JP2013112630A - Trimethallyl isocyanurate derivative oligomer and its application - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel substance which can be utilized as a crosslinking agent to a cross linking polymer without causing a bloom.SOLUTION: A trimethallyl isocyanurate derivative oligomer is formed by oligomerizing a monomer of a trimethallyl isocyanurate derivative represented by general formula (I) and has the degree of polymerization of 2 to 6 obtained from number average molecular weight expressed in terms of polystyrene measured by GPC. (In formula (I), each R independently denotes a hydrogen atom or a methyl group).

Description

  The present invention relates to a trimethallyl isocyanurate derivative oligomer and its application, and more particularly to a trimethallyl isocyanurate derivative oligomer having a novel structure and its application.

  Liquid triallyl isocyanurate (“TAIC” (registered trademark)) is known as a useful crosslinking agent for a crosslinkable polymer such as a crosslinkable elastomer or a crosslinkable thermoplastic resin (Patent Documents 1 and 2).

  However, when TAIC is kneaded into a crosslinkable polymer to form a kneaded product (compound) and then molded and crosslinked, the surface of the molded body bleeds, and mold contamination and dirt on the molded product (product) are removed. There is a problem of inducing it. In some cases, the TAIC kneading step and the cross-linking step may be performed separately, and in such a case, the cross-linkable polymer composition obtained as a kneaded product is prepared, for example, for storage. After several days, it is crosslinked and commercialized. In such a case, since the bleed of liquid TAIC is caused during storage, the problem of mold contamination and product contamination becomes more prominent. TAIC oligomerization can be considered as one means of preventing TAIC bleeding, but TAIC oligomerization is difficult.

JP 2003-2992 A JP 2005-238477 A

  The present invention has been made in view of the above circumstances, and an object thereof is to provide a novel substance that is solid and can be used as a crosslinking agent for a crosslinkable polymer without causing bloom. Another object of the present invention is to provide application of the above novel substance.

As a result of intensive studies, the present inventors have compared trimethallyl isocyanurate derivatives in which the 2-propenyl group (allyl group: —CH ₂ CH═CH ₂ ) of triallyl isocyanurate is substituted with a methyl group. We obtained knowledge that oligomerization can be easily performed.

  The present invention has been made on the basis of the above findings, and is composed of a group of a plurality of related inventions. The gist of each invention is as follows.

  The first gist of the present invention is obtained by oligomerizing a monomer of a trimethallyl isocyanurate derivative represented by the general formula (I), and the degree of polymerization determined from the number average molecular weight in terms of polystyrene measured by GPC is 2 It exists in the trimethallyl isocyanurate derivative oligomer characterized by being -6.

（式（Ｉ）中、各Ｒは、各々独立に、水素原子またはメチル基を示す。）

(In formula (I), each R independently represents a hydrogen atom or a methyl group.)

  The second gist of the present invention resides in a crosslinking agent characterized by using the above-mentioned trimethallyl isocyanurate derivative oligomer as a crosslinking component.

  The third gist of the present invention is that the crosslinkable polymer is blended with at least the above-mentioned trimethallyl isocyanurate derivative oligomer as a crosslinker, and the ratio of the crosslinker to 100 parts by weight of the crosslinkable polymer is 0.05 to 15. It exists in the crosslinkable polymer composition characterized by being a weight part.

  According to a fourth aspect of the present invention, there is provided a method for producing a polymer molded body comprising the above-described trimethallyl isocyanurate derivative oligomer as a crosslinking agent in a method for producing a polymer molded body for curing a crosslinkable polymer. Lies in the way.

  The fifth gist of the present invention is a polymer molded body cured by the action of a crosslinking agent, comprising the above-mentioned trimethallyl isocyanurate derivative oligomer as a crosslinking agent. Exist.

  According to the present invention, the above-mentioned problems are solved.

  Hereinafter, the present invention will be described in detail.

<Trimethallyl isocyanurate derivative oligomer>
The trimethallyl isocyanurate derivative oligomer of the present invention is obtained by oligomerizing a monomer of a trimethallyl isocyanurate derivative represented by the general formula (I).

（式（Ｉ）中、各Ｒは、各々独立に、水素原子またはメチル基を示す。）

(In formula (I), each R independently represents a hydrogen atom or a methyl group.)

