JP5732731B2 - Urethane bond-containing sulfonium salt compound and process for producing the same - Google Patents

Description

  The present invention relates to a urethane bond-containing sulfonium salt compound and a method for producing the same. More specifically, the present invention relates to a urethane bond-containing sulfonium salt compound that is effectively used as a cationic polymerization initiator and a method for producing the same.

Various sulfonium salt compounds having non-nucleophilic anion residues such as B (C ₆ F ₅ ) ₄ , BF ₄ , PF ₆ , SbF ₆ , AsF ₆ , SbCl ₆ effectively act as a cationic polymerization initiator. It is known.

Ar₁：置換されてもよいフェニル基、ナフチル基
Ar₂：置換されてもよいフェニル基
R₁，R₂：炭素数1〜4のアルキル基
X^-：非求核性アニオン残基
で表わされるスルホニウム塩化合物がカチオン重合開始剤として用いられること、100℃以下の温度でカチオン重合性化合物を硬化させることが可能であること、重合性化合物と混合したときの一液保存性がすぐれていることなどが記載されている。 For example, Patent Document 1 discloses a general formula.

Ar ₁ : phenyl group which may be substituted, naphthyl group
Ar ₂ : an optionally substituted phenyl group
R ₁ and R ₂ : alkyl groups having 1 to 4 carbon atoms
X ⁻ : a sulfonium salt compound represented by a non-nucleophilic anion residue is used as a cationic polymerization initiator, the cationic polymerizable compound can be cured at a temperature of 100 ° C. or less, and the polymerizable compound It describes that the one-part storability when mixed is excellent.

  In Patent Document 2, although the bissulfonium salt has a higher photopolymerization initiating ability than the monosulfonium salt, the solubility in the cationic polymerizable monomer and the diluting solvent is low, so that the sulfonium salt precipitates and settles with time. The cationic polymerizable composition containing a bissulfonium salt tends to thicken with time and cannot be stored for a long time.

Ar：置換されてもよいアリール基
R¹，R₂：置換されてもよい炭化水素基、複素環基
X^-：BF₄ ^-、PF₆ ^-、AsF₆ ^-、SbF₆ ^-
で表わされるモノスルホニウム塩を製造し、このモノスルホニウム塩は有機溶剤に対する溶解性にすぐれたカチオン重合開始剤であり、さらに長期保存性の良好な硬化性組成物を形成し得ると述べられている。 In this Patent Document 2, an aryl compound, a sulfoxide compound, a dehydrating agent and an alkali (earth) metal BF ₄ , PF ₆ , AsF ₆ or SbF ₆ salt are charged into a reaction system, and then an inorganic acid is charged. And sulfoxide compounds are dehydrated and condensed to form a general formula

Ar: aryl group which may be substituted
R ¹ and R ₂ : optionally substituted hydrocarbon group, heterocyclic group
_{^{X -: BF 4 -, PF}} 6 -, AsF 6 -, SbF 6 -
It is stated that this monosulfonium salt is a cationic polymerization initiator excellent in solubility in an organic solvent and can form a curable composition having good long-term storage stability. .

  As seen from these descriptions, when a monosulfonium salt or bissulfonium salt is used as a cationic polymerization initiator, its storage stability and curability are important factors.

JP-A-10-152469 WO 2005/000801

  An object of the present invention is to provide a sulfonium salt compound having improved curability and a method for producing the same, when the sulfonium salt compound is used as a cationic polymerization initiator without substantially deteriorating its storage stability.

(ここで、R¹は芳香族炭化水素基であり、R²は炭素数1〜6のアルキル基であり、R³は置換基を有してもよい芳香族炭化水素基であり、X^-は非求核性アニオン性基であり、nは1〜10の整数であり、mは0または1である)で表わされるウレタン結合含有スルホニウム塩化合物が提供される。 According to the invention, the general formula

(Where R ¹ is an aromatic hydrocarbon group , R ² is an alkyl group having 1 to 6 carbon atoms, R ³ is an aromatic hydrocarbon group which may have a substituent, and X ⁻ Is a non-nucleophilic anionic group, n is an integer of 1 to 10, and m is 0 or 1.

