Triallyl isocyanurate polymer, method for producing the same, crosslinkable composition, and polymer molded article

Abstract

To provide a triallyl isocyanurate polymer having excellent crosslinking strength, a method for producing the same, a crosslinkable composition and a polymer molding.SOLUTION: A triallyl isocyanurate polymer has a mass average molecular weight (Mw) of 2000 or more in terms of polystyrene as measured by gel permeation chromatography, and has a signal (peak) observed in 4.5-5.0 ppm and 5.4-5.8 ppm in a 1H-NMR spectrum as measured at 30°C with heavy chloroform as a solvent.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a triallyl isocyanurate polymer, a method for producing the same, a crosslinkable composition, and a polymer molded article.

Background Art

[0002] Polymers of triallyl isocyanurate (hereinafter sometimes referred to as "TAIC") are widely used as crosslinking agents for crosslinkable polymers such as crosslinkable elastomers or crosslinkable thermoplastic resins, and are known to be useful for improving the heat resistance, chemical resistance, mechanical properties, etc. of these crosslinkable polymers (Patent Document 1, Patent Document 2, Patent Document 3, Patent Document 4). As a polymerization method of TAIC, a radical polymerization method is known (Patent Document 5, Patent Document 6).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Summary of the Invention

Problems to be Solved by the Invention

[0004] The TAIC polymer (for example, the TAIC prepolymer commercially available from Mitsubishi Chemical Corporation) is solid and has excellent handleability. However, when used as a crosslinking agent for a crosslinkable polymer such as ethylene vinyl acetate copolymer, there is a drawback that the crosslinking rate is slow, so that the time of the crosslinking process becomes long, and the crosslinking strength is not sufficiently high (Patent Document 4). In the crosslinking reaction of a crosslinkable polymer using a TAIC polymer, as one candidate for a means of improving the crosslinking strength, it is conceivable to synthesize a TAIC polymer having many carbon-carbon double bonds serving as reaction points of the crosslinking reaction. However, in the radical polymerization reactions described in Patent Document 5 and Patent Document 6, the polymerization reaction proceeds by the cleavage of carbon-carbon double bonds to form carbon-carbon single bonds. Therefore, a TAIC polymer in which TAIC units are bonded by carbon-carbon single bonds that do not contribute to the crosslinking reaction is obtained.

[0005] The present invention has been made to solve the above problems, and an object thereof is to provide a triallyl isocyanurate polymer in which TAIC units are bonded by carbon-carbon double bonds and which has excellent crosslinking strength, a method for producing the same, a crosslinkable composition, and a polymer molded article. [Means for Solving the Problems]

[0006] [1] A triallyl isocyanurate polymer having a polystyrene-reduced mass average molecular weight (Mw) of 2000 or more measured by gel permeation chromatography and measured at a measurement temperature of 30 ° C using deuterated chloroform as a solvent 1 In the 1H-NMR spectrum, a signal (peak) is observed at 4.5 to 5.0 ppm and 5.4 to 5.8 ppm. [2] The triallyl isocyanurate polymer according to [1], which is solid at 30 ° C. [3] A triallyl isocyanurate polymer containing a structural unit represented by the following formula (1) and having a polystyrene-reduced mass average molecular weight (Mw) of 2000 or more measured by gel permeation chromatography. However, in the formula (1), * represents a bonding point. [4] The triallyl isocyanurate polymer according to any one of [1] to [3], which has a structure represented by the following formula (2). However, in formula (2), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 each independently represents a hydrogen atom or a hydrocarbon group which may contain a hetero atom, m is an integer of 1 or more, n is an integer of 0 or more, m and n satisfy 11 ≦ m + n, and L 1 represents a tetravalent linking group containing two double bonds or a divalent linking group derived from a carbon-carbon double bond when n ≠ 0, and represents a divalent group represented by the following formula (a) when n = 0. However, in formula (a), L 2 represents a tetravalent linking group containing two double bonds or a divalent linking group derived from a carbon-carbon double bond, and R 9 and R 10 each independently represents a hydrogen atom or a hydrocarbon group which may contain a hetero atom. [5] The triallyl isocyanurate polymer represented by the following formula (2). However, in formula (2), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 each independently represents a hydrogen atom or a hydrocarbon group which may contain a hetero atom, m is an integer of 1 or more, n is an integer of 0 or more, m and n satisfy 11 ≦ m + n, and L 1 represents a tetravalent linking group containing two double bonds or a divalent linking group derived from a carbon-carbon double bond when n ≠ 0, and represents a divalent group represented by the following formula (a) when n = 0. However, in formula (a), L 2 represents a tetravalent linking group containing two double bonds or a divalent linking group derived from a carbon-carbon double bond, and R 9 and R 10 each independently represents a hydrogen atom or a hydrocarbon group which may contain a hetero atom. [6] The method for producing a triallyl isocyanurate polymer according to any one of [1] to [5], wherein the triallyl isocyanurate is polymerized by an olefin metathesis reaction. [7] A crosslinkable composition comprising the triallyl isocyanurate polymer according to any one of [1] to [5] and a crosslinkable polymer. [8] A polymer molded article obtained by crosslinking the crosslinkable composition according to [7]. [Advantages of the Invention]

