component of the monomer (A), a solid cannot be formed by absorbing an oily component, or the content of the oily component is extremely high. Sometimes only low solids are obtained.

Monomers having a solubility parameter (SP value) of 9 or less and one polymerizable unsaturated group in the molecule include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, t- Butyl (meta)
Acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate,
Phenyl (meth) acrylate, octylphenyl (meth) acrylate, nonylphenyl (meth) acrylate, dinonylphenyl (meth) acrylate, cyclohexyl (meth) acrylate, menthyl (meth) acrylate, dibutyl maleate, didodecyl maleate,
Unsaturated carboxylic esters such as dodecyl rotonate and didodecyl itaconate; (di) butyl (meth) acrylamide, (di) dodecyl (meth) acrylamide,
(Di) stearyl (meth) acrylamide, (di) butylphenyl (meth) acrylamide, (di) octylphenyl (meth) acrylamide and other (meth) acrylamide having a hydrocarbon group; 1-hexene, 1-octene, isooctene, Α-olefins such as 1-nonene, 1-decene and 1-dodecene; alicyclic vinyl compounds such as vinylcyclohexane; allyl ethers having an aliphatic hydrocarbon group such as dodecyl allyl ether; vinyl caproate, vinyl laurate; Vinyl esters having an aliphatic hydrocarbon group such as vinyl palmitate and vinyl stearate; vinyl ethers having an aliphatic hydrocarbon group such as butyl vinyl ether and dodecyl vinyl ether;
Examples thereof include aromatic vinyl compounds such as styrene, t-butylstyrene, and octylstyrene, and one or more of these monomers can be used.

Among these, as a monomer that provides an oily component-containing solid resin composition having better performance as described above, at least one aliphatic hydrocarbon group having 3 to 30 carbon atoms, and an alkyl (meth) acrylate , Alkylaryl (meth) acrylate, alkyl (meth) acrylamide,
The monomer (A) mainly containing at least one unsaturated compound (a) selected from the group consisting of alkylaryl (meth) acrylamide, alkylstyrene and α-olefin is particularly preferred.

The amount of the monomer having a solubility parameter (SP value) of 9 or less in the monomer (A) is 50% by weight or more, more preferably 70% by weight, based on the total amount of the monomer (A). weight%
This is the ratio above. The solubility parameter (SP value)
Is 50% by weight in the monomer (A) of the monomer having a content of 9 or less.
If it is less than 1, no solid is formed, or only a solid having an extremely low oil content is obtained.

In the present invention, a monomer having a solubility parameter (SP value) of 9 or less must be contained in the monomer (A) in an amount of 50% by weight or more. And a monomer having a solubility parameter (SP value) of more than 9 at a ratio of 9 may be contained. Such monomers include, for example, (meth) acrylic acid, acrylonitrile, maleic anhydride,
Examples thereof include fumaric acid, hydroxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate, and methoxypolyethylene glycol (meth) acrylate.

Examples of the crosslinkable monomer (B) used in the present invention include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and polyethylene glycol-polypropylene glycol di (meth) acrylate. , Polypropylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate,
1,6-hexasandiol di (meth) acrylate, N,
N'-methylenebisacrylamide, N, N'-propylenebisacrylamide, glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, polyhydric alcohols (for example, glycerin, trimethylol Examples include polyfunctional (meth) acrylates obtained by esterification of an alkylene oxide adduct of propane or tetramethylol methane) with (meth) acrylic acid, dihinylbenzene, and the like. Alternatively, two or more kinds can be used.

The ratio of the monomer (A) and the crosslinkable monomer (B) in the monomer components used in producing the crosslinked polymer (I) is determined by the ratio of the monomer (A) and the crosslinkable monomer. The monomer (A) is in the range of 96 to 99.999% by weight, and the crosslinkable polymer (B) is in the range of 0.001 to 4% by weight, based on the total of (B).

When the amount of the monomer (A) is less than 96% by weight or the amount of the crosslinkable monomer (B) exceeds 4% by weight, the obtained crosslinked polymer is
The crosslinking density is too high to absorb and retain a large amount of oily component, and only a solid resin composition having a low oily component content is obtained, which is not preferable. In addition, 99.9% of monomer (A)
If the content exceeds 99% by weight, the solubility of the obtained polymer in the oily component is increased, and the obtained oily component is not preferable because fluidity is generated in the solid resin composition or the solid itself is not formed.

In order to produce the crosslinked polymer (I), the monomer component may be copolymerized using a polymerization initiator. Copolymerization can be performed by a known method such as suspension polymerization or bulk polymerization.

