JPH1149748A - Benzoyl peroxide composition and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition useful as a curing agent for an unsaturated polyester resin, etc., being stable for a long period of time without causing a layer separation and safely handleable with respect to prevention of fire, by including benzoyl peroxide, water and a chlorinated paraffin. SOLUTION: This composition comprises (A) 45-20 pts.wt. of benzoyl peroxide, (B) 15-1 pts.wt. of water and (C) 40-79 pts.wt. of an 8-32C chlorinated paraffin having <=1,000 average molecular weight and 60-40% chlorine content. The composition can contain a phthalic ester such as dibutyl phthalate. The objective composition is useful as a polymerization initiator or a curing agent for a vinyl ester resin, an acrylic resin and an acrylic syrup.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a benzoyl peroxide composition which can be safely handled, is stable over time and has good fluidity, and its use.

[0002]

BACKGROUND OF THE INVENTION Benzoyl peroxide is widely used as a polymerization initiator or a curing agent for radically polymerizable ethylenically unsaturated monomers or copolymers, thermosetting resins and the like. In particular, benzoyl peroxide has been widely used for curing thermosetting resins represented by unsaturated polyester resins and vinyl ester resins, but resins cured with benzoyl peroxide have mechanical properties and adhesive properties. It is characterized by having excellent properties such as chemical resistance and heat resistance.

On the other hand, pure benzoyl peroxide is powdery, exhibits explosive properties due to relatively weak impact, and has extremely dangerous properties such as detonation at that time. It is used with safety properties by dilution with a plasticizer or the like. Also, benzoyl peroxide compositions usually lack solubility or fluidity with respect to monomers or resins.
No. 17816 and US Pat. No. 3,723,336 disclose a method for improving the solubility of a benzoyl peroxide composition in a monomer or a resin, and a method for improving fluidity so as to enable use in a spray-up machine. .

[0004] However, for example, in a suspension in which benzoyl peroxide is dispersed only in water, it is generally difficult to use a large amount of water contained in the suspension because it has an adverse effect on the curing speed and physical properties of the resin. Therefore, for example, a 75% wet product of benzoyl peroxide containing 25% water is used as a raw material, and dimethyl phthalate (DMP) or dibutyl phthalate (DB) is used.
A suspension prepared by using a phthalic acid ester such as P) is used. However, it has been pointed out that there is a quality problem that water contained in the suspension occurs during long-term storage. Phthalates such as DMP and DBP are flammable and are classified as Class 4 and Class 2 petroleum as dangerous goods under the Fire Service Law, so special consideration is required for their handling and usage. .

[0005]

In view of the above situation, there is provided a benzoyl peroxide composition which does not cause layer separation, is stable for a long period of time, and can be safely handled in the prevention of fire. Further, there is a strong demand for the development of a benzoyl peroxide composition having fluidity that can be used for spray-up.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, a part or all of phthalate esters such as DMP and DBP used for the preparation of a suspension have been prepared. By replacing with chlorinated paraffin, they have found that a benzoyl peroxide composition having excellent quality stability, high safety and high fluidity can be obtained, and have completed the present invention.

That is, the present invention provides (1) a benzoyl peroxide composition characterized by containing benzoyl peroxide, water and chlorinated paraffin as essential components. (2) benzoyl peroxide, water, chlorinated paraffin and Benzoyl peroxide composition characterized by containing phthalic acid ester as an essential component (3) 45 to 20 parts by weight of benzoyl peroxide, 15 to 1 part by weight of water, and 40 to 79 parts by weight of chlorinated paraffin ( Benzoyl peroxide composition of 1) (4) 45 to 20 parts by weight of benzoyl peroxide, 15 to 1 part by weight of water, 78 to 1 part by weight of chlorinated paraffin and 1 to 39 parts by weight of phthalic acid ester (2) (5) The benzoyl peroxide according to (1) to (4). (6) The method for polymerization according to (5), wherein the ethylenically unsaturated monomer composition is an acrylic monomer composition. (7) The method for polymerizing (6), wherein the acrylic monomer composition is acrylic syrup (8) A thermosetting resin using the benzoyl peroxide composition according to any one of (1) to (4). (9) The curing method of (8), wherein the thermosetting resin is an unsaturated polyester resin. (10) The curing method of (8), wherein the thermosetting resin is a vinyl ester resin.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail. The benzoyl peroxide composition of the present invention is a suspension having fluidity at room temperature, and contains benzoyl peroxide, water, and phthalate as essential components, and also contains phthalate as necessary.