[0007] According to the present invention, it is possible to provide a triallyl isocyanurate polymer excellent in crosslinking strength, a method for producing the same, a crosslinkable composition, and a polymer molded article. [Brief Description of the Drawings]

[0008]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Figure 8

Figure 9

Mode for Carrying Out the Invention

[0009] "TAIC" means triallyl isocyanurate. "TAIC polymer" means a triallyl isocyanurate polymer. In the present invention, in particular, it means a polymer of triallyl isocyanurate obtained by polymerizing triallyl isocyanurate by olefin metathesis reaction. A compound from which a structural unit of a polymer is derived is called a monomer. A numerical range represented using "~" includes the numerical values at both ends within the range. "GPC" is an abbreviation for Gel Permeation Chromatography. The mass average molecular weight (Mw) and number average molecular weight (Mn) of a compound are molecular weights in terms of standard polystyrene measured by GPC. The molecular weight of a compound having a single molecular weight and no molecular weight distribution is represented by the formula weight.

[0010] [Triallyl Isocyanurate Polymer] <First Aspect> The first aspect of the TAIC polymer of the present invention has a polystyrene-equivalent mass average molecular weight (Mw) measured by gel permeation chromatography of 2000 or more, and is measured at a measurement temperature of 30 °C using deuterated chloroform as a solvent 1 in the 1H-NMR spectrum, a TAIC polymer in which signals (peaks) are observed at 4.5 to 5.0 ppm and 5.4 to 5.8 ppm.

[0011] 《Mass Average Molecular Weight (Mw), Number Average Molecular Weight (Mn), Molecular Weight Distribution (Mw / Mn)》 The mass average molecular weight (Mw) and number average molecular weight (Mn) are values in terms of polystyrene measured by gel permeation chromatography. Details of the measurement method will be described later. The molecular weight distribution (Mw / Mn) is a value calculated from the above mass average molecular weight (Mw) and number average molecular weight (Mn).

[0012] The weight-average molecular weight (Mw) of the TAIC polymer of this embodiment is 2000 or more, preferably 3000 or more. The upper limit of the weight-average molecular weight (Mw) of the TAIC polymer of this embodiment is not particularly limited, but is preferably 1000000 or less, more preferably 100000 or less, and even more preferably 60000 or less. When the weight-average molecular weight (Mw) of the TAIC polymer of this embodiment is 2000 or more, it becomes solid at 30°C, and it is easier to mix the TAIC polymer and the resin, and further has excellent handleability. Also, when the number-average molecular weight (Mn) of the TAIC polymer of this embodiment is 1000000 or less, the synthesis is easy and it is more suitable for mass production.

[0013] The lower limit of the number-average molecular weight (Mn) of the TAIC polymer of this embodiment is not particularly limited, but is preferably 500 or more, more preferably 1000 or more. The upper limit of the number-average molecular weight (Mn) of the TAIC polymer of this embodiment is not particularly limited, but is preferably 10000 or less, more preferably 5000 or less.

[0014] The molecular weight distribution (Mw / Mn) of the TAIC polymer of this embodiment is not particularly limited, but is preferably 1.1 to 15, more preferably 1.1 to 10, and even more preferably 1.1 to 5. The closer the molecular weight distribution is to 1, the narrower the molecular weight distribution means.

[0015] (Measurement method) After collecting about 5 mg of the TAIC polymer in a glass vial, about 5 g of reagent-grade chloroform containing ethanol as a stabilizer (ethanol concentration = 0.3 to 1.0% by mass) is added and left standing overnight to prepare a sample solution with a concentration of about 0.1% by mass. The sample solution filtered through a 0.45 μm pretreatment filter (manufactured by GL Sciences Inc., Chromatodisk 13N) is subjected to GPC measurement. Next, GPC measurement is carried out using Shodex HK-404L (4.6×150 mm, 3.5 μm) manufactured by Showa Denko, Shodex HK-401 (4.6×150 mm, 3 μm), and HLC-8420GPC manufactured by Tosoh Corporation equipped with an RI detector. The measurement conditions are as follows. Sample injection volume: 20 μL Column temperature: 40 °C Elution solvent: reagent-grade chloroform Liquid feed flow rate: 0.7 mL / min The calculation of the converted average molecular weight is performed as follows. That is, commercially available monodisperse polystyrene (manufactured by Tosoh Corporation, F-128, 80, 40, 20, 10, 4, 2, 1, A-5000, 2500, 1000, 500) and dibutylhydroxytoluene (abbreviation "BHT", molecular weight 220) are used as standard samples. After creating a calibration curve regarding the retention times and molecular weights of the polystyrene standard samples and BHT, the polystyrene-converted weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of the TAIC polymer are calculated based on the calibration curve.

[0016] 《 1 1H NMR Spectrum》 In the TAIC polymer of this embodiment, measurement was carried out at a measurement temperature of 30 °C using deuterated chloroform as a solvent. 1 In the 1H-NMR spectrum, signals (peaks) are observed at 4.5 to 5.0 ppm and 5.4 to 5.8 ppm.

