JP2012021129A - Method for producing polyisocyanurate compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide method for producing a polyisocyanurate compound having outstanding thermal stability, in which the residual ratio of an isocyanate group is low.SOLUTION: The method for producing a polyisocyanurate compound having a structural unit represented by formula (2) (in formula, * represents a bond, and Rrepresents a divalent 1-20C organic group) includes a step to polymerize a compound represented by general formula OCN-R-NCO (in formula, Ris synonymous with that described above) in the presence of an oxygen-containing solvent.

Description

  The present invention relates to a method for producing a polyisocyanurate compound by polymerizing a diisocyanate compound.

  Polyisocyanurate compounds are used as raw materials for films, paints, adhesives, elastomers, artificial leather, foams, etc. for the purpose of improving heat insulation, weather resistance, abrasion resistance, heat resistance, chemical resistance, etc. .

  Further, it is known that the polyisocyanurate compound can be produced in one pot via isocyanurate by polymerizing a diisocyanate compound. As a method for producing such a polyisocyanurate compound, for example, in order to improve heat resistance, chemical resistance and hardness, the alicyclic diisocyanate compound is self-crosslinked to a residual NCO group amount of 13% by weight or less. A method (Patent Document 1) and a method of reacting in an N, N′-dimethylformaldehyde (DMF) solvent in the presence of a nitrogen-containing heterocyclic carbene (Non-Patent Document 1) have been reported.

JP 2001-98042 A

Chem. Eur. J. 2009, 15, 1077-1081

However, the polyisocyanurate compounds obtained by the conventional production methods have a high residual ratio of isocyanate groups in the polyisocyanurate skeleton, and are not satisfactory in terms of thermal stability.
Accordingly, an object of the present invention is to provide a method for producing a polyisocyanurate compound having a low residual ratio of isocyanate groups and having excellent thermal stability.

In the above Patent Document 1, when a polyisocyanurate compound is synthesized by self-crosslinking a diisocyanate compound, if a solvent is present, the remaining solvent affects the physical properties of the polyisocyanurate compound. It is stated not to.
However, as a result of intensive studies to solve the above problems, the present inventors polymerized the diisocyanate compound in the presence of a specific solvent, so that the residual ratio of the isocyanate group is low and has excellent thermal stability. It has been found that a polyisocyanurate compound can be obtained.

  That is, 1) The present invention provides the following formula (1)

(In the formula, R ¹ represents a divalent organic group having 1 to 20 carbon atoms.)
Wherein the compound represented by formula (hereinafter also referred to as compound (1)) is polymerized in the presence of an oxygen-containing solvent.

(In the formula, * represents a bond, and R ¹ has the same meaning as described above.)
The manufacturing method of the polyisocyanurate compound (henceforth a compound (2)) which has a structural unit represented by these is provided.

  2) The present invention provides the above compound (1) and the following formula (3):

(In the formula, R ² represents an organic group having 1 to 20 carbon atoms.)
And a compound represented by the following formula (4), wherein the compound is polymerized in the presence of an oxygen-containing solvent:

(In the formula, R ¹ , R ² and * are as defined above.)
The manufacturing method of the polyisocyanurate compound (henceforth a compound (4)) which has a structural unit represented by these is provided.

  Furthermore, the present invention provides a polyisocyanurate compound having a structural unit represented by the above formula (2) and having a 5% weight reduction temperature of 380 ° C. or higher and a 10% weight reduction temperature of 395 ° C. or higher. To do.

  Furthermore, 4) this invention provides the film formed by containing the compound as described in said 3).

  According to the production method of the present invention, a transparent polyisocyanurate compound having a low residual ratio of isocyanate groups in the molecule and having both excellent thermal stability and excellent flexibility can be produced easily and efficiently.

It is a figure which shows the IR spectrum measurement result of the hardened | cured material 1. FIG. It is a figure which shows the result of TGA of the hardened | cured material 1. It is a figure which shows the result of DSC of hardened | cured material 1. It is a figure which shows the IR spectrum measurement result of hardened | cured material 2. FIG. It is a figure which shows the result of TGA of the hardened | cured material 2. It is a figure which shows the result of DSC of hardened | cured material 2. It is a figure which shows the IR spectrum measurement result of hardened | cured material 3-7. It is a figure which shows the result of TGA of hardened | cured material 3-7. It is a figure which shows the result of DSC of hardened | cured material 3-7. It is a figure which shows the IR spectrum measurement result of hardened | cured material 8-10. It is a figure which shows the result of TGA of hardened | cured material 8-10. It is a figure which shows the result of DSC of hardened | cured material 8-10.

First, definitions of symbols used in this specification will be described.
R ¹ is a divalent organic group having 1 to 20 carbon atoms. Here, the “divalent organic group” is a divalent hydrocarbon group, a divalent heterocyclic group, or a divalent group in which two or more groups selected from these are bonded directly or via a hetero atom as a spacer. It is a concept including the group of The divalent organic group having 1 to 20 carbon atoms is preferably a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. The “divalent hydrocarbon group having 1 to 20 carbon atoms” is preferably a divalent hydrocarbon group having 1 to 16 carbon atoms from the viewpoint of thermal stability, transparency, and reaction efficiency. 14 divalent hydrocarbon groups are more preferable, and divalent hydrocarbon groups having 5 to 14 carbon atoms are particularly preferable.
Here, the “divalent hydrocarbon group” includes a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, a divalent aromatic hydrocarbon group, and two or more selected from these. Although it is a concept including a bonded divalent hydrocarbon group, a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group are preferred from the viewpoint of thermal stability, transparency, and reaction efficiency. The divalent hydrocarbon group may have an unsaturated bond in the molecule.

