TW201041938A - Terminal hydrogenpolysiloxane having isocyanuric ring - Google Patents

Abstract

A terminal hydrogenpolysiloxane having isocyanuric ring is provided and is suitable for being used in a sealant for optical semiconductors. A hydrogenpolysiloxane is provided, and the hydrogenpolysiloxane, as shown in formula (1), has an isocyanuric ring and at least two terminal hydrogen siloxy groups. (X are independent univalence organic groups without unsaturated bonding, R are independent methyl or phenyl, n is an integer between 1 and 50, m is an integer between 0 and 5, and P is an integer between 1 and 10.)

Description

[Technical Field] The present invention relates to an organic polyoxoxiene which has a hydrogen polyoxyalkylene moiety at its end and is capable of producing electrical properties such as heat resistance, mechanical strength, electrical insulation, and the like. A cured product excellent in optical properties such as gas permeability and transparency such as water vapor permeability and chemical resistance, and chemical resistance and water resistance. [Prior Art] In the past, a hardenable silicone rubber composition to which an addition hardening reaction was applied was widely used. Such a curable ruthenium rubber composition is excellent in weather resistance, heat resistance, and electrical insulation, and is widely used as a gasket material, a potting material, and a coating for electric and electronic parts. Forming materials such as coating materials, roll materials, impression materials, wire coating materials, and automotive parts materials. Further, it is effective in utilizing its optical characteristics and is used as a sealing material or an adhesive for an optical semiconductor. However, such a sclerosing ruthenium rubber composition has a siloxane bond peculiar to anthrone, and therefore, due to its ion binding property, there is a phenomenon that it is extremely humidified at a high temperature. In a strict use environment, excellent properties such as chemical resistance, water resistance, and gas permeability of an anthrone are not exhibited. Further, there are disadvantages in that the surface of the cured product is sticky, and dust is easily attached. In particular, a polymer containing a ruthenium oxygen bond is excellent in gas permeability and can be used as an oxygen enrichment membrane. However, as a sealing material for semiconductors, the water vapor permeability is problematic. In the present invention, the inventors of the present invention have conducted an intensive study on ninth and sigma, and found that an organic polyfluorene oxide containing an iso-cyanuric acid ring can produce a cured product excellent in the above characteristics. ❹ 已知 There are known f compounds in polymers, polymers and sealants containing iso-cyanuric acid rings. It is known that a polyisocyanin-containing disulfide-containing polydisulfide-containing di-propyl propyl-containing poly-glycolyl group-containing polyoxo-oxygen is obtained by performing an addition reaction. A compound obtained by hardening a ring-opening reaction of an oxy group = a compound of the invention, and a compound obtained by an addition reaction of a poly-trimerized oxygen-containing wire containing Si_H (Japanese Patent) Special open 2〇〇815〇5〇6 bulletin), let's triallyl iSGeyanumte & containing &-H poly-wei Qiang addition reaction hardening shouting compound (Japanese 'this Japanese Patent No. 9-291214, and the compound of the prefecture containing the iso-cyanuric acid ring and the &-Η-containing compound is subjected to a domain reaction and hardening (Japanese Patent No.) Japanese Patent Laid-Open Publication No. Hei. No. 2006-291044, Japanese Patent Application Laid-Open No. Hei No. Hei. However, the polymer containing an iso-cyanuric acid ring of the Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The compatibility of the crosslinking agent is poor. In addition, the Japanese Patent Special Open Toilet - (10) No. 54 and the Japanese Laid-Open No. 2008-150506 contain the difference of the presence of the singapore: the position of the gynecological base is fixed, so it is difficult to harden the addition reaction, and the 201041938 34300pif cannot be effectively used. Characteristics of hydrazine hydrogenation (addition reaction) (rapid hardening reaction). The intersection of a polymer containing iso-cyanuric acid of JP-A-2007-291044, JP-A-2006-291044, and JP-A-2007-9041 The joint density is high, straight and lacks softness. These compounds are an addition reaction of a polydecane which contains an iso-cyanuric acid ring and a polysiloxane containing Si—H to form softness, hardenability, compatibility, and excellent optical property resistance. Hardened material. DISCLOSURE OF THE INVENTION An object of the present invention is to provide a terminal hydrogen polyoxyalkylene containing an iso-cyanocyanate ring which can be suitably used in a photo-blocking agent or the like. Oxygen Λ Λ Λ - - 财 财 财 财 财 财 财 财 财 财 财 财 财 财 财 财 财 财 财 财 财 财 财 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如

