JP4889097B2 - Polycycloolefin functional polysiloxane - Google Patents

Description

  The present invention relates to polycycloolefin functional polysiloxanes. A resin obtained from a compound having such a cyclopolyolefin structure and a polysiloxane structure is expected as a functional polymer having characteristics of both structures.

  In recent years, polycycloolefins have attracted attention as functional plastics for optical applications because of their excellent transparency, heat resistance, strength, and good film properties. On the other hand, organopolysiloxane has been put to practical use in a wide range of fields as a functional polymer having excellent heat resistance, water resistance and chemical resistance. A resin having such a polycycloolefin structure and a polysiloxane structure can be a functional polymer having the characteristics of both resins.

Monomers that can be used to prepare such polymers include norbornene functional siloxanes. Examples of the siloxane include 1,3-bis-bicyclo [2.2.1] hept-5 obtained by addition reaction of 2,5-norbornadiene and tetramethyldisiloxane in the presence of a platinum catalyst as shown below. -En-2-yl-1,1,3,3-tetramethyldisiloxane is known (Patent Document 1, Example 1).

  As a similar norbornene functional siloxane, the following is synthesized by addition reaction of norbornadiene and a corresponding SiH functional siloxane (Non-patent Document 1).

  Further, the following compounds obtained by subjecting cyclopentadiene and vinylsilanes to Diels-Alder reaction are known (Non-patent Document 2).

WO02 / 062859 JP 2003-252881 A Pierre M.M. Chevalier et al., “Ring-Opening Material Materials Polymerization (ROMP) as a Potential Cross-Linking Mechanical for Siloxane Polymers 15 (Journal of Inorganic 9”). Robert F. Cunico et al., “The Diels-Alder Reaction of α, β-Unactivated Trihalosilanes with Cyclopentadiene”, J. Am. Org. Chem. , Vol 36, No. 7, 1971

All the polysiloxanes mentioned above are bicyclic, that is, only k = 0 in the following formula (1). In order to utilize the excellent optical transparency, heat resistance, strength, and good film properties of polycycloolefin, polysiloxanes having more polycyclic groups are desired, but such polysiloxanes are still unknown. It is not done. Accordingly, an object of the present invention is to provide a polysiloxane having more cyclo rings than bicyclic groups.
In any of the polysiloxanes described above, silicon is difunctional or less, that is, two or more organic groups are bonded to the silicon. Therefore, an object of the present invention is also to provide a polysiloxane having trifunctional silicon.

  That is, the present invention is a polycycloolefin functional polysiloxane represented by the following average composition formula (1).

（式中Ｒ¹は互いに異なっていてよい、不飽和結合を有さず、フッ素原子で置換されていてもよい、炭素原子数１〜１０の一価炭化水素基であり、ｋは０より大きい数であり、ｎは０．０１以上４未満の数であり、ｍは０又は４未満の正の数であり、但しｍ＋ｎ＜４である）
また、本発明は、下記構造式（２）で示されるポリシクロオレフィン官能性ポリシロキサンである。

(Wherein R ¹ may be different from each other, without being have a unsaturated bond, a fluorine atom may be substituted, a monovalent hydrocarbon group having 1 to 10 carbon atoms, k is greater than 0 And n is a number from 0.01 to less than 4, and m is a positive number less than 0 or less than 4, provided that m + n <4)
Moreover, this invention is polycycloolefin functional polysiloxane shown by following Structural formula (2).

（式中Ｒ^２は、互いに独立に、炭素数１〜１２の、フッ素原子で置換されていてもよいアルキル基であり、ｊは０〜２の整数である）

(Wherein R ^2, independently of one another, from 1 to 12 carbon atoms or an alkyl group which may be substituted with a fluorine atom, j is an integer of 0 to 2)

  The above polycycloolefin functional polysiloxane is a material for thermosetting silicone resins having metathesis polymerizability and improved strength, hardness, transparency, refractive index, low moisture permeability, and adhesion based on the polycycloolefin structure. As expected.

  The above formula (1) is a composition formula, which includes a mixture of two or more types of polycycloolefin functional polysiloxanes and represents an average of their structures according to their amounts. For example, in the formula (1), k = 1.1 is a mixture (1.1 = 1 × 0.9 + 2 × 0.1) of 90 mol% for k = 1 and 10 mol% for k = 2. . It is only necessary to include those having k of 1 or more, and therefore k is a number greater than 0, preferably a number of 1 or more. The composition can be confirmed by gas chromatography analysis and elemental analysis as shown in the examples of the present invention. If the molecular weight of each polysiloxane is small and there is a sufficient difference between their boiling points, it can be isolated by distillation.