  Although the carbon number of the said bivalent aliphatic hydrocarbon group is 1-20, 1-16 are preferable from the point of thermal stability, transparency, and reaction efficiency, 1-14 are more preferable, and 1-12 are More preferably, 5-12 are especially preferable. The divalent aliphatic hydrocarbon group may be linear or branched. Specific examples include a methylene group, an alkylene group, an alkenylene group, and an alkynylene group, and a methylene group and an alkylene group are preferable from the viewpoint of thermal stability, transparency, and reaction efficiency. Examples of the alkylene group include ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, 2,2,4-trimethylhexamethylene group, 2, Examples include 4,4-trimethylhexamethylene group, decamethylene group, undecamethylene group, dodecamethylene group and the like. Among these, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, 2,2,4-trimethylhexamethylene group, 2,4,4-trimethylhexamethylene group, decamethylene group, undecamethylene group Group, dodecamethylene group is preferable.

Moreover, although carbon number of the said bivalent alicyclic hydrocarbon group is 3-20, 3-12 are preferable and 3-8 are more preferable. Specifically, a cycloalkylene group such as a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, and a cyclohexylene group; a cycloalkenylene group such as a cyclobutenylene group, a cyclopentenylene group, and a cyclohexenylene group; xylene - methylene - cyclohexylene -, a group represented by - cyclohexylene - ethylene - cyclohexylene - -C ₃ ~ ₇ of groups represented by cycloalkylene -C ₁ ~ ₆ alkylene -C ₃ ~ ₇ And a group represented by cycloalkylene-. The binding site of the alicyclic hydrocarbon group may be on any carbon on the alicyclic ring.

  As carbon number of the said bivalent aromatic hydrocarbon group, 6-18 are preferable from the point of thermal stability, transparency, and reaction efficiency, and 6-14 are more preferable. Specifically, arylene groups such as a phenylene group, a biphenylene group, a naphthylene group, a phenanthrene group, an anthrylene group; the following formula (5)

(In the formula, R ³ represents a divalent hydrocarbon group having 1 to 6 carbon atoms.)
The group represented by these is mentioned. Among these, a group represented by the formula (5) is preferable from the viewpoint of thermal stability, transparency, and reaction efficiency. The binding site of the aromatic hydrocarbon group may be on any carbon on the aromatic ring, but the 4-position and 4'-position are preferred.

Examples of the divalent hydrocarbon group having 1 to 6 carbon atoms represented by R ³ include those similar to the divalent hydrocarbon group in R ¹ , but the points of thermal stability, transparency, and reaction efficiency. Therefore, a C1-C6 bivalent aliphatic hydrocarbon group is preferable, a methylene group and a C2-C6 alkylene group are more preferable, and a methylene group and a C2-C3 alkylene group are especially preferable.

The divalent hydrocarbon group is a divalent carbon in which two or more selected from a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, and a divalent aromatic hydrocarbon group are bonded. including but hydrogen group, as a preferred embodiment, -C ₁ ~ ₆ alkylene -C ₃ ~ ₇ cycloalkylene -C ₁ ~ ₆ alkylene -, a group represented by, -C ₁ ~ ₆ alkylene - phenylene -C _1-6 alkylene - in include groups represented, -C ₁ ~ ₃ alkylene -C ₃ ~ ₇ cycloalkylene -C ₁ ~ ₃ alkylene -, a group represented by, -C ₁ ~ ₃ alkylene - phenylene -C A group represented by ₁ to ₃ alkylene- is preferred.

  Examples of the group that can be substituted with the divalent hydrocarbon group having 1 to 20 carbon atoms include, for example, an alkoxy group having 1 to 12 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a cyclohexyloxy group; Group, ethyl group, n-propyl group, isopropyl group and other alkyl groups having 1 to 3 carbon atoms; halogen atoms such as fluorine, chlorine, bromine and iodine; cyano group; amino group; oxo group; tert-butylcarbonyl group and the like An alkanoyl group having 2 to 10 carbon atoms; an alkoxycarbonyl group such as a methoxycarbonyl group and an ethoxycarbonyl group; The position and number of these substituents are arbitrary, and when having two or more substituents, the substituents may be the same or different.

R ² represents an organic group having 1 to 20 carbon atoms. The “organic group” is a concept including a hydrocarbon group, a heterocyclic group and the like. Moreover, as a C1-C20 organic group, the C1-C20 hydrocarbon group which may have a substituent is preferable. Here, the “hydrocarbon group” is a concept including an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group, but from the viewpoint of thermal stability, transparency, and reaction efficiency, An aliphatic hydrocarbon group and an aromatic hydrocarbon group are preferable. Among these, an aromatic hydrocarbon group is particularly preferable from the viewpoint of thermal stability, flexibility, and chemical resistance. Note that the hydrocarbon group may have an unsaturated bond in the molecule.

Examples of the aliphatic hydrocarbon group include an alkyl group and an allyl group. Although the carbon number of the said alkyl group is 1-20, 3-18 are preferable from the volatility point of a compound (3), and 3-10 are more preferable. In addition, it is estimated that the ratio which occupies the whole network polymer of isocyanurate becomes high by making carbon number of an alkyl group into 20 or less, and the outstanding thermal stability and heat resistance are acquired.
Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group Group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-hexadecyl group, n -Heptadecyl group, n-octadecyl group, etc. are mentioned. Among these, n-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group and 2-ethylhexyl group are preferable. Among these, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and tert-butyl group are preferable.

  The alicyclic hydrocarbon group has 3 to 20 carbon atoms, preferably 5 to 10 carbon atoms. In addition, the alicyclic hydrocarbon group may contain 1 or 2 or more rings, and alkyl may be substituted in addition to the following substituents. The alicyclic hydrocarbon group is preferably a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a norbornyl group, and an adamantyl group.