[0017] In the TAIC polymer of this embodiment, TAIC units are bonded to each other by a carbon-carbon double bond. That is, the TAIC polymer of this embodiment has an internal olefin. The presence of this internal olefin can be confirmed by the fact that signals (peaks) are observed at 4.5 to 5.0 ppm and 5.4 to 5.8 ppm in the 1H-NMR spectrum measured at a measurement temperature of 30 °C using deuterated chloroform as a solvent. 1 These signals are derived from the internal olefin.

[0018] The fact that TAIC units are bonded by carbon-carbon double bonds is one of the characteristics of the TAIC polymer of this embodiment. When the TAIC monomer is polymerized by radical polymerization, the carbon-carbon double bond cleaves to form a carbon-carbon single bond. However, since the TAIC polymer of this embodiment is obtained by polymerizing the TAIC monomer by olefin metathesis polymerization, as described above, the TAIC units are bonded by carbon-carbon double bonds.

[0019] (Measurement method) 1 1H NMR measurement is performed using a superconducting digital NMR apparatus (AVANCE NEO 400, manufactured by BRUKER). Deuterated chloroform is used as the solvent. The measurement temperature is set to 30 °C, and the number of integration times for the measurement is set to 16 times. The chemical shift of the signal (peak) of deuterated chloroform is set to 7.26 ppm.

[0020] 《Solid at 30 °C》 The TAIC polymer of this embodiment is preferably solid at 30 °C. When the TAIC polymer of this embodiment is solid at 30 °C, it is easier to mix the TAIC polymer and the resin, and the handleability is further excellent.

[0021] 《Structure》 The TAIC polymer of this embodiment preferably has a structure represented by formula (2).

[0022]

Chemical formula

[0023] In formula (2), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 each independently represent a hydrogen atom or a hydrocarbon group which may contain a hetero atom, m is an integer of 1 or more, n is an integer of 0 or more, and m and n satisfy 11 ≦ m + n, L 1 when n ≠ 0, represents a tetravalent linking group containing two double bonds or divalent linking groups derived from carbon-carbon double bonds, and when n = 0, represents a divalent group represented by formula (a).

[0024]

Chemical formula

[0025] 〈Second aspect〉 The second aspect of the TAIC polymer of the present invention is a TAIC polymer containing a structural unit represented by formula (1) and having a polystyrene-reduced mass average molecular weight (Mw) of 2000 or more as measured by gel permeation chromatography.

[0026] In the TAIC polymer of this aspect, TAIC monomers are bonded to each other by carbon-carbon double bonds. Therefore, it has excellent crosslinking strength.

[0027]

Chemical formula

[0028] The TAIC polymer of this aspect preferably has the structure represented by the aforementioned formula (2).

[0029] 《Mass average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution (Mw / Mn)》 The mass average molecular weight (Mw) of the TAIC polymer of this aspect is 2000 or more, and preferably 3000 or more. The upper limit of the weight average molecular weight (Mw) of the TAIC polymer of this aspect is not particularly limited, but is preferably 1,000,000 or less, more preferably 100,000 or less, and even more preferably 60,000 or less. When the weight average molecular weight (Mw) of the TAIC polymer of this aspect is 2,000 or more, it becomes solid at 30 °C, and it is easier to mix the TAIC polymer and the resin, and the handleability is further excellent. Also, when the number average molecular weight (Mn) of the TAIC polymer of this aspect is 1,000,000 or less, the synthesis is easy and it is more suitable for mass production.

[0030] The lower limit of the number average molecular weight (Mn) of the TAIC polymer of this aspect is not particularly limited, but is preferably 500 or more, and more preferably 1,000 or more. The upper limit of the number average molecular weight (Mn) of the TAIC polymer of this aspect is not particularly limited, but is preferably 10,000 or less, and more preferably 5,000 or less.

[0031] The molecular weight distribution (Mw / Mn) of the TAIC polymer of this aspect is not particularly limited, but is preferably 1.1 to 15, more preferably 1.1 to 10, and even more preferably 1.1 to 5. The closer the molecular weight distribution is to 1, the narrower the molecular weight distribution means.

[0032] (Measurement method) The measurement methods of the weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of the TAIC polymer of this aspect are the same as those in the first aspect described above.

[0033] 《1H NMR spectrum》 In the TAIC polymer of this aspect, measured at a measurement temperature of 30 °C using deuterated chloroform as a solvent 1 In the 1H-NMR spectrum, it is preferable that signals (peaks) are observed at 4.5 to 5.0 ppm and 5.4 to 5.8 ppm. These signals are derived from internal olefins.

[0034] (Measurement method) Of the TAIC polymer of this aspect 1The measurement method of 1H NMR is the same as that in the first aspect described above.

[0035] 《Solid at 30 °C》 The TAIC polymer of this aspect is preferably solid at 30 °C. When the TAIC polymer of this aspect is solid at 30 °C, the TAIC polymer and the resin are more easily mixed and the handleability is further excellent.

[0036] 〈Third Aspect〉 The third aspect of the TAIC polymer of the present invention is the TAIC polymer represented by the above formula (2).

[0037] In the TAIC polymer of this aspect, TAIC monomers are bonded to each other by a carbon-carbon double bond. Therefore, it has excellent crosslinking strength.