In Formula (1), R ¹ is a monovalent organic group having no unsaturated bond, which may be different from each other. Preferably, R ¹ is a monovalent hydrocarbon group having 1 to 10 carbon atoms, for example, an alkyl group such as methyl group, ethyl group, n-propyl group, butyl group, pentyl group, phenyl group, tolyl group, xylyl group. And these may have a substituent such as a fluorine atom. Among these, a methyl group, a phenyl group, and a trifluoropropyl group are preferable.

  Formula (2) is a structural formula. In the same formula

Ｒ^２は、互いに独立に、炭素数１〜１２の、置換されていてよいアルキル基であり、Ｒ¹について例示したものと同様の基が例示される。好ましくは、メチル基、フェニル基及びトリフロロプロピル基である。ｊは０〜２の整数である。後述する調製法により、通常、異なるｊを有する複数の化合物の混合物が得られる。これを、分離、例えば精密蒸留、することによって、一のｊに相当する単一化合物を得ることができる。式（１）において、ｋ＝０のいくつかのものは、上述したように公知であるが、式（２）においてｊ＝０のものは知られていない。

R ² is independently an alkyl group having 1 to 12 carbon atoms which may be substituted, and examples thereof are the same as those exemplified for R ¹ . Preferably, they are a methyl group, a phenyl group and a trifluoropropyl group. j is an integer of 0-2. A mixture of a plurality of compounds having different j is usually obtained by the preparation method described later. By separating this, for example, by precision distillation, a single compound corresponding to one j can be obtained. In Equation (1), some of k = 0 are known as described above, but in Equation (2), j = 0 is not known.

  The polycycloolefin functional polysiloxane of the above formula (1) is obtained from, for example, a vinyl group-containing polysiloxane represented by the formula (3) and cyclopentadiene.

該不飽和基含有ポリシロキサンとして、下記のものが包含される。

Examples of the unsaturated group-containing polysiloxane include the following.

In the formula, R ¹ is as described for formula (1). R ³ is a vinyl group.

  a and b are 0 or 1, and x, y, z, p and q are 0 or an integer of 1 or more, provided that when x, y and z are 0, a is 1, and a, x and p are In the case of 0, b is 1. Preferably, 0 ≦ x ≦ 50, 0 ≦ y ≦ 100, 0 ≦ z ≦ 20, 0 ≦ p ≦ 50, 0 ≦ q ≦ 100, 0 ≦ x + y + z ≦ 100, and 0 ≦ p + q ≦ 100. Further, s is an integer of 1 or more, and t is 0 or an integer of 1 or more, and 3 ≦ s + t ≦ 8.

Preferred as the unsaturated group-containing _{polysiloxane, ViMe 2 SiOSiMe 2 Vi, ViMe} 2 SiOSiMe 2 OSiMe 2 Vi, ViMe 2 Si (OSiMe 2) 10 Vi, (ViMeSiO) 4 ViMe 2 SiOSiViMeOSiMe 2 Vi, ViMe 2 Si (OSiMe 2) ₁₅₀ (OSiMeVi) ₃ OSiMe2Vi, Me ₃ SiO (MeViSiO) ₅ (CF ₃ CH ₂ CH ₂ SiMeO) ₁₅ (Me ₂ SiO) ₁₅ SiMe _{3 and the} like (where Me represents a methyl group and Vi represents a vinyl group) ).

Dicyclopentadiene is pyrolyzed to give 2 moles of cyclopentadiene (Organic Syntheses Collect, Vol. IV, p238).

  Pyrolysis occurs efficiently around 150 ° C. Since the produced cyclopentadiene is unstable and easily returns to dicyclopentadiene at room temperature, the produced cyclopentadiene is immediately reacted with bistrimethylsiloxymethyl vinyl silane “in-situ”. The 1 mol of dicyclopentadiene produced reacts with 2 mol of vinylsiloxane to give 2 mol of polysiloxane A as shown in the following formula (5).

Excess dicyclopentadiene reacts with polysiloxane A to give polysiloxane B as shown by the following formula (6).

Further excess dicyclopentadiene further reacts with polysiloxane B to give polysiloxane C as shown by the following formula (7).