  As a specific example of the trimethallyl isocyanurate derivative represented by the general formula (I), a trimethallyl which is typically a compound in which the 2-position of the 2-propenyl group of triallyl isocyanurate (TAIC) is substituted with a methyl group is used. And isocyanurate (TMAIC: registered trademark).

  The oligomerization of the monomer of the trimethallyl isocyanurate derivative represented by the general formula (I) can be achieved by various methods. For example, a method of heat treatment at an appropriate temperature (for example, 50 to 130 ° C.) in the presence of oxygen for an appropriate period (for example, 1 to 6 days), a method of using a radical polymerization initiator or ultraviolet light may be mentioned.

  The trimethallyl isocyanurate derivative oligomer of the present invention has a degree of polymerization of 2 to 6 determined from a polystyrene-reduced number average molecular weight measured by GPC. When the degree of polymerization is less than 2, it may bloom when kneaded into a crosslinkable polymer to form a kneaded product (compound), and when the degree of polymerization is more than 6, the crosslinking performance may be lowered. The degree of polymerization is preferably 3-4.

<Crosslinking agent>
The crosslinking agent of the present invention uses the above-mentioned trimethallyl isocyanurate derivative oligomer as a crosslinking component. The above-mentioned trimethallyl isocyanurate derivative oligomer is formed by oligomerizing the monomer of the trimethallyl isocyanurate derivative represented by the general formula (I), but the monomer itself also acts as a crosslinking agent. It is not necessary for the oligomerization of to be 100%.

  That is, the cross-linking agent of the present invention uses the above-mentioned trimethallyl isocyanurate derivative oligomer as a cross-linking component, and the proportion thereof is usually 10% by weight or more, preferably 20% by weight or more, as a proportion of the total amount including monomers. More preferably, it is 25% by weight or more. The upper limit is not particularly limited, but is usually 70% by weight, preferably 65% by weight, and more preferably 60% by weight. The kind of the crosslinkable polymer to which the crosslinking agent of the present invention can be applied and the usage of the crosslinking agent will be described in other inventions described later.

<Crosslinkable polymer composition>
The crosslinkable polymer composition of the present invention comprises at least the above-mentioned trimethallyl isocyanurate derivative oligomer as a crosslinker in a crosslinkable polymer, and the ratio of the crosslinker to 100 parts by weight of the crosslinkable polymer is 0.05. ~ 15 parts by weight.

  The crosslinkable polymer used in the present invention is a crosslinkable elastomer and a crosslinkable thermoplastic resin.

  The crosslinkable elastomer refers to an elastomer having an active site that can be cross-linked by radical generation. The type of the crosslinkable elastomer is not particularly limited. For example, natural rubber, isoprene rubber, butadiene rubber, ethylene propylene rubber, styrene rubber, nitrile rubber, hydrogenated nitrile rubber, chloroprene rubber, chlorosulfonated polyethylene, acrylic rubber, ethylene Acrylic rubber, silicone rubber, fluorine rubber, hydrin rubber and the like can be mentioned. Moreover, the substituted polyolefin which is a copolymer of olefins, such as ethylene and propylene, and vinyl alcohol, acrylic acid, methacrylic acid, ethyl acrylate, glycidyl methacrylate, vinyl acetate, etc. is mentioned. Further, a blend rubber composed of two or more of these may be used. Preferred is fluororubber. The kind of fluororubber is not particularly limited, and examples thereof include FKM, FFKM, FEPM, and TFE. Among these, substituted polyolefin such as ethylene vinyl acetate copolymer or fluororubber is preferable. The vinyl acetate content of the ethylene vinyl acetate copolymer is usually 10 to 40% by weight, preferably 20 to 35% by weight.

The crosslinkable thermoplastic resin refers to a thermoplastic resin having an active site that can be cross-linked by radical generation. The type of the crosslinkable thermoplastic resin is not particularly limited, and examples thereof include vinyl chloride resin, polyolefin resin, acrylic resin, polystyrene resin, polycarbonate resin, polyester resin, polyamide resin, polyphenylene ether resin, polyacetal resin, and fluorine resin. These two or more kinds of blend resins may be used. Polyamide resins and polyester resins are preferable, and polyamide 6, polyamide 66, and polybutylene terephthalate are more preferable.

  The blending ratio of the crosslinking agent is preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the crosslinkable polymer.