[0038] 《Weight-average molecular weight (Mw), number-average molecular weight (Mn), molecular weight distribution (Mw / Mn)》 The weight-average molecular weight (Mw) of the TAIC polymer of this aspect is preferably 2000 or more, more preferably 3000 or more. The upper limit of the weight-average molecular weight (Mw) of the TAIC polymer of this aspect is not particularly limited, but is preferably 1000000 or less, more preferably 100000 or less, and even more preferably 60000 or less. When the weight-average molecular weight (Mw) of the TAIC polymer of this aspect is 2000 or more, it becomes solid at 30 °C, the TAIC polymer and the resin are more easily mixed, and the handleability is further excellent. Also, when the number-average molecular weight (Mn) of the TAIC polymer of this aspect is 1000000 or less, the synthesis is easy and it is more suitable for mass production.

[0039] The lower limit of the number-average molecular weight (Mn) of the TAIC polymer of this aspect is not particularly limited, but is preferably 500 or more, more preferably 1000 or more. The upper limit of the number-average molecular weight (Mn) of the TAIC polymer of this aspect is not particularly limited, but is preferably 10000 or less, more preferably 5000 or less.

[0040] Although the molecular weight distribution (Mw / Mn) of the TAIC polymer of this embodiment is not particularly limited, it is preferably from 1.1 to 15, more preferably from 1.1 to 10, and even more preferably from 1.1 to 5. The closer the molecular weight distribution is to 1, the narrower the molecular weight distribution means.

[0041] (Measurement method) The measurement methods for the weight-average molecular weight (Mw), number-average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of the TAIC polymer of this embodiment are the same as those in the first embodiment described above.

[0042] 《1H NMR spectrum》 In the TAIC polymer of this embodiment, measured at a measurement temperature of 30 °C using deuterated chloroform as a solvent 1 In the 1H-NMR spectrum, it is preferable that signals (peaks) are observed at 4.5 to 5.0 ppm and 5.4 to 5.8 ppm. These signals are derived from internal olefins.

[0043] (Measurement method) For the TAIC polymer of this embodiment 1 The measurement method of 1H NMR is the same as that in the first embodiment described above.

[0044] 《Solid at 30 °C》 The TAIC polymer of this embodiment is preferably solid at 30 °C. When the TAIC polymer of this embodiment is solid at 30 °C, it is easier to mix the TAIC polymer and the resin, and further has excellent handleability.

[0045] [Production method of triallyl isocyanurate polymer] The production method of the TAIC polymer of the present invention is characterized by polymerizing a TAIC monomer by an olefin metathesis reaction.

[0046] The olefin metathesis reaction is a catalytic reaction in which recombination of bonds occurs between two types of olefins. In the method for producing the TAIC polymer of the present invention, allyl groups react between TAIC monomers to newly form a carbon-carbon double bond and one molecule of ethylene is eliminated. In the polymerization of TAIC monomers by the olefin metathesis reaction, one carbon-carbon double bond is formed from two carbon-carbon double bonds. In this regard, it is different from radical polymerization in which a carbon-carbon double bond is cleaved to form a carbon-carbon single bond.

[0047] That the TAIC units are bonded by a carbon-carbon double bond means, in other words, that the TAIC polymer of the present invention has an internal olefin. The presence of this internal olefin can be observed using a nuclear magnetic resonance apparatus. Specifically, in the 1H-NMR spectrum measured using deuterated chloroform as a solvent, signals (peaks) derived from the internal olefin are observed at 4.5 to 5.0 ppm and 5.4 to 5.8 ppm.

[0048] Examples of the catalyst used in the olefin metathesis reaction include compounds of transition metal elements such as molybdenum or tungsten (Schrock, R. R., Hoveyda, A. H., Molybdenum and Tungsten Imido Alkylidene Complexes as Efficient Olefin‐Metathesis Catalysts, Angewandte Chemie International Edition, Vol. 42, No. 38, October 1, 2003, P. 4592-4633). In addition, polymerization catalysts obtained by reacting metal halides such as tungsten hexachloride, molybdenum pentachloride, tungsten oxytetrachloride or molybdenum oxytetrachloride with an organotin compound or an organoaluminum compound can also be used (Ivin, K. J., Mol, J. C., Olefin Metathesis and Metathesis Polymerization, Academic Pres, San Diego, CA, 1997). Further, transition metal compounds of ruthenium can also be used (Ogba, O. M., Warner, N. C., O’Leary, D. J., Grubbs, R. H., Recent advances in ruthenium-based olefin metathesis, Chemical Society Reviews, Vol. 47, No. 12, May 1, 2018, p. 4510-4544). Among them, compounds of molybdenum or tungsten are preferred, imido complexes or oxo complexes of molybdenum or tungsten are more preferred, imido complexes of molybdenum or tungsten are more preferred, and complexes described by the chemical formula M(NAr)(CHR 11 )(OR 12 )2 are more preferred. In this chemical formula, M represents molybdenum or tungsten, Ar represents an aryl group which may have a substituent, and R 11 and R 12 each independently represent a hydrocarbon group which may contain a heteroatom.