, 11 mutually to 5 (X is independently of each other, the monovalent group containing no unsaturated bond is independently methyl or phenyl, η is an integer of 1 to 5 G, m is an integer, and P is 1 to 10 Integer). The above features and advantages of the present invention will become more apparent from the following description. [Embodiment] The present invention has an isomeric cyanuric acid-containing organic polyoxo-oxygenate of the above formula (1), which has at least two upper terminal hydrofluorenyloxy groups. In the formula (1), R is a methyl group, and is preferably a methyl group from the viewpoint of hardening properties, flexibility, and synthetic properties of the composition, and preferably 50 mol% or more of all R is a mercapto group. The X-point is turned upside down to a monovalent organic group containing no unsaturated bond. For example, a mercapto group or an aryl group is preferably a group having a carbon number of 1 to 4, more preferably a mercapto group. η is an integer of 1 to 50, preferably an integer of 1 to 3 Å. m is an integer of 0 to 5, preferably an integer of 0 to 2. P is an integer of 1 to 30, preferably an integer of 1 to 1 Å. The organopolyoxyalkylene has a weight average molecular weight of 5 Å to 1 Torr, preferably 600 to 5,000. 〇 The viscosity of the organopolyoxane at 25 ° C is Pa.s~1〇〇

Pa · S, preferably 0.5 Pa · S 10 10 Pa · S. The polyisocyanate containing organic polyfluorene oxide of the present invention can be obtained by using a monopropyl isopropyl isocyanate represented by the following formula (2) and a terminal represented by the following formula (3). The hydroxyloxy group-terminated organopolyoxane is produced by an addition reaction. The reaction temperature is from room temperature to 25 (rc, ^ is selected from 50 ° C to 180 ° C. Further, the reaction time is 〇·丨 hours to 丨 2 〇 hours, preferably from 1 hour to 10 hours. (2) 201041938 34300pif

RR Γ R 1 { "R 1 | a SUCH —SK) - 1 ILR · n-1 « 0 e ShH i RR - SI IH (3) Here, R, X, n, m are as described above. The organic polyoxo-oxygen is based on the equivalent of propyl i, the amount of si_H f is U * amount ~ 2. i equivalent, preferably U equivalent: 5; the amount of Qingna has, for example, a releasable hull (four) 11 Wei Kefeng - face to face money, fH3 ch3 1 divination ch3 ch3 8 201041938 343ϋϋριί Η

CH3 Si~ i CH3

Ch3 Y ch3

H~Si-O-Si-0-Si- gs I I I 〇 ch3 o CH3

H3C-Si-CH3 H

H3C-—i—CH3 H 201041938 34300pif

CH3 Ning H3 (1) ~ This b n-Θ-〇一由·——Ο

i u I I ch3 o ch3 3 1 H3C-甲一 CH3

H In the reaction, for example, a compound containing platinum, rhodium or palladium can be used as a catalyst. Among them, a platinum-containing compound is preferably used, and hexa-uranyl uric acid hexahydrate, platinum-carbonyl vinyl fluorenyl complex, platinum-divinyltetradecyl sulphur gas, and platinum-cyclovinylmethyl group can be used. A sulphur-oxygen complex, a platinum octane octanol complex, or a surface supported on activated carbon. The amount of the catalyst to be added is preferably 0.01 ppm to 1,000,000 ppm, more preferably 〇a ppm to i〇〇ppm, based on the compound of the formula (7). Further, in the production of the polyorganosiloxane of the present invention, it may be necessary to add a solvent to the reaction mixture. As the solvent, toluene, xylene, mesitylene, diethylbenzene, tetrahydrofuran, diethyl ether, 1,4-dioxane, diphenyl ether or the like can be used. The following compounds can be exemplified for the organic polyoxoxime which is produced by the above method. 201041938 j4juupir

有机 明 有 的 的 的 的 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机Hardened material. The cured product is an optical material such as a lens for LED or a sealing material for LED which is required for transparency, or a material for a sealing material of a semiconductor. [Examples] Hereinafter, the present invention will be further described with reference to examples and comparative examples, but the present invention is not limited by the examples. [Example 1] 1,1,3,3-tetramethyldioxane 3〇〇g (2.24 mol) of the following formula (4), 300 g of toluene was charged into a separable separation of 2 L In a flask (separabie flask), after heating to 8 (rc, adding toluene solution of toluene solution 〇42g (containing 0.5% by weight of platinum), monodecyl diallyl isocyanurate 25 was added dropwise. A mixed solution of 〇g (1.12 mol) and 25 g of toluene was stirred at 100 ° C for 10 hours at 201041938 34300 pif, and then the benzene was distilled off under reduced pressure to obtain a colorless, transparent liquid.