(ここで、R²は炭素数1〜6のアルキル基であり、R³は芳香族炭化水素基であり、X^-は非求核性アニオン性基である)で表わされる水酸基含有スルホニウム塩を、芳香族系炭化水素イソシアネート化合物〔III〕と反応させることにより製造される。 Such urethane bond-containing sulfonium salt compounds have the general formula

(Wherein R ² is an alkyl group having 1 to 6 carbon atoms, R ³ is an aromatic hydrocarbon group, and X ⁻ is a non-nucleophilic anionic group). It is produced by reacting with an aromatic hydrocarbon isocyanate compound [III].

  The novel urethane bond-containing sulfonium salt compound of the present invention is used as a cationic polymerization initiator as a curing agent for a monomer or polymer having a vinyl ether group and / or an epoxy group, and storage of a curable composition containing these components. There is an effect that the curability is remarkably improved without impairing the stability.

The urethane bond-containing sulfonium salt compound [I] is produced by reacting a hydroxyl group-containing sulfonium salt [II] with an aromatic hydrocarbon isocyanate compound [III].

In the hydroxyl group-containing sulfonium salt represented by the general formula [II], R ² is an alkyl group having 1 to 6 carbon atoms, preferably a methyl group or an ethyl group, and R ³ is an aromatic hydrocarbon group, preferably a phenyl group. 1-naphthyl group (α-naphthyl group), and these aromatic hydrocarbon groups are mono-substituted or poly-substituted by alkyl groups, halogen atoms, hydroxyl groups, alkoxy groups, alkylcarbonyloxy groups, vinyl groups, nitro groups, etc. It may be what was done. X ^- is a non-nucleophilic anionic group such as B (C ₆ F ₅ ) ₄ , BF ₄ , PF ₆ , SbF ₆ , AsF ₆ , SbCl _4, etc., preferably curable, corrosion resistant From the viewpoint of the properties, anionic borate groups are used, and tetrakis (pentafluorophenyl) borate B (C ₆ F ₅ ) ₄ is particularly preferably used.

As the aromatic hydrocarbon isocyanate compound [III] that reacts with such a hydroxyl group-containing sulfonium salt [II], monoisocyanate, diisocyanate, trifunctional or higher isocyanate compounds are used, and n = 1, 2, or 3 or more, respectively. The urethane bond-containing sulfonium salt compound is formed.

Examples of monoisocyanates include phenyl isocyanate , benzenesulfonyl isocyanate, p-toluenesulfonyl isocyanate, and the like. Diisocyanates include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, tetramethylxylylene diisocyanate , 1,5-naphthalene diisocyanate, o -Xylylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, triphenylmethane triisocyanate, norbornane diisocyanate, etc., preferably TDI, MDI, polymeric MDI, TODI, PPDI, NDI etc. used for polyurethane formation Aromatic diisocyanates are used.
Note) TDI: Toluene diisocyanate
MDI: 4,4'-diphenylmethane diisocyanate
TODI: Tolidine diisocyanate
PPDI: p-phenylene diisocyanate
NDI: Naphthalene diisocyanate

Examples of the trifunctional or higher functional isocyanate compound include burette, allophanate, carbodiimide, uretidinedione, and isocyanurate of these diisocyanate compounds .

  The urethanization reaction between the two is carried out by a catalyst such as triethylamine, triethylenediamine, tertiary amine such as 1,8-diazabicyclo [5.4.0] undecene-7, tin dibutyl dilaurate, tin dioctyl dilaurate, lead naphthenate, etc. In the presence or absence, a solvent such as α-butyrolactone, propylene glycol monomethyl ether acetate, isophorone, butyl carbitol and the like is used at about 5 to 40 ° C., preferably at room temperature.