[0049] In carrying out the polymerization reaction, a vinyl compound or a diene compound may be added to the polymerization system in order to adjust the molecular weight of the resulting TAIC polymer. The vinyl compound is not particularly limited as long as it is an organic compound having a vinyl group, and examples thereof include 1-butene, 1-pentene, 1-hexene, 1-octene, styrene, and the like. The diene compound is not particularly limited as long as it is an organic compound having two double bonds, and examples thereof include 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,6-heptadiene, 2-methyl-1,4-pentadiene, 2,5-dimethyl-1,5-hexadiene, 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, and the like.

[0050] The production of the TAIC polymer of the present invention is preferably carried out by dissolving the TAIC monomer as a raw material in a solvent and stirring while heating in the presence of a catalyst. The temperature during heating is not particularly limited as long as it is lower than the boiling point of the solvent, but in order to improve the reaction rate, it is preferably 30°C or higher, more preferably 35°C or higher. For example, when toluene is used as the solvent, it is preferably about 110°C or lower, which is the boiling point of toluene under 1013 hPa. The intensity and time of stirring are not particularly limited. It is preferable to stir so that the formation of the TAIC polymer proceeds sufficiently. For example, the stirring time may be in the range of 10 minutes to 8 hours.

[0051] The solvent is not particularly limited as long as it can dissolve or disperse the TAIC monomer, but because of its low cost and good availability, examples thereof include toluene, hexane, dichloromethane, chloroform, and tetrahydrofuran.

[0052] [Crosslinkable Composition] The crosslinkable composition of the present invention contains the above-described TAIC polymer and a crosslinkable polymer. Examples of the crosslinkable polymer include polymers that were conventionally crosslinked with TAIC. Examples of the crosslinkable polymer include epoxy resins, phenolic resins, polyester resins, unsaturated polyester resins, polyamide resins, polyether ketone resins, polyether ether ketone resins, polyether ketone ketone resins, polyether ether ketone resins, polyphenylene ether resins, modified polyphenylene ether resins, vinyl chloride resins, polyolefin resins, acrylic resins, polystyrene resins, polycarbonate resins, polyacetal resins, fluororesins, ethylene vinyl acetate copolymer resins, and the like. The crosslinkable composition of the present invention may further contain a crosslinking aid, a reaction initiator, a filler, and the like. Examples of the crosslinking aid include TAIC, TAIC derivatives, trimethallyl isocyanurate, trimethallyl isocyanurate derivatives, triallyl cyanurate, triallyl cyanurate derivatives, and the like. Examples of the reaction initiator include di-t-butyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, t-butyl peroxy-(2-ethylhexyl) carbonate, 1,1-bis(t-butylperoxy)-3,5,5-trimethylcyclohexane, 2,5-dimethylhexane-2,5-dihydroxyperoxide, t-butyl α-cumyl peroxide, 1,3-bis(t-butylperoxyisopropyl)benzene, 1,4-bis(t-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne, benzoyl peroxide, t-butyl peroxybenzene, and the like. Examples of the filler include silica, carbon black, calcium carbonate, aluminum hydroxide, aluminum borate, zinc oxide, clay, barium sulfate, mica, talc, titanium oxide, alumina, glass fiber, and the like.

[0053] [Polymer Molded Body] The polymer molded body of the present invention is obtained by crosslinking the above-described crosslinkable composition. The crosslinking of the crosslinkable composition of the present invention can be carried out, for example, by heating. Examples of the crosslinking conditions include a method of heating at 100 to 200 °C for 1 to 30 minutes and then heating at 120 to 300 °C for 1 to 72 hours.

Example

[0054] Hereinafter, the present invention will be described more specifically by way of examples. However, the present invention is not limited to the examples described below, and various modifications are possible without departing from the gist of the present invention. Hereinafter, the isopropyl group (propan-2-yl group) may be denoted as "iPr" and the methyl group may be denoted as "Me".

[0055] [Measurement method and test method] 〈Mass average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn)〉 After collecting about 5 mg of the TAIC polymer in a glass vial, about 5 g of reagent-grade chloroform containing ethanol as a stabilizer (ethanol concentration = 0.3 to 1.0% by mass) was added and allowed to stand overnight to prepare a sample solution with a concentration of about 0.1% by mass. The obtained sample solution was filtered through a 0.45 μm pretreatment filter (manufactured by GL Sciences Inc., Chromatodisk 13N) and subjected to GPC measurement. Next, GPC measurement was performed using Shodex HK-404L (4.6 × 150 mm, 3.5 μm) and Shodex HK-401 (4.6 × 150 mm, 3 μm) manufactured by Showa Denko as columns and HLC-8420GPC manufactured by Tosoh Corporation equipped with an RI detector. The measurement conditions were as follows. Sample injection volume: 20 μL Column temperature: 40 °C Elution solvent: Reagent-grade chloroform Liquid feed flow rate: 0.7 mL / min The conversion average molecular weight was calculated as follows. That is, commercially available monodisperse polystyrene (manufactured by Tosoh Corporation, F-128, 80, 40, 20, 10, 4, 2, 1, A-5000, 2500, 1000, 500) and BHT (molecular weight 220) were used as standard samples. After creating a calibration curve regarding the retention time and molecular weight of the polystyrene standard sample and BHT, the polystyrene-reduced weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of the TAIC polymer were calculated based on the calibration curve.

