KR20100123616A - Organopolysiloxane comprising monomethylallylisocyanuric ring on both ends - Google Patents

Abstract

(상기 화학식 1에 있어서, X는 서로 독립적으로 불포화 결합을 포함하지 않는 1가의 유기기, R은 서로 독립적으로 메틸기 또는 페닐기, n은 1~50의 정수 및 P는 1~10의 정수임)The present invention relates to both terminal monomethylallyl isocyanuric ring block organopolysiloxane,
Isocyanate which is an organopolysiloxane having an allyl isocyanuric ring structure represented by the following formula (1) at both ends and an alkenyl group at both terminals to give a cured product utilizing the characteristics of hydrosilylation (addition reaction). It is an object to provide a pressurized ring containing organopolysiloxane:
(Formula 1)

(In Formula 1, X is a monovalent organic group that does not contain an unsaturated bond independently of each other, R is a methyl group or a phenyl group independently of each other, n is an integer of 1-50 and P is an integer of 1-10)

Description

Both terminal monomethylallyl isocyanur ring block organopolysiloxane {ORGANOPOLYSILOXANE COMPRISING MONOMETHYLALLYLISOCYANURIC RING ON BOTH ENDS}

The present invention has a monomethyl allyl isocyanur ring at both terminals, and has excellent electrical properties such as heat resistance, mechanical strength, electrical insulation, gas permeability such as water vapor permeability, optical properties such as transparency, chemical resistance, and water resistance. It relates to an organopolysiloxane for imparting a cargo.

Conventionally, the curable silicone rubber composition which applied the addition hardening reaction is widely used. Such a curable silicone rubber composition is excellent in weather resistance, heat resistance and electrical insulation, and is widely used as a molding material such as a gasket material, a potting material, a coating material, a roll material, a mold removing material, an insulation coating material, and an automotive part material for electric and electronic parts. It is used. Moreover, utilizing the optical characteristic, it is utilized as a sealing material and adhesive agent of an optical semiconductor.

However, since such curable silicone rubber compositions have siloxane bonds unique to silicones, their ionic bondability prevents silicones from exhibiting excellent properties such as chemical resistance, water resistance, and gas permeability under extremely stringent use environments under high temperature and humidification. have. In addition, there is a drawback in that the surface of the cured product has wrinkles and is easily attached to dust or the like. In particular, polymers containing siloxane bonds are excellent in gas permeability and are utilized as oxygen enrichment membranes, but their water vapor permeability is a problem as a sealing material for semiconductors.

This invention was made | formed in view of the said situation, and the present inventors earnestly examined and discovered that the isocyanuric ring containing organopolysiloxane gives the hardened | cured material excellent in the said characteristic.

Various are known as a polymer containing a isocyanur ring, a polymer, and a sealant. As Si-H containing polysiloxane, what hardened isocyanuric group containing polysiloxane which addition-reacted diallyl monoglycidyl isocyanurate by ring-opening reaction of an epoxy group (patent document 1), isocyanur ring containing polysiloxane and Si- The thing which hardened | cured by addition-reacting H containing polysiloxane (patent document 2), the thing which hardened | cured by addition-reacting the triallyl isocyanurate and Si-H containing polysiloxane (patent document 3), the isocyanuric ring, and Si-H The thing which hardened by addition-reacting the polysiloxane to contain and an alkenyl-group containing compound (patent documents 4-6) is known.

However, since the isocyanurate ring containing polymer of patent documents 1 and 2 contains a siloxane bond in a subject, although it is flexible, it is bad in compatibility with a crosslinking agent.

Moreover, since the isocyanuric ring containing polymers of patent documents 1 and 2 are indefinite in the presence position of an alkenyl group, hardening by addition reaction is difficult, and the characteristic (fast curing reaction) of hydrosilylation (addition reaction) is not utilized. Do not. The isocyanuric acid containing polymer of patent documents 3-6 has a high crosslinking density, is rigid, and lacks flexibility.

As a hardened | cured material by addition reaction of isocyanuric ring containing polysiloxane and Si-H containing polysiloxane, there is no hardened | cured material which is excellent in flexibility, hardening characteristic, and compatibility, and excellent in optical characteristic and water vapor permeability.

Japanese Laid-Open Patent Publication No. 2008-143954 Japanese Laid-Open Patent Publication No. 2008-150506 Japanese Patent Laid-Open No. 9-291214 Japanese Patent Publication No. 4073223 Japanese Laid-Open Patent Publication No. 2006-291044 Japanese Laid-Open Patent Publication No. 2007-9041

An object of the present invention is to provide an isocyanur ring-containing organopolysiloxane capable of imparting a cured product utilizing the characteristics of hydrosilylation (addition reaction) by providing alkenyl groups at both ends.