  The urethane bond-containing sulfonium salt compound [I], which is a reaction product, is used as a cationic polymerization initiator as a curing agent for a monomer or polymer having a vinyl ether group and / or an epoxy group. The proportion of the urethane bond-containing sulfonium salt compound used is about 0.1 to 10 parts by weight, preferably about 0.5 to 3 parts by weight per 100 parts by weight of the monomer or polymer to be cured, and this is added to the monomer or polymer to be cured. The cationic polymerization is started by heating to about 80 to 200 ° C., and each cured product is obtained.

  Examples of vinyl ether compounds that are cationically polymerized by urethane bond-containing sulfonium salt compounds include ethylene glycol divinyl ether, butanediol divinyl ether, cyclohexanedimethanol divinyl ether, cyclohexanediol divinyl ether, trimethylolpropane trivinyl ether, pentaerythritol tetravinyl ether, glycerol trivinyl ether. , Triethylene glycol divinyl ether, diethylene glycol divinyl ether, dipropylene glycol divinyl ether, tripropylene glycol divinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, cyclohexanedimethanol monovinyl ether, cyclohexanediol monovinyl ether 9-hydroxynonyl vinyl ether, propylene glycol monovinyl ether, neopentyl glycol monovinyl ether, glycerol divinyl ether, glycerol monovinyl ether, trimethylolpropane divinyl ether, trimethylolpropane monovinyl ether, pentaerythritol trivinyl ether, pentaerythritol divinyl ether, pentaerythritol Examples thereof include monovinyl ether, diethylene glycol monovinyl ether, triethylene glycol monovinyl ether, tetraethylene glycol monovinyl ether, tricyclodecanediol monovinyl ether, and tricyclodecane dimethanol monovinyl ether.

  Moreover, as an epoxy compound cationically polymerized by a urethane bond containing sulfonium salt compound, a glycidyl ether type epoxy resin and an alicyclic epoxy compound are mentioned, for example.

  Specific examples of glycidyl ether type epoxy compounds include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, phenol novolac type epoxy compounds, cresol novolac type epoxy compounds, hydrogenated bisphenol A type epoxy compounds, and bisphenol A alkylene oxide adducts. Diglycidyl ether, alkylene oxide adduct diglycidyl ether of bisphenol F, diglycidyl ether of hydrogenated bisphenol A alkylene oxide adduct, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, Butanediol diglycidyl ether, hexanediol diglycidyl ether, cyclohexanedimethanol diglycol Diyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, trimethylolpropane di- or tri-glycidyl ether, pentaerythritol tri- or tetra-glycidyl ether, sorbitol hepta- or hexa-glycidyl ether, resorcin diglycidyl ether, Examples include dicyclopentadiene / phenol-added glycidyl ether, methylenebis (2,7-dihydroxynaphthalene) tetraglycidyl ether, 1,6-dihydroxynaphthalenediglycidyl ether, and the like.

Specific examples of the alicyclic epoxy compound, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) Cyclohexane-m-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene dioxide, 4-vinylepoxycyclohexane, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy -6-methylcyclohexyl-3,4-epoxy-6-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di (3,4-epoxycyclohexylmethyl) ether, ethylene Bis (3,4-epoxycyclohexanecarboxylate), propylene bis (3,4-epoxycyclohexane) Hexane carboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1,4-cyclohexanedimethanol di (3,4-epoxycyclohexanecarboxylate), and the like.

  Next, the present invention will be described with reference to examples.