  In the present invention, another cross-linking agent may be used in combination with the trimethallyl isocyanurate derivative oligomer. The other crosslinking agent is not particularly limited, but is preferably a monomer of a trimethallyl isocyanurate derivative represented by the general formula (I), and the content of such a monomer is the above-described oligomerization. It can be arbitrarily adjusted according to the degree. Further, a compound obtained before substitution with a methyl group of the trimethallyl isocyanurate derivative represented by the general formula (I), typically triallyl isocyanurate (TAIC), can also be suitably used. The amount of other crosslinking agent used is not particularly limited, but is generally 0.05 to 15 parts by weight, preferably 0.5 to 100 parts by weight with respect to 100 parts by weight of the crosslinkable polymer as the total amount with the crosslinking agent of the present invention. 5 parts by weight.

  An organic peroxide can be blended in the crosslinkable polymer composition. The organic peroxide is a component generally used for heat crosslinking, and is not particularly limited as long as it is a known organic peroxide that generates a peroxy radical under vulcanization conditions. For example, di-t-butyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) ) Hexane, t-butylperoxy-2-ethylhexyl-monocarbonate, 1,1-bis (t-butylperoxy) -3,5,5-trimethylcyclohexane, 2,5-dimethylhexane-2,5-dihydroxy Peroxide, t-butylcumyl peroxide, α, α′-bis (t-butylperoxy) -p-diisopropylbenzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne, benzoyl Peroxide, t-butyl peroxybenzene, etc. are mentioned.

  The compounding amount of the organic peroxide varies depending on the crosslinkable polymer to be used, but is usually 0.1 to 10% by weight, preferably 0.5 to 5% by weight based on 100 parts by weight of the crosslinkable polymer. . In the case of radiation crosslinking, an organic peroxide is not always necessary.

  In the present invention, for example, known polymerization inhibitors, fillers, pigments, stabilizers, lubricants, mold release agents, plasticizers, anti-aging agents, silane coupling agents, ultraviolet absorbers, flame retardants, acid acceptors, etc. Can be used.

  For example, anti-aging agents include di-t-butyl-P-cresol, pentaerythrityl-tetraxy [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2'methylenebis (2-methyl-6-tert-butylphenyl), bis (2,2,6,6-tetramethyl-4-piperazyl) sebacate, N, N′-hexane-1,6-diylbis [3- (3 5-di-tert-butyl-4-hydroxyphenyl) propionamide], bis (2,2,6,6-tetramethyl-4-piperazyl) sebacate, hydroquinone monomethyl ether, methyl hydroquinone and the like.

  Examples of the silane coupling agent include γ-chloropropyltrimethoxysilane, vinyltriethoxysilane, vinyl-tris- (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4- Ethoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane Etc.

Examples of ultraviolet absorbers include 2-hydroxy-4-n-octyloxybenzophenone, 2,2-hydroxy-4,4-dimethoxybenzophenone, 2- (2′-hydroxy-5-
Methylphenyl) benzotriazole, pt-butylphenyl salsylate, and the like.

  The ratio of the above additives is usually 10 parts by weight or less, preferably 5 parts by weight or less with respect to 100 parts by weight of the crosslinkable polymer.

  Each of the above components is mixed with a conventional kneader such as a Banbury mixer, a kneader, or an open roll to obtain a crosslinkable polymer composition.

<Method for producing polymer molded body>
The production method of the present invention is a method for producing a polymer molded body for curing a crosslinkable polymer. And the said trimethallyl isocyanurate derivative oligomer is used as a crosslinking agent. Either heat crosslinking or radiation crosslinking may be used, but heat crosslinking is preferred.

  The heat crosslinking is performed by filling a mold having a desired shape with a predetermined amount of the crosslinkable polymer composition, performing primary crosslinking by a heating process, and then performing secondary crosslinking in an oven as necessary. The shape of the mold of the molding machine can be arbitrarily selected according to the use of the polymer molded body to be obtained, such as a sheet shape, a rod shape, a ring shape, and various complicated block shapes.

  The primary crosslinking is performed, for example, by using an injection molding machine, a pressure molding machine, or the like, and usually heating at 120 ° C. to 200 ° C. for 2 to 30 minutes.

  The secondary crosslinking is performed under the conditions of 120 ° C. to 300 ° C. for 1 to 72 hours. In particular, when secondary crosslinking is performed by heating at 200 ° C. to 300 ° C. for 1 to 72 hours, a polymer molded article having good mechanical strength is obtained.