  4-18 are preferable from the point of thermal stability, transparency, and reaction efficiency, 6-12 are more preferable, and, as for carbon number of the said aromatic hydrocarbon group, 6-10 are especially preferable. Specific examples include aryl groups such as a phenyl group, a biphenyl group, a naphthyl group, a phenanthryl group, and an anthryl group. Among them, an aryl group is preferable and a phenyl group is particularly preferable from the viewpoint of thermal stability, transparency, and reaction efficiency. The bonding site of the aromatic hydrocarbon group may be on any carbon on the aromatic ring.

Examples of the group that can be substituted with the “hydrocarbon group having 1 to 20 carbon atoms” include alkoxy groups having 1 to 12 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a cyclohexyloxy group; C1-C3 alkyl groups such as methyl, ethyl, n-propyl and isopropyl; halogen atoms such as fluorine, chlorine, bromine and iodine; cyano groups; amino groups; oxo groups; tert-butylcarbonyl groups Alkanoyloxy groups such as methacryloyloxy group and acryloyloxy group; Alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group; C6-C10 aryl groups such as phenyl group ; nitroaryl group having 6 to 10 carbon atoms such as nitrophenyl group; 3- isopropenylphenyl group C _{1 6} such alkenyl -C ₁ ~ ₆ aryl group. The position and number of these substituents are arbitrary, and when having two or more substituents, the substituents may be the same or different.

Next, the manufacturing method of this invention is demonstrated.
The method for producing the compound (2) of the present invention comprises a step of polymerizing the compound (1) in the presence of an oxygen-containing solvent.
Examples of the compound (1) used in the present invention include 1-isocyanate-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate. 2,4,4-trimethylhexamethylene diisocyanate, dodecamethylene diisocyanate, 2,6-diisocyanatomethyl caproate, 1,3-cyclohexyl diisocyanate, 1,4-cyclohexyldi Isocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), methyl-2,4-cyclohexanediisocyanate, methyl-2,6-cyclohexanediisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, m -Xylylene diisocyanate, p-xylylene diisocyanate Sodiumate, 1,3-tetramethylxylylene diisocyanate, 1,4-tetramethylxylylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, methylene diphenyl-2,4'- Examples thereof include diisocyanate, methylenediphenyl-4,4′-diisocyanate, 1,5-naphthalene diisocyanate, 1,8-naphthalene diisocyanate and the like. Among these, hexamethylene diisocyanate and methylene diphenyl-4,4′-diisocyanate are particularly preferable from the viewpoints of thermal stability, transparency, and reaction efficiency. In addition, in the manufacturing method of this invention, the said compound (1) may be used independently, and 2 or more types may be mixed and used for it.

  In the production method of the present invention, not only the chemical resistance and transparency are excellent, but also the compound (1) is combined with the compound (3) from the viewpoint of achieving both excellent thermal stability and excellent flexibility. ) Is preferably used in combination. Thereby, the said compound (4) can be obtained.

Examples of the compound (3) include phenyl isocyanate, 4-methoxyphenyl isocyanate, 4-ethoxyphenyl isocyanate, difluoro (4-nitrophenyl) methyl isocyanate, m-tolyl isocyanate, p-tolyl isocyanate, 3,5-dimethylphenyl isocyanate, 3,5-diethylphenyl isocyanate, 1-naphthyl isocyanate, dimethylbenzyl isocyanate, ethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 2-acryloyloxyethyl isocyanate, 1 , 1-bis (acryloyloxymethyl) ethyl isocyanate, n-propyl isocyanate, isopropyl isocyanate, 3-isopropenyl cumyl isocyanate, n-butyl isocyanate Octadecyl isocyanate, cyclohexyl isocyanate, p- toluenesulfonyl isocyanate, and the like. Of these, phenyl isocyanate, n-propyl isocyanate, and butyl isocyanate are preferable.
In addition, in the manufacturing method of this invention, the said compound (3) may be used independently, and 2 or more types may be mixed and used for it.
When the compound (3) is used in combination, the amount of the compound (3) used is preferably 0.0001 to 2.0 molar equivalents relative to the compound (1) from the viewpoint of reaction efficiency. More preferred is 5 molar equivalents. Among them, the upper limit is preferably 1.2 molar equivalents, more preferably 0.75 molar equivalents, still more preferably 0.5 molar equivalents, from the viewpoint of achieving both excellent thermal stability and excellent flexibility. .3 molar equivalents are particularly preferred.

The oxygen-containing solvent used in the production method of the present invention may be any solvent having an oxygen atom in the molecule. For example, imidazolidinones such as 1,3-dialkyl-2-imidazolidinone; pyrrolidone such as alkylpyrrolidone Amides such as N, N-dimethylformamide; ketones such as methyl ethyl ketone and methyl isobutyl ketone; sulfoxides such as dimethyl sulfoxide; ethers such as diethylene glycol dimethyl ether (diglyme) and triethylene glycol dimethyl ether (triglyme); A mixed solvent etc. are mentioned. Among them, from the viewpoint of thermal stability, flexibility, chemical resistance, transparency and reaction efficiency, an oxygen-containing polar solvent is preferable, an oxygen-containing aprotic polar solvent is more preferable, and imidazolidinones are more preferable. Imidazolidinones are particularly preferred. Moreover, as a boiling point of the said solvent, 150 degreeC or more is preferable, 150-300 degreeC is more preferable, 200-250 degreeC is especially preferable.
Preferable specific examples of the solvent include 1,3-dimethyl-2-imidazolidinone, alkylpyrrolidone, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, N, N-dimethylformamide, dimethyl sulfoxide and the like. Among them, from the viewpoint of thermal stability, transparency and reaction efficiency, 1,3-dialkyl-2-imidazolidinone such as 1,3-dimethyl-2-imidazolidinone and alkylpyrrolidone such as N-methylpyrrolidone are preferable. 1,3-dialkyl-2-imidazolidinone is particularly preferred. In addition, as carbon number of this alkyl group, 1-6 are preferable.
The amount of the solvent used is preferably 10 ^{−7 to} 6 parts by mass, more preferably 10 ^{−5 to} 3 parts by mass, and more preferably 10 ⁻³ to 1 part from the viewpoint of reaction efficiency with respect to 1 part by mass of compound (1). .4 parts by mass is particularly preferred.