The benzoyl peroxide used for preparing the benzoyl peroxide composition of the present invention is a known peroxide, and a commercially available product can be easily obtained. Dried products are often treated as wet products because of danger, and 75% wet products are usually easily available. Next, the chlorinated paraffin has an average molecular weight of 1
000 or less, C8 to C containing 60 to 40% chlorine
32 paraffins can be used. Chlorinated paraffins are commercially available as transparent or amber colored viscous liquids. Further, phthalic acid esters include dimethyl phthalate (DMP) and diethyl phthalate (DMP).
EP), dipropyl phthalate, dibutyl phthalate (DBP) and the like are used, but preferred are DMP and DBP.

In the benzoyl peroxide composition of the present invention, the benzoyl peroxide is preferably 45 to 45.
20 parts by weight, water preferably contains 15 to 1 part by weight, and chlorinated paraffin preferably contains 40 to 79 parts by weight. When a phthalic acid ester is contained, 45 to 20 parts by weight of benzoyl peroxide and 1 part of water are preferably used.
5 to 1 part by weight, 78 to 1 part by weight of chlorinated paraffin, and 1 to 39 parts by weight of phthalic ester. In the benzoyl peroxide composition of the present invention, a pigment, a coloring agent such as a dye, an antioxidant such as BHT, a thixotropic agent such as silica, etc. are used as long as the performance of the benzoyl peroxide composition of the present invention is not impaired. It can also be added. In addition, even when a phthalic acid ester is used, it is possible to obtain a composition in which the fire service law is not applied by suppressing the content thereof.

The benzoyl peroxide composition of the present invention is prepared, for example, as follows. 75% of commercial water content
Add chlorinated paraffin and phthalic acid ester as needed to benzoyl peroxide (wet product), stir with a stirrer such as homodisper, separate and vacuum if necessary to adjust the water content, Can be manufactured. Also, as described above, if necessary, a pigment,
Colorants such as dyes, antioxidants such as BHT, and thixotropic agents such as silica may be added.

The benzoyl peroxide composition of the present invention can be used for applications such as polymerization of an ethylenically unsaturated monomer composition having an unsaturated group or curing of a thermosetting resin. Among them, a preferred example of the ethylenically unsaturated monomer having an unsaturated group is an acrylic monomer. Specific examples of acrylic monomers include acrylic acid,
Methacrylic acid or an ester thereof, a compound comprising them and an amide, such as methacrylic acid methyl ester, ethylene glycol dimethacrylate, acrylonitrile,
Examples include allyl acrylate and each acrylate solution containing these prepolymers.

The acrylic monomer composition may be a so-called acrylic syrup. Acrylic syrup is a publicly known one, and refers to a product obtained by pre-polymerizing a methacrylate to form a polymethacrylate and dissolving it in a methacrylate monomer. If necessary, vinyl acetate, styrene, methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, cyclohexyl acrylate, acrylonitrile,
(Co) polymerizable monomers such as ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, methacrylonitrile, and polyfunctional acrylate monomers may be used alone or in combination. .

Preferred examples of the thermosetting resin include unsaturated polyester resins and vinyl ester resins.
Of these, the unsaturated polyester resin always contains an unsaturated dibasic acid as one component, and if necessary, a reaction product obtained by heating and dehydrating and condensing with a glycol in combination with a saturated dibasic acid is used as a vinyl monomer such as styrene. It is obtained by diluting with the body. Examples of unsaturated dibasic acids that can be used include maleic anhydride, fumaric acid, citraconic acid, chloromaleic acid and the like.

Examples of saturated dibasic acids that can be used include:
Examples include phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid and the like. Examples of glycols that can be used include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, hexanediol, bisphenol A,
And propylene oxide adducts.