In the above formula (5), by reacting tristrimethylsiloxymethylvinylsilane instead of bistrimethylsiloxymethylvinylsilane, as shown in formula (8), polysiloxane having trifunctional silicon of formula (2) Obtainable. Further, as in the formulas (6) and (7), a structure in which cyclopentadiene is added to the polysiloxane is obtained.

  As described above, a polycycloolefin-functional polysiloxane having a polysiloxane skeleton and a polycycloolefin skeleton can be synthesized. Examples thereof include the following.

上式でｐは 2〜1,000 である。

In the above formula, p is 2 to 1,000.

The above reaction proceeds by heating to 100 to 250 ° C. under atmospheric pressure, preferably under a nitrogen stream. Preferably it heats to 140 to 200 degreeC. At 140 ° C. or lower, the reaction is extremely slow and takes time to produce, and at 200 ° C. or higher, side reactions such as thermal decomposition may occur and the purity of the target product may be reduced.
Example

  EXAMPLES Hereinafter, although this invention is demonstrated in detail with reference to an Example, this invention is not limited to these Examples.

下記構造式で表される化合物が11モル％

の混合物であることが確認された。 [Example 1]
13 g (0.10 mol) of dicyclopentadiene and 50 g (0.20 mol) of bistrimethylsiloxymethylvinylsilane were charged into a 100 ml reactor and reacted at 160-175 ° C. for 4 hours under a nitrogen stream. When the reaction solution was distilled under reduced pressure, 37 g of a fraction having a boiling point of 97-102 ° C./9 mmHg was obtained. The fraction had a refractive index (n _D ²⁵ ) of 1.444. ^The structure was confirmed by ¹ H-NMR analysis (measurement device LAMBDA LA-300W manufactured by JEOL) (FIG. 1) and infrared spectroscopic analysis (measurement device Perkin Elmer FT-IR Spectrometer Spectrum One) (FIG. 2). From the peak area ratio of chromatographic analysis (GC-14B, manufactured by Shimadzu Corporation) and the like, this fraction contains 89 mol% of a compound represented by the following structural formula,

11 mol% of compounds represented by the following structural formula

It was confirmed to be a mixture of

下記化合物が７モル％の混合物であり、下記平均組成式

で表されるものであった。 [Example 2]
Dicyclopentadiene 50 g (0.38 mol) and bistrimethylsiloxymethylvinylsilane 50 g (0.20 mol) were charged into a 200 ml reactor and reacted at 160-175 ° C. for 4 hours under a nitrogen stream. When the reaction solution was distilled under reduced pressure, 42 g of a fraction having a boiling point of 104-110 ° C./5 mmHg was obtained. The refractive index (n _D ²⁵ ) of the fraction was 1.470. When gas chromatographic analysis, NMR analysis (FIG. 3) and infrared spectroscopic analysis (FIG. 4) were conducted in the same manner as in Example 1, this fraction was found to contain 93 mol% of the compound of the following formula:

The following compound is a mixture of 7 mol%, and the following average composition formula

It was represented by.

下記式の化合物12モル％、

の混合物であり、下記平均組成式

で表されるものであった。収率は91％であった。 [Example 3]
76.3 g (0.58 mol) of dicyclopentadiene and 100 g of methylvinyltetrasiloxane (vinyl number: 0.29 mol / 100 g) were charged into a 200 ml reactor and reacted at 160-175 ° C. for 6 hours under a nitrogen stream. . When the low boiling point component was removed by heating to 140 ° C. under a reduced pressure of 5 mmHg, 160 g of a light yellow viscous liquid was obtained at room temperature. The liquid had a refractive index (n _D ²⁵ ) of 1.501. When gas chromatographic analysis, NMR analysis and infrared spectroscopic analysis were performed in the same manner as in Example 1 (FIG. 5), this fraction was composed of a compound of the following formula, 88 mol%,

12 mol% of a compound of the formula

The following average composition formula

It was represented by. The yield was 91%.

［表１］

[Example 4]
141 g (1.07 mol) of dicyclopentadiene and 100 g (0.54 mol) of 1,3-divinyltetramethyldisiloxane were charged into a 500 ml reactor and reacted at 160 to 175 ° C. for 6 hours in a nitrogen stream. When the low boiling point component was removed by heating to 140 ° C. under a reduced pressure of 5 mmHg, 230 g of a pale yellow viscous liquid was obtained at room temperature. The refractive index (n _D ²⁵ ) of the liquid was 1.515. When the structure was confirmed by the result of infrared spectroscopic analysis (FIG. 6) and composition analysis (Table 1), this liquid had a structure represented by the following average composition formula.

