JPS60139331A - Stabilized organic peroxide composition - Google Patents

Abstract

PURPOSE:To obtain an org. peroxide composition containing a specific amount of an unsaturated polyester resin and stabilized to shock, by microencapsulating org. peroxide sensible to shock by the unsaturated polyester resin. CONSTITUTION:Org. peroxide (e.g., dibenzoyl peroxide) sensible to shock and solid at a room temp. is microencapsulated by an unsaturated polyester resin to obtain an org. peroxide composition containing 20-70wt% of the aforementioned resin and stabilized to shock. That is, org. peroxide is preliminarily dispersed in a solvent not dissolving org. peroxide, for example, water and a resin solution, in which the unsaturated polyester resin is dissolved, is dripped in the aforementioned aqueous phase and the unsaturated polyester resin becoming insoluble is deposited to the surface of org. peroxide to microencapsulate said org. peroxide. Furthermore, the concn. of org. peroxide in a product can be freely regulated by the amount of the unsaturated polyester resin to be added.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is a method of producing a shock-sensitive, room-temperature solid organic peroxide, obtained by microencapsulating it with an unsaturated polyester resin, containing 20 to 70% of said resin. The present invention relates to a shock-stabilized organic peroxide composition characterized by the following characteristics. The organic peroxides that are solid at room temperature and are sensitive to gIIIR as used herein refer to those that show explosive decomposition at 20- or less according to the JLSK'4810 method.

Organic peroxides that are sensitive to solid impacts at room temperature, such as dibenzoyl peroxide (hereinafter referred to as B and PO), 2.4
- Dichlorobenzoyl peroxide, etc. must be handled with great care in pure form. Conventionally, this has been stabilized by adding water to make it into a wet form, or adding plasticizers or solvents such as dioctyl phthalate or silicone oil to make it into a paste. It has been used. However, these conventional methods have the following drawbacks. for example,
When these catalysts are used in polymerization or curing reactions, there are problems such as the additives in these catalysts being extracted from the resin, or the resin being plasticized, and furthermore, these organic peroxide compositions There were drawbacks such as separation from additives during storage. For example, in the field of curing agents, that is, as catalysts for curing unsaturated polyester resins, it has been desired to improve the above-mentioned drawbacks.

The present inventors have conducted intensive research to stabilize organic peroxides that are sensitive to *j14 by microencapsulating them with unsaturated polyester resin, and have thus arrived at the present invention. That is, the unsaturated polyester resin increases the impact stability of the organic peroxide, and as a result of a drop hammer sensitivity test conducted according to the JiSK4810 method, a non-exploding organic peroxide composition was obtained at 3 Qct.

To explain more specifically, since the method for producing the organic peroxide composition obtained in the present invention involves handling dangerous organic peroxides, it is believed that a solvent-based resin phase separation method is most appropriate for safety reasons. it was thought.

In other words, by dispersing the organic peroxide in a solvent in which the organic peroxide is insoluble, for example, water, and dropping a resin solution containing the unsaturated polyester resin into the aqueous phase, the unsaturated polyester becomes insolubilized. Microcapsules are formed by depositing on the surface of resin or organic peroxide.