The vinyl ester resin is obtained by diluting an equivalent reaction product of a polyepoxide and an α, β-unsaturated monobasic acid with a vinyl monomer such as styrene. Examples of polyepoxides that can be used include nitrogen-containing polyepoxides such as epibis glycidyl ether such as bisphenol A and bisphenol F, novolak glycidyl ether, brominated glycidyl ether and triglycidyl isocyanurate, and glycidyl such as phthalic acid and hexahydrophthalic acid. Esters, glycol-type glycidyl ethers and the like. Examples of the unsaturated monobasic acid that can be used include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid and the like.

When the benzoyl peroxide composition of the present invention is used for polymerization or curing, a known peroxide such as tertiary butyl peroxybenzoate or tertiary butyl peroxy 2-ethylhexanoate is used in the benzoyl peroxide composition of the present invention. You may use together with a peroxide composition. In general, at 50 ° C. or higher, polymerization or curing is carried out by using the benzoyl peroxide composition of the present invention alone or in combination with the peroxide as described above.
In the following polymerization or curing, dimethylaniline (DMA),
Generally, a tertiary aromatic amine such as diethylaniline (DEA) is used in combination as a polymerization accelerator.

The benzoyl peroxide composition of the present invention is used as a copolymerization initiator in a suspension, bulk or solution polymerization process of a radically polymerizable ethylenically unsaturated monomer (eg, styrene or (meth) acrylic acid). , Alone or in combination with other peroxides. The addition amount is 0.05 with respect to the ethylenically unsaturated monomer.
~ 5% by weight is preferred.

The polymerization of the ethylenically unsaturated monomer composition using the benzoyl peroxide composition of the present invention is carried out, for example, as follows. One type of (meth) acrylates such as n-butyl acrylate, methyl methacrylate, hydroxyethyl methacrylate or the like in an ester solvent such as ethyl acetate or an aromatic hydrocarbon solvent such as toluene or The benzoyl peroxide composition of the present invention is added to a mixture obtained by adding styrene, acrylic acid, vinyl acetate, or the like, if necessary, to a mixture of two or more kinds or, if necessary, 0.05 to 5 parts by weight based on 100 parts by weight of the mixture. The polymerization is carried out at 80 to 110 ° C for 1 to 10 hours by adding parts by weight. In the polymerization of acrylic syrup, the polymerization can be performed as follows. At room temperature, acrylic syrup 100
With respect to parts by weight, a polymerization accelerator such as dimethylaniline or diethyl paratoluidine is added in an amount of 0.05 to 2 parts by weight, and after stirring well, 0.05 to 5 parts by weight of the benzoyl peroxide composition of the present invention is added. And mix well. After several minutes to several days, the polymerization is completed. Also, by adding 0.05 to 5 parts by weight of the benzoyl peroxide composition of the present invention to 100 parts by weight of acrylic syrup, and heating the mixture to 50 ° C., preferably about 80 ° C. or more, for several minutes to several hours. It can also be polymerized.

When the thermosetting resin is cured using the benzoyl peroxide composition of the present invention, the amount of the thermosetting resin used is 0.1 to 5 parts by weight based on 100 parts by weight of the thermosetting resin. And preferably 0.5 to 3 parts by weight. When the amount is less than 0.1 part by weight, the effect as a curing agent is insufficient.
It is not so different from the case of about parts by weight, so it is disadvantageous in terms of economy.

The curing of the thermosetting resin using the benzoyl peroxide composition of the present invention can be performed, for example, as follows. At room temperature, 0.05 to 1 part by weight of a curing accelerator such as dimethylaniline is added to 100 parts by weight of a thermosetting resin such as an unsaturated polyester resin, a vinyl ester resin, and an acrylic syrup, and after stirring well,
0.1 to 3 of the benzoyl peroxide composition of the present invention
Add parts by weight and stir well. It can be cured by leaving it for several minutes to several hours.

The benzoyl peroxide composition of the present invention is characterized by being excellent in stability over time and, depending on the embodiment, being a composition that is not a dangerous substance under the Fire Service Law and is easy to handle. . The benzoyl peroxide composition of the present invention exhibits excellent polymerization or curing action as a polymerization initiator for a monomer having an ethylenically unsaturated group or a curing agent for a thermosetting resin.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, these are merely examples and do not limit the present invention.