Suspension polymerization, for example, using an emulsifier having a high HLB value, a protective colloid agent such as polyvinyl alcohol, hydroxyethyl cellulose, gelatin, and the like, suspending the monomer components in water, in the presence of an oil-soluble polymerization initiator The polymerization may be carried out. Examples of the polymerization initiator include organic peroxides such as benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, 2,2'-azobisisobutyronitrile, and 2,2'-azobisdimethylvaleronitrile. An azo compound or the like can be used.
A range from 50 to 150 ° C is preferred. The obtained aqueous suspension of the finely divided resin of about 10 to 1000 µm is filtered and dried to obtain the desired crosslinked polymer (I).

In the bulk polymerization, for example, the desired crosslinked polymer (I) is obtained by pouring a monomer component into a mold in the presence of the above-mentioned polymerization initiator and performing polymerization at 50 to 150 ° C.

As the oily component used in the present invention, for example, n-pentane, isopentane, neopentane, n-hexane,
2-methylpentane, 3-methylpentane, n-heptane, n-octane, 2,2,4-trimethylpentane, n-
Aliphatic hydrocarbons such as decane; alicyclic compounds such as cyclopentane, cyclohexane and cycloheptane; aromatic compounds such as benzene, toluene, xylene, ethylbenzene, n-propylbenzene and isopropylase; alcohols such as hexanol and cyclohexanol Compounds; paraffins such as paraffin and isoparaffin;
Examples thereof include petroleum such as light oil, kerosene, and gasoline, and one or more of these liquid oil components can be used. Such an oily component is an oily organic compound that can be ignited at room temperature and has high combustion energy and is commonly used as a fuel, and preferably has an organic heat of combustion of 8000 cal / g or more at 25 ° C at a constant pressure. Compound.

The oily component-containing solid resin composition of the present invention is obtained by including a liquid oily component in the crosslinked polymer (I). For example, it can be easily obtained by mixing the crosslinked polymer (I) and the liquid oily component to absorb and hold the liquid oily component in the crosslinked polymer (I) to form a gel. In addition, the mixture can be heated to such an extent that the liquid oil component does not volatilize or deteriorate, thereby increasing the absorption rate of the liquid oil component into the crosslinked polymer (I).

The mixing ratio of the crosslinked polymer (I) and the oily component is not particularly limited, but the crosslinked polymer (I) is preferably in the range of 2 to 50% by weight, and the oily component is preferably in the range of 50 to 98% by weight. . When the use amount of the crosslinked polymer (I) is less than 2% by weight, it becomes difficult to completely absorb and maintain the oily component in the crosslinked polymer (I), and the resulting composition may have fluidity, It may become insufficient to suppress the volatilization of the oily component. When the crosslinked polymer (I) is used in an amount exceeding 50% by weight, the content of the oily component is too low, and it becomes difficult to stably maintain a high calorific value for a long time and burn.

Further, as a preferable method for producing the oily component-containing solid resin composition of the present invention, the crosslinked polymer (I) is immersed in a large amount of the oily component, and the oily component is absorbed and held in the crosslinked polymer (I). Thereafter, a method of pulling up the gelled substance of the crosslinked polymer (I) swollen by the obtained oily component from the liquid oily component can be adopted.

Since the crosslinked polymer (I) used in the oily component-containing solid resin composition of the present invention absorbs and swells a large amount of the oily component even at ordinary temperature to form a gel-like product, the oily component-containing solid resin composition of the present invention During or after use of crosslinked polymer (I)
When is remaining, the composition can be used repeatedly by adding the oily component to the composition again.

Furthermore, the oily component-containing solid resin composition of the present invention can be added with or mixed with a solid fuel such as charcoal or bean charcoal, if necessary. Further, the oily component-containing solid resin composition of the present invention can be used by filling it in a nonflammable or flammable container or the like.

The oily component-containing solid resin composition of the present invention is a crosslinked polymer obtained by polymerizing a specific monomer, which is made into a gel by absorbing and retaining a large amount of an oily component. Also does not give rise to fluidity.

Therefore, when this is used as a solid fuel, the oily component can be burned with a stable thermal power when ignited, and since the oily component is unlikely to leak or volatilize during combustion or storage, toxic gas is removed. It is safe without any emission, and it has strong thermal power for a long time.It can be downsized compared to solid fuel using conventional alcohols, for camping, home table cooking, business use In addition to exhibiting excellent performance as such, when the crosslinked polymer remains after use, it can be used repeatedly.

〔Example〕

Next, the present invention will be described in detail with reference to the present invention and comparative examples, but the present invention is not limited thereto. Unless otherwise specified in the examples, parts are parts by weight.