That is, this invention is organopolysiloxane which has the allyl isocyanur ring structure represented by following General formula (1) at both ends.

(In Formula 1, X is a monovalent organic group that does not contain an unsaturated bond independently of each other, R is a methyl group or a phenyl group independently of each other, n is an integer of 1-50 and P is an integer of 1-10)

1 is an NMR spectrum of Compound I prepared in Examples; And
2 is a GPC spectrum of Compound I prepared in Example.

The organopolysiloxane of the present invention is an isocyanuric ring-containing organopolysiloxane represented by the formula (1), and is characterized by having a diallyl isocyanuric ring at both ends of the polymer.

In formula (1), each R is independently a methyl group or a phenyl group, preferably a methyl group due to the curing properties, flexibility, and ease of synthesis of the composition, and 50 mol% or more of the total R is preferably a methyl group.

X is a monovalent organic group which does not contain an unsaturated bond each independently. X is an alkyl group and an aryl group, for example, a C1-C4 alkyl group is especially preferable, More preferably, it is a methyl group.

n is an integer of 1-50, Preferably it is an integer of 1-30.

P is an integer of 1-30, Preferably it is an integer of 1-10.

The weight average molecular weight of the said organopolysiloxane is 500-10000, Preferably it is 600-5000.

The viscosity at 25 degrees C of the said organopolysiloxane is 0.5-1000 Pa * S, Preferably it is 1-100 Pa * S.

The isocyanurate ring containing organopolysiloxane of this invention can be manufactured by addition-reacting the diallyl isocyanurate represented by following formula (2), and the terminal hydrogen siloxy group-blocked organopolysiloxane represented by following formula (3). have. The reaction temperature is room temperature to 250 ° C, preferably 50 to 180 ° C. Moreover, reaction time is 0.1 to 120 hours, Preferably it is 1 to 10 hours.

(In the above formula, R, X, n are as described above).

The organopolysiloxane of the formula (3) is reacted with the compound of the formula (2) in an amount such that the Si—H group is 0.1-0.9 equivalents, preferably 0.4-0.7 equivalents (allyl-based excess) relative to 1 equivalent of allyl group. Thereby, the organopolysiloxane which has a diallyl isocyanur ring at both ends can be obtained.

For the reaction, a compound containing, for example, platinum, rhodium or palladium can be used as the catalyst. Especially, the compound containing platinum is preferable, Hexachloro platinum (IV) acid hexahydrate, platinum carbonyl vinyl methyl complex, platinum- divinyl tetramethyl disiloxane complex, platinum-cyclovinyl methylsiloxane complex, platinum-octylaldehyde Platinum supported on a / octanol complex or activated carbon can be used. It is preferable that the compounding quantity of a catalyst becomes 0.01-10,000 ppm of metals with respect to the compound of General formula (2), More preferably, it is 0.1-100 ppm.

Moreover, in manufacture of the polyorganosiloxane of this invention, a solvent can be added to a reaction mixture as needed. Toluene, xylene, mesitylene, diethylbenzene, tetrahydrofran, diethyl ether, 1, 4-dioxane, diphenyl ether, etc. can be used as a solvent.

The isocyanurate ring-containing organopolysiloxane of the present invention may be reacted with a compound having a SiH group to give a cured product excellent in mechanical properties, heat resistance, electrical insulation, chemical resistance, water resistance, gas permeability, and optical properties. The said hardened | cured material is an optimal material for optical materials, such as a lens for LEDs and a sealing material for LEDs which require transparency, and especially the sealing material of a semiconductor.

(Example)

Hereinafter, although this invention is further demonstrated with reference to an Example and a comparative example, this invention is not limited to these Examples.

(Example 1)

400 g (1.79 mol) of monomethyldiallyl isocyanurate, 400 g of toluene, and 0.32 g of toluene solution containing chloroplatinic acid (containing 0.5% by weight of platinum) in a 2 L separable flask and heated to 100 ° C. 120 g (0.89 mol) of 1,1,3,3 tetramethyldisiloxane of this was dripped, and after stirring at 100 degreeC for 8 hours, toluene was removed under reduced pressure and the colorless transparent liquid was obtained.

