JP6899095B2 - Peroxycarbamate compound - Google Patents

Description

The present invention relates to peroxycarbamate compounds.

Conventionally, a peroxycarbamate compound represented by the following general formula (A) having one alkoxysilyl group and one peroxide bond in the molecule has been known (Patent Document 1).

In the peroxycarbamate compound represented by the above general formula (A), the peroxide bond is cleaved by heat to generate a t-butoxy radical and an aminyl radical having an alkoxysilyl group. As a feature of such an aminyl radical having an alkoxysilyl group, for example, since the aminyl radical can react with a polyester resin and the alkoxysilyl group can react with glass, the peroxycarbamate represented by the general formula (A) is described. Compounds are known to be useful as radical generators used in the reaction of polyester resins with glass.

Japanese Unexamined Patent Publication No. 48-40726

However, when the peroxycarbamate compound represented by the general formula (A) is used as a radical generator such as a modification of a polymer (rubber, polyolefin, etc.) or a polymerization initiator of a polymer using a vinyl monomer or the like. (1) Since the alkoxysilyl group is introduced into the polymer and the t-butoxy group is also introduced by the t-butoxy radical, the introduction efficiency of the alkoxysilyl group in the polymer is lowered, and (2) Since t-butoxy radicals have a high hydrogen abstraction reactivity, there is a problem that a cross-linking reaction (side reaction) between polymers is caused to reduce the processability of the polymer, and a problem that the molecular weight distribution of the produced polymer is significantly increased. Occurs.

Therefore, in order to solve the above problems, the present invention provides a peroxycarbamate compound capable of generating only aminyl radicals having an alkoxysilyl group as radical generators without generating t-butoxy radicals. The purpose is.

で表されるパーオキシカーバメート化合物に関する。 That is, the present invention has the general formula (1):

It relates to a peroxycarbamate compound represented by.

The peroxycarbamate compound of the present invention is a compound having two alkoxysilyl groups and two peroxide bonds in the molecule, and the peroxide bond is cleaved by heat or the like, and one alkoxy radical and one molecule per molecule. An aminyl radical having two alkoxysilyl groups is generated per group, and it is presumed that the alkoxy radical becomes acetone and ethylene by β-cleavage. Therefore, since the peroxycarbamate compound of the present invention can generate only the aminyl radical having an alkoxysilyl group without generating the t-butoxy radical, the aminyl radical having an alkoxysilyl group can be efficiently used. Since it can be formed, it is useful as a radical generator such as a modification of a polymer (rubber, polyolefin, etc.) or a polymerization initiator of a polymer using a vinyl monomer or the like.

<Peroxycarbamate compound>
The peroxycarbamate compound of the present invention can be represented by the following general formula (1).

で表されるパーオキシエステル化合物と、一般式（３）：

で表されるケイ素化合物を反応させる工程（以下、工程（Ａ）とも称す）を含む製造方法が挙げられる。 <Manufacturing method of peroxycarbamate compound>
The method for producing the peroxycarbamate compound represented by the general formula (1) is not limited in any way, but for example, the general formula (2):

The peroxyester compound represented by and the general formula (3):

Examples thereof include a production method including a step of reacting the silicon compound represented by (hereinafter, also referred to as step (A)).

In the step (A), as the peroxyester compound represented by the general formula (2), a commercially available product may be used, and when there is no commercially available product, for example, it is described in JP-A-62-043404. It can be manufactured by the manufacturing method of.

In the step (A), the silicon compound represented by the general formula (3) has a viewpoint of increasing the yield of the target product with respect to 1.0 mol of the peroxyester compound represented by the general formula (2). Therefore, it is preferable to react 1.0 mol or more, and 1.1 mol or less is preferable.

The reaction temperature in the step (A) is preferably 0 ° C. or higher, more preferably 5 ° C. or higher, and 15 ° C. or lower from the viewpoint of safety, from the viewpoint of increasing the yield of the target product. Is preferable, and the temperature is more preferably 10 ° C. or lower.

The reaction time of the step (A) cannot be unconditionally determined because it varies depending on the raw material, the reaction temperature, etc., but it is usually preferably 0.5 hours or more from the viewpoint of increasing the yield of the target product. It is more preferably .0 hours or more, and preferably 2 hours or less.

The step (A) can be performed under normal pressure and in an air atmosphere, but is preferably performed under a nitrogen air flow or a nitrogen atmosphere.

It is preferable to use an organic solvent in the step (A). The organic solvent is not particularly limited, but is preferably an organic solvent that is inert in the reaction system. Examples of the organic solvent include non-polar compounds such as pentane, hexane and toluene; and polar compounds such as acetone and acetonitrile. The organic solvent may be used alone or in combination of two or more.