[0056] 〈 1 1H NMR〉 1 1H NMR measurement was performed using a superconducting digital NMR apparatus (AVANCE NEO 400, manufactured by BRUKER). Deuterated chloroform was used as the solvent. The measurement temperature was set at 30 °C, and the number of integration times for the measurement was 16 times. The chemical shift of the signal (peak) of deuterated chloroform was set at 7.26 ppm.

[0057] 〈Crosslinking test〉 100 parts by weight of ethylene vinyl acetate copolymer (EVA; vinyl acetate content 28% by weight), 1 part by weight of Perbutyl E (manufactured by NOF Corporation), and 1 part by weight of TAIC polymer or TAIC prepolymer were kneaded at 70 °C using an open roll to obtain a composition. The torque of the obtained composition was measured using a curastometer set at a temperature of 150 °C by reading the value over 30 minutes. The torque value 5 minutes after the start of the measurement was defined as the "torque after 5 minutes", and the value of 90% of the maximum torque value was defined as the "torque at 90% crosslinking".

[0058] [Example 1] 〈Synthesis of TAIC polymer〉 Mo(N-2,6-iPr2C6H3)(CHCMe2Ph)(OCMe(CF3)2)2 (47.1 mg, 0.0615 mmol) was weighed into a two-necked eggplant flask, and toluene (3 mL) was added to prepare a catalyst solution. TAIC (36.8 g, 148 mmol) was weighed into another two-necked eggplant flask. After adding toluene (5 mL), tri-n-octylaluminum (0.070 mmol) was added and stirred to prepare a raw material solution. The catalyst solution was added to the raw material solution, and the mixture was stirred at 40 °C for 3 hours. After stirring, benzaldehyde was added to the reaction solution to terminate the reaction. After the reaction was terminated, the reaction solution was added to methanol to precipitate the polymer. After filtration, it was dried under reduced pressure at 50 °C for 5 hours to obtain 27.8 g of a TAIC polymer (hereinafter referred to as "TAIC polymer 1") as a white solid. 〈Measurement and Test〉 The weight-average molecular weight (Mw), number-average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of the synthesized TAIC polymer 1 were measured, and a cross-linking test was conducted. The measurement results and test results are shown in Table 1. Also, 1 The results (spectrum) of 1H NMR measurement are shown in Figure 1.

[0059] [Example 2] 〈Synthesis of TAIC Polymer〉 Mo(N-2,6-iPr2C6H3)(CHCMe2Ph)(OCMe(CF3)2)2 (17.1 mg, 0.0223 mmol) was weighed into a two-necked eggplant flask, and toluene (3 mL) was added to prepare a catalyst solution. TAIC (10.8 g, 43.1 mmol) was weighed into another two-necked eggplant flask. After adding toluene (1 mL), tri-n-octylaluminum (0.020 mmol) was added and stirred to prepare a raw material solution. The catalyst solution was added to the raw material solution, and the mixture was stirred at 40 °C for 90 minutes. After stirring, benzaldehyde was added to the reaction solution to terminate the reaction. After the reaction was terminated, the reaction solution was added to methanol to precipitate the polymer. After filtration, it was dried under reduced pressure at 50 °C for 2 hours to obtain 8.76 g of a TAIC polymer (hereinafter referred to as "TAIC polymer 2") as a white solid. 〈Measurement and Test〉 The weight-average molecular weight (Mw), number-average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of the synthesized TAIC polymer 2 were measured, and a cross-linking test was conducted. The measurement results and test results are shown in Table 1. Also, 1 The results (spectra) of 1H NMR measurement are shown in Figure 2.

[0060] [Example 3] 〈Synthesis of TAIC Polymer〉 Mo(N-2,6-iPr2C6H3)(CHCMe2Ph)(OCMe(CF3)2)2 (103 mg, 0.135 mmol) was weighed into a two-necked eggplant flask, and toluene (3 mL) was added to prepare a catalyst solution. TAIC (33.6 g, 135 mmol) was weighed into another two-necked flask, toluene (5 mL) was added, and then tri-n-octylaluminum (0.070 mmol) was added and stirred to prepare a raw material solution. The catalyst solution was added to the raw material solution, and the mixture was stirred at 40 °C for 50 minutes. After stirring, benzaldehyde was added to the reaction solution to stop the reaction. After the reaction was stopped, the reaction solution was added to methanol to precipitate the polymer. After filtration, it was dried under reduced pressure at 50 °C for 5 hours to obtain 24.7 g of TAIC polymer (hereinafter referred to as "TAIC polymer 3") as a white solid. 〈Measurement and Test〉 The weight-average molecular weight (Mw), measurement results, and test results of the synthesized TAIC polymer 3 are shown in Table 1. Also, 1 The results (spectra) of 1H NMR measurement are shown in Figure 3.