  In addition, as a radiation used for radiation bridge | crosslinking, an accelerated electron beam, an X-ray, an alpha ray, a beta ray, a gamma ray etc. can be utilized. The irradiation dose is usually 0.1 to 500 kGy although it varies depending on the crosslinkable elastomer used.

<Polymer molded product>
The polymer molded body of the present invention is a polymer molded body cured by the action of a cross-linking agent, and is formed using the trimethallyl isocyanurate derivative oligomer described above as a cross-linking agent. The manufacturing method is as described above.

  EXAMPLES Hereinafter, although this invention is demonstrated in more detail than an Example, this invention is not limited to a following example, unless the summary is exceeded.

Example 1:
<Preparation of trimethallyl isocyanurate derivative oligomer>
300 g of trimethallyl isocyanurate (Nippon Kasei Co., Ltd .: TMAIC) was collected in an open container, placed in a forced circulation oven, and heat-treated at 60 ° C. for 4 weeks to oligomerize TMAIC. The results of GPC measurement of the obtained oligomerized product under the following conditions were as follows. That is, the ratio of the oligomer (the ratio of the peak area of GPC measurement) was about 25%, and the composition included a mixture of TMAIC dimer and trimer. Incidentally, the polystyrene-equivalent number average molecular weight (Mn) is TMAIC (monomer): 547, dimer: 1094, trimer: 1641.

(GPC measurement conditions)

<Crosslinking test>
Each component shown in Table 2 was kneaded into the fluororubber at 90 ° C. at a rate shown in the same table using an open roll. Using the obtained composition as a raw material, press crosslinking (primary crosslinking) and secondary crosslinking were performed under the conditions shown in Table 2. And the mechanical characteristic of each crosslinked material was evaluated. The results are shown in Table 2. The evaluation methods used in the following examples are as described later.

(1) Rheometer measurement:
Using “FLAT DIE THEOMETER VR-310” manufactured by Tsuchishima Seisakusho, the vulcanization characteristics of the composition obtained by kneading the open roll were measured according to JIS K 6300-2 (ISO 6502).

(2) Normal strength:
Each physical property of tensile strength (MPa), 100% modulus (MPa), and elongation at break (%) was performed according to ASTM D638. Hardness (shore A) was measured in accordance with JIS K 6253 (ISO 48,7619).

(3) Evaluation by imaging IR:
Regarding the cross section of the crosslinked sample, imaging IR was measured using “Thermo Fisher 6700” manufactured by Thermo Fisher, and the presence or absence of color unevenness was determined to evaluate the uniformity of the composition. A heterogeneous composition means that TMAIC is localized.

  From the results shown in Table 2, the following is clear. That is, in terms of normal strength and crosslinking rate, Example 1 using the oligomerized product was not inferior to Comparative Example 1 using the oligomerized untreated product (TMAIC). The cross-linking performance is maintained at the same level as TMAIC. In terms of evaluation by imaging IR, Example 1 is uniform, while Comparative Example 1 is non-uniform, which is determined to be caused by localization due to TMAIC bloom. As a result, it is clear that the TMAIC oligomerized product can be used as a crosslinking agent for the crosslinkable polymer without causing bloom.

Claims (5)

It is obtained by oligomerizing a monomer of a trimethallyl isocyanurate derivative represented by the general formula (I), and has a polymerization degree of 2 to 6 determined from a number average molecular weight in terms of polystyrene measured by GPC. Trimethallyl isocyanurate derivative oligomer.

(In formula (I), each R independently represents a hydrogen atom or a methyl group.)   A crosslinking agent comprising the trimethallyl isocyanurate derivative oligomer according to claim 1 as a crosslinking component.   The crosslinkable polymer is blended with at least the trimethallyl isocyanurate derivative oligomer according to claim 1 as a crosslinker, and the ratio of the crosslinker to 100 parts by weight of the crosslinkable polymer is 0.05 to 15 parts by weight. A crosslinkable polymer composition characterized by the above.   In the manufacturing method of the polymer molded object which hardens a crosslinkable polymer, the trimethallyl isocyanurate derivative oligomer of Claim 1 is used as a crosslinking agent, The manufacturing method of the polymer molded object characterized by the above-mentioned.   A polymer molded body cured by the action of a crosslinking agent, comprising the trimethallyl isocyanurate derivative oligomer according to claim 1 as a crosslinking agent.