X^-：B(C₆F₅)₄ ^-
で表わされる、アモルファス状固体のウレタン結合含有スルホニウム塩化合物〔BSF-PI〕3.0g(収率88％)を得た。
赤外線吸収スペクトル：1735cm^-1 (-NHCOO-)
¹H NMR(CDCl₃)：4.55ppm (2H,C₆H₅CH ₂S＝)
3.02ppm (3H,-C₆H₄S(CH ₃)CH₂C₆H₅)
7.05−7.50ppm (10H,-C₆ H ₄S(CH₃)CH₂C₆ H ₅) Example 1
3.0 g (3.3 mmol) of benzyl-4-hydroxyphenylmethylsulfonium tetrakis (pentafluorophenyl) borate [BSF] was dissolved in 2.32 g of dry γ-butyrolactone, and 0.39 g (3.3 mmol) of phenyl isocyanate and triethylamine were dissolved in the solution. Add 1 μl, react for 1 hour at room temperature, precipitate in distilled water,

_{^{X -: B (C 6 F}} 5) 4 -
Thus, 3.0 g (yield 88%) of an amorphous solid urethane bond-containing sulfonium salt compound [BSF-PI] represented by
Infrared absorption spectrum: 1735cm ^-1 (-NHCOO-)
¹ H NMR (CDCl ₃ ): 4.55 ppm (2H, C ₆ H ₅ C H ₂ S =)
3.02ppm (3H, -C ₆ H ₄ S (C H ₃ ) CH ₂ C ₆ H ₅ )
7.05-7.50ppm (10H, -C ₆ H ₄ S (CH ₃ ) CH ₂ C ₆ H ₅ )

X^-：B(C₆F₅)₄ ^-
で表わされる、アモルファス状固体のウレタン結合含有スルホニウム塩化合物〔NSF-MDI〕2.1g(収率93％)を得た。
赤外線吸収スペクトル：1735cm^-1 (-NHCOO-)
¹H NMR(CDCl₃)：5.01ppm (4H,C₁₀H₇CH ₂S＝)
2.88ppm (6H,-C₆H₄S(CH ₃)CH₂C₁₀H₇)
3.89ppm (2H, -C₆H₄CH ₂C₆H₄-)
7.05−7.50ppm (10H,-C₆ H ₄S(CH₃)CH₂C₁₀ H ₇) Example 2
Naphthylmethyl-4-hydroxyphenylmethylsulfonium tetrakis (pentafluorophenyl) borate [NSF] 2.0 g (2.1 mmol) was dissolved in 1.26 g of dried γ-butyrolactone, and 4,4′-diphenylmethane diisocyanate [MDI ] 0.27 g (1 mmol) and 1 μl of triethylamine were added and reacted at room temperature for 1 hour, and then precipitated in distilled water.

_{^{X -: B (C 6 F}} 5) 4 -
As a result, 2.1 g (93% yield) of an amorphous solid urethane bond-containing sulfonium salt compound [NSF-MDI] represented by the formula:
Infrared absorption spectrum: 1735cm ^-1 (-NHCOO-)
¹ H NMR (CDCl ₃ ): 5.01 ppm (4H, C ₁₀ H ₇ C H ₂ S =)
2.88ppm (6H, -C ₆ H ₄ S (C H ₃ ) CH ₂ C ₁₀ H ₇ )
_{3.89ppm (2H, -C 6 H 4} C H 2 C 6 H 4 -)
7.05-7.50ppm (10H, -C ₆ H ₄ S (CH ₃ ) CH ₂ C ₁₀ H ₇ )

X^-：B(C₆F₅)₄ ^-
で表わされる、アモルファス状固体のウレタン結合含有スルホニウム塩化合物〔NSF-TI〕2.2g(収率90％)を得た。
赤外線吸収スペクトル：1720cm^-1 (-NHCOO-)
¹H NMR(CDCl₃)：2.45ppm (3H,-C₆H₄CH ₃)
3.05ppm (3H,-C₆H₄S(CH ₃)CH₂C₁₀H₇)
5.01ppm (2H,-C₆H₄S(CH₃)CH ₂C₁₀H₇)
7.0−8.0ppm (15H,C₆ H ₄SO₂NHCOOC₆ H ₄S(CH₃)CH₂C₁₀ H ₇) Example 3
Naphthylmethyl-4-hydroxyphenylmethylsulfonium tetrakis (pentafluorophenyl) borate [NSF] (2.0 g, 2.1 mmol) was dissolved in 2.4 g of dry γ-butyrolactone, and 0.43 g (2.1 wt. Mmol) and allowed to react at room temperature for 1 hour, then precipitated in distilled water,