[0061] [Example 4] 〈Synthesis of TAIC Polymer〉 Mo(N-2,6-iPr2C6H3)(CHCMe2Ph)(OCMe(CF3)2)2 (21.0 mg, 0.0274 mmol) was weighed into a two-necked eggplant flask, and toluene (3 mL) was added to prepare a catalyst solution. TAIC (11.4 g, 45.7 mmol) was weighed into another two-necked eggplant flask. After adding toluene (5 mL), tri-n-octylaluminum (0.020 mmol) was added and stirred to prepare a raw material solution. The catalyst solution was added to the raw material solution, and the mixture was stirred at 40 °C for 2.5 hours. After stirring, benzaldehyde was added to the reaction solution to terminate the reaction. After the reaction was terminated, the reaction solution was added to methanol to precipitate the polymer. After filtration, it was dried under reduced pressure at 50 °C for 2 hours to obtain 9.26 g of a TAIC polymer (hereinafter referred to as "TAIC polymer 4") as a white solid. <Measurement and Test> The weight-average molecular weight (Mw), number-average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of the synthesized TAIC polymer 4 were measured, and a cross-linking test was conducted. The measurement results and test results are shown in Table 1. Also, 1 The results (spectra) of 1H NMR measurement are shown in Figure 4.

[0062] [Example 5] <Synthesis of TAIC Polymer> Mo(N-2,6-iPr2C6H3)(CHCMe2Ph)(OCMe(CF3)2)2 (20.5 mg, 0.0268 mmol) was weighed into a two-necked eggplant flask, and toluene (3 mL) was added to prepare a catalyst solution. TAIC (11.0 g, 44.1 mmol) was weighed into another two-necked eggplant flask. After adding toluene (15 mL), tri-n-octylaluminum (0.020 mmol) was added and stirred to prepare a raw material solution. The catalyst solution was added to the raw material solution, and the mixture was stirred at 40 °C for 1 hour. After stirring, benzaldehyde was added to the reaction solution to terminate the reaction. After the reaction was terminated, the reaction solution was added to methanol to precipitate the polymer. After filtration, it was dried under reduced pressure at 50 °C for 2 hours to obtain 9.59 g of a TAIC polymer (hereinafter referred to as "TAIC polymer 5") as a white solid. <Measurement and Test> The weight-average molecular weight (Mw), number-average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of the synthesized TAIC polymer 5 were measured, and a cross-linking test was conducted. The measurement results and test results are shown in Table 1. Also, 1 The results (spectra) of 1H NMR measurement are shown in Figure 5.

[0063] [Example 6] 〈Synthesis of TAIC Polymer〉 Mo(N-2,6-iPr2C6H3)(CHCMe2Ph)(OCMe(CF3)2)2 (15.8 mg, 0.0206 mmol) was weighed into a two-necked eggplant flask, and toluene (3 mL) was added to prepare a catalyst solution. TAIC (10.4 g, 41.7 mmol) was weighed into another two-necked eggplant flask, toluene (5 mL) was added, and then tri-n-octylaluminum (0.020 mmol) was added and stirred to prepare a raw material solution. The catalyst solution was added to the raw material solution, and the mixture was stirred at 40 °C for 3 hours. After stirring, benzaldehyde was added to the reaction solution to stop the reaction. After the reaction was stopped, the reaction solution was added to methanol to precipitate the polymer. After filtration, it was dried under reduced pressure at 50 °C for 2 hours to obtain 9.42 g of TAIC polymer (hereinafter referred to as "TAIC polymer 6") as a white solid. 〈Measurement and Test〉 A cross-linking test of the synthesized TAIC polymer 6 was conducted. The results are shown in Table 1. Also, 1 The results (spectra) of 1H NMR measurement are shown in Figure 6. Since TAIC polymer 7 did not dissolve in chloroform, the measurement of the weight-average molecular weight (Mw), number-average molecular weight (Mn), and molecular weight distribution (Mw / Mn) by the above-described measurement method could not be carried out. However, regarding the weight-average molecular weight (Mw), since the weight-average molecular weight (Mw) of TAIC polymer 5 in Example 5 was 60,000, it is obvious that it exceeds that.

[0064] [Example 7] 〈Synthesis of TAIC Polymer〉 Mo(N-2,6-iPr2C6H3)(CHCMe2Ph)(OCMe(CF3)2)2 (85.0 mg, 0.111 mmol) was weighed into a two-necked eggplant flask, and toluene (3 mL) was added to prepare a catalyst solution. TAIC (27.8 g, 112 mmol) was weighed into another two-necked eggplant flask, toluene (5 mL) was added, and then tri-n-octylaluminum (0.070 mmol) was added and stirred to prepare a raw material solution. The catalyst solution was added to the raw material solution, and the mixture was stirred at 40 °C for 3 hours. After stirring, benzaldehyde was added to the reaction solution to stop the reaction. After the reaction was stopped, drying under reduced pressure was carried out at 50 °C for 5 hours to obtain 27.1 g of a TAIC polymer (hereinafter referred to as "TAIC polymer 7") as a yellow solid. <Measurement and Test> A cross-linking test of the synthesized TAIC polymer 7 was carried out. The results are shown in Table 1. Also, 1 The results (spectra) of 1H NMR measurement are shown in Figure 7. Since TAIC polymer 7 was insoluble in chloroform, the measurement of the weight-average molecular weight (Mw), number-average molecular weight (Mn), and molecular weight distribution (Mw / Mn) by the above-described measurement method could not be carried out. However, regarding the weight-average molecular weight (Mw), since the weight-average molecular weight (Mw) of TAIC polymer 5 in Example 5 was 60,000, it is obvious that it exceeds that.