  The production method of the present invention can be carried out in the presence of a catalyst and in the absence of a catalyst, but is preferably carried out in the presence of a catalyst from the viewpoint of reaction efficiency. Examples of the catalyst include organic quaternary ammonium salts such as tetrabutylammonium iodide, tetrabutylammonium bromide, tetrabutylammonium fluoride, benzyltriethylammonium chloride, tetrabutylammonium hydroxide, and tetrabutylammonium hydrogen sulfate; triethylamine, dimethyl Examples include organic tertiary amines such as octylamine and dimethyllaurylamine; organic sulfinic acids or salts thereof, and two or more of these may be used. Of these, organic quaternary ammonium salts and organic sulfinates are preferable from the viewpoint of thermal stability, transparency, and reaction efficiency. Among these, organic sulfinates are particularly preferable from the viewpoint of color tone.

The organic sulfinic acid is preferably an aromatic sulfinate from the viewpoint of thermal stability, color tone, transparency and reaction efficiency. Examples of the salt include alkali metal salts and alkaline earth metal salts. Specific examples include alkali metal salts of p-toluenesulfinic acid, alkali metal salts of o-toluenesulfinic acid, and alkaline earth metal salts of benzenesulfinic acid. Among these, an alkali metal salt of p-toluenesulfinic acid is particularly preferable from the viewpoint of achieving both color tone and transparency.
The amount of the catalyst used is preferably 10 ^{−4 to} 0.5 part by mass, and more preferably 10 ^{−3 to} 0.1 part by mass with respect to 1 part by mass of the compound (1).

  Although the reaction temperature of the said reaction is not specifically limited, 20-200 degreeC is preferable. Moreover, it is preferable to perform the said reaction in inert gas atmosphere from the point of reaction efficiency. The inert gas is not particularly limited, and examples thereof include argon gas, nitrogen gas, and helium gas.

  When the compound (3) is used in combination, from the viewpoint of flexibility, in addition to the compound (1) and the compound (3), (i) a polyalkylene glycol compound, (ii) a polyvinyl compound, (iii) a polyallyl compound (Iv) One or more compounds selected from poly (meth) acryl compounds may be used in combination.

  (I) Examples of the polyalkylene glycol compound include polyethylene glycol (PEG) and polypropylene glycol. Among these, polyethylene glycol is preferable.

  (Ii) Examples of the polyvinyl compound include divinylbenzene and N, N-methylenebisacrylamide.

  (Iii) Examples of the polyallyl compound include N, N-diallylacrylamide, diallylamine, diallylmethacrylamide, diallyl phthalate, diallyl malate, diallyl terephthalate, triallyl cyanurate, triallyl phosphate and the like.

  (Iv) As the poly (meth) acrylic compound, (a) ethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6 -Hexanediol di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, alkoxylated hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, caprolactone modified neopentyl glycol hydroxypivalate di (meth) acrylate , Cyclohexanedimethanol di (meth) acrylate, diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, bisphenol-A di (meth) acrylate, ethoxylated bisphenol -A di (meth) acrylate, hydroxypivalaldehyde-modified trimethylolpropane di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, propoxy Neopentyl glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, etc. Functional acrylate compounds; (b) glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethoxylated tri (meth) acrylate (e.g. Toxylated trimethylolpropane tri (meth) acrylate, etc.), pentaerythritol tri (meth) acrylate, glycerin tri (meth) acrylate, propoxylated tri (meth) acrylate (eg propoxylated glyceryl tri (meth) acrylate, propoxylated tri Trifunctional acrylate compounds such as methylolpropane tri (meth) acrylate) and tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate; (c) ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) Acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) Tetrafunctional or more acrylate compounds such as acrylate.

  Although the usage-amount of the said compound (i)-(iv) is not specifically limited, From the point of thermal stability and a softness | flexibility, it is about 0-20 mass% with respect to a compound (1), Preferably it is 0-10. It is about mass%.

Compound (2) and Compound (4) should be isolated and purified from the reaction system by appropriately combining ordinary means such as filtration, washing, drying, recrystallization, centrifugation, extraction with various solvents, and chromatography. Can be separated.
Moreover, as said compound (4), not only it is excellent in chemical resistance and transparency, but the structural unit represented by Formula (2) from the point which combines the outstanding thermal stability and the outstanding softness | flexibility. What has is preferable.

In addition, as shown in the following Examples, the compound (2) and the compound (4) obtained by the production method of the present invention have a high conversion rate of isocyanate groups in the molecule of 99% or more, and the remaining isocyanate groups remain. Since the rate is low, it has excellent thermal stability.
As the 5% weight loss temperature of the compound (2) and the compound (4) (T _d5), preferably at least 380 ° C., more preferably from 400 to 600 ° C., more preferably 405-500 ° C., 410 to 450 ° C. Is particularly preferred. Further, the 10% weight loss temperature (T _d10 ) is preferably 395 ° C. or more, more preferably 400 ° C. or more, more preferably 420 to 600 ° C., more preferably 425 to 550 ° C., and still more preferably 430 to 500 ° C. 440 to 475 ° C is particularly preferable. And in thermogravimetric analysis (TGA), what does not have a weight reduction of a compound (2) to 375 degreeC, Preferably it is 400 degreeC is preferable. The measurement of T _d5 and T _d10 is subject to the conditions described in the examples below.
Moreover, as a residual carbon rate under 500 degreeC, 50%-100% are preferable, 60%-100% are more preferable, and 70-100% are especially preferable. The residual carbon ratio refers to the mass ratio of carbon remaining when the compound is heated from 50 ° C. to 500 ° C. in 10 ° C. and baked for 45 minutes in a non-oxidizing atmosphere.
Further, the glass transition temperatures of the compound (2) and the compound (4) are not particularly limited, but the lower limit is preferably 100 ° C., more preferably 250 ° C., further preferably 275 ° C., particularly from the viewpoint of thermal stability. The upper limit is preferably 450 ° C, particularly preferably 400 ° C.