Example 1 Commercially available Lucidol 75W (trade name, 75% benzoyl peroxide, manufactured by Akzo) in a 500cc beaker
And 135 g of DBP, and the mixture is stirred with a mixer. At this time, 15 g of separated water was removed.
Furthermore, chlorinated paraffin (Empara K manufactured by Ajinomoto Co., Inc.)
-43) 65 g was added and stirred with a mixer to obtain 300 g of the benzoyl peroxide composition of the present invention. Its active oxygen content was 2.63%. The content of DBP is 38% by weight.

The amount of active oxygen was calculated by the following method and equation. 30 ml of isopropyl alcohol, 2 ml each of glacial acetic acid and a saturated aqueous solution of potassium iodide are placed in a 300 ml flask, and about 2 ml of a benzoyl peroxide composition
Is weighed, sealed and heated at 30 ° C. for 15 minutes. Immediately titrate with N / 10 sodium thiosulfate solution. The end point is the point at which the iodine color disappears. Active oxygen content (%) = ((A × F × 0.0008) / W)
× 100 A: m of N / 10 sodium thiosulfate solution required for the test
l F: titer of N / 10 sodium thiosulfate solution W: sample weight

Example 2 The above-mentioned Lucidol 75W 135 was placed in a 500 cc beaker.
g, and 100 g of DBP and stir with a mixer.
At this time, 15 g of separated water was removed. Further, 80 g of Empara K-43 was added and stirred with a mixer to obtain 300 g of the benzoyl peroxide composition of the present invention. Its active oxygen content was 2.62%. The content of DBP is 33% by weight.

Example 3 The above-mentioned Lucidol 75W 135 was placed in a 500 cc beaker.
g and then 45 g of DBP and stir with a mixer. At this time, 15 g of separated water was removed. Further, 135 g of the above-mentioned empara-K-43 was added thereto, and the mixture was stirred with a mixer, and the mixture was stirred.
0 g was obtained. Its active oxygen content was 2.61%. The content of DBP is 15% by weight.

Comparative Example 1 The above-mentioned Lucidol 75W 135 was placed in a 500 cc beaker.
g of DBP and 45 g of DBP were further stirred with a mixer. At this time, 15 g of separated water was removed. Further, 135 g of DBP was added and stirred with a mixer to obtain 300 g of a benzoyl peroxide composition for comparison. Its active oxygen content was 2.60%. The content of DBP is 60% by weight. In addition, the benzoyl peroxide composition obtained here is equivalent to the 4th dangerous substance in the Fire Defense Law.

Performance Test (1) Each of the benzoyl peroxide compositions of the present invention prepared in Examples 1 to 3 was added to 100 cc of polyvin each for 50 minutes.
g each and stored in a thermostat at 30 ° C., and after 3 months, the presence or absence of separation was visually confirmed to examine their stability. Table 1 shows the results.

[0030]

Table 1 Table 1 Benzoyl peroxide composition Presence or absence of separation after 3 months at 30 ° C. Composition of Example 1 No layer separation Composition of Example 2 組成 Composition of Example 3 組成 Composition of Comparative Example 1 Transparent layer was seen at the top

The above results show that the benzoyl peroxide composition of the present invention does not cause phase separation and is stable over time.

Performance Test (2) For each of the benzoyl peroxide compositions of the present invention obtained in Examples 1 to 3, the flash point, the burning point, the pressure vessel test (PVT) and the differential scanning were performed by the method based on the Fire Service Law. The danger of explosion was measured by a calorimeter (DSC). Table 2 shows the results.