II Η-Si-Ο-Si-Η (Α\ ! I (4) οη3 οη3 The result of iH-NMR measurement is based on the disappearance of the peak of vinyl proton (5.0 ppm~5.4 ppm, near 5.7 ppm~6.0 ppm), based on The peak of the Si-H proton (near 4.6 ppm) remains, thereby confirming the allyl group of monodecyl diallyl isocyanurate and the above 1,1,3,3-tetradecyldifluoride The Si-H group of one end of the oxane is reacted. The product is a mixture of unreacted raw materials and a reaction product having a different degree of polymerization. According to the results of GPC and NMR measurement, it is confirmed that the following formula (5) is contained as a main component (remember The result of the GPC measurement was a weight-converted molecular weight of 1,260. (P: average of 2.9, SiH value: 3.69 mmol/g, viscosity (25t: ): 1.1 Pa · S)

The NMR and GPC of the compound I are shown in Fig. 1 and Fig. 2 . 12 201041938 ^^f^uupil NMR: JMNLA-300WB (manufactured by JEOL Co., Ltd.), iH-NMR GPC: SC-8020 (manufactured by Tosoh Corporation) The viscosity of each compound was measured at 25 ° C using a BM type rotational viscometer. [Example 2] 650 g (0.89 mol) of terminal hydrooxane of the following formula (6) and 650 g of toluene were placed in a 3 L separable flask, heated to 80 ° C, and gas platinum acid was added dropwise. After 0.84 g of a toluene solution (containing 0.5 wt% of platinum), a mixed solution of 100 g (0.44 mol) of monomethyldiallyl isocyanurate and 1 g of hydrazine was added dropwise. After stirring at 100 ° C for 8 hours, toluene was distilled off under reduced pressure to give a colorless, transparent liquid.

The result of CH3 ch3 η m 9 b-NMR measurement is based on the disappearance of the peak of vinyl proton (5.0 ppm to 5.4 ppm, near 5.7 ppm to 6.0 ppm), and the peak based on Si-H proton (near 4.6 ppm) remains. This confirmed that the allyl group of monomethyldiallyl isocyanurate was reacted with the Si-H group at one end of the terminal hydroxylane of the above formula (6). The product was a mixture of unreacted raw materials and a reaction product having a different degree of polymerization. According to the results of GPC and NMR measurement, it was confirmed that the following formula 13 201041938 34300 pif (7 ) was contained as a main component (referred to as "compound ΙΓ"). The result was a weight-converted molecular weight of 2440. (P: average 1.8, SiH value: 0.59 mmol/g, viscosity (25 ° C): 0.2 Pa · S)

[Example 3] 900 g (2.73 mol) of terminal hydroxane of the following formula (8) and 900 g of toluene were placed in a 3 L separable flask, heated to 100 ° C, and bismuth ruthenium silicate was added dropwise. After a benzene solution of 71 g (containing 0.5 wt% of platinum), a mixed solution of 300 g (1.34 mol) of monodecyl diallyl isocyanurate and 300 g of toluene was added dropwise. After stirring at 10 ° C for 8 hours, the benzene was distilled off under reduced pressure to give a colorless, transparent liquid. ·

CH3 ch3 ο H3C-Si-CH3 H (8) ch3

The result of iH-NMR measurement is based on the disappearance of the peak of the vinyl proton (5.0 ppm to 5.4 ppm, near 5.7 ppm to 6.0 ppm), and the peak based on the Si-H 14 201041938 34300 pif proton (near 4-6 ppm) remains. The propyl group of the fluorenyl mono-l-propyl iso-trimeric acid S is reacted with the Si-H group at one end of the terminal hydroxylane of the above formula (8). The product was a mixture of an unreacted raw material and a reaction product having a different degree of polymerization. From the results of GPC and NMR measurement, it was confirmed that the following formula (9) was contained as a main component (referred to as "compound III"). As a result of GPC measurement, the molecular weight in terms of weight conversion was 2,470. (P: average 3.8, SiH value: 4.54 ^ mmol/g, viscosity (25.): 0.4 Pa · S)

The NMR and GPC of the compound III are shown in Fig. 3 and Fig. 4 . [Industrial Applicability] The organopolydecane containing an iso-cyanocyanate ring of the present invention has at least two terminal hydrogen oxime groups, and thus can react with a compound having a vinyl group to produce an organic stone eve. A cured product having excellent mechanical properties, richness, electrical insulating properties, chemical resistance, water resistance, gas permeability, and optical properties of the ketone skeleton. The cured product is an optical material such as an LED lens or a sealing material for LED which is required to have transparency, or a material which is particularly a semiconductor sealing material. Although the present invention has been disclosed in the above embodiments, it is not intended to limit the scope of the present invention. Any one of ordinary skill in the art can make a few changes without departing from the spirit and scope of the present invention. Retouching, the original, the scope of protection of the Ming Dynasty is attached to the scope of the patent application [simplified description of the diagram] test for the car. Figure 1 is an NMR spectrum of Compound I prepared in the examples. Figure 2 is a Gpc spectrum of compound j prepared in the examples. Figure 3 is a NMR spectrum of the compound III 调制 prepared in the examples. Figure 4 is an example of the preparation of the towel i 曰 [Main component symbol description] Nine% None 16

Claims (1)

201041938 34300pif VII. Applying for a patented version ······································· (1) - is an integer of 〇~5, and an integer of the whole I 5〇 of PW~10'. 2) H) is a material in the first item, where X is a carbon number. Is an alkyl group of i~4. 17