^{As a} result of the measurement by ¹ H-NMR, the peak based on Si-H proton (near 4.6 ppm) was lost, and the peak based on vinyl proton (near 5.0 to 5.4 and around 5.7 to 6.0 ppm) remained, resulting in monomethyldiallyl. It was confirmed that a part of the allyl group of isocyanurate reacts with 1,1,3,3 tetramethyldisiloxane of the formula (4). The weight conversion molecular weight was 1200 as a result of the measurement by GPC. [P average: 2.6, vinyl value: 2.48 mmol / g, viscosity (25 ° C.): 3.0 Pa · s]

The product is a mixture of an unreacted raw material (monomethyldiallylisocyanurate) and a reaction product having a different degree of polymerization, but contains the following chemical formula 5 as a main component from the results of the GPC and NMR measurements (called "Compound I"). Was confirmed. As a result of measurement by GPC, unreacted material (monomethyldiallyl isocyanurate) was 18.5% by weight, P = 1 in Formula 5 was 27.3% by weight, P = 2 was 22.3% by weight, P = 3 was 14.8% by weight, P = 4 was 8.1 weight%, P = 5 or more was 9.0 weight%, and the weight conversion molecular weight of compound I except the unreacted substance was 1468 (P: average 3.3).

NMR and GPC of Compound I are shown in FIGS. 1 and 2.

NMR: AVANCE3400 type (manufactured by Buruka Biospin, Inc.), ¹ H-NMR

GPC: SC-8020 (made by Tosoh Corporation)

The viscosity of each compound was measured at 25 degreeC using the BM-type rotational viscometer.

(Example 2)

500 g (2.24 mol) of monomethyldiallyl isocyanurate, 500 g of toluene and 0.79 g of toluene solution containing chloroplatinic acid (containing 0.5 wt% as platinum) were placed in a 3 L separable flask and heated to 100 ° C., 820 g (1.12 mol) of terminal hydrogensiloxane was added dropwise, and after stirring at 100 ° C. for 8 hours, toluene was distilled off under reduced pressure to obtain a colorless transparent liquid.

^{As a} result of the measurement by ¹ H-NMR, the peak based on Si-H proton (near 4.6 ppm) was lost, and the peak based on vinyl proton (near 5.0 to 5.4 and around 5.7 to 6.0 ppm) remained, resulting in monomethyldiallyl. It was confirmed that part of the allyl group of the isocyanurate reacts with the terminal hydrogensiloxane. The weight conversion molecular weight was 1830 as a result of the measurement by GPC. [P Average: 1.7, Vinyl Value: 1.67 mmol / g, Viscosity (25 ° C): 0.2 Pa.s]

Although the product is a mixture of unreacted raw materials and reaction products having different degrees of polymerization, it was confirmed from the measurement results of GPC and NMR that the following were contained as main components (called "Compound II"). The weight-average molecular weight of Compound II, excluding the unreacted product, was 2650 (P: average 2.6).

(Example 3)

0.5 kg (2.24 mol) of monomethyldiallyl isocyanurate, 1.0 kg of toluene and 1.17 g of toluene solution of chloroplatinic acid (containing 0.5 wt% as platinum) were placed in a 5 L separable flask and heated to 100 ° C. 1.63 kg (1.12 mol) of terminal hydrogensiloxane of the formula (8) was added dropwise, stirred at 100 ° C. for 8 hours, and then toluene was distilled off under reduced pressure to obtain a colorless transparent liquid.

^{As a} result of the measurement by ¹ H-NMR, the peak based on Si-H proton (near 4.6 ppm) was lost, and the peak based on vinyl proton (near 5.0 to 5.4 and around 5.7 to 6.0 ppm) remained, resulting in monomethyldiallyl. It was confirmed that a part of the allyl group of the isocyanurate reacts with the terminal hydrogensiloxane of the formula (8). The weight conversion molecular weight was 4200 as a result of the measurement by GPC. [P average: 2.3, vinyl number: 1.05 mmol / g, viscosity (25 ° C.): 0.1 Pa · s]

Although the product is a mixture of unreacted raw materials and reaction products having different degrees of polymerization, it was confirmed from the measurement results of GPC and NMR that the following formula (9) was included as a main component (called "Compound III"). The weight-average molecular weight of Compound III, excluding the unreacted product, was 5530 (P: average 3.2).

Since the isocyanurate ring-containing organopolysiloxane of the present invention has an alkenyl group at both ends, the organosilicon skeleton reacts with a compound having a SiH group so that the organic silicone skeleton has mechanical properties, heat resistance, electrical insulation, chemical resistance, water resistance, gas permeability, and optical properties. Excellent hardened | cured material can be provided. The said hardened | cured material is an optimal material for optical materials, such as an LED lens and LED sealing material which require transparency, and a sealing material of especially a semiconductor.

Claims (2)

Organopolysiloxane having an allyl isocyanuric ring structure represented by the following formula (1) at both ends:
(Formula 1)

(In Formula 1, X is a monovalent organic group that does not contain an unsaturated bond independently of each other, R is a methyl group or a phenyl group independently of each other, n is an integer of 1-50 and P is an integer of 1-10) The method of claim 1,
X in the formula (1) is an organopolysiloxane, characterized in that an alkyl group having 1 to 4 carbon atoms.

Images