In the step (A), the amount of the organic solvent used is not particularly limited, but is usually about 200 to 600 parts by weight with respect to 100 parts by weight of the total amount of the raw materials.

The obtained object can be identified by using liquid chromatography (LC), nuclear magnetic resonance spectroscopy (NMR), infrared spectroscopy (IR), or the like.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

<Manufacturing example 1>
(1) Synthesis of peroxycarbamate compound In a 1 L beaker, 2,5-dimethyl-2,5-dihydroperoxyhexane (95.8% product, 95.95 g, 0.5 mL) was added to pyridine (172 g, 2.2 mL). It was dissolved and stirred inside, and cooled to 10 ° C. or lower. Subsequently, phenylchloroformate (170 g, 1.0 mol) was diluted with pentane (170 g) and added dropwise to the above pyridine solution at 10 ° C. After completion of the dropping, the mixture was stirred for 1 hour, and the precipitate and dipyridine hydrochloride were separated by filtration. The separated precipitate was washed with pentane and water, washed with methanol, dried, and the peroxyester compound represented by the above general formula (2) (2,5-dimethyl-2,5-di (2,5-dimethyl-2,5-di). Peroxy-phenylmonocarbonate)) (165 g, purity 97.3%, yield 71%).
The purity was calculated from the theoretical amount of active oxygen of 2,5-dimethyl-2,5-di (peroxy-phenylmonocarbonate) by determining the content of peroxy group from the amount of active oxygen by iodometry.

Next, the 2,5-dimethylhexane-2,5-di (peroxy-phenylmonocarbonate) (100 g, 0.23 mL) obtained above was dissolved in toluene (200 g). Aminopropyltriethoxylan (101 g, 0.46 mL) was added dropwise to this toluene solution at 5 ° C., and the mixture was stirred for 1 hour, and 2,5-dimethylhexane-2,5 represented by the above general formula (1) was added. -Di [N- (3-triethoxysilyl) propyl] peroxycarbamate was obtained (diluted toluene and phenol (by-product), 400 g, concentration 37%).

The structure of the 2,5-dimethylhexane-2,5-di [N- (3-triethoxysilyl) propyl] peroxycarbamate represented by the above general formula (1) is an AVANCE 400 NMR spectrum meter (manufactured by BRUCKER). ) ^{Was identified by 1} H-NMR measurement [0.68 (t, 4H), 1.23 (t, 18H), 1.53 (s, 12H), 1.66-1.73 (m). , 4H), 2.20 (s, 4H), 3.26-3.31 (m, 4H), 3.81-3.87 (q, 12H), 6.03 (t, 2H)].
The concentration is determined by determining the content of peroxy groups from the amount of active oxygen by iodometry, and the theoretical active oxygen of 2,5-dimethylhexane-2,5-di [N- (3-triethoxysilyl) propyl] peroxycarbamate. Calculated from the amount.

<Example 1>
<Crosslink test>
The roll machine (manufactured by Toyo Seiki Co., Ltd.) was heated to 80 ° C., and E-SBR (trade name "JSR 1502", manufactured by JSR Corporation) was kneaded. While kneading, 1.48 mmоl of 2,5-dimethylhexane-2,5-di [N- (3-triethoxysilyl) propyl] peroxycarbamate obtained above was mixed with 100 g of E-SBR. , E-SBR rubber sheet (10 cm × 20 cm) was obtained. The obtained rubber sheet was subjected to a cross-linking test at 130 ° C. using a JSR Trading Co., Ltd. curast meter. The results are shown in Tables 1 and 2.

<Example 2>
Same as in Example 1 except that the amount of 2,5-dimethylhexane-2,5-di [N- (3-triethoxysilyl) propyl] peroxycarbamate used in Example 1 was 0.74 mmоl. A cross-linking test was performed by the operation method. The results are shown in Tables 1 and 2.

<Comparative example 1>
Except that the 2,5-dimethylhexane-2,5-di [N- (3-triethoxysilyl) propyl] peroxycarbamate of Example 1 was changed to the peroxycarbamate compound represented by the following general formula (A). Performed a cross-linking test by the same operation method as in Example 1. The results are shown in Tables 1 and 2.

As a result of the evaluation, the maximum torque values of Example 1 and Example 2 using the compound represented by the general formula (1) were higher than those of Comparative Example 1 using the compound represented by the general formula (A). It was confirmed that it decreased and the cross-linking reaction was suppressed. Further, as a result of comparing Example 2 to which an equal amount of alkoxysilyl group was added and Comparative Example 1, it was confirmed that the cross-linking reaction was further suppressed.

Claims (1)

General formula (1):

A peroxycarbamate compound characterized by being represented by.