The bl of unsaturated polyester resin added by troweling:
Organic peroxide production in C products can be easily controlled. In addition, for the purpose of increasing safety against impact, the resin content in the product was generally 20% by weight or more. However, due to the user's desire to reduce the amount of additives other than organic peroxide as much as possible, and the organic peroxide concentration in commercially available organic peroxide compositions, it is normal to have an organic peroxide concentration of 30% by weight or more. The resin content in the product obtained by the present invention was preferably 70% or less. Organic peroxides that are solid at room temperature and are sensitive to impact include benzoyl peroxide, 2,4-chlorobenzoyl peroxide, P-chlorobenzoyl peroxide, and P-1-chlorbenzoyl peroxide.
Examples include toluyl peroxide, toluyl peroxide, diacetyl peroxide, and acetylcyclohexylsulfonyl peroxide. The unsaturated polyester resin here refers to the reaction between a polybasic acid component consisting of an aliphatic or aromatic saturated polybasic acid and an aliphatic unsaturated polyhydrochloric acid, and an aliphatic polyhydric alcohol or/and a cyclic polyhydric alcohol. It is an unsaturated polyester resin obtained by. Examples of the aliphatic unsaturated polybasic acids include maleic anhydride, fumaric acid, citraconic acid, and itaconic acid, which may be used alone or as a mixture. Saturated polybasic acids used in combination with such unsaturated polybasic acids include, for example, phthalic acid, isophthalic acid, terephthalic acid, phthalic anhydride, hexahydrophthalic anhydride,
Aromatic saturated polybasic acids such as trimellitic acid and pyromellitic acid and aliphatic saturated polybasic acids such as co/'% phosphoric acid, glutaric acid, adipic acid, sebacic acid, azelaic acid, etc.
These can be used alone or as a mixture of two or more (71).Also, examples of aliphatic polyhydric alcohols include propylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 2- These are polyhydric alcohols such as 3-butylene glycol and neopentyl glycol, and cyclic polyhydric alcohols are polyhydric alcohols with a cyclic structure such as propylene oxide adducts of bisphenol A and hydrogenated bisphenol A. Alternatively, they may be used as a mixture of two or more.Here, 1) ethylene glycol, diethylene glycol, etc. are used as the polyhydric alcohol other than those mentioned above. Now, unsaturated polyester resins suitable for use in the present invention may be those having the following characteristics. In other words, since the commonly used microencapsulation method is a phase separation method using a solvent, the unsaturated polyester resin that becomes the wall material of the microcapsules is made of acetone, dioxane,
Dissolve in tetrahydrofuran or other suitable solvent that will not induce decomposition of organic peroxides. Furthermore, it is an object of the present invention to demonstrate the effect of increasing the impact stability of organic peroxides. Preferably, the softening point of the unsaturated polyester resin is the self-decomposition promoting temperature of the organic peroxide serving as the core material of the microcapsule (for example, 106°C in the case of BPO).
It is. ) are selected from among those having a lower temperature.

Next, specific examples will be given and explained, but the present invention is not limited thereto.

Example 1 A 31-sized round-bottom colben equipped with a stirring spatula was charged with water wet product BPO 1477 manufactured by Sanken Kako and 660 V of distilled water, and the BPO powder was dispersed in the water while stirring. Thereafter, unsaturated polyester resin (hereinafter [J P
It is written as =1. ) Immediately drop a resin solution containing ilcl. After that, a free at-effect powder can be obtained by converting the 13]) O powder microencapsulated by resin into P;(='SL, 1'j''1. It was 2167.

The content of 13 PO in the powder was determined to be 50% by standard chemical analysis after dissolving the sample in chloroform. Furthermore, a drop hammer sensitivity test conducted on this product in accordance with the JIS K4810 method was 60 (non-explosive).

Actual %+B Example 2 An unsaturated polyester resin (hereinafter referred to as tJ P-2) obtained by a conventional method using phthalic acid, maleic anhydride, and propylene glycol as raw materials was subjected to microcoagulation under the same conditions as in Example 1. As a result of encapsulation, the resulting product was blocked and rubbery at room temperature. In addition, in the drop hammer sensitivity test, even 100 (7) was not explosive.

Comparative Example 3 A powder obtained by the same method as in Example 1 (but using 132 UP-1 as the unsaturated polyester resin) contained 90% BPO. Furthermore, in a drop hammer sensitivity test conducted on this product in accordance with the JIS K4810 method, it did not explode at 30 pulls, but exploded at 60 pulls.

The results of Example 1.2 and Comparative Example 3 are summarized in Table 1.

Table 1 *I BPO pure product = 10 cIn explosion The self-decomposition acceleration temperature of BPO is 106°C (in unsaturated polyester resin).

Furthermore, for the purpose of practical testing, we conducted a curing test of unsaturated polyester resin using commercially available unsaturated polyester resin.
This was carried out using the SK6901 method. The results are shown in Table 2.

Table 2 Resin used: Unsaturated polyester resin smear knob P-100 manufactured by Sanken Kako ■

Claims (1)

[Claims] A shock-stabilized product obtained by microencapsulating a shock-sensitive room-temperature solid organic peroxide with an unsaturated polyester resin and containing 20 to 70% by weight of said resin. Organic peroxide composition.