Moreover, as a Young's modulus (GPa) of a compound (2) and a compound (4), 0.5-2 are preferable. Further, the elongation at break (%) is preferably 3 or less, and more preferably 2 or less.
In addition, the measurement of a Young's modulus and breaking elongation rate shall follow the conditions as described in the following Example.

  Moreover, as a compound (2) and a compound (4), a transparent thing is preferable and a colorless and transparent thing is more preferable. The shape is preferably a film.

Therefore, the compound (2) and the compound (4) are a film or sheet such as a heat resistant film / sheet or an optical film / sheet, a lens material, an optical communication component, an optical material such as an optical disk, a coating agent, or a polyisocyanurate. It is useful as a raw material for molded articles, polyisocyanurate molded articles, polyisocyanurate foams, rigid polyurethane foams, paints, adhesives, elastomers, artificial leather, flame retardant low dielectric constant thermosetting materials, and semiconductor resist materials. In addition, when making a compound (2) and a compound (4) into the form of a film or a sheet | seat, it can manufacture by a well-known method using a spin coater, a bar coater, a spray coat, an inkjet, or a die coater.
The molded body may be molded in accordance with a conventional method, and examples thereof include extrusion molding and compression molding. When the above compound (2) and compound (4) are used as a raw material for a polyisocyanurate molded body, foaming is performed. Other polymers such as agents, foam stabilizers, polyols, additives, fillers, and the like may be used.

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

The reagents used in the examples are as shown below.
1,6-hexamethylene diisocyanate, phenyl isocyanate and n-propyl isocyanate are from Tokyo Chemical Industry, and methylene diphenyl-4,4′-diisocyanate (methylene diphenyl 4,4′-diisocyanate) is a sum. Each was purchased from Kojun Pharmaceutical Co., Ltd., and both were distilled under reduced pressure.
Further, sodium p-toluenesulfinate was purchased from Tokyo Chemical Industry, and tetrabutylammonium iodide was purchased from Wako Pure Chemical Industries, Ltd., both of which were used after drying under reduced pressure at room temperature.
1,3-dimethyl-2-imidazolidinone was purchased from Wako Pure Chemical Industries, dried over calcium hydride, and then used after vacuum distillation.

The analysis conditions of the cured product in the examples are as shown below.
<IR spectrum>
Absorption derived from isocyanate was confirmed by IR spectrum, and the conversion rate of isocyanate group was determined. The IR spectrum was measured by the ATR method using a NICOLET iS10 with a SMARTiTR sampling unit manufactured by Thermo Scientific.

<Thermogravimetric analysis>
Thermogravimetric analysis (TGA) was measured with a TG-DTA6200 manufactured by Seiko Instruments Inc. by using an aluminum pan and raising the temperature in a nitrogen stream of 50 mL / min at 10 ° C./min. In thermogravimetric analysis, T _d5 and T _d10 mean 5% weight reduction temperature and 10% weight reduction temperature of the compound, respectively.

<Differential scanning thermal analysis>
Differential scanning calorimetry (DSC) was performed using a DSC6200 manufactured by Seiko Instruments Inc., and 10 mg of the cured product was enclosed in an aluminum pan and heated from 50 ° C. to 300 ° C. at a rate of 5 ° C./min in a nitrogen stream. And measured.

<Flexibility test>
Flexibility was measured by a tensile test. That is, with a stress / strain control TMA device (manufactured by SII Nano Technology Co., Ltd.), a cured product (3 mm × 10 mm) was subjected to a load of 5.9 N at room temperature and atmospheric pressure, and strained to 1000 μm at 10 μm / min. The measurement was performed by determining the Young's modulus (GPa) and the elongation at break (%).

<Chemical resistance test>
The cured product was immersed in a 5% hydrochloric acid solution and a 5% sodium hydroxide solution at room temperature for two days, and the subsequent appearance was observed.

Example 1 Synthesis of polyisocyanurate compound (1)
According to the following synthesis route (self-crosslinking reaction), a polyisocyanurate compound was synthesized (networked) using 1,6-hexamethylene diisocyanate (HMDI) as a substrate.

Sodium p-toluenesulfinate (27 mg, 0.15 mmol) and tetrabutylammonium iodide (TBAI, 28 mg, 0.075 mmol) were added to 1,3-dimethyl-2-imidazolidinone (DMI, 1.0 mL). Dissolved. HMDI (1.2 mL, 7.5 mmol) was added to this solution and stirred at 150 ° C. for 2 hours under a nitrogen atmosphere to obtain a HMDI varnish. Subsequently, the obtained varnish was poured into a petri dish to obtain a light yellow transparent film-like cured product 1.
After this cured product 1 was cooled to room temperature, absorption of isocyanate groups was confirmed by IR spectrum.
As a result of the IR spectrum (FIG. 1), the absorption derived from the isocyanate group near 2200 cm ⁻¹ almost completely disappeared, and the absorption near 1700 cm ⁻¹ derived from the carbonyl group of the isocyanurate skeleton was newly increased. From this result, it was found that the isocyanate group was almost completely consumed (conversion rate of 99%) and was networked in a high density with an isocyanurate skeleton.

The obtained cured product 1 was Soxhlet extracted with chloroform for 24 hours, dried in a vacuum dryer at 120 ° C. overnight, and then subjected to TGA and DSC. The results of TGA are shown in FIG. 2, and the results of DSC are shown in FIG.
Table 1 below shows the appearance, shape, T _d5 , T _d10 , and glass transition temperature measured by the TGA.

As a result of TGA, weight reduction of the cured product 1 was not observed up to 400 ° C., and T _d5 and T _d10 were 431 ° C. and 449 ° C., respectively.
Moreover, as a result of DSC, it was found that the glass transition temperature (Tg) of the cured product 1 was 114 ° C.

Example 2 Synthesis of polyisocyanurate compound (2)
According to the following synthesis route (self-crosslinking reaction), a polyisocyanurate compound was synthesized (networked) using methylenediphenyl-4,4′-diisocyanate (MDI) as a substrate.

MDI (0.75 g, 3 mmol) was dissolved in DMI (0.7 mL) and this solution was mixed with sodium p-toluenesulfinate (5.4 mg, 0.03 mmol) and TBAI (5.5 mg, 0.015 mmol). The solution dissolved in DMI (0.3 mL) was mixed under a nitrogen atmosphere and allowed to stand at room temperature for 15 minutes. The reaction proceeded rapidly, and an MDI varnish was obtained in 15 minutes. Subsequently, the obtained varnish was poured into a petri dish to obtain a light yellow transparent film-like cured product 2.
As a result of IR spectrum of cured product 2 (FIG. 4), the absorption derived from the isocyanate group near 2200 cm ⁻¹ almost completely disappeared, and the absorption near 1700 cm ⁻¹ derived from the carbonyl group of the isocyanurate skeleton increased. It was. From this result, it was found that the isocyanate group was almost completely consumed (conversion rate of 99%) and was networked in a high density with an isocyanurate skeleton.

The cured product 2 was subjected to Soxhlet extraction with chloroform for 24 hours and dried overnight in a vacuum dryer at 120 ° C., and then TGA and DSC were performed. The TGA result of the cured product 2 is shown in FIG. 5, and the DSC result is shown in FIG.
Table 2 below shows the appearance and shape of the cured product 2, the T _d5 and T _d10 measured by the TGA, the residual carbon ratio at 500 ° C., and the glass transition temperature.

As a result of TGA, weight reduction of cured product 2 was not observed up to 400 ° C., and T _d5 and T _d10 were 411 ° C. and 445 ° C., respectively. Furthermore, the hardened | cured material 2 showed the high residual carbon rate of 70 mass% or more also under 500 degreeC.
Moreover, as a result of DSC, glass transition did not occur up to 300 ° C. From this result, it was found that the glass transition temperature (Tg) of the cured product 2 is a temperature exceeding at least 300 ° C., and the cured product 2 has extremely high heat resistance.

Example 3 Synthesis of polyisocyanurate compound (3)
According to the following synthesis route (self-crosslinking reaction), polyisocyanurate using methylenediphenyl-4,4′-diisocyanate (MDI) and phenyl isocyanate (PhNCO) as substrates (MDI: phenyl isocyanate = 3: 3) Compounds were synthesized (networked).

  MDI (0.75 g, 3 mmol) and phenyl isocyanate (0.36 g, 3 mmol) were dissolved in DMI (0.1 mL) and this solution was mixed with sodium p-toluenesulfinate (8.0 mg, 0.045 mmol). The solution dissolved in DMI (0.9 mL) was mixed under a nitrogen atmosphere and allowed to stand at room temperature for 15 minutes. The reaction proceeded rapidly, and a varnish of MDI and phenyl isocyanate was obtained in 15 minutes. Next, the obtained varnish was poured into a petri dish to obtain a cured product 3 in the form of a colorless transparent film.

Example 4 Synthesis of polyisocyanurate compound (4)
The synthesis was carried out in the same manner as in Example 3 except that the amount of reagent used was changed (MDI: phenyl isocyanate = 3: 2).
That is, MDI (0.75 g, 3 mmol) and phenyl isocyanate (0.24 g, 2 mmol) were dissolved in DMI (0.2 mL), and this solution was mixed with sodium p-toluenesulfinate (7.1 mg, 0.04 mmol). ) In DMI (0.8 mL) was mixed under a nitrogen atmosphere and allowed to stand at room temperature for 15 minutes. The reaction proceeded rapidly, and a varnish of MDI and phenyl isocyanate was obtained in 15 minutes. Subsequently, the obtained varnish was poured into a petri dish to obtain a cured product 4 in the form of a colorless transparent film.

Example 5 Synthesis of polyisocyanurate compound (5)
The synthesis was performed in the same manner as in Example 3 except that the amount of the reagent used was changed (MDI: phenyl isocyanate = 3: 1.2).
That is, MDI (0.75 g, 3 mmol) and phenyl isocyanate (0.14 g, 1.2 mmol) were dissolved in DMI (0.72 mL), and this solution was mixed with sodium p-toluenesulfinate (6.4 mg, 0 mmol). 0.036 mmol) in DMI (0.28 mL) was mixed under a nitrogen atmosphere and allowed to stand at room temperature for 15 minutes. The reaction proceeded rapidly, and a varnish of MDI and phenyl isocyanate was obtained in 15 minutes. Next, the obtained varnish was poured into a petri dish to obtain a cured product 5 in the form of a colorless transparent film.

Example 6 Synthesis of polyisocyanurate compound (6)
The synthesis was performed in the same manner as in Example 3 except that the amount of the reagent used was changed (MDI: phenyl isocyanate = 3: 0.55).
That is, MDI (0.75 g, 3 mmol) and phenyl isocyanate (0.065 g, 0.55 mmol) were dissolved in DMI (0.35 mL), and this solution was mixed with sodium p-toluenesulfinate (5.8 mg, 0 mg). 0.033 mmol) in DMI (0.65 mL) was mixed under a nitrogen atmosphere and allowed to stand at room temperature for 15 minutes. The reaction proceeded rapidly, and a varnish of MDI and phenyl isocyanate was obtained in 15 minutes. Next, the obtained varnish was poured into a petri dish to obtain a cured product 6 in the form of a colorless transparent film.

Example 7 Synthesis of polyisocyanurate compound (7)
The synthesis was carried out in the same manner as in Example 2 except that the type of catalyst was changed (MDI: phenyl isocyanate = 3: 0).
That is, MDI (0.75 g, 3 mmol) was dissolved in DMI (0.4 mL), and this solution and sodium p-toluenesulfinate (5.3 mg, 0.03 mmol) were dissolved in DMI (0.6 mL). The solution was mixed under a nitrogen atmosphere and allowed to stand at room temperature for 15 minutes. The reaction proceeded rapidly, and a varnish of MDI and phenyl isocyanate was obtained in 15 minutes. Subsequently, the obtained varnish was poured into a petri dish to obtain a cured product 7 in the form of a colorless transparent film.

As a result of IR spectrum of cured products 3 to 7 obtained in Examples 3 to 7 (FIG. 7), absorption derived from an isocyanate group near 2200 cm ⁻¹ disappeared almost completely, and a new carbonyl of an isocyanurate skeleton was obtained. Absorption around 1700 cm ⁻¹ derived from the group increased. From this result, it was found that the isocyanate group was almost completely consumed (conversion rate of 99%) and was networked in a high density with an isocyanurate skeleton.

  The cured products 3 to 7 were Soxhlet extracted with chloroform for 24 hours, dried in a vacuum dryer at 120 ° C. overnight, and then subjected to TGA and DSC. The TGA results of the cured products 3 to 7 are shown in FIG. 8, and the DSC results are shown in FIG.

Film thickness, appearance, shape of cured products 3-7, T _d5 , T _d10 measured by TGA and residual carbon ratio under 500 ° C., glass transition temperature, Young's modulus, elongation at break, and chemical resistance, It is shown in Table 3 below.

As a result of TGA, almost no weight reduction was observed up to 400 ° C. for any of the cured products 3 to 7, and a high residual carbon ratio of 58% by mass or more was exhibited even at 500 ° C.
From this result, it was found that all of the cured products 3 to 7 have excellent thermal stability.

Moreover, as a result of DSC, no glass transition occurred up to 300 ° C. in any of the cured products 3 to 7.
From this result, it was found that the glass transition temperatures (Tg) of the cured products 3 to 7 were temperatures exceeding at least 300 ° C., and the cured products 3 to 7 all had extremely excellent heat resistance.

In addition, as a result of the flexibility test, all of the cured products 3 to 7 exhibited excellent elongation at break (%).
From this result, it turned out that all the hardened | cured materials 3-7 have the outstanding softness | flexibility.
Furthermore, the cured product 3 had an extremely low elongation at break (1.55%), and for the cured products 4 to 6, the elongation at break was not measurable due to remarkable flexibility.
From this result, it was found that the cured products 3 to 6 have superior flexibility as compared with the cured product 7.

Moreover, as a result of the chemical resistance test, the cured products 3 to 7 were not confirmed to change in appearance in any of the hydrochloric acid solution and the sodium hydroxide solution.
From this result, it was found that the cured products 3 to 7 all have excellent chemical resistance.

Example 8 Synthesis of polyisocyanurate compound (8)
According to the following synthesis route (self-crosslinking reaction), using methylenediphenyl-4,4′-diisocyanate (MDI) and n-propyl isocyanate (n-PropylNCO) as substrates (MDI: n-propyl isocyanate = 3: 3) A polyisocyanurate compound was synthesized (networked).

  MDI (0.75 g, 3 mmol) and n-propyl isocyanate (0.26 g, 3 mmol) were dissolved in DMI (0.1 mL) and this solution was mixed with sodium p-toluenesulfinate (8.0 mg, 0.045 mmol). ) Was dissolved in DMI (0.9 mL) under a nitrogen atmosphere and allowed to stand at room temperature for 15 minutes. The reaction proceeded rapidly, and a varnish of MDI and n-propyl isocyanate was obtained in 15 minutes. Next, the obtained varnish was poured into a petri dish to obtain a cured product 8 in the form of a colorless transparent film.

Example 9 Synthesis of polyisocyanurate compound (9)
The synthesis was performed in the same manner as in Example 8 except that the amount of reagent used was changed (MDI: n-propyl isocyanate = 3: 2).
That is, MDI (0.75 g, 3 mmol) and n-propyl isocyanate (0.17 g, 2 mmol) were dissolved in DMI (0.2 mL), and this solution was mixed with sodium p-toluenesulfinate (7.1 mg, 0 mmol). .04 mmol) in DMI (0.8 mL) was mixed under a nitrogen atmosphere and allowed to stand at room temperature for 15 minutes. The reaction proceeded rapidly, and a varnish of MDI and n-propyl isocyanate was obtained in 15 minutes. Next, the obtained varnish was poured into a petri dish to obtain a cured product 9 in the form of a colorless transparent film.

Example 10 Synthesis of polyisocyanurate compound (10)
The synthesis was performed in the same manner as in Example 8 except that the amount of reagent used was changed (MDI: n-propyl isocyanate = 3: 1.2).
That is, MDI (0.75 g, 3 mmol) and n-propyl isocyanate (0.10 g, 1.2 mmol) were dissolved in DMI (0.72 mL), and this solution was mixed with sodium p-toluenesulfinate (6.4 mg). , 0.036 mmol) in DMI (0.28 mL) was mixed under a nitrogen atmosphere and allowed to stand at room temperature for 15 minutes. The reaction proceeded rapidly, and a varnish of MDI and n-propyl isocyanate was obtained in 15 minutes. Next, the obtained varnish was poured into a petri dish to obtain a cured product 10 in the form of a colorless transparent film.

As a result of IR spectrum of cured products 8 to 10 obtained in Examples 8 to 10 (FIG. 10), absorption derived from an isocyanate group in the vicinity of 2200 cm ⁻¹ disappeared almost completely, and a new carbonyl having an isocyanurate skeleton was obtained. Absorption around 1700 cm ⁻¹ derived from the group increased. From this result, it was found that the isocyanate group was almost completely consumed (conversion rate of 99%) and was networked in a high density with an isocyanurate skeleton.

  The cured products 8 to 10 were Soxhlet extracted with chloroform for 24 hours, dried in a vacuum dryer at 120 ° C. overnight, and then subjected to TGA and DSC. The TGA results of the cured products 8 to 10 are shown in FIG. 11, and the DSC results are shown in FIG.

Table 4 shows the appearance and shape of the cured products 8 to 10, T _d5 and T _d10 measured by the above TGA, the residual carbon ratio (mass%) at 500 ° C., and the glass transition temperature (° C.).

As a result of TGA, almost no weight reduction was observed up to 380 ° C. in any of the cured products 8 to 10, and a high residual carbon ratio of 55% by mass or more was exhibited even at 500 ° C.
From this result, it was found that the cured products 8 to 10 all have excellent thermal stability.

Moreover, as a result of DSC, no glass transition occurred up to 300 ° C. in any of the cured products 8 to 10.
From this result, it was found that the glass transition temperature (Tg) of the cured products 8 to 10 was a temperature exceeding at least 300 ° C., and the cured products 8 to 10 all had extremely high heat resistance.

The polyisocyanurate compound obtained by the production method of the present invention has flexibility and chemical resistance, and has a very low residual ratio of isocyanate groups, and thus has high heat resistance and thermal stability.
Accordingly, the high molecular weight polyisocyanurate obtained in the present invention is an optical material such as a lens material, an optical communication component, a heat resistant film or sheet, an optical film or sheet, a flame retardant low dielectric constant thermosetting material, and an optical disk. It can be used as a resist material for semiconductors.

Claims (16)

Following formula (1)

(In the formula, R ¹ represents a divalent organic group having 1 to 20 carbon atoms.)
Comprising the step of polymerizing the compound represented by formula (2) in the presence of an oxygen-containing solvent.

(In the formula, * represents a bond, and R ¹ has the same meaning as described above.)
The manufacturing method of the polyisocyanurate compound which has a structural unit represented by these. Following formula (1)

(In the formula, R ¹ represents a divalent organic group having 1 to 20 carbon atoms.)
And a compound represented by the following formula (3)

(In the formula, R ² represents an organic group having 1 to 20 carbon atoms.)
And a step of polymerizing the compound represented by formula (4) in the presence of an oxygen-containing solvent.

(In the formula, * represents a bond, and R ¹ and R ² are as defined above.)
The manufacturing method of the polyisocyanurate compound which has a structural unit represented by these. The polyisocyanurate compound is further represented by the following formula (2):

(In the formula, R ¹ and * are as defined above.)
The production method according to claim 2, which has a structural unit represented by:   The manufacturing method according to claim 1, wherein the oxygen-containing solvent is an oxygen-containing polar solvent.   The manufacturing method according to claim 1, wherein the oxygen-containing solvent has a boiling point of 150 ° C. or higher.   The production method according to any one of claims 1 to 4, wherein the oxygen-containing solvent is an imidazolidinone. R ¹ is an optionally substituted divalent hydrocarbon group having 1 to 20 carbon atoms, and R ² is an optionally substituted hydrocarbon group having 1 to 20 carbon atoms. The manufacturing method according to any one of claims 2 to 6. The production method according to claim 7, wherein R ¹ is a divalent hydrocarbon group having 5 to 14 carbon atoms which may have a substituent. R ² may have a substituent, an aryl group having 6 to 20 carbon atoms, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an allyl optionally having a substituent. The production method according to claim 7 or 8, which is a cycloalkyl group having 3 to 20 carbon atoms which may have a group or a substituent. Following formula (2)

(In the formula, R ¹ represents a divalent organic group having 1 to 20 carbon atoms, and * represents a bond.)
A polyisocyanurate compound having a structural unit represented by the formula: 5% weight loss temperature of 380 ° C. or higher and 10% weight loss temperature of 395 ° C. or higher. Further, the following formula (4)

(In the formula, R ² represents an organic group having 1 to 20 carbon atoms, and R ¹ and * are as defined above.)
The compound of Claim 10 which has a structural unit represented by these. R ¹ is an optionally substituted divalent hydrocarbon group having 1 to 20 carbon atoms, and R ² is an optionally substituted hydrocarbon group having 1 to 20 carbon atoms. The compound according to claim 11. R ¹ is an optionally substituted methylene group or an alkylene group having 2 to 20 carbon atoms, an optionally substituted arylene group having 6 to 18 carbon atoms, or the following formula (5):

(In formula, R < ³ > shows the methylene group or C2-C6 alkylene group which may have a substituent.)
The compound of Claim 12 which is group represented by these. 14. The compound according to claim 12, wherein R ² is an optionally substituted aryl group having 6 to 20 carbon atoms, or an optionally substituted alkyl group having 1 to 20 carbon atoms. .   The compound according to any one of claims 10 to 14, wherein the residual carbon ratio at 500 ° C is 50% or more and the glass transition temperature is 275 ° C or more.   The film formed by containing the compound of any one of Claims 10-15.

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