Example 1 In a 500 ml flask equipped with a thermometer, a stirrer, a gas inlet tube, and a reflux condenser, 3 parts of gelatin was dissolved in 300 parts of water and charged.
Heated to 40 ° C. Then, 99.794 parts of nonylphenyl acrylate (SP value: 8.3) as the monomer (A) and 0.2 of 1,6-hexanediol acrylate as the crosslinkable monomer (B).
06 parts and benzoyl peroxide 0.1 as a polymerization initiator.
A solution consisting of 5 parts was added to the flask at a time and stirred vigorously at 400 rpm.

Then, the temperature in the flask was raised to 80 ° C., and the polymerization reaction was carried out at the same temperature for 2 hours. Thereafter, the temperature in the flask was further raised to 90 ° C., and maintained for 2 hours to complete the polymerization.
After the polymerization is completed, the granular product is filtered off, washed with water and then dried.
The crosslinked polymer (1) having a particle size of 100 to 1000 µm was obtained by drying at a temperature of ° C.

The obtained crosslinked polymer (1) was immersed and swelled in n-octane (calorific value: 11,450 cal / g) at room temperature for 24 hours to obtain an oily component-containing solid resin composition (1). The n-octane content in the oily component-containing solid resin composition (1) was 92.3% by weight.

Example 2 In Example 1, 49.930 parts of hexadecyl methacrylate (SP value: 7.8) and 49.930 parts of N-octyl methacrylamide (SP value: 8.6) were used as the carbon unit (A), and divinylbenze was used as the crosslinking monomer (B). Except that 0.140 part was used instead, a particle size of 100 to 1000 μm was obtained in the same manner as in Example 1.
m of the crosslinked polymer (2) was obtained.

The obtained crosslinked polymer (2) was immersed and swelled in n-decane (calorific value: 11390 cal / g) at room temperature for 24 hours to obtain an oily component-containing solid resin composition (2). The n-decane content in the oily component-containing solid resin composition (2) was 89.2% by weight.

Example 3 In Example 1, 57.772 parts of dodecyl acrylate (SP value: 7.9) and 38.515 parts of N, N-dioctylacrylamide (SP value: 8.2) as the monomer (A), and polypropylene as the crosslinkable monomer (B) A crosslinked polymer (3) having a particle size of 100 to 1000 µm was obtained in the same manner as in Example 1 except that 3.713 parts of glycol dimethacrylate (molecular weight 4000) was used instead.

The obtained crosslinked polymer (3) was immersed and swelled in n-decane (calorific value: 11390 cal / g) at normal temperature for 24 hours to obtain an oily component-containing solid resin composition (3). The n-decane content in the oily component-containing solid resin composition (3) was 89.5% by weight.

Example 4 A monomer (A) was placed in a glass casting polymerization mold (a tray having a size of 5 × 5 × 1 cm) equipped with a thermometer and a gas inlet tube.
A mixed solution consisting of 99.823 parts of dodecyl acrylate (SP value: 7.9), 0.177 part of ethylene glycol diacrylate as a crosslinkable monomer (B) and 0.1 part of 2,2'-azobisdimethylvaleronitrile as a polymerization initiator And heated at 50 ° C for 2 hours under a nitrogen stream to carry out the polymerization reaction.
Thereafter, the temperature was raised to 80 ° C. and maintained for 2 hours to cause the polymerization to react. After cooling, the gel was released from the mold to obtain a crosslinked polymer (4).

The obtained crosslinked polymer (4) was immersed and swelled in kerosene (calorific value: about 11000 cal / g) at room temperature for 7 days to obtain an oily component-containing solid resin composition (4). The kerosene content in this oily component-containing solid resin composition (4) was 93.5% by weight.

Example 5 In Example 4, 54.881 parts of t-butylstyrene (SP value: 7.9) and 1-decene (SP value: 7.
0) A crosslinked polymer (5) was obtained in the same manner as in Example 4, except that 44.903 parts and 0.216 part of divinylbenzene were used instead of the crosslinkable monomer (B).

The obtained crosslinked polymer (5) was immersed and swelled in toluene (calorific value: 10170 cal / g) at room temperature for 7 days to obtain an oily component-containing solid resin composition (5). The toluene content in the oily component-containing solid resin composition (5) is
94.1% by weight.

Example 6 In Example 4, 74.793 parts of nonylphenyl acrylate (SP value: 8.3) and 24.931 parts of hydroxyethyl acrylate (SP value: 10.3) as the monomer (A), and 1,6 as the crosslinkable monomer (B) -Hexanediol diacrylate
A crosslinked polymer (6) was obtained in the same manner as in Example 4 except that 0.276 part was used instead.

The obtained crosslinked polymer (6) was immersed and swelled in decanol (calorific value: 9960 cal / g) at room temperature for 7 days to obtain an oily component-containing solid resin composition (6). The decanol content in the oily component-containing solid resin composition (6) was 85.1% by weight.