[Table 1]

［表２］

[Example 5]
153 g (1.15 mol) of dicyclopentadiene and 100 g of methylvinylcyclotetrasiloxane (vinyl number: 1.16 mol / 100 g) were charged into a 500 ml reactor and reacted at 160-175 ° C. for 6 hours under a nitrogen stream. When the low boiling point component was removed by heating to 140 ° C. under a reduced pressure of 5 mmHg, 240 g of a pale yellow viscous liquid was obtained at room temperature. The refractive index (n _D ²⁵ ) of the liquid was 1.5230. When the structure was confirmed by the result of infrared spectroscopic analysis (FIG. 7) and composition analysis, this liquid had a structure represented by the following average composition formula.

[Table 2]

下記構造式で表される化合物が５％の混合物であることが確認された。

[Example 6]
132 g (1.00 mol) of dicyclopentadiene and 322 g (1.00 mol) of tristrimethylsiloxyvinylsilane were charged into a 500 ml reactor and reacted at 160-175 ° C. for 4 hours under a nitrogen seal. When the reaction solution was distilled under reduced pressure, 220 g of a fraction having a boiling point of 118-120 ° C./5 mmHg was obtained. The structure was confirmed by H-NMR analysis (measurement device LAMBDA LA-300W manufactured by JEOL) and infrared spectroscopic analysis (measurement device FT-IR Spectrometer Spectrum One manufactured by Perkin Elmer), and gas chromatography analysis (GC-manufactured by Shimadzu Corporation) From the peak area ratio of 14B), the compound represented by the following structural formula is 95%,

It was confirmed that the compound represented by the following structural formula was a 5% mixture.

[Example 7]
132 g (1.00 mol) of dicyclopentadiene and 322 g (1.00 mol) of tristrimethylsiloxyvinylsilane were charged into a 500 ml reactor and reacted at 160-175 ° C. for 4 hours under a nitrogen seal. When the reaction solution was precision distilled, 200 g of a fraction having a boiling point of 118 ° C./5 mmHg was obtained. The fraction had a refractive index (n _D ²⁵ ) of 1.4311 and a purity of 99% as a result of gas chromatography analysis (GC-14B, manufactured by Shimadzu Corporation). ^The structure was confirmed by ¹ H-NMR analysis (measuring device LAMBDA LA-300W manufactured by JEOL) (FIG. 8) and infrared spectroscopic analysis (measurement device Perkin Elmer FT-IR Spectrometer Spectrum One) (FIG. 9). It was confirmed that the compound was represented by the structural formula.

  The polycycloolefin functional polysiloxane of the present invention is expected to be used as a raw material for thermosetting silicone resins and as a modifier for polyolefin resins. The polycycloolefin functional polysiloxane having trifunctional silicon is expected to be used particularly for a film having high oxygen permeability.

2 is an NMR spectrum of the polysiloxane synthesized in Example 1. 2 is an IR spectrum of the polysiloxane synthesized in Example 1. 3 is an NMR spectrum of the polysiloxane synthesized in Example 2. 3 is an IR spectrum of the polysiloxane synthesized in Example 2. 3 is an IR spectrum of the polysiloxane synthesized in Example 3. 4 is an IR spectrum of the polysiloxane synthesized in Example 4. 6 is an IR spectrum of the polysiloxane synthesized in Example 5. 3 is an NMR spectrum of the polysiloxane synthesized in Example 7. 4 is an IR spectrum of the polysiloxane synthesized in Example 7.

Claims (4)

A polycycloolefin functional polysiloxane represented by the following average composition formula (1)

(Wherein R ¹ may be different from each other, without being have a unsaturated bond, a fluorine atom may be substituted, a monovalent hydrocarbon group having 1 to 10 carbon atoms, k is greater than 0 And n is a number not less than 0.01 and less than 4, and m is a positive number less than 0 or less than 4, provided that m + n <4). The polycycloolefin functional polysiloxane according to claim 1, wherein k is 1 to 2, n is 1/4 to 1, and R ¹ is a methyl group, a phenyl group, or a trifluoropropyl group. Polycycloolefin functional polysiloxane represented by the following structural formula (2)

(Wherein ^{R 2,} independently of one another, from 1 to 12 carbon atoms or an alkyl group which may be substituted with a fluorine atom, j is an integer of 0 to 2). R ² is methyl group, j is 0, polycycloolefin-functional polysiloxane according to claim 3, wherein.

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