[0033]

Table 2 Composition used Flash point PVT Burning point DSC Composition of Example 1 100 ° C or more and 1mm or less 100 ° C or more No danger Composition of Example 2 100 ° C or more and 1mm or less 100 ° C or more No danger Composition of Example 3 100 ° C or more and 1mm or less 100 ° C or more No danger

In the Fire Service Law, the conditions that do not correspond to the category 4 hazardous materials are that the flash point is 40 ° C. or more, the burning point is 60 ° C. or more, and the flammable liquid is 40% or less. Therefore, the benzoyl peroxide compositions of the present invention (Examples 1 to 3) satisfy the above conditions and do not fall under the category 4 dangerous goods. In addition, the benzoyl peroxide compositions (Examples 1 to 3) of the present invention all have a PVT of 1 mm or less, have no danger of DSC, and do not fall under the fifth category of dangerous substances. The above measurement results show that the benzoyl peroxide composition of the present invention is a non-dangerous substance and can be handled safely.

Examples 4, 5, and 6 Using a commercially available unsaturated polyester resin (Polylite 8010 manufactured by Dainippon Ink and Chemicals, Inc.), JIS-K
Based on the room temperature curing characteristics of -6901, the benzoyl peroxide composition of the present invention was added at 20 ° C. in the amount shown in Table 3, and gelation time (hereinafter abbreviated as GT) and curing time (hereinafter abbreviated as CT and Abbreviated), maximum heat generation temperature (hereinafter PET)
Abbreviated). The Barcol hardness of the obtained cured product was measured using a Barcol hardness meter (934-1). Table 3 shows the results.

[0036]

Table 3 Table 3 Addition amount GT CT PET (° C) Barcol hardness composition (phr) (min) (min) (934-1) Composition of Example 1 2.5 18.1 35.2 146 35 Composition of Example 2 Product 2.5 18.0 35.0 145 35 Composition of Example 3 2.5 18.5 35.3 144 35 (Note) In the table, from the top in the order of Example 4, Example 5, and Example 6, dimethylaniline was added in an amount of 0.3 phr. Addition

Examples 7, 8, and 9 A commercial acrylic syrup (DR-415, manufactured by Mitsubishi Rayon Co., Ltd.) was added to a 100-cc polycop at room temperature of 25 ° C.
30 g were weighed, each benzoyl peroxide composition of the present invention was added in the amount shown in Table 4, and the time until the glass rod could not be pierced was measured, and this was defined as the curing time. Table 4 shows the results.

[0038]

Table 4 Composition used Addition amount Curing time (phr) (min) Example 7 Composition of Example 1 2.5 20 minutes Example 8 Composition of Example 2 2.5 20 minutes Example 9 Composition of Example 3 2.5 20 minutes

From the above results, it can be seen that the benzoyl peroxide composition of the present invention gives a result which can be applied to the curing of acrylic syrup.

[0040]

The benzoyl peroxide composition of the present invention is excellent in stability over time and, in a preferred embodiment, stability under the firefighting method, and is useful for polymerization of unsaturated polyester resin, vinyl ester resin, acrylic resin and acrylic syrup. It has an excellent effect as a catalyst for radical polymerization or curing for copolymerization, and its industrial value is extremely large.

Claims (10)

[Claims] 1. A benzoyl peroxide composition comprising benzoyl peroxide, water and chlorinated paraffin as essential components. 2. A benzoyl peroxide composition containing benzoyl peroxide, water, chlorinated paraffin and phthalic acid ester as essential components. 3. The benzoyl peroxide composition according to claim 1, which contains 45 to 20 parts by weight of benzoyl peroxide, 15 to 1 part by weight of water, and 40 to 79 parts by weight of chlorinated paraffin. 4. The benzoyl peroxide composition according to claim 2, comprising 45 to 20 parts by weight of benzoyl peroxide, 15 to 1 part by weight of water, 78 to 1 part by weight of chlorinated paraffin and 1 to 39 parts by weight of phthalic acid ester. 5. A method for polymerizing an ethylenically unsaturated monomer composition, comprising using the benzoyl peroxide composition according to claim 1. 6. The polymerization method according to claim 5, wherein the ethylenically unsaturated monomer composition is an acrylic monomer composition. 7. The polymerization method according to claim 6, wherein the acrylic monomer composition is an acrylic syrup. 8. A method for curing a thermosetting resin, comprising using the benzoyl peroxide composition according to claim 1. 9. The method according to claim 8, wherein the thermosetting resin is an unsaturated polyester resin. 10. The curing method according to claim 8, wherein the thermosetting resin is a vinyl ester resin.