Comparative Example 1 The amount of dodecyl acrylate in Example 4 was changed to 94.637.
Add 5.363 parts of ethylene glycol diacrylate to
A crosslinked polymer (7) was obtained in the same manner as in Example 4, except that the respective parts were changed.

By immersing the obtained crosslinked polymer (7) in kerosene (calorific value: about 11000 cal / g) at room temperature for 7 days,
A comparative oily component-containing solid resin composition (1) was obtained. However, the crosslinked polymer (7) did not swell greatly during this immersion,
The kerosene content in this comparative oily component-containing solid resin composition (1) was 42.6% by weight.

Comparative Example 2 Example 4 was repeated except that 39.854 parts of dodecyl acrylate and 59.780 parts of methacrylic acid (SP value: 10.1) were used instead of 99.823 parts of dodecyl acrylate and the amount of ethylene glycol diacrylate was changed to 0.366 part. A crosslinked polymer (8) was obtained in the same manner as described above.

By immersing the obtained crosslinked polymer (8) in kerosene (calorific value: about 11000 cal / g) at room temperature for 7 days,
A comparative oily component-containing solid resin composition (2) was obtained. However, the crosslinked polymer (8) did not swell greatly during this immersion,
The kerosene content in this comparative oily component-containing solid resin composition (2) was 25.1% by weight.

Comparative Example 3 A polymer (9) was obtained in the same manner as in Example 4, except that ethylene glycol diacrylate was not used.

The obtained polymer (9) was converted into kerosene (calorific value: about
When the polymer (9) was immersed in 11,000 cal / g) for 7 days, the polymer (9) was dissolved in kerosene and no solid was produced.

Comparative Example 4 In a 500 ml flask equipped with a thermometer, a stirrer and a reflux condenser, sodium stearate 10 was used as a gelling agent.
Part, methanol as an oily component (calorific value: 5550 cal / g) 90
After stirring, while heating at 60 ° C. for 15 minutes, the mixture was allowed to cool to obtain a comparative oily component-containing solid resin composition (3).

Example 7 Oil-based component-containing solid resin compositions (1) to (6) obtained in Examples 1 to 6 and comparative oil-based component-containing solid resin compositions (1) to obtained in Comparative Examples 1, 2, and 4 20g each of (3)
Was filled in an aluminum petri dish having a diameter of 6 cm, ignited at room temperature, the burning time of each was measured, and the appearance of the oily component-containing solid resin composition during burning was visually observed.

 The results are shown in Table 1.

(Effect of the Invention) The oily component-containing solid resin composition according to the present invention is a gel-like material obtained by absorbing and holding the oily component in a crosslinked polymer obtained by polymerizing a specific monomer. No fluidity occurs even at high temperatures.

────────────────────────────────────────────────── ─── of the front page continued (72) inventor Goto RyuKiyoshi Kawasaki-shi, Kanagawa-ku, Kawasaki Chidori-cho 14th No. 1 Nippon Shokubai Kagaku Kogyo Co., Ltd. Kawasaki the laboratory (58) investigated the field (Int.Cl. ^6, DB Name) C10L 7/00-7/04 WPI / L (QUESTEL)

Claims (4)

(57) [Claims] (1) 96 to 99.999% by weight of a monomer (A) having one polymerizable unsaturated group in a molecule mainly composed of a monomer having a solubility parameter (SP value) of 9 or less, and Containing a crosslinkable monomer (B) having at least two polymerizable unsaturated groups in an amount of 0.001 to 4% by weight (the total of the monomers (A) and (B) is 100% by weight). An oily component-containing solid resin composition in which a crosslinked polymer (I) obtained by polymerizing a body component absorbs and holds a liquid oily component to prevent fluidization at a high temperature. 2. The monomer (A) has at least one aliphatic hydrocarbon group having 3 to 30 carbon atoms, and has an alkyl (meth) acrylate, an alkylaryl (meth) acrylate, or an alkyl (meth) acrylate. The oil-based component-containing solid resin composition according to claim 1, wherein the main component is at least one unsaturated compound (a) selected from the group consisting of acrylamide, alkylaryl (meth) acrylamide, alkylstyrene, and α-olefin. Stuff. 3. The method of claim 1, wherein the oil component has a heat of combustion at 25 ° C. at a constant pressure.
The solid resin composition containing an oily component according to claim 1 or 2, which comprises an organic compound of 8000 cal / g or more as a main component. 4. The compounding ratio of the crosslinked polymer (I) and the oily component is in the range of 2 to 50% by weight of the crosslinked polymer (I) and 50 to 98% by weight of the oily component. The solid resin composition containing an oily component according to any one of the above.