[0065] [Comparative Example 1] <Synthesis of TAIC Polymer> Mo(N-2,6-iPr2C6H3)(CHCMe2Ph)(OCMe(CF3)2)2 (59.4 mg, 0.0776 mmol) was weighed into a two-necked eggplant flask, and toluene (3 mL) was added to prepare a catalyst solution. TAIC (35.9 g, 144 mmol) was weighed into another two-necked eggplant flask, toluene (5 mL) was added, and then tri-n-octylaluminum (0.070 mmol) was added and stirred to prepare a raw material solution. The catalyst solution was added to the raw material solution, and the mixture was stirred at 40 °C for 40 minutes. After stirring, benzaldehyde was added to the reaction solution to terminate the reaction. After termination of the reaction, toluene was distilled off under reduced pressure from the reaction vessel to obtain 29.5 g of a TAIC polymer (hereinafter referred to as "TAIC polymer 8") as a pale yellow viscous liquid. <Measurement and Test> The weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of the synthesized TAIC polymer 8 were measured, and a crosslinking test was conducted. The measurement results and test results are shown in Table 2. Also, 1 The results (spectrum) of 1H NMR measurement are shown in Fig. 8.

[0066] [Comparative Example 2] Using a TAIC prepolymer (Lot No. 19090404) commercially available from Mitsubishi Chemical Corporation, the weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) were measured by the above-described measurement method, and a crosslinking test was conducted by the above-described test method. The measurement results and test results are shown in Table 2. Also, 1 The results (spectrum) of 1H NMR measurement are shown in Fig. 9.

[0067] [Table 1]

[0068] [Table 2]

[0069] [Explanation of Results] In Examples 1 to 7, since the torque value after 5 minutes was larger compared to Comparative Example 2, it was shown that the TAIC polymer of the present invention has a faster crosslinking rate than the conventional TAIC polymer. In Examples 1 to 7, since the torque value at 90% crosslinking was larger compared to Comparative Example 2, it was shown that the TAIC polymer of the present invention is superior in crosslinking strength to the conventional TAIC polymer. Different from Comparative Example 1 in which the TAIC polymer is a liquid, the TAIC polymers used in Examples 1 to 7 are solid, similar to the conventional TAIC polymer, and have excellent handleability.

Industrial Applicability

[0070] The TAIC polymer of the present invention is superior to conventional TAIC polymers in terms of crosslinking speed and crosslinking strength. Furthermore, like conventional TAIC polymers, it is in a solid state and has excellent handleability, so it can be used in place of conventional TAIC polymers.

Claims

1. A triallyl isocyanurate polymer having a polystyrene-reduced weight average molecular weight (Mw) of 2000 or more as measured by gel permeation chromatography and measured at a measurement temperature of 30 ° C. using deuterated chloroform as a solvent. １ In the 1H-NMR spectrum, signals (peaks) are observed at 4.5 to 5.0 ppm and 5.4 to 5.8 ppm, and having a structure represented by the following formula (2). 【Chemical Formula 1】 In formula (2), R1, R2, R3, R4, R5, R6, R7 and R8 each independently represent a hydrogen atom or a hydrocarbon group which may contain a hetero atom, m is an integer of 1 or more, n is an integer of 0 or more, and m and n satisfy 11 ≦ m + n, L1 represents a tetravalent linking group containing two double bonds or a divalent linking group derived from a carbon-carbon double bond when n ≠ 0, and represents a divalent group represented by formula (a) when n = 0. 【Chemical Formula 2】 In formula (a), L2 represents a tetravalent linking group containing two double bonds or a divalent linking group derived from a carbon-carbon double bond, and R9 and R10 each independently represent a hydrogen atom or a hydrocarbon group which may contain a hetero atom.

2. A triallyl isocyanurate polymer having a structure represented by the following formula (2) and having a polystyrene-reduced weight average molecular weight (Mw) of 2000 or more as measured by gel permeation chromatography. 【Chemical Formula 3】 In formula (2), R1, R2, R3, R4, R5, R6, R7 and R8 each independently represent a hydrogen atom or a hydrocarbon group which may contain a hetero atom, m is an integer of 1 or more, n is an integer of 0 or more, and m and n satisfy 11 ≦ m + n, When n≠0, L1 represents a tetravalent linking group containing two double bonds or divalent linking groups derived from carbon-carbon double bonds. When n = 0, L1 represents a divalent group represented by formula (a). 【Chemical Formula 4】 In formula (a), L2 represents a tetravalent linking group containing two double bonds or divalent linking groups derived from carbon-carbon double bonds, and R9 and R10 each independently represent a hydrogen atom or a hydrocarbon group which may contain a hetero atom.

3. The triallyl isocyanurate polymer according to claim 1 or 2, which is solid at 30°C.

4. A method for producing a triallyl isocyanurate polymer according to any one of claims 1 to 3, by polymerizing triallyl isocyanurate by olefin metathesis reaction.

5. A crosslinkable composition comprising the triallyl isocyanurate polymer according to any one of claims 1 to 3 and a crosslinkable polymer.

6. A polymer molded article obtained by crosslinking the crosslinkable composition according to claim 5.

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