_{^{X -: B (C 6 F}} 5) 4 -
As a result, 2.2 g (yield 90%) of an amorphous solid urethane bond-containing sulfonium salt compound [NSF-TI] was obtained.
Infrared absorption spectrum: 1720cm ^-1 (-NHCOO-)
¹ H NMR (CDCl ₃ ): 2.45 ppm (3H, -C ₆ H ₄ C H ₃ )
3.05ppm (3H, -C ₆ H ₄ S (C H ₃ ) CH ₂ C ₁₀ H ₇ )
5.01ppm (2H, -C ₆ H ₄ S (CH ₃ ) C H ₂ C ₁₀ H ₇ )
7.0−8.0ppm (15H, C ₆ H ₄ SO ₂ NHCOOC ₆ H ₄ S (CH ₃ ) CH ₂ C ₁₀ H ₇ )

Reference Examples 1-3, Comparative Examples 1-3
To 100 parts by weight of bisphenol A type epoxy resin (ADEKA product EP4100E), 1 part by weight of each of the urethane bond-containing sulfonium salt compounds obtained in Examples 1 to 3 was added, and the resulting epoxy resin composition Items were measured.
Storage stability: Measure the viscosity after 30 days at 0 ° C and calculate the rate of increase Curability: Yasuda-style gel time tester (No.153 gel time tester manufactured by Yasuda Seiki Seisakusho)
-) To measure the gel time at 150 ° C

The obtained results are shown in the following table together with the type of the urethane bond-containing sulfonium salt compound used. BSF-Ac is benzyl-4-acetoxyphenylmethylsulfonium tetrakis (pentafurphenyl) oborate.
table
Example Urethane bond-containing sulfonium storage stability curability (seconds)
Reference Example 1 BSF-PI 1.12 17
〃 2 NSF-MDI 1.02 15
３ 3 NSF-TI 1.01 15
Comparative Example 1 BSF 1.15 56
〃 2 NSF 1.18 21
〃 3 BSF-Ac 1.55 18

From the above results, the following can be said.
(1) The storage stability (increased viscosity) hardly changes in Reference Examples 2 to 3, and is suppressed to a little over 10% in Reference Examples 1 and Comparative Examples 1 and 2, whereas the curability is good. In Comparative Example 3 (fast curing), the increase in viscosity is slightly over 1.5 times.
(2) In Comparative Examples 1 and 2 having good storage stability, the curability (curing time) is inferior to that of each Example, and in Comparative Example 1 in particular, it is remarkable.

Claims (5)

General formula

(Here, R ¹ is an aromatic hydrocarbon group , R ² is an alkyl group having 1 to 6 carbon atoms, R ³ is an optionally substituted aromatic hydrocarbon group, and X ^- is a non-nucleophilic anionic group, n is an integer from 1 to 10, m is urethane sulfonium salt compound represented by 0 or 1 in a). Compound [I] is

The urethane bond-containing sulfonium salt compound according to claim 1. Compound [I] is

The urethane bond-containing sulfonium salt compound according to claim 1. General formula

The urethane bond-containing sulfonium salt compound according to claim 1. General formula

(Wherein R ² is an alkyl group having 1 to 6 carbon atoms, R ³ is an aromatic hydrocarbon group which may have a substituent, and X ⁻ is a non-nucleophilic anionic group. The method for producing a urethane bond-containing sulfonium salt compound according to claim 1, wherein the hydroxyl group-containing sulfonium salt represented by formula (II) is reacted with an aromatic hydrocarbon